Literature Reviews Recombinant Enzyme Production for Pulp and Paper Industry and Its Prospect in Indonesia

ISBN : 978-602-17761-4-8 36 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech in the future along with the advancement of human civilization and population increase. Such increase one day can not be overcome with processing results of conventional iber stuffs esp. natural forest woods as their potencies become depleted and scarce [2,3]. One way to cope with those problems is introducing alternative ibers, and among them are plantation forest PF woods [4]. Being located in tropical region, Indonesia can have a huge diversity in its vegetations including forest trees with respect to species or related sorts. This can also lead to variation in PF wood species and hence their basic properties. Variation in wood species can bring about ineficiency in their utilization and processing into pulppaper, and therefore deserve thorough attention [5]. Indicatively, wood pulping with kraft process can tolerate species difference to some extent through an appropriate process modiication. The modiication is such that kraft pulping affords effective active-selective deligniication, high screen-pulp yield, low pulp rejects, and high pulp strengths, as those are related to qualities of paper or other pulp derivatives that result [1,6]. Variables in kraft pulping that affect those properties are among others temperature and duration of cooking. For simpliication, those two variables can be expressed as a single variable, called the H-factor [7]. Relevantly, there has been experimented to assess the role of particular basic properties wood density, lignin content, and ratio of syringilvanillin-based monomers in lignin of four tropical PF wood species, i.e. sengon, gmelina, meranti kuning, and kapur, on the deligniication extentintensity and properties of kraft pulp that resulted at various H-factor levels [5,8].

2. Literature Reviews

Plantation forest PF woods as also the case for natural forest woods and woods in common, in their iber wall contain lignin, cellulose, and hemicellulose [5]; and accordingly PF woods are technically worth for pulppaper processing. Several PF wood species have been adopted for the establishment of PF, e.g. sengon, gmelina, meranti kuning, and kapur 4. Different PF wood species can affect pulping properties e.g. deligniication extent and pulp yield; and further qualitiesproperties of pulp, paper, and other pulp derivatives [5,8]. Kraft process indicatively can tolerate wood species difference, thereby expectedly appropriate for the pulping of various tropical wood species, including PF woods through properly modifying condition of processcooking [5,6]. Such condition e.g. cooking temperature and duration can also affect deligniication extent, pulp yield, and ultimately kraft pulp properties. Cooking temperature and duration is inter-dependent, whereby the greater the temperature the shorter the duration; and vice versa. Further, Vroom developed a method that smartly simpliied those two variables into a single variable H-factor. Greater H-factor implies that kraft cooking condition becomes more severe and therefore intensiies the deligniication action; and vice versa. In this way, accordingly, H-factor can be regarded as theoretical deligniication intensity, regardless of differences in wood or other ligno-cellulose iber species and other varying kraft cooking conditions e.g. active alkali, sulidity, and wood-to-liquor ratio than cooking temperature and durations as such [1,6,7]. 3. Methodology 3.1. Main Materials The main materials were tropical plantation-forest PF woods that consisted of four species, i.e. sengon, gmelina, meranti kuning, and kapur Table 1. Fist two species were obtained from Jatinangor, Sumedang West Java, while the latter two from Berau East Kalimantan. 3.2. Methods 3.2.1. Analysis on Wood Samples Wood samples were prepared from each of those four FP species for the determination of basic density and lignin content Table 1 in accordance with procedures and standards of TAPPI [9]. The ISBN : 978-602-17761-4-8 37 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech obtained lignin was subjected to exhaustive nitrobenzene oxidation to convert sinapyl alcohol and coniferyl alcohol monomers inside into consecutively syringil and vanillin units Figure 1. The ratio of syringil-to-vanillin units could further be igured out Table 1 through gas chromatography procedures developed by McNair and Bonelli [7]. 3.2.2. Kraft Pulping on PF Woods and Further Related-Scrutinies Wood samples of each PF wood species were manually reduced in size to chips measuring 3-4 cm length by 2.25-2.50 cm width by 2-3 mm thickness, and then allowed for some time under the roof to reach their air-dry moisture content 12-14. Afterwards, the wood chips of each PF species were cooked into pulp by kraft process in an electrically heated rotary digester of 20-liter capacity per batch. Fixed cooking conditions were active alkali 13, sulidity 22.5, wood-to-liquor ratio 1:4, wv, and ramping-duration rate to maximumkeeping temperature 1.580 o Cminute. Variable conditions were two levels of maximum temperature 170 o C and 175 o C; and the overall total cooking- durations of those required from room temperature to reach each of those two maximum keeping temperature, added with the durations held at those maximum temperatures i.e. 0, 30, 60, and 90 minutes. The combination of those overall cooking durations t and maximum temperatures T was further manipulated using Vroom method Equation I, thereby bringing-out 8 varying H-factor values 117.88-2182.67 Table 2, and accordingly 8 softened cooked-chip varieties pulp candidates for any of the four PF wood species Figure 2a; Appendix A. where: • t = particular cooking duration beginning from room temperature, ramping temperature, until end of keeping temperature; • T = absolute cooking temperature in o K = o C + 273 at end of particular cooking duration t, including the room temperature where the cooking starts, raising ramping temperature, and keeping temperature After kraft cooking, the 8 varieties of softened chips were each vigorously agitated using a stirrer into separated ibers pulp. Afterwards, the resulting kraft pulp was passed through a 0.25-mm- slotted packer sceen. Before screening, some amount of pulp was taken for the determination of total unscreened pulp yield, while the portion passing through the screen was determined as screened- pulp yield. Pulp reject was calculated by subtracting unscreened-pulp yield with screened-pulp yield. Further, residual lignin content in unscreened pulp was determined according to TAPPI standards [9]. The actual deligniication intensity was virtually approached ≈ by dividing the particular H-factor value theoretical deligniication intensity in kraft cooking pulping by residual lignin content in its corresponding unscreened pulp corrected to the totalunscreened pulp yield and then oven-dry weight of the related cooked wood chips [6,7], and then transformed into e logarithmic Ln, as follows: Figure 1. Phenyl-propane lignin monomer as conifery al cohol A with vanillin-type unit V; and another phenyl-propane lignin monomer as sinapyl alcohol B with syringil-type unit S [6,10, 11] ISBN : 978-602-17761-4-8 38 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Actual deligniication intensity Li ≈ [ H ΔL ] [Y 100 ] ------------------------------------ II where: • H = calculated H-factor refer to Equation I; ΔL = residual lignin content in unscreened pulp; Y = total unscreened pulp yield ; the obtained actual deligniication intensity Li was further transformed into e logarithmic ln; e = 2.71828 or in other words went through the ln transformation Figure 2a; Appendix A

3.2.3. The Forming of Kraft Pulp Sheet

Kraft screened-pulp yield that reached the highest over particular H factor was selected and further formed into handsheet without beating. Afterwards, the pulpsheets were conditioned for about 24 hours and then tested for their physical-strength properties also in accodance with the TAPPI standards [9]. 4. Results and Discussion 4.1. Wood Basic Properties The examined wood properties covered basic density, lignin content, and ratio of syringil-to-vanillin lignin monomers Table 1. There was strong indication that those properties differed among the four FP wood species Table 1: Basic properties of four tropical plantation-forest wood species [8] 1 No Wood species Basic density gramcm 3 Lignin content SyrngilVanillin ratio 1 Sengon Paraserianthes falcataria L Nielsen 0.45 26.72 2.03 2 Gmelina Gmelina arborea Roxb 0.48 25.50 2.02 3 Meranti kuning Shorea spp. 0.57 24.89 1.87 4 Kapur Dryobalanops spp. 0.62 26.40 1.30 F-test for signiicant difference Remarks: 1 Average of 5 replications; = signiicant at P = 0.05; = signiicant at P = 0.01

4.2. The Obtained H-factors

The H-factor values as obtained are presented in Table 2. Greater H-factor values i.e. theoretical deligniication intensity implied the more severe intense kraft coking condition; and vice versa. Table 2. H-factors as obtained by manipulating cooking duration and temperature as single variable [5,8] T max o C t Tr à Tm minutes t TM minutes T Tot minutes H-factors 170 90.00 0.00 90.00 117.88 170 90.00 30.00 120.00 579.34 170 90.00 60.00 150.00 1040.81 170 90.00 90.00 180.00 1502.25 175 93.15 0.00 93.15 173.87 175 93.15 30.00 123.15 866.56 175 93.15 60.00 153.15 1559.25 175 93.15 90.00 183.15 2182.67 Remarks: T max = maximum cooking temperature; t Tr à Tm = the duration that took from the room temperature raising to maximum cooking temperature; t TM = the duration at maximum cooking temperature; t Tot = total duration of t Tr à Tm + t TM; Calculated using Vroom formula refer to Equation I ISBN : 978-602-17761-4-8 39 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech

4.3. Properties of Kraft Pulping

Data on pulping properties varied with wood species as well as H-factors Appendix A. Greater H-factors clearly induced actual deligniication intensity Figure 2a, causing more intensive dissolution of lignin. This was implied by the decrease of total unscreened pulp yield Figure 2b. More intensive lignin dissolution also rendered iber separation more perfect, thereby increasing screened-pulp yield to some extent Figure 2c and concurrently decreasing pulp reject Figure 2d. Beyond H-factor at 1502.25, overall screened-pulp yield from four PF wood species apparently tended to decrease Figure 2c. Presumably besides more intensive iber separation, such was caused by more severe wood carbohydrate degradation esp. cellulose and hemicellulose with more severe cooking-condition H-factor 1502.25. As described before, H-factor served just as theoretical deligniication intensity, regardless of e.g. different cooked-wood species. Should the H-factor values be linked to the actual deligniication intensity, there appeared a difference in such intensity among PF wood species at particular H-factors, whereby highest actual deligniication intensity occurred to gmelina wood, followed in decreasing order by sengon, meranti kuning, and kapur Figure 2a. This indicated that lignin removal dissolution at the irst two species proceeded easier than the latest two species. It is interesting that the irst two species exhibited greater ratio of syringil-to-vanillin SV units, while the latest two species revealed the lower ratio Table 1. This also implied that the active-selective actual kraft deligniication intensity seemed affected by ratio of SV units correlation coeff: R 2 =0.2026; R=+0.4501 Figure 3a. However, wood density also correlated with such active-selective actual kraft deligniication intensity, but less strongly R 2 =0.2005; R=-0.4478 Figure 3b; while wood initial lignin content did so, yet insignicantly R 2 =0.0688 tn ; R=+0.2623 tn Figure 3c. In all this suggested that SV ratio affected the active-selective actual deligniication intensity the strongest, followed in decreasing order by wood density and initial lignin content. Further, the active selective deligniication correlated positively with screen-pulp yield R=+0.3529 Figure 4a and negatively with pulp rejects R=-0.7739 Figure 4b. This was explicable, as such active-selective action induced more lignin dissolution and lessened carbohydrate degradation, thereby intensifying iber-to-iber separation 45 50 55 60 65 100 400 700 1000 1300 1600 1900 2200 H-factor T o ta l p ul p y ie ld , Sengon Gmelina Meranti kuning Kapur B 3 4 5 6 7 8 100 400 700 1000 1300 1600 1900 2200 H-factor D e li g ni fi c a ti o n in te n s it y ln t ra n s fo rm a ti o n Sengon Gmelina Meranti kuning Kapur A 35 37 39 41 43 45 47 49 51 53 55 100 400 700 1000 1300 1600 1900 2200 H-factor S c reened- pul p y iel d, Sengon Gmelina Meranti kuning Kapur C 5 10 15 20 25 100 400 700 1000 1300 1600 1900 2200 H-factor P u lp r e je c t, Sengon Gmelina Meranti kuning Kapur D Figure 2. Relationship of H-factor consecutively with deligniication intensity A, with total unscreened pulp yield B, with screened-pulp yield C, and with pulp reject D [8] ISBN : 978-602-17761-4-8 40 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 3 4 5 6 7 8 0,4 0,45 0,5 0,55 0,6 0,65 Wood basic density, gcm 3 D e li g ni fi c a ti o n in te n s it y L

n. tr

a n s f R = - 0,4478 R 2 = 0,2005 B 3 4 5 6 7 8 1,25 1,45 1,65 1,85 2,05 SyringilVanillin Ratio D e li g n if ic a ti o n i n te n s it y L n . tr a n s f R = +0.4501 R 2 = 0.2026 A 3 4 5 6 7 8 24 25 26 27 Wood initial lignin content, D e li gni fi c a ti on i nt e ns it y Ln. tr a ns f R = + 0.2623 R 2 = 0.0688 ns C Figure 3. Correlation between syringl-to-vanillin SV unit ratio and deligniication intensity A; between wood basic density and deligniication intensity B; and between wood initial lignin content and deligniication intensity C 2 4 6 8 10 12 14 16 18 20 22 3 4 5 6 7 8 Delignification intensity, ln transformation P ul p r ej ec t, Sengon Gmelina Meranti kuning Kapur R = - 0,7739 37 39 41 43 45 47 49 51 3 4 5 6 7 8 Delignification intensity, ln transformation Sc r e e n e d -p u lp y ie ld , Sengon Gmelina Meranti kuning Kapur R = + 0.3529 Figure 4. Correlation of actual deligniication intensity with consecutively screened-pulp yield A; and with pulp rejects B Regarding the initial lignin content, despite signiicant variation among the four FP woods Table 1, its insignicant correlation with actual deligniication intensity Figure 3c suggested that such variation to some particular range did not affect the deligniication kinetics [1,6]. About wood density, its lower role despite existing on actual deligniication intensity than SV ratio was also explicable Figure 3b. Theoretically woods with greater density necessitated more energy input for the deligniication process. This meant deligniication of greater-density PF woods would require e.g. greater H-factor as well, in cooking; and vice versa. However, such was not too problematic to some extent for kraft cooking, as the strong alkaline liquor during the kraft cooking could diffuse at nearly almost equal rate in longitudinal, radial, and tangential directions of the cooked wood chips [6,8]. . The greatest role of SV ratio at the initial wood lignin entity on deligniication intensity Figure 3a indicatively owed to the more possibility of reaction mechanism I Figure 5 particularly for FP ISBN : 978-602-17761-4-8 41 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech woods with higher SV ratios, such as gmelina and sengon Table 1, i.e. de-methylation de-alkilation on fragmented lignins, thereby rendering them more soluble; in addition to the regular deligniication that prevalently occurs through the cleavage of α-O-4 and β-O-4 bonds at the lignin during the kraft cooking [6,10]. This situation induced more intensive iber separation; and explained greater screen- pulp yield and concurrently lower pulp reject from meranti kuning and kapur woods Figures 2c and 2d. Conversely, lignin with lower SV ratio that implied containing more vanillin units Figure 1 such as meranti kuning and meranti, might inlict more possibility on mechanism reaction II condensation between the fragmented lignins that afforded greater-sized fragments aggregates which were less soluble Figure 6. Such phenomena besides retarding deligniication rate intensity could also induce more severe degradation on wood carbohydrates esp. cellulose and hemicellulose. It seemed that such condensation and degradation occurrence contributed their role signiicantly in decreasing the screened-pulp yields from meranti kuning and kapur woods with the elevated H-factor; and also their lower screened-yields than from gmelina and sengon woods Figures 2c. Further beyond 1502.25 H-factor, condensation reaction during the kraft cooking of meranti kuning and kapur woods apparently became more intensive that rendered their pulp rejects increasing to the point which exceeded the rejects from gmelina and sengon Figure 2d.

4.4. Physical and Strength Properties of Kraft Pulp Sheet

Kraft pulp handsheets were only formed and tested from the kraft cooking pulpng at 1502.25 H-factor, as such could achieve the highest screened-pulp yield and lowest pulp reject, particularly from gmelina and sengon woods Figures 2c and 2d. It appeared that highest basis weight and strengths of pulp sheets were from sengon, followed in decreasing order by consecutively gmelina, meranti kuning and kapur Table 3. Such decreasing order was seemingly correlated with the lowering SV ratio at each of the four PF woods R = [+0.5665] - [+0.6542]. This again strengthened the previous indication of active-selective kraft deligniication which became less effective with the more intensive condensation reaction, imperfect iber separation, and more wood carbohydrate degradation, especially for meranti kuning and kapur woods [6,10]. Figure 5. Reaction mechanisms, in which the syringil-type monomer units in the lignin entities during the kraft cooking are partially de-methylated de-alkilated forming more soluble lignin fragments [6,10] Figure 6. Condensation reactions A and B types that can occur between the already fragmented lignins at the unoccupied C-5 position of the vanillin-type monomers during the kraft cooking forming less soluble larger-sized lignin fragments aggregates [10,11] ISBN : 978-602-17761-4-8 42 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Correlation between pulp basis weightpulp strengths and wood density also occurred negatively, but less strongly R = [-0.5078] - [-0.5663] compared to the case for SV ratio, whereby the greater the density, then the lower those two pulp properties. This was explicable as wood with low density tended to have thin iber-walls, thereby intensifying iber-to-iber bonds and felting during the sheet forming; and vice versa. On the other hand, insigniicant correlation between initial lignin content and pulp basis weightstrengths R ns = [+0.3219] - [+0.4646] seemed strongly attributable to the insigniicant correlation between lignin content and deligniication intensity Figure 3c Tabel 3. Basis weight and strength properties of unbeaten kraft pulp from four plantation forest’s wood species [8] 1 Wood species Basis weight gm 2 Tear factor mN.m 2 g Breaking length Km Sengon 61.55 5.09 5.55 Gmelina 61.13 2.29 2.67 Meranti kuning 61.08 0.33 0.36 Kapur 57.23 0.24 0.26 Correlation R with SyringilVanillin Ratio: + 0.5857 + 0.6542 + 0.5665 Highest Correlation R with Wood Basic Density: - 0.5391 - 0.5663 - 0.5078 ns Second Highest Correlation R with Lignin Content: + 0,3219 ns + 0,4646 ns + 0,4518 ns Lowest 1 Average of 5 replications

4. Conclusions and Suggestions

Satisfactory qualities of kraft pulp from four plantation forest PF wood species can be obtained by thoroughly accounting for their varying wood basic properties i.e. density, initial lignin content, and ratio of syringil-to-vanillin lignin monomers as well as implementing appropriate cooking condition varying theoretical deligniication intensities or H-factors at 117.88-2182.67. Supporting details are forthcoming: Actual deligniication intensities increased with the elevated H-factors. At 1502.25 H-factor was obtained the kraft pulp apparently with highest screened-pulp yield, lowest pulp reject. Therefore, highest pulp strengths were strongly presumed at such H-factor Actual deligniication intensity, screened-pulp yield, and pulp strengths seemed affected by ratio of syringil-to-vanillin SV units the strongest, followed by wood density less strongly and initial wood lignin content insigniicantly. Such phenomena implied that increasing SV ratio besides enhancing active-selective kraft deligniication also concurrently lessened wood carbohydrate degradation; and vice versa. Based on such implication, sengon wood afforded the greatest prospect for kraft pulp, followed in decreasing order by gmelina, meranti kuning, and kapur woods. PF woods which were less prospective for kraft pulp i.e. meranti kuning and kapur expectedly can be improved by enhancing active-selective kraft cooking liquor, e.g. regulating sulidity and introducing little amount of additives anhtraquinoneAQ and polysulidePS. The seemingly prospective results of kraft pulping on those four PF woods expectedly can bring beneits towards more eficiency in ibrous stuff utilization and lessening dependency on conventional iber sources natural forest woods, thereby reducing forest degradation rate and sustain renewable natural sources. ISBN : 978-602-17761-4-8 43 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech References 1. Smook, G.A. Handbook for Pulp and Paper Technologists. Atlanta, Georgia. USA Joint Textbook Committee of the Paper Industry; 2002. 2. Anonim. Indonesia’s Statistics. Jakarta, Indonesia. Agency for Statistics Center; 2015. Heading and Content in Indonesian as well as in English 3. Anonim. Forest Resources: Current Indonesia’s deforestation rate at 0.5 million ha per year. Environment. Kompas Newspaper, May 9, 2012, p. 13 Jakarta, Indonesia; 2012. Heading and Content in Indonesian 4. Anonim. The management and governance of industrial plantation forest evaluated. Republika On- line. 11 August 2012. Accessed on 28 January 2013 Heading and Content in Indonesian 5. Anggraini, D., Eiyanti, L., Tampubolon, R.M. Pulp manufacture for wrapping paper. Draft still under evaluation for publication. Bogor, Indonesia. Center for Forest Products Research and Development; 2014. Title and Abstract in Indonesia as well as in English; Content in Indonesian 6. Casey, J.P. Pulp and Paper: Chemistry and Technology. 3rd ed. Vol I. New York USA. A Wiley - Interscience Publisher; 1980. 7. Anonim. Kraft pulping kinetics. Derivation of H-factor. PSE. Lecture 12. Seattle, Washington, USA. College of Forest Resources. Univ. of Washington; 2009. website: http:ses.washington. edipowerpoint. Accessed on 17 January 2016. 8. Roliadi, H. and Rahmawati, N. Explicability of the H-factor to account for the deligniication extent and properties of plantation forest wood in the kraft cooking process. Bogor, Indonesia. Center for Forest Products Research and Development Center. Journal of Forest Products Research, vol. 24 4: 275-299; 2006. Title and Abstract in English as well as in Indonesian; Content in English 9. Technical Association of the Pulp and Paper Industries TAPPI’s Test Methods. Atlanta, Georgia, USA. TAPPI; 2007. 10. Lourenci, A., Cominho, J., A. VeletPeresa, M.H. Reactivity of syringil and guaiacyl lignin units and deligniication kinetics in kraft pulping of Eucalyptus globulus using Py-GC - MSFID. DOI: 10.10169.biotech.2012.7.092. Portugal. Bioresource Technology, 123: 296-32; 2012 website: http:www.researchgate-net publication. Accessed on August 17, 2015. 11. Prentti, O. Wood: Structure and Properties. New York, USA. Trans Technical Publications; 2006. ISBN : 978-602-17761-4-8 44 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Appendix A. Kraft pulping properties of four plantation-forest wood species [8] 1 Wood species H-factor Total- pulp yield, Screened- pulp yield, Pulp reject, Residual lignin content in pulp, Residual lignin content ΔL, 2 Actual deligniication intensity Actual deligniication intensity ln transformation 3 Sengon 117.88 63.02 42.75 20.27 4.97 3.13209 37.63616 3.62797 173.87 60.75 44.51 16.24 4.72 2.86740 60.63681 4.10490 579.34 57.05 48.55 8.50 4.65 2.65283 218.38606 5.38626 866.56 55.40 49.15 6.25 4.37 2.42098 357.93769 5.88036 1040.81 54.32 49.15 5.17 4.12 2.23798 465.06588 6.14218 1502.25 51.32 49.98 1.34 3.34 1.71409 876.41358 6.77584 1559.25 50.94 50.02 0.92 3.23 1.64536 947.66380 6.85400 2182.67 48.81 47.83 0.98 3.02 1.47406 1480.71787 7.30028 Gmelina 117.88 61.35 44.25 17.10 4.90 3.00615 39.21295 3.66901 173.87 59.62 44.25 15.37 4.91 2.92734 59.39518 4.08421 579.34 59.05 44.40 14.65 4.52 2.66906 217.05769 5.38016 866.56 59.22 44.37 14.85 4.09 2.42210 357.77248 5.87990 1040.81 57.40 49.15 8.25 3.80 2.18120 477.17312 6.16788 1502.25 54.59 49.90 4.69 3.04 1.65954 905.22291 6.80818 1559.25 54.20 48.79 5.41 2.95 1.59890 975.20170 6.88264 2182.67 49.68 46.72 2.96 2.48 1.23206 1771.55570 7.47961 Meranti kunng 117.88 65.40 43.60 21.80 6.30 4.12020 28.61026 3.35377 173.87 64.58 43.00 21.58 6.04 3.90063 44.57483 3.79717 579.34 61.94 40.80 21.14 5.26 3.25804 177.81835 5.18076 866.56 55.10 39.91 15.19 4.76 2.62276 330.40004 5.80030 1040.81 52.15 39.48 12.67 4.61 2.40412 432.92854 6.07057 1502.25 50.18 38.55 11.63 4.52 2.26814 662.32801 6.49576 1559.25 51.65 39.45 12.20 4.43 2.28810 681.46209 6.52424 2182.67 49.67 38.01 11.66 4.08 2.02654 1077.04477 6.98198 Kapur 117.88 61.12 44.65 16.47 6.01 3.67331 32.09093 3.46857 173.87 60.33 43.96 16.37 5.96 3.59567 48.35541 3.87858 579.34 57.44 42.07 15.37 5.42 3.11325 186.08861 5.22622 866.56 55.88 40.86 15.02 5.03 2.81076 308.30052 5.73108 1040.81 55.02 39.70 15.32 4.76 2.61895 397.41469 5.98498 1502.25 52.91 40.20 12.71 4.50 2.38095 630.94563 6.44722 1559.25 52.67 40.86 11.81 4.41 2.32275 671.29567 6.50921 2182.67 50.17 39.14 11.03 4.08 2.04694 1066.31082 6.97196 Remarks: 1 Average of 5 replications; 2 Corrected to total-pulp yield and original oven-dry weight of the cooked wood chips; 3 Ln transformation ISBN : 978-602-17761-4-8 45 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech LIGNIN STRUCTURE OF ACACIA AND EUCALYPTUS SPECIES AND ITS RELATION TO DELIGNIFICATION Deded S. Nawawi

a,b

, Wasrin Syaii a , Takuya Akiyama b , Tomoya Yokoyama b ,Yuji Matsumoto b1 a Department of Forest Products, Faculty of Forestry, Bogor Agricultural University IPB, Bogor, Indonesia b Wood Chemistry Laboratory, Graduate School of Agricultural and Life Sciences, The University of Tokyo, Tokyo, Japan 1 amatsumomail.ecc.u-tokyo.ac.jp ABSTRACT Lignin structure of 15 acacia woods and 13 eucalyptus woods were analyzed and the relationships between lignin structure and lignin reactivity were examined. Generally hardwood lignins are different from softwood lignins by the presence of syringyl type aromatic nuclei. In addition, there are wide varieties in the structure and amount of hardwood lignins depending on wood species, environment of growing site, portion in the wood, portion in the cell wall, and so on. We have shown that the wide variety of lignin structure and amount can be sorted out by taking the syringylguaiacyl ratio as an index. Furthermore, we have also shown that lignin structure can be quantitatively related to the chemical reactivity such as deligniication during chemical pulping by taking the syringylguaiacyl ratio as an index. In this report, we review our recent achievements about the quantitative relationships between lignin structure and reactivity . Keywords: lignin; structure; deligniication; pulp; aromatic; stereo structure Lignin Aromatic Structures and b-O-4 Structures Generally, hardwood lignin contains syringyl nuclei and guaiacyl nuclei as aromatic ring types Fig.1. Syringylguaiacyl ratio is a very important structural characteristics of lignin and greatly different each other depending on the difference of wood species, position in the wood, environment of growing site, portion in a cell wall, and so on. C O OCH 3 C CH 2 OH O OCH 3 H H OH C O OCH 3 C CH 2 OH O OCH 3 H HO H erythro β-O-4 structure threo β-O-4 structure O OCH 3 O OCH 3 H 3 CO syringyl guaiacyl aromatic ring type side-chain stereo structure OH OCH 3 O OCH 3 C non-phenolic phenolic aromatic ring type Fig. 1 Important Chemical Characteristics of Lignin from the Point of Reactivity Another important difference of aromatic structure is phenolic or non-phenolic. Although the difference of whether guaiacyl or syringyl doesn’t change the reaction mechanism, it greatly affects the reactivity. On the other hand, difference of whether phenolic or non-phenolic sometimes results in the different reaction mechanism. As a most important structure in lignin, b-O-4 structure is present in both hardwood and softwood lignins. This structure has two stereo isomers, erythro and threo at its side-chain Fig. 1. All of these differences affect the reactivity of lignin. Therefore, if lignin structure is different, the pulping performance can be greatly different. ISBN : 978-602-17761-4-8 46 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech General Tendency of Lignin Chemical Structure Based on the analysis of 21 wood species, Akiyama et al. 2005 reported that the general tendency of lignin chemical structure can be visualized by taking syringylguaiacyl ratio as an index. General tendency was as following: the higher the syringylguaiacyl ratio, the higher the erythrothreo ratio of b-O-4 side chain stereo structure, the higher the proportion of b-O-4 structure, the higher the proportion of non-condensed structure, the lower the lignin content, and so on. These general tendency can be seen not only among different wood species, but also in different portions of the same wood. For example, Akiyama et al. 2003 demonstrated that the tension part of reaction wood can be characterized by higher syringylguaiacyl ratio, higher erythrothreo ratio, higher proportion of b-O-4 structure, and, lower lignin content compared with the compression part by the analysis of samples obtained from the different portion within the same wood disc of yellow poplar stem which was standing on the slope before harvest. Later, Nawawi et al. applied the same analysis to various type of reaction wood samples and conirmed the same tendency Nawawi et al. 2016A, B. The relation can be recognized not only in the wide range of wood species but also in the same group of trees in which the structural difference is rather small. If the structural difference is small, it will be dificult to establish a correlation between two structural factors. However, Nawawi et al. 2016C successfully demonstrated that the general tendency can be well recognized among the same group of trees, such as genus Acacia and genus Eucalyptus Table 1. Table 1. List of wood samples examined in this study Sample Wood species Sample Wood species Genus Acacia Genus Eucalyptus 1 Acacia auriculiformis 16 Eucalyptus camaldulensis A 2 Acacia hybrid A 1 17 Eucalyptus camaldulensis B 3 Acacia hybrid B 1 18 Eucalyptus deglupta 4 Acacia hybrid C 1 19 Eucalyptus dunii 5 Acacia hybrid D 1 20 Eucalyptus globulus A 6 Acacia hybrid E 1 21 Eucalyptus globulus B 7 Acacia hybrid F 1 22 Eucalyptus grandis A 8 Acacia mangium A 23 Eucalyptus grandis B 9 Acacia mangium B 24 Eucalyptus grandis C 10 Acacia mangium C-1 2 25 Eucalyptus hybrid 3 11 Acacia mangium C-2 2 26 Eucalyptus nitens 12 Acacia mangium D 27 Eucalyptus saligna 13 Acacia mangium E 28 Eucalyptus urophylla 14 Acacia mangium F 15 Acacia meransii Same wood species with different alphabets are from different growing area. 1 : Hybrid of Acacia mangium and Acacia auriculiformis with different mother trees 2 : Same species from the same plantation area but C-1 was 8 years and C-2 was 12 years old 3 : Hybrid of Eucalyptus camaldulensis and Eucalyptus deglupta For example, Fig. 2 shows the relation between lignin content and syringylguaiacyl ratio. Here, the ratio between syringyl and guaiacyl is expressed as syringyl ratio proportion of syringyl among the total of syringyl and guaiacyl. It is clearly shown that lignin content is signiicantly related to the syringyl ratio within each genus. Among the general tendency of lignin chemical structure, the correlation between the syringyl guaiacyl ratio and erythrothreo ratio of b-O-4 side-chain stereo structure is very high and this relation is quite important from the point of chemical reactivity of lignin as will be seen in the following sections. This correlation was irst established by Akiyama et al. 2005 for 21 wood species 15 hardwoods and 6 softwoods and later we have demonstrated that all the native lignins it this correlation. Fig. 3 shows the correlation between the syringylguaiacyl ratio and erythrothreo ratio when they are expressed as ISBN : 978-602-17761-4-8 47 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech erythro ratio proportion of erythro and syringyl ratio, respectively. In this igure, the correlation found for 21 wood species by Akiyama et al. 2005 and that found for genus Acacia and genus Eucalyptus by Nawawi et al. 2016C are expressed together. Since softwood has no syringyl nucleus, the erythro ratio is exactly 0.5, which means the amount of erythro and threo b-O-4 structure is equal. Fig. 2 Relationship between lignin content and s yringyl ratio. ฀ Acacia ฀ Eucalyptus syringyl ratio = syringylsyringyl+guaiacyl Fig. 3 Correlation between erythro ratio of b-O-4 structure and syringyl ratio. ฀ Acacia ฀ Eucalyptus ○ 21 wood species by Akiyama et al. 2005 erythro ratio = erythroerythro+threo Structure-Reactivity Relationships of Lignin During alkali pulping including kraft pulping, the most important reaction is the cleavage of non- phenolic b-O-4 structure shown in Fig. 4. In this mechanism, ionized a-hydroxyl group nucleophilically attacks the b-carbon from the backside of b-O-4 ether resulting in the cleavage of this linkage. Fig. 4 Alkaline cleavage of non-phenolic b-O-4 structure Considering the presence of 2 types of aromatic structures syringyl and guaiacyl and 2 types of side-chain stereo structures erythro and threo, basically 8 types of b-O-4 structures are possibly present in lignin. In Fig. 5, structures of model compounds which represent these 8 types of b-O-4 structures are shown. The number below each structure is the alkali cleavage rate constant obtained by the alkali treatment under 160 ºC at 2 molar NaOH concentration. Since softwood lignin has only guaiacyl type aromatic nucleus, there are only two types of b-O-4 erythro and threo of GG, Fig. 5 in softwood. The ratio between erythro and threo of softwood lignin is exactly 1:1. On the other hand, hardwood lignin has totally 8 types of b-O-4 erythro and threo of GS, SG, SS in addition to GG, Fig. 5. Proportion between GG, GS, SG and SS can be different in different lignins depending on the ratio between syringyl and guaiacyl of the lignin. Reactivity of these 8 types of b-O-4 structures can be summarized as following: 1. erythro isomer is always more reactive than threo isomer when the aromatic composition is the same 2. substitution of guaiacyl with syringyl nucleus at any position results in the increase of reactivity 3. the effect of substitution from guaiacyl to syringyl is greater when etherifying guaiacyl is substituted than when guaiacyl in the carbon main skeleton is substituted. It is very important to note that syringyl ratio could be higher than 0.8 in some wood species Fig. ISBN : 978-602-17761-4-8 48 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 3. Since the proportion of erythro b-O-4 becomes higher when the syringyl ratio is higher, erythro type of SS can be predominant b-O-4 structure in these wood species. In softwood lignin, half of b-O- 4 structure is threo GG type, while majority of b-O-4 structure is erythro SS type in these hardwood species. The alkali cleavage rate constant of the former type is 16.7 and that of latter is as high as 217. By this comparison, it is easily predicted that hardwood lignin with higher proportion of syringyl nuclei is much more easily degraded during alkali pulping process such as kraft pulping than softwood lignin or hardwood lignin with lower syringyl proportion Shimizu et al. 2012, 2013, 2015. Fig. 5 Model compounds of 8 types of non-phenolic b-O-4 structures and their alkali cleavage reaction rate constant in 2 molar aqueous NaOH under 160 ºC. S: syringyl, G: guaiacyl Shimizu et al., 2012 Pulping Result In the previous section, it was predicted that hardwood with higher proportion of syringyl is easily deligniied from the point of chemical reactivity of non-phenolic b-O-4 structures. One more factor which beneits the woods with higher syringyl proportion is the lower lignin content of such woods. Nawawi et al. conirmed this prediction by subjecting wood species belonging to genus acacia and eucalyptus to kraft pulping Nawawi et al. 2016C. Fig. 6 clearly shows that woods with higher syringyl ratio needs less alkali charge to reach kappa 19. Fig. 6 Relationship between syringyl ratio and deligniication. ฀ Acacia ฀ Eucalyptus ISBN : 978-602-17761-4-8 49 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech References 1. Akiyama, T., Matsumoto, Y., Okuyama, T., Meshitsuka, G. Phytochemistry 64, 1157–1162 2003 2. Akiyama, T., Goto, H., Nawawi, D.S., Syaii, W., Matsumoto, Y., Meshitsuka, G. Holzforschung, 593, 276-281 2005 3. Nawawi, D.S, Syaii, W., Akiyama, T., Matsumoto, Y. Holzforschung 707:593-602. 2016A 4. Nawawi, D.S., Akiyama, T., Syaii, W., Matsumoto, Y. 2016. Holzforschung Holz.2016.0100: Accepted 12-Aug-2016. 2016B 5. Nawawi, D.S., Syaii, W., Tomoda, I., Uchida, Y., Akiyama, T., Yokoyama, T., Matsumoto, Y. Submitted to Journal Wood Chemistry and Technology. 2016C 6. Shimizu, S., Yokoyama, T., Akiyama, T., Matsumoto, Y. J. Agric. Food Chem., 60, 6471−6476 2012 7. Shimizu, S., Posoknistakul, P., Yokoyama, T., Matsumoto, Y. BioResources, 8 3, 4312-4322 2013 8. Shimizu, S., Yokoyama, T., Matsumoto, Y. J. Wood Sci., 61 5, 529-536 2015 ISBN : 978-602-17761-4-8 50 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 51 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech A NOVEL PAPER-BASED SENSOR FOR COLORIMETRIC AND FLUORESCENT DETECTION OF COPPER IONS IN WATER Yinchao Xu a1 , Toshiharu Enomae b2 a Research fellow of Japan Society for the Promotion of Science; Graduate School of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305-8572, Japan b Faculty of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305- 8572, Japan 1 xuyinchaopaperscience.org 2 tenomae.com ABSTRACT In this research, we have developed a user-friendly, low-cost, sensitive and ion-species-selective paper-based sensor to inspect drinking and industrial water for excessive levels of copper ions. The paper-based sensor was simply fabricated by printing an anthraquinone derivative acetone solution onto ilter paper. In the colorimetric detection, by 10 min immersion in a 5 mL test water sample, the paper- based sensor was proven to be feasible to indicate a Cu 2+ concentration of as low as 2 ppm, through the visible colour change from yellow to light purple. In the instrumental luorescence detection, the linear relationship was successfully obtained between the resulting surface luorescence intensity of the paper- based sensor and Cu 2+ concentration. Based on this linear relationship, more accurate concentrations are available. In addition, the high selectivity of the paper-based sensor ensured applications to detect practical contaminated water samples. Keywords: copper ion detection, inkjet printing, paper-based sensor Introduction Heavy metals, commonly deined as metals with densities higher than 5 gm 3 [1], exist naturally in the environment. However, in past decades, heavy metals have caused serious environmental pollution, originating from industrial efluents and, more recently, metal ions leached from soil by acid rain.[2] As heavy metals form complexes with nitrogen, sulfur, and oxygen ligands in biosystems, excessive concentrations of heavy metals are harmful, or even deadly, to human and animals.[3] Copper, one of the most abundant and fundamental trace elements, can adopt distinct redox states, oxidized CuII or reduced CuI, allowing the metal to play a pivotal role in cell physiology as a catalytic cofactor in the redox chemistry of enzymes, mitochondrial respiration, iron absorption, free radical scavenging, and elastin cross-linking.[4] In contrast, excessive concentrations of copper cause oxidative stress and related symptoms, which can lead to diabetes and many neurodegenerative disorders, such as Alzheimer’s disease[5], and Menkes disease[6], and Wilson disease[7]. Conventionally, inductively coupled plasma–optical emission spectroscopy ICP–OES is the most common and sensitive method used to determine metal ion concentrations [8].However, it is an expensive and laborious analytical method, limited to high-demand laboratory research analysis and, thus, inaccessible to nonprofessionals. To explore other analytical approaches, published alternative methods are mostly based on colorimetric analysis and luorescence spectroscopy, combining modiied dyes, synthesized organic compounds, or nanomaterials to achieve highly selective and sensitive detection. Mahapatra et al . developed a colorimetric and turn-off luorimetric sensor for Cu 2+ detection using a synthesized triphenylamine-based indolylmethane derivative [9]. Liu et al. developed a colorimetric Cu 2+ sensor using DNA-functionalized gold nanoparticles [10]. Chen et al . developed a luorescence sensor for Cu 2+ detection using synthesized highly-luorescent glutathione-capped gold nanoparticles [11]. Maity et al. [12] used thiourea-salicylaldehyde to realize visible and near-IR sensing of Cu 2+ based on the coordination reaction.Many more effective synthesized chemicals and methods have also been proposed and developed, all showing remarkable sensing selectivity and sensitivity. However, these approaches are still costly and limit the methods to laboratory use as an alternative to ICP–OES. ISBN : 978-602-17761-4-8 52 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Therefore, the development of a high-performance, user-friendly method to detect heavy metal ions, such as Cu 2+ , in water is in strong demand, and would allow nonprofessionals to determine water safety, especially in Third World countries. Herein, we proposed and developed a simple low-cost method, using inkjet printing technology to fabricate a paper-based copper ion sensor for both qualitative and quantitative detection. A commercial anthraquinone dye and common ilter paper were used as the main chemical and substrate, respectively, for sensor fabrication. Consequently, the developed paper- based sensor can realize both qualitative detection of Cu 2+ in water and quantitative detection based on luorescence spectroscopy for high ion species selectivity and sensitivity. Experimental 2.1 Materials An anthraquinone derivative Sigma-Aldrich and ilter paper No. 1, Advantec were used as the sensing dye and substrate of the sensor, respectively. Metal nitrate salts, including sodium, potassium, calcium, ferric, cobalt, cadmium, manganese, mercury, lead, nickel, zinc, and silver nitrates Japanese Industrial Standard [JIS] special grade, Wako Pure Chemical, were used in the experiment to evaluate interference by metal ions other than Cu 2+ . Copper standard solution Cu 100, Wako Pure Chemical was used to calibrate Cu 2+ concentrations measured by ICP–OES Optima-7300DV, PerkinElmer, USA and the paper-based sensor.

2.2 Fabrication

A lab-made ink, comprising a 1 gL anthraquinone derivative acetone solution, was irst prepared. An inkjet printer DMP-2831, Dimatix, Fujiilm, Japan was then used to fabricate the paper-based sensor by printing this ink onto ilter paper. The designed printing pattern was a rectangle with a 30-mm length and 20-mm width, which was the most appropriate size for the sample holder in luorescence spectroscopy in luorescence detection. The ink dried in 10 s after printing, and the anthraquinone derivative was adsorbed onto the cellulose ibers through non-covalent interactions. Filter paper printed with the rectangular pattern is denoted as the “paper-based sensor” throughout. The paper-based sensors were cut out from the ilter paper for further use.

2.3 Characterization

In the experiment, a confocal laser scanning microscope CLSM LSM-700, Carl Zeiss, Germany was used to observe the distribution of the anthraquinone derivative on iber surfaces and in iber networks. The ilter paper was irst stained with a 0.01 gmL Nile blue–acetone solution by pipetting. After drying, a 0.5 gL anthraquinone derivative acetone solution was printed onto the stained ilter paper using the Dimatix inkjet printer. A paper sample with a 45° beveled cross-section was then prepared by cutting paper sandwiched between polystyrene blocks with a 45° beveled plane using a razor blade. The prepared paper sample was then pasted onto a glass slide and observed using CLSM. Double-track mode was applied to the laser scan. In one laser scanning track, the Ar laser at 488 nm was selected to excite and detect anthraquinone derivative, while in the other track, the He–Ne laser at 634 nm was selected to excite Nile blue in order to reveal the whole iber network. The scanning depth was 200 μm, which was approximately equal to the ilter paper thickness. Finally, 3D images of the paper-based sensor were captured.

2.4 Visible and Fluorescence Detections

In the visible detection, also referred to as qualitative detection, the paper-based sensors fabricated using 0.6 gL anthraquinone derivative acetone solution were immersed in 5-mL Cu 2+ aqueous solutions with concentrations of 1, 2, 3, 4, and 5 ppm for 10 min. After immersion, the sensor color was observed by the naked eye and captured using a digital camera. ISBN : 978-602-17761-4-8 53 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech In the luorescence detection, also referred to as quantitative detection by applying luorescence spectroscopy F-4500, Hitachi, Japan, the surface luorescence intensity of the paper-based sensor was measured. The excitation and emission wavelengths were 490 nm and 567 nm, respectively. As anthraquinone derivative was quenched by Cu 2+ in solution, the surface luorescence intensity of paper- based sensors immersed in Cu 2+ solutions of various concentrations was determined. Paper-based sensors, fabricated using a 1 gL anthraquinone derivative acetone solution, were immersed in 5-mL Cu 2+ solutions with concentrations of 1, 2, 3, 4, 5, and 6 ppm for 10 min. Additionally, to achieve higher sensitivity, paper-based sensors were fabricated using an anthraquinone derivative acetone solution of lower concentration 0.4 gL. Subsequently, these fabricated sensors were immersed in 5-mL Cu 2+ solutions with concentrations of 200, 400, 600, and 800 ppb for 10 min. After immersion, excess water was removed with a paper wiper. Before drying, the surface luorescence intensity of the paper-based sensors was measured, and the relationship between surface luorescence intensity and Cu 2+ concentration was determined. All aqueous samples in this research were adjusted to pH 7 using a buffer solution containing 4-2-hydroxyethyl-1-piperazineethanesulfonic acid HEPES and NaOH, which is widely used in research related to heavy metal solutions.

2.5 Interference

To determine the selectivity of the paper-based sensor, interference by other metal ions was studied in both visible and luorescence detections. Na + , K + , Ca 2+ , Fe 3+ , Co 2+ , Cd 2+ , Mn 2+ , Hg 2+ , Pb 2+ , Ni 2+ , Zn 2+ , and Ag + were tested. The paper-based sensors were immersed in a 5-mL 20-ppm aqueous solution of each metal ion. After 10 min immersion, the color of the sensor was observed by the naked eye and captured using a digital camera. In luorescence detection, excess water on the paper-based sensors was removed and surface luorescence intensity was measured. Results and Discussion 3.1 Fabrication and Characterization A quick and easy fabrication method was developed using inkjet printing technology. The anthraquinone derivative was irmly adsorbed on cellulose iber surfaces through non-covalent bonds, including hydrogen bonds, hydrophobic forces, and CH–π interactions. 16 The fabrication method developed in this research has the following advantages: i although acetone evaporated quickly, perhaps causing anthraquinone derivative to block the nozzle of the printer head, the ink easily lowed in the nozzle, redissolving anthraquinone derivative and preventing the printer head nozzle from being blocked; ii acetone is non-destructive to the ilter paper iber network; and iii inkjet printing technology makes lexible pattern design and homogeneous distribution of anthraquinone derivative possible. Furthermore, as shown in Fig. 1, anthraquinone derivative is only concentrated in the top layer with a total thickness of 150 μm, suggesting that it was possible to easily control and reduce the amount of anthraquinone derivative, and accelerate and accentuate the color reaction, compared with other fabrication methods, such as immersion. Fig. 2 shows a CLSM image of the anthraquinone derivative distributed evenly on cellulose ibers by inkjet printing. Even distribution was important for detection, especially for luorescence detection, and dificult to achieve using any other method. Consequently, inkjet printing appeared to be an ideal method for this fabrication regarding pattern design, operation, and cost.

3.2 Qualitative and Quantitative Detection

Fig. 3 shows a photograph of paper-based sensors immersed in Cu 2+ aqueous solutions. The color of the dye on the paper-based sensors changed from yellow to purple with increasing Cu 2+ concentration. This result conirmed that the paper-based sensor was able to detect Cu 2+ at concentration as low as 2 ppm, which is the maximum allowed amount in drinking water, according to the WHO. The entire ISBN : 978-602-17761-4-8 54 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech detection process took only 10 min and sensitive detection of Cu 2+ was successfully achieved. The 10-min immersion time was determined in the preliminary test, in which no additional obvious color change was observed with immersion times longer than 10 min. This user-friendly detection provided the possibility for non-professionals to perform an on-site water safety check. Fig. 4 shows the luorescence spectra of paper-based sensors after immersion in Cu 2+ aqueous solutions. As the Cu 2+ concentration increased, the luorescence intensity at 567 nm decreased. Fig. 5 shows a linear relationship between the surface luorescence intensity of the paper-based sensor and Cu 2+ concentration, which provided the possibility for quantitative detection of Cu 2+ concentration using the paper-based sensor by simply combining with luorescence spectroscopy. In addition, low Cu 2+ Fig. 1. CLSM image representing the 3D structure and the anthraquinone derivative distribution of a paper-based sensor cross-sectioned at 45 o on one side. Fig. 2. CLSM image of the anthraquinone derivative distribution on cellulose ibers. Fig. 3. Paper-based sensors after immersion in Cu2+ aqueous solutions at different concentrations for 10 min. ISBN : 978-602-17761-4-8 55 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech concentrations, at ppb levels, were detected accurately by applying a low-concentration anthraquinone derivative acetone solution in the fabrication, as shown in Fig. 6. The detection mechanism can be explained by the quenching effect of Cu 2+ on the anthraquinone derivative. The complexation between Cu 2+ and the anthraquinone derivative results in electron or energy transfer from the anthraquinone derivative moiety to Cu 2+ , quenching the luorescence emission 17 . Regarding the kinetics of the chemical reaction at the solid–liquid interface, the amount of the anthraquinone derivative per unit area and the Cu 2+ concentration were important factors in the detection reaction. After 10 min, the paper-based sensors printed with a certain amount of anthraquinone derivative decreased the luorescence intensity because of an increasing quenching level, caused by the formation of more Cu 2+ and the anthraquinone derivative complexes with an increasing Cu 2+ concentration, within a certain range. In this research, the paper-based sensor printed with 5.7 × 10 –9 molcm 2 anthraquinone derivative was suitable for the visible detection of a 2 ppm Cu 2+ aqueous solution, while the paper- based sensors printed with 9.5 × 10 –9 and 3.8 × 10 –9 molcm 2 anthraquinone derivative were suitable for measuring Cu 2+ concentrations in the ranges 0–5 ppm and 0–600 ppb, respectively. This revealed the positive correlation between the amount of the anthraquinone derivative per unit area and the detection range of Cu 2+ concentration. Based on this relationship, paper-based sensors for various detection ranges could be fabricated by controlling the amount of the anthraquinone derivative printed. Fig. 5. Fluorescence intensity of paper-based sensor, fabricated with 1 gL anthraquinone derivative solution, after immersion in Cu2+ aqueous solutions of various concentrations, from 0 to 5 ppm. Fig. 6. Fluorescence intensity of paper-based sensor fabricated with 0.4 gL anthraquinone derivative solution, after immersion in Cu2+ aqueous solutions at various concentrations, from 0 to 600 ppb.

3.3 Interference

Fig. 7 shows that, after immersion in each 20 ppm aqueous solution of Na + , K + , Ca 2+ , Fe 3+ , Co 2+ , Cd 2+ , Mn 2+ , Hg 2+ , Pb 2+ , Ni 2+ , Zn 2+ , and Ag + , no color change was observed in the paper-based sensors, except with the Cu 2+ solution, even though the concentrations of other metal ions were all ten times that of Cu 2+ . This strongly indicated the high selectivity of the anthraquinone derivative for detecting Cu 2+ without interference by other metal ions. In addition, Fig. 8 shows a result measured by luorescence detection, which revealed that among these metal ion species, only Cu 2+ could quench the anthraquinone derivative, and other metal ions had little impact on the surface luorescence intensity of the paper- based sensors. Therefore, the paper-based sensors could function adequately in the detection of practical contaminated water. ISBN : 978-602-17761-4-8 56 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Fig. 4. Fluorescence spectrum of paper-based sensors after immersion in Cu2+ aqueous solutions of various concentrations. Fig. 8. Surface luorescence intensity of paper-based sensors after immersion in 20 ppm aqueous solutions of Na+, K+, Ca2+, Fe3+, Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+. Conclusions A quick, low-cost, and lexible method for fabricating an effective paper-based sensor using inkjet printing technology has been developed. Inkjet printing proved to be a standout fabrication method for the paper-based sensor, due to its low cost, lexible pattern design, and homogeneous distribution of the anthraquinone derivative. The paper-based sensor provided dual-function detection of Cu 2+ in water. Visible detection provided semi-quantitative detection of Cu 2+ , which was beneicial for nonprofessionals, especially people in Third World countries, to quickly ascertain the safety of drinking water on-site. Fluorescence detection enabled the paper-based sensor to be an alternative method for ICP–OES, providing high measurement accuracy at a lower cost and with less laborious analysis and instrumental maintenance than ICP–OES. In addition, the high selectivity of the paper-based sensor ensured applications to detect practical contaminated water samples. In conclusion, a dual-functional paper-based sensor was successfully fabricated using inkjet printing technology for the semi-quantitative and quantitative detection of Cu 2+ in water, and has great potential in practical applications, due to its low-cost fabrication, user-friendly operation, and high-accuracy detection. Acknowledgements This research is inancially supported by the Japan Society for the Promotion of Science JSPS KAKENHI Grant Number 15J01942. The authors would like to thank the Research Facility Center for ISBN : 978-602-17761-4-8 57 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Science and Technology and Gene Research Center of University of Tsukuba for providing frequent opportunities to use their measurement equipment. Fig. 7. Paper-based sensors after immersion in 20 ppm aqueous solutions of Na+, K+, Ca2+, Fe3+, Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+. References 1. Jarup L. Hazards of heavy metal contamination. Brit Med Bull 2003; 68: 167–182. 2. Khan M. Biomanagement of metal-contaminated soils. Springer Dordrecht 2011. 3. Aragay G, Pons J, Merkoçi A. Recent Trends in Macro-, Micro-, and Nanomaterial-Based Tools and Strategies for Heavy-Metal Detection. Chem Rev 2011; 111: 3433–3458. 4. Tapiero H, Townsend D, Tew K. Trace elements in human physiology and pathology. Copper. Biomed Pharmacother 2003; 57: 386–398. 5. Barnham K, Masters C, Bush A. Neurodegenerative diseases and oxidative stress. Nat Rev Drug Discov 2004; 3: 205–214. 6. Copper in drinking water. National Academy Press Washington, D.C. 2000. 7. Fatemi N, Sarkar B, Molecular mechanism of copper transport in Wilson disease. Environ Health Perspect 2002; 110: 695–698. 8. Ponce de Lén Hill C. Inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectoscopy used in the determination and speciation of trace elements, PhD Thesis, University of Cincinatti, 2001. 9. Mahapatra A, Hazra G, Das, Goswami S. A highly selective triphenylamine-based indolylmethane derivatives as colorimetric and turn-off luorimetric sensor toward Cu2+ detection by deprotonation of secondary amines. Sensor Actuat B-Chem 2011; 156: 456–462. 10. Liu J, Lu Y. An invasive DNA approach toward a general method for portable quantiication of metal ions using a personal glucose meter. Chem Commun 2007; 46: 4872–4874. 11. Chen W, Tu X, Guo X. Fluorescent gold nanoparticles-based luorescence sensor for Cu2+ ions. Chem Commun 2009; 13: 1736–1738. 12. Maity D, Govindaraju T. Highly Selective UVVisible-Near Infrared and Fluorescence Sensing of Cu2+

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ISBN : 978-602-17761-4-8 58 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 59 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech PERFORMANCE OF GERONGGANG Cratoxylon arborescens AT 4.5 YEARS OLD AS POTENTIAL SUBSTITUTE FOR Acacia crassicarpa IN PEAT LAND Opik Taupik Akbar 1 , Yeni Aprianis 2 , Eka Novriyanti 3 Research and Development Institute for Forest Plant Fiber Technology Balai Penelitian dan Pengembangan Teknologi Serat Tanaman Hutan BP2TSTH Ministry of Environmental and Forestry Jl. Raya Bangkinang-Kuok Km. 9 PO. BOX 4BKN Bangkinang 28401, Indonesia 1 opik_taupik_akbaryahoo.com 2 yennie_dieyahoo.co.id 3 kee.november09gmail.com ABSTRACT Geronggang Cratoxylonarborescens is fast growing, medium to large sized, evergreen tree, usually found in freshwater or peat-swamp forest or sandy or sandy-loamy soils, and sometimes in coastal dipterocarp swamp forest. Geronggang trees often occur abundantly in secondary forest after felling, and they grow rapidly. Preliminary works have been carried out by Research and Development Institute of Forest Plant Fiber Technology BP2TSTH to cultivate geronggang as alternative species in peat- land. At 4.5 years, the survival rate, mean annual increment MAI, and current annual increment CAI were 85, 12.79 m 3 hayear, and 27.17 m 3 hayear respectively. The survival rate was higher than that of Acacia crassicarpa but the MAI and CAI were lower. The 4.5 years old geronggang was analyzed for its wood and pulp properties. The results showed that speciic gravity of geronggang was 0.43 0.38-0.50, and iber dimension and derivatives were in quality I-II. The resulted pulp yield, pulp lignin, pulp reject, and kappa number were 48.15, 2.09, 0.08 and 16.09, respectively. Overall, based on speciic gravity, iber dimension, and pulp properties, geronggang is suitable as raw material for pulp and paper. Keywords: Cratoxylon arborescens, Acacia crassicarpa, wood properties, pulping properties, pulp and paper, peat land Introduction Indonesia has the largest peat-land among tropical countries, which is about 21 million hectares, scattered mainly in Sumatra, Kalimantan and Papua. On the island of Sumatra itself, peat-land area is about 6.2 million hectares which most of it, about 4 million hectares is located in Riau Province. In addition to having the largest peat-land area, Riau also has one of the largest pulp and paper industry in Indonesia. In 2013 Riau Province contributes 86.35 of the total pulp production in Indonesia [1]. There are two pulp factories i.e. PT. Indah Kiat Pulp and Paper IKPP and PT. Riau Andalan Pulp and Paper RAPP. Until recently, the main source of raw wood material of peat areas is Acacia crassicarpa [1]. Both companies develop plantation of A. crassicarpa in their respective concession area. This monoculture plantation and the invasive nature of acacia species may cause an imbalance in the local ecosystem. The likely of using native wood species in pulp and paper plantation may reduce the imbalance in the local ecosystem. A potential local wood species for the purpose is geronggang Cratoxylon arborescen. Previous exploration by Research and Development Institute of Forest Plant Fiber Technology BP2TSTH showed geronggang population in Riau ranging from 93 to 168 treesha that suggested relatively abundant potential yet there is no adequate utilization [2]. Using local species in plantation also has several advantages, i.e. the planting and maintaining would be considerably easier because they are proven to be able to adapt to local conditions; tolerant to environmental conditions i.e. including pests and diseases; may maintain or even improve the ecological function and biodiversity; possibility to optimize its productivity through tree breedingimprovement program; providing balance and sustainability of habitats for other organisms fauna and lora because it is a natural part of the ISBN : 978-602-17761-4-8 60 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ecosystem; may contribute to the bigger land productivity and can create typical landscapes [3],[4]. Geronggang Cratoxylon arborescens is in family of Gutiferae or Hypericaceae. It is a fast growing, medium to large-sized, evergreen tree up to 50 m tall, and bole up to 65 cm in diameter. It can be found in Sumatra, Borneo, Southern Burma, and Peninsular Malaysia. Geronggang tree is pioneer species. They are abundantly and grow rapidly in secondary forest after felling or ire [5]. Geronggang typically occurs in freshwater or peat-swamp forest on sandy or sandy-loamy soils, and sometimes in coastal dipterocarp swamp forest. It generally appears scattered but it sometimes abundantly clustered and can even become dominant. Several enrichment plantings with nursery-cultivated seedlings of geronggang in experimental scale by various institutions in Indonesia showed good results in swamp forest. [5] According to Center for Pulp and Paper, the characteristic of wood needed as a raw material for pulp are low density 0.3-0.8, iber length 0.8 mm or more, lignin content less than 23, cellulose content 40-45, pulp yield more than 40 un-bleached pulp. From silviculture point of view, wood species to be developed as raw material for pulp industry must meet certain criteria such as fast growing, short cycle on harvesting, fewer tree branches, bole height or straight trunk, easy to grow and easy to cultivate, and free of pests and diseases [6] This paper provides data to support geronggang as an alternative species for pulp raw material that could potentially replace A. crassicarpa plantation in peat-lands. The study presented in this paper addressed growth characteristic, wood density, iber dimension, and pulp properties of geronggang as a potential pulp wood. Methods and Materials This paper is half review and half research paper. Data of A. crassicarpa and geronggang growth characteristic are review from other paper. Wood density, iber dimension, and pulp properties were conducted by authors. Geronggang sample was harvested from Lubuk Ogong, Pangkalan Kerinci, Riau Province, Indonesia. The trees planted in research area of Research and Development Institute of Forest Plant Fiber Technology BP2TSTH. Three trees of 4.5 years old with different diameter at breast height 1.3 m were selected. The log s were sent to BP2TSTH to prepare and analyzed. Speciic gravity was determined in accordance with ASTM D 2395 – 07a using B method volume by water immersion. Meanwhile, wood sticks sample 0.5 mm x 20 mm for iber dimension analysis was taken from middle part of knotless trunk. The sticks were immersed in glacial acetic acid and 35 hydrogen peroxide 1:20 vv and boiled for 1-2 hours until the stick’s color turned white. After the removal of chemical with distilled water, the now-separated wood iber was colorized with 10-15 drops of 2 safranin and then mounted to slide-glass and the iber dimension was measured under light microscope. The pulping process used in this study was kraft method that was done at sulphidity of 25 and active alkali of 18, with 4:1 liquor to iber ratio. The cooking was using rotary digester with maximum temperature was set at 165 o C and cooking time 90 minutes. The resulted pulp was washed, screened, dried, prior to determination of pulp yield, reject, and kappa number. Results and Discussion The performance of geronggang i.e. tree growth, wood density, iber dimension and pulping condition was irstly compared with A. crassicarpa by reviewing previous works. Growth Geronggang showed higher survival rate than A. crassicarpa, yet it had inferior growth performance height and DBH than A. crassicarpa Table 1. But it must be noted that geronggang in this study was originated from wildlings while A. crassicarpa was supplied from advanced tree improvement program. Nonetheless, supposedly geronggang already accustom to their natural habitat e.g. better in overcoming the threat of pests or diseases thus it showed higher survival rate than the introduced-A. ISBN : 978-602-17761-4-8 61 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech crassicarpa. Termites and fungi Ceratocystis sp were suspected to be the main cause of higher mortality of crassicarpa [7]. Table 1. The growth of geronggang Cratoxylon arborescens and Acacia crassicarpa at age of 3 - 4.5 years old in drained-peatland experimental plots [7] Species Age yo Survival rate Height m Dbh cm MAI m 3 ha -1 year -1 CAI m 3 ha -1 year - 1 Cratoxylon arborescens Acacia crassicarpa 3 86.4 ± 1,60 6.83 ± 0.394 7.81 ± 0,823 5.25 11.03 3.5 85.6 ± 2,19 7.72 ± 0.245 8.44 ± 0,385 8.68 17.26 4.5 85.6 ± 2,19 10.01± 0.50 10.16 ± 0,50 12.79 27.14 3 53.6 ± 4,49 16.6 ± 0.662 15.69 ± 1,64 No data available No data available 3.5 28.8 ± 15,00 18.04 ± 1.528 18,31 ± 1,349 4.5 25.6 ± 11.17 18.87 ± 0.99 22.99 ± 2,33 32.54 Note: Dbh = Diameter at breast height; MAI = Mean Annual Increment; CAI = Current Annual Increment. The high mortality may greatly diminish the higher growth performance of A. crassicarpa and eventually may reduce its standing stock MAI and CAI in the further future. On the other hand, higher survival rate may favour geronggang to increase its standing stock, especially once its growth performance is improved through tree breedingimprovement program. Maintaining a broad genetic base is very important for large scale tree improvement program. Although have lower survival rate, A. crassicarpa provide higher productivity because has larger dimension in diameter and height. There was no intersection curve of MAI and CAI of geronggang at the measurement period of 2.5 - 4.5 years old, they even tended to still sharply increase. The result suggested that optimal volume was not obtained yet at those periods. Thus, it is necessary to further observe the growth and productivity of geronggang igure 1 [7]. Figure 1. MAI and CAI curve of geronggang in drained-peatland experimental plots [7] The MAI can be improved by progeny test, clonal test, control pollination, and tissue culture. After using the program of silviculture and the improvement method of vegetative and clonal in fact can increase the productivity of MAI Table 3 [8]. The chance to improve the growth of geronggang and in turn increase MAI through tree breedingimprovement program, however, is still widely open to match the impressive growth of the improved-A. crassicarpa. ISBN : 978-602-17761-4-8 62 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 2. The MAI of Acacia mangium, Acacia crassicarpa, and Eucalyptus pellita in PT. RAPP after tree improvement program [8] Species Age year MAI m 3 hayear Remark Acacia mangium 7 22 No improvement in 1996 6 29 With tree improvement in 2006 6 40 Using vegetative family forestry materials in 2009 Acacia crassicarpa 7 18 No improvement in 2001 6 29 Using vegetative family forestry materials in 2009 Eucalyptus pellita data not available 20 No improvement in 2000 35 Using clonal materials in 2009 Thus far, A. crassicarpa dominated peatland plantation for pulp and paper. However, in the recent years, A. crassicarpa shows various serious problems. In addition, few cases of broken trunk or even uprooted tree were found in the plot of A. crassicarpa which were not occurred in the nearby plot of geronggang [7]. Tree’s biomass increases with age and the development of biomass of A. crassicarpa was considerably large. This immense biomass development was not equal to the low itness of the root system to the less favorable characteristics of peat soil thus A. crassicarpa is prone to fell or uprooted by severe wind blows. PT Arara Abadi [9] reported the stands of A. crassicarpa at age 3 years old showed survival rate of 49.82 and noticeably decreased to only 27.38 at age of 4 years old. Table 3. Potency and stand volume of A. crassicarpa [9] Plant of Age years Height m Dbh cm Survival rate Volume m 3 ha MAI m 3 ha year CAI m 3 hayear 1 4.1 4.6 22.89 1.9 1.9 - 2 9.3 8.4 38.18 22.9 11.5 21.0 3 14.0 11.8 36.96 66.5 22.2 43.6 4 17.9 15.0 29.79 110..2 27.6 43.7 5 20.9 18.0 21.97 136.9 27.4 26.7 6 23.4 20.8 16.32 152.0 25.3 15.1 7 25.2 23.5 12.36 158.3 18 6.3 Speciic Gravity Speciic gravity SG is a complex physical property corresponded to both anatomical structure and chemical composition of the wood, and considerably responsive to genetic, environmental and physiological inluences. On the other hand, SG is also corresponded to the most of the resistance properties of the timber durability, shrinkage, etc. as well as many aspects of wood processing chipping, transporting, pulping and product quality. In fact, SG and pulp yield are considered as key parameters in tree-selection for pulping, in addition to tree growth wood biomass. SG is important consideration in determining wood species for raw material of pulp. General requirement of SG for pulp-wood is 0.3-0.8 [6]. The speciic gravity of 4.5 years old geronggang was 0.43 0.38-0.50, which was almost similar to that of crassicarpa [7]. The density of geronggang is classiied as class I-II and is categorized as low to medium [10]. In this range of wood density, diffusion and penetration of chemicals in pulping process will take place easier thus it will more effectively dissolve lignin in the middle lamella and consequently will resulted better ibers separation [11]. ISBN : 978-602-17761-4-8 63 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 4. Speciic density of geronggang Cratoxylon arborescens and Acacia crassicarpa Species Age years Speciic density Class Source Cratoxylon arborescens - 0.4-0.47 I-II [10] - 0.47 0,36-0,71 I-II [13] - 0.35-0.71 [5] 4.5 0.43 0.38-0.50 [7] Acacia crassicarpa 4.5 -s 0.44 0.37-0.51 0.67-0.71 [7] [5] Fiber Dimension Fiber dimension can be used to determine the value of the ibers parameter i.e. runkle ratio, felting power, mulsteph ratio, lexibility ration, and coeficient of rigidity. Fiber dimension parameters, i.e. iber length, iber diameter, cell wall thickness, and lumen diameter have complex relation of each other and have a fundamental inluence on the physical properties of pulp and paper [12]. The 4 and 5 years old A. crassicarpa had relatively long ibers Table 5 classiied as quality II medium. Meanwhile iber diameter is classiied as quality I good. Long ibers produce higher tear strength and wide diameter ibers produce better paper compact [13]. The values of iber derivative of A. crassicarpa showed almost similar class quality. Based on the iber dimensions in Table 5, the 4-5 years old A. crassicarpa were classiied in class quality I - II. In general, the iber properties of crassicarpa meet the requirement of the pulp and paper industry [2]. The resulting data of iber dimensions and their derivatives values were compared with the criteria standard. The quality of iber as a raw material for pulp is categorized into classes I and II. Generally, Geronggang has thin to medium cell wall with wide lumen. In making pulp’s sheet, iber is easy to be lat. The connectivity between iber and derivatives was good. Meanwhile, it was made for paper that was predicted has tensile, tearing, and burst strength medium to high [10]. Table 5. Fiber dimension and its derivatives of geronggang Cratoxylon arborescens and A. crassicarpa [9],[12],[14] Species Ages Properties Cratoxylon arborescens Acacia crassicarpa Unknown [11] Unknown [14] 4 years old [9] 5 years old [9] Value Class Value Class Value Class Fiber length mm 1.180 II 1.230-1.327 II 1.343 II 1.307 II Fiber diameter µm 22.3 II 28.09-31.18 II 35.68 I 34.24 I Runkle ratio 0.3 II 0.16-0.18 I 0.14 I 0.14 I Felting power 53 II 43.63 III 38.01 III 38.09 III Mulsteph ratio 41.2 II 26.27 I 22.00 I 20.20 I Flexibility ratio 0.77 II 0.86 I 0.88 I 0.88 I Coeff. of rigidity 0.12 II 0.07 I 0.06 I 0.06 I ISBN : 978-602-17761-4-8 64 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Pulp Properties Kraft process was conducted to determine pulp properties of geronggang wood. The kraft method was 25 sulphidity, 18 active alkali AA at 165 o C of cooking temperature and 90 minutes of cooking time at the maximum temperature, as generally conducted in pulp and paper industry. The resulted pulp properties of the process are presented in Table 6 [15],[16]. Pulp yield, kappa number and pulp lignin have been considered as adequate parameters to describe pulp quality. Pulp yield of geronggang in this study is in consent with which stated pulp yield of hardwood is ranging from 45-50 [17]. Pulp yield is substantially affected by speciic gravity SG, and since SG of geronggang is lower than that of A. crassicarpa SG is 0.49 thus it is understandable that pulp yield of geronggang was lower than that of A. crassicarpa as well Table 6. Table 6. The pulp properties of geronggang Cratoxylon arborescens and Acacia crassicarpa [16] Parameter C. arborescens A. crassicarpa [16] Pulp yield 48.15 53.48 Kappa Number 16.09 17.77 Pulp lignin 2.09 2.31 Kappa number determination is an indirect method to estimate the residual lignin in the pulp and thus an indicator of the degree of lignin dissolution in the pulping process. Kappa number is very important tool to identify 1 the degree of deligniication during cooking process, 2 to determine the chemical concentration in bleaching process [18]. Kappa number bigger than 20 means that it is not feasible to bleach the pulp because it will require higher concentration of bleaching chemical. In this study, kappa number of crassicarpa was bigger than that of geronggang which implied the suitability of geronggang for pulp wood [19]. Pulp lignin is a function of the Kappa number of pulp, where a high kappa number relect a high content of lignin remaining in the pulp [20]. In this research pulp lignin as Klason lignin. Lignin content in the pulp was calculated as 0.13 x Kappa number [22]. In this case, pulping condition of geronggang produced the highest residual lignin and caused the pulp lignin of geronggang lowest than pulp lignin crassicarpa. Pulp lignin of geronggang and crassicarpa were 2.09 and 2.31 respectively Table 6. Based on data, geronggang was more effective for deligniication of lignin polymer than crassicarpa. In the sulfate process, sulfur enters the lignin molecule to form alkali-soluble thiolignin [19] Conclusion Geronggang had higher survival rate but lower MAI and CAI than Acacia crassicarpa . Speciic gravity of geronggang was 0.43 0.38-0.50 thus it is suitable for pulp wood. Fiber dimensions and values of iber derivative of geronggang were in class quality I-II. The resulted pulp yield, pulp lignin, pulp reject, and kappa number of with 25 sulphidity and 18 active alkali AA at 170 o C for 90 minutes were 48.15, 2.09, 0.08 and 16.09, respectively. Although SG, iber dimension, and pulp properties of geronggang at 4.5 years old are suitable as raw material for pulp and have potential to substitute A. crassicarpa, but the wood productivity MAI CAI still lower than A. crassicarpa. Wood productivity of geronggang needs improvement in diameter and height to substitute A. crassicarpa. Geronggang not optimal productivity at the age 4.5 years old because the wood productivity not optimal yet. Acknowledgments We would like to express our gratitude to Ahmad Junaedi Institute of Research and Development on Forest Plant Fiber Technology for sharing his knowledge in silviculture of geronggang and prepare the sample. ISBN : 978-602-17761-4-8 65 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech References 1. Statistik Kehutanan Indonesia. Ministry of Forestry Statistic 2013. Kementerian Kehutanan Indonesia. Jakarta. 2014 2. Suhartati, S. Rahmayanti, A. Junaedi E. Nurrohman. Sebaran dan Persyaratan Tumbuh Jenis Alternatif Penghasil Pulp di Wilayah Riau. Kementerian Kehutanan. Badan Penelitian dan Pengembangan Kehutanan. Jakarta. 2012 3. Johnson, H. Stawell. The beneits of using indigenous. Plants.Landcare Notes.State of Victoria Department of Natural Resources and Environment. Australia. 2001 4. Harrison, S., T.J. Venn, R. Sales, E.O. Mangaoang J. F. Herbohn. Estimated inancial performance of exotic and indigenous tree species in smallholder plantations in Leyte Province. 2005.Annals of Tropical Research 271: 67-80 5. Soerinegara, I dan R.H.M.J. Lemmens eds. Plant resources of South-East Asia. Timber trees, Major Commercial Timber 5 1: 143-148. Prosea. Bogor. 2001. 6. Mindawati, N. Beberapa Jenis Pohon Alternatif untuk Dikembangkan Sebagai bahan Baku Industri Pulp. Mitra Hutan Tanaman 2 1 : 1-7. Pusat Penelitian dan Pengembangan Hutan Tanaman. Bogor. 2007. 7. Junaidi, A., Novriyanti E., Rahmayanti, S., Hendalastuti, H., Aprianis, Y. Akbar, O.T., Rizqiani, K.D. Silvikultur jenis Pohon Lokal Potensial Native Sspecies Pada lahan Kritis Marginal di Riau. Laporan Hasil Penelitian Tahun 2015. Balai Penelitian Teknologi Serat Tanaman Hutan. Riau. 2015. 8. Suhartati, Y. Aprianis, A. Pribadi, Y. Rahcmayanto. Study of Reduction Cycle Impact of Acacia crassicarpa A. Cunn Plantation to Production Value and Social Aspect. Jurnal Penelitian Hutan Tanaman Vol. 10 No. 2Junu 2013. 9. Golani, G.D., Siregar, S.T.H., Gofur, A. Tree Improvement and SIlviculture Research Progress at PT Riau Andalan Pulp and Paper APRIL Group-Chalenges and Opportunitie. Proceedngs International Seminar Research on Plantation Forest Management: Challenges and Opportunities. Bogor 2009. 10. Pasaribu R.A. and tampubolon. Persyaratan Teknis Bahan Baku, Air dan bahan Penolong untuk Industri Kertas dan rayon. Diklat Pelatihan Veriikasi Eksportir Terdaftar Produk Industri Kehutanan ETPIK. Puslitbang Hasil Hutan. Bogor. 2007. 11. Casey, J.P. 1980. Pulp, Paper Chemistry and Chemical Technology. Third Edition. Vol I. Willey Interscience Publisher Inc. New York. 12. Nurrachman, A and T. Silitonga. DImensi serat beberapa jenis kayu Sumatra Selatan. Laporan No. 2, Lembaga Penelitian Hasil Hutan, Bogor. 1972. 13. Martawijaya, A., Kartasujana, I., Kadir, K., Prawira, S.A. Atlas Kayu Indonesia Jilid I edisi revisi. Departemen Kehutanan. Balai Penelitian dan Pengembangan Kehutanan. Bogor. 2005. 14. Rinanda. R. Sifat dasar dan Kegunaan Kayu Sumatera. Laporan Hasil Penelitian. Balai Penelitian Teknologi Serat Tanaman Hutan. Riau. 2012. 15. Aprianis, Y., Novriyanti, E., Wahyudi, A., Akbar, O.T., Rizqiani, K.D. Diversiikasi Produk Serat: Bambu Sumatera dan Kayu Potensial Gambut. Laporan Hasil Penelitian Tahun 2015. Balai Penelitian Teknologi Serat Tanaman Hutan. Riau. 2015. 16. PT. Arara Abadi. Rencana Kerja Periode Tahun 2008-2017. Riau. 2008. 17. Fengel, D Wegener, G,. Chemistry, ultrastructure, reaction. Walter de Gruyter, Berlin. 1989. 18. Smook, A.G. Handbook for pulp and paper technologist Second Edition. Angus Wilde Publication Inc. Bellingham. 1992. 19. Casey, J.P. Pulp and paper chemistry and chemical technology Second Edition. Vol. 1, Interscience Publishers, Inc., New York. 1980.. 20. Fatriasari, W., Suriyanto Iswanto, A.P. The kraft pulp and paper properties of sweet sorghum bagasse Sorghum bicolor L Moench. 2015.Journal Engineering Technology Science. Vol. 47 2: 149-159. 21. Sjöström, E. Wood chemistry: fundamental and application Second Edition. Academic Press, San Diego, USA. 1981. 22. TAPPI. Kappa Number of Pulp. TAPPI Press, Atlanta, Georgia. 1996 ISBN : 978-602-17761-4-8 66 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 67 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech KRAFT PULPING CONDITION FOR SUMATRAN THORNY BAMBOO, POTENTIAL MATERIAL FOR VISCOSE PULP Kanti Rizqiani 1 , Eka Novriyanti 2 , Dodi Frianto 3 Research and Development Institute for Forest Plant Fiber Technology Balai Penelitian dan Pengembangan Teknologi Serat Tanaman Hutan BP2TSTH Ministry of Environmental and Forestry Jl. Raya Bangkinang-Kuok Km. 9 PO. BOX 4BKN Bangkinang 28401, Indonesia 1 kanti.drizqianigmail.com 2 kee.november09gmail.com 3 dfriantogmail.com ABSTRACT Thus far, Sumatran thorny bamboo, namely duri bamboo Bambusa blumeana, has not utilized economically by communities or business holders. Given the best quality of bamboo iber in general and in an effort to determine the suitability of Sumatran thorny bamboo for viscose pulp, B. blumeana were pre-hydrolyzed with 0, 2.5 and 5 acetic acid prior to kraft pulping process. Chemical analysis on pre-hydrolyzed bamboo chips showed that 2.5 acetic acid gave the optimum result. The kraft method was done in 3 levels of active alkali AA , 18, 20 and 22 and 3 levels of sulidity 22, 25 and 28. The analyses on the kraft method showed that the best holocellulose, a-cellulose and lignin values were resulted by combined-treatment of AA 20 and sulidity 22, AA 22 and sulidity 22, and AA 22 and sulidity 25, respectively. In general, kraft method with AA 22 and sulidity 25 gave the optimum result for this Sumatran thorny bamboo. The yield resulted from this treatment was 51.91, reject 0.32, kappa number 13.11, ash content 0.52, total extractives 14.57, holocellulose 93.72, a-cellulose 79.08 and lignin content 4.46. This condition of kraft pulping could be considered for the procedure in further observation of the suitability of duri bamboo for viscose pulp. Keywords: Bambusa blumeana; pre-hydrolyzed; kraft pulp; viscose; active alkali; sulidity. Introduction Bamboo is a perennial plant in the family Graminaeae sub family Bambusoideae. Among 1250 of the world-recorded bamboo species, 159 species are found in Indonesia. Most of bamboo species grow in tropical or subtropical regions, but some are spread along temperate area such as in China and Japan Widjaya 1998. In Indonesia, although bamboo spreads widely from the outmost western to the foremost eastern part of the country’s islands, the utilization of bamboos is economically less recognized. Bamboo could be found from lowland to 3000 m asl in highland Latif Razak 1991, on various types of habitat and almost on all of soil types except on alkaline, desert and mangrove Lee et al. 1994. Bamboo reaches it maximum height at 4-6 months old with daily increment of 15-18 cm. A well grown bamboo’s clump could consist of 40-50 culms with rate of addition of 10-20 culmsyear Aminuddin Latif 1991. According to Lee et al. 1994 mature 3-5 years old bamboo culm in a well- managed clumps can be harvested in 3 years rotation. These conditions enlighten the immense potency of bamboo’s stock. Mostly, bamboo is used to substitute wood in construction due to its equal strength Marsoem et al. 2009. Fiber of bamboo is categorized as long or semi long iber to which it usually being compared with that of softwood Ma et al . 2012. Bamboo ibers have been used in production of high grade-papers and other high grade products, e.g. ester-cellulose, ether-cellulose, textile ibers, etc. Christov et al. 1998. The big potency of bamboo’s stock and the high grade ibers have encourage various bamboo-related researches in Indonesia. Chemical content in bamboo deine its suitability as material for pulp industry. This lignocellulose material contains 60-70 holocellulose, 20-25 pentose, 20-30 lignin, a small percentage of resin, ISBN : 978-602-17761-4-8 68 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech tannin and wax. In general, the chemical content of bamboo is similar to that of hardwood, but bamboo has higher silica and NaOH-soluble extractives Ogunsile Uwajeh 2009. Anatomically, bamboo iber is classiied as long iber and is categorized in quality class I for pulp. Fatriasari and Hermiyati 2008 revealed the length of bamboo ibers are varied from 2299 to 4693 µm. Based on its chemical content and iber anatomy feature, bamboo is highly suitable material for pulp and paper industry. The high grade of bamboo iber has made this material usually used for high grade paper or high grade derivative- cellulose products. This recent study addresses the possible utilization of Sumatran thorny bamboo, called duri bamboo, for viscose pulp; yet this paper presented the progress up to the results of kraft pulping process of this bamboo. Pulping process for lignocellulosic-material is similar for wood and bamboo; it depends on what the inal product to be made. In order to produce viscose pulp, the Sumatran thorny bamboo Bambusa blumeana Schult. f. was undergone kraft pulping process. Materials and Methods The internode sections from culms of 3-4 years old Sumatran thorny bamboo Bambusa blumeana Schult. f. were debarked and de-pitted and subsequently chipped with size 2.5 x 2.5 x 0.5 cm and air dried. Prior to kraft process, the chips were pre-hydrolyzed with 5 acetic acid in a stainless steel kettle at ±100°C for 60 minutes. The pre-hydrolysis was aimed to enhance the removal of lignin from this lignocellulosic material. The chips were then pulped in kraft process as presented in Table 1. Table 1. Conditions of kraft process on duri bamboo Condition Level Active alkali Sulphidity Chips to liquor ratio Maximum temperature °C Cooking time at max Temperature 18 A1, 20 A2, 22 A3 22 S1, 25 S2, 28 S3 1:4 165 60 The resulted pulp was washed to free it from the cooking liquor, screened and dried with centrifuge drier. The brown pulp was determined for yield, reject, kappa number, and chemical content e.g. cellulose, holocellulose and lignin. The lignin content was determined in accordance with SNI 0492- 2008, holocellulose with SNI 01-1389-1989 and cellulose with SNI 14-0444-1989. Results and Discussion Pre-hydrolysis prior to kraft pulping is aimed to obtain dissolving pulp with higher degree of cellulose content and lower hemicellulose Li et al. 2015. With pre-hydrolysis process, the hemicellulose was degraded in two stages, which are prior to and at the kraft cooking process Asim 2012. Water pre- hydrolysis at a particular temperature and cooking time will break xylan chains and separate acetyl groups as the result of hydrolysis reaction by hydronium ions. In the further stage of hydrolysis, acetic acid resulted from the acetyl group provides extra hydronium ions that may enhance the hydrolysis kinetic Li et al. 2015. The duri bamboo chips’ yield after pre-hydrolyzed with 5 vw acetic acid was 67.08 with kappa number 69.29, while the water-hydrolyzed chips had yield and kappa number of 81.94 and 78.72, respectively. In the previous study, it was noted that the higher the concentration of acetic acid used in the pre-hydrolysis the lower the resulted yield and kappa number. Kappa number is a considerable-predictor for lignin content in particular material. Lower kappa number usually indicates lower lignin content in wood chip or pulp. Pre-hydrolysis with 5 VW acetic acid considerably reduced ash and extractives content, as well as lignin content, compare to those of bamboo without pre-hydrolysis Table 2. As lignin content was lower in hydrolyzed-bamboo than that in un-hydrolyzed one, alpha-cellulose of pre-hydrolyzed bamboo ISBN : 978-602-17761-4-8 69 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech was also lower than that of un-hydrolyzed bamboo Table 2. The lower lignin content in the hydrolyzed- bamboo suggested the occurrence of ligniication in the bamboo’s chips, as expected. This hydrolysis, however, cost the bamboo a reduce content of alpha-cellulose as it may degraded as well in the process of deligniication Table 2. Table 2. Chemicals content of pre-hydrolyzed and un-treated bamboo chips Parameter Content after pre-hydrolyzed with 5 VW acetic acid Without pre- hydrolysis Moisture content 7.52 5.55 Ash content 2.68 5.13 Extractives soluble in benzene 1.23 4.32 Extractives soluble in hot water 5.07 9.26 Extractives soluble in cold water 3.86 6.23 Holocellulose 79.87 79.59 Alpha-cellulose 48.55 51.28 Lignin 11.53 17.57 Despite it lower content of alpha-cellulose, pre-hydrolysis noticeably lowered ash and extractives content in duri bamboo which unwanted in the further process of viscose production. Thus in this case, pre-hydrolysis with acetic acid may favor the process in term of lower lignin, ash and extractives content. However, concerning the also lowered content of alpha-cellulose due to pre-hydrolysis with acetic acid, thus it is necessary to ind the proper condition and acid concentration in the pre-hydrolysis for duri bamboo to obtain optimum alpha-cellulose, lignin, ash and extractives content. The hydrolyzed-chips of duri bamboo were then pulped in kraft method to obtain brown kraft pulp prior to further process to produce viscose pulp. The resulted pulp yield, reject percentage and kappa number of the brown pulp are presented in Table 3. Although active alkali AA 20 separately with sulphidity 28 seemed to give highest pulp yield, 60.20 and 57.74 respectively Table 3. However, since both AA and sulphidity altogether are accounted in kraft process that they must not credited separately, thus AA 20 and sulphidity 25 gave the highest pulp yield in this study, 64.46 Table 3. Reject is the percentage of ibers that could not pass through mesh in the screening process. Usually, higher AA and sulphidity will cause smaller reject in kraft pulping. This lower reject is because more ibers would be effectively separated with higher AA and sulphidity thus could pass through the screener. Combination of AA 22 and sulphidity 25 gave the lowest reject in this study, 0.32 Table 3. Separately from sulphidity, AA 22 gave the lowest reject which was 0.69. Sulphidity, in the other hand, showed insigniicant different in affecting reject. In similar magnitude with reject, the higher the AA and sulphidity the lower the resulted kappa number Table 3. This suggested the bigger portion of lignin had been effectively removed from the pulp. Although statistically showed insigniicant different, however combination of AA 22 and sulphidity 25 tended to give the lowest kappa number which was 13.11 Table 3. ANOVA test revealed that ash content was signiicantly affected by AA, although Duncan-Wallis Test showed that AA 20 did not give signiicantly different result with AA 22 in reducing ash content of the pulp. Separately from AA, sulphidity had no different effect on ash content of the pulp as it was shown by one way ANOVA. However, combination of AA 22 and sulphidity 28 signiicantly gave the best lowest ash content, 0.31 Table 4. ISBN : 978-602-17761-4-8 70 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 3. Pulp yield, reject and kappa number of brown pulp of duri bamboo resulted by various level of active alkali and sulphidity in kraft process Active alkali Sulphidity Yield Reject Kappa number 18 22 56.04 ± 0.95 6.38 ± 0.71 30.46 ± 2.47 25 56.03 ± 0.48 8.47 ± 2.19 35.45 ± 4.47 28 57.85 ± 5.36 8.74 ± 3.38 42.05 ± 7.14 Total 56.64 ± 2.88 7.86 ± 2.33 35.99 ± 6.68 20 22 59.88 ± 4.74 9.70 ± 4.23 37.16 ± 11.19 25 64.46 ± 6.36 7.05 ± 1.65 36.38 ± 5.81 28 56.26 ± 12.06 6.82 ± 0.41 37.09 ± 3.35 Total 60.20 ± 8.05 7.85 ± 2.67 36.88 ± 6.54 22 22 55.59 ± 7.27 1.09 ± 1.27 16.62 ± 6.48 25 51.91 ± 1.36 0.32 ± 0.23 13.11 ± 0.60 28 59.11 ± 3.52 0.66 ± 0.16 14.52 ± 1.25 Total 55.54 ± 5.15 0.69 ± 0.73 14.75 ± 3.65 Total 22 57.17 ± 4.82 5.72 ± 4.37 28.08 ± 11.21 25 57.47 ± 6.43 5.28 ± 4.02 28.31 ± 11.99 28 57.74 ± 6.94 5.40 ± 4.03 31.22 ± 13.32 TOTAL 57.46 ± 5.89 5.47 ± 3.99 29.20 ± 11.81 Remarks: ANOVA test with a= 0.05 Table 4. Chemical properties of kraft brown pulp of duri bamboo in various level of active alkali and sulphidity Active alkali Sulphidity Ash content Extractive Benzene Extractive Hot water Extractive Cold water Holocellulose Alpha cellulose Lignin 18 22 0.39 3.57 6.60 3.92 91.41 77.21 5.14 25 0.69 3.07 5.99 3.32 91.68 71.90 5.29 28 1.04 3.32 9.10 3.99 90.36 70.85 7.00 Total 0.71 3.32 7.23 3.75 91.15 73.32 5.81 20 22 1.43 3.72 8.30 4.50 90.28 72.04 6.64 25 0.54 1.94 4.02 2.19 92.61 73.09 5.84 28 0.66 3.02 5.77 3.04 92.44 78.12 5.04 Total 0.88 2.89 6.03 3.25 91.78 74.42 5.84 22 22 0.54 2.18 5.72 2.64 92.63 79.11 5.52 25 0.52 2.48 7.67 4.42 93.72 79.08 4.46 28 0.31 2.40 7.92 4.05 92.77 78.44 5.66 Total 0.46 2.35 7.10 3.70 93.04 78.88 5.21 Total 22 0.79 3.16 6.88 3.69 91.44 76.12 5.77 25 0.58 2.50 5.89 3.31 92.67 74.69 5.20 28 0.67 2.91 7.59 3.70 91.86 75.80 5.90 TOTAL 0.68 2.86 6.79 3.57 91.99 75.54 5.62 Remarks: ANOVA test with a= 0.05 The analysis of extractives content of the pulp was approached by three extractives solubility, namely solubility in alcohol-benzene, hot water and cold water. The AA and sulphidity, separately or in combination, signiicantly affected extractive dissolved in alcohol-benzene. The AA 22 gave the lowest extractive in alcohol-benzene which was 2.35, meanwhile sulphidity 25 gave the lowest extractive ISBN : 978-602-17761-4-8 71 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech in alcohol benzene which was 2.50, and combination of AA 20 and sulphidity 25 gave the lowest extractive in alcohol benzene, 1.84 Table 4. Combination of AA and sulphidity signiicantly affected extractive in hot water in which AA20 and sulphidity 25 gave the lowest 4.02 of extractive in hot water. However, there was no different result found on extractive in cold water cause by various levels of AA and sulphidity and their combination. In general, combination of AA 20 and sulphidity 25 gave the lowest extractive content in the pulp of duri bamboo Table 4. Holocelluose can be used to predict the hemicellulose content in the pulp. The adequate dissolving pulp must have higher content of alpha-cellulose ≥ 95, low holocellulose ≤ 10 and lignin content ≤ 0.05. In this study, brown pulp kraft of duri bamboo was have not yet bleached to further dissolved hemicellulose and lignin. The resulted alpha-celluose was only ± 79 and the holocellulose content ±93 which suggested hemicellulose may around 14 Table 4. These results had not yet meet the requirement for dissolving pulp thus bleaching must be conducted to further reduced holocellulose and lignin from the brown pulp. Active alkali a 0.05, sulphidity a = 0.05 and their combination a = 0.1 signiicantly affected holocelluose content of duri bamboo’s brown pulp in which AA 20 and sulphidity 22 resulted the lowest holocellulose, 90.22. Alpha-cellulose and lignin were signiicantly a = 0.1 affected by combination of AA and sulphidity. Duncan-Wallis test showed that combination of AA 22 and sulphidity 22 or with sulphidity 25 did not give different result and gave the highest alpha-cellulose content, ±79. Meanwhile, combination of AA 22 and sulphidity 25 gave the lowest lignin content which was 4.46 Table 4. In this study, higher AA was likely gave higher alpha-cellulose and tended to reduce lignin content better. In general, combination of AA 22 and sulphidity 25 gave the optimal result for kraft brown-pulp of duri bamboo. This cooking condition gave pulp yield 51.91, reject 0.32, holocellulose 93.72, alpha-cellulose 79.08 and lignin 4.46. This result was different with that of Ma et al 2012 that examined dissolving pulp from Dendrocalamus oldhamii. The bamboo was water pre-hydrolyzed max temperature 170°C, 60’, in rotary digester and kraft cooking condition AA 23, sulphidity 26, max temperature 170°C for 60 minutes. They obtained pulp yield 32.4, kappa nuber 6.3, pentosan 5 and alpha-cellulose 90.2. Although this study had higher pulp yield and lower lignin content, yet the resulted alpha-cellulose was lower than Ma et al. 2012. Presumably, the different bamboo species used in this study and in Ma et al 2012 gave that different result. The using of rotary-digester in pre-hydrolysis may also accountable for the different result in Ma et al 2012. Rotary digester would distributed pre-hydrolysis process evenly in the whole bamboo chips and kept the higher and stabile temperature than stainless steel kettle. Conclusion The kraft process for duri bamboo that gave the best result was AA 22 and sulphidity 25, chips to liquor ratio 1:4, max temperature 165 °C and cooking time 60’ at the max temperature. The resulted kraft brown pulp had pulp yield 51.91, reject 0.32, kappa number 13.11, ash content 0.52, total extractives 14.57, holocellulose 93.72, alpha-cellulose 79.08 and lignin content 4.46. Acknowledgement Authors would like to express our sincere gratitude to Dissemination Division of BP2TSTH for supporting this manuscript, Sub District of Puhun Pintu Kabun, Bukittinggi City, for providing bamboo materials, and Center for Forest Product Technology for providing laboratory facility, Center for Pulp and Paper for discussion input. References 1. Widjaya, EA. Bamboo genetic resources in Indonesia In Vivekanadan K, A.N. Rao, V, Ramanatha Rao eds. 1998. Bamboo and rattan genetic resources in certain Asian countries. IPGRI-APO, Serdang, Malaysia.1998. ISBN : 978-602-17761-4-8 72 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 2. Lee, AWC, Xuesong, B, Perry NP. Selected physical and mechanical properties of giant timber bamboo grown in South Carolina. Forest Prod J 1994; 449: 40-46. 3. Aminuddin, M. and Latif MA. Bamboo in Malaysia: past, present and future research. In 4 th International Bamboo Workshop, Bamboo in Asia and the Paciic, Chianmai, Tahiland, 27-30 November 1991. Proceedings, pp 349-354. 4. Marsoem SN, Prasetyo, VE, Rachman WB, Sudarwoko, AD. Pemanfaatan serat monokotil bambu legi Gigantochloa atter sebagai bahan baku pulp secara mekano-organosolv. Proceeding National Seminar MAPEKI XII Bnadung, West Java, 23-25 July 2009. 5. Ma, X, Huang, L, Cao, S, Chen, Y, Luo, X, Chen, L. Preparation of dissolving pulp from bamboo for textile application. Part 2: Optimation of pulping condition of Hydrolyzed bamboo and its kinetics. Bioresources 2012; 72: 1866-1875. 6. Christov, LP, Akhtar, M, Prior, BA. The potential of bio-sulphite pulping in dissolving pulp production. Enzyme and Microbial Tech 1998; 23: 70-74 7. Ogunsile B.O and Uwajeh C.F. Evaluation of the pulp and paper potentials of Nigerian grown Bambusa vulgaris. World Applied Science Journal 2009; 64: 536-541 8. Li, G, Fu, S, Zhou, A, Zhan, H. Improved cellulose yield in the production of dissolving pulp from bamboo using acetic acid in prehydrolysis. BioResources 2015; 101: 877-886. ISBN : 978-602-17761-4-8 73 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech THE DAMAGE OF PAPER-BASED ARCHIVES IN FOUR ARCHIVAL INSTITUTIONS Sari Hasanah ANRI, Jl. Ampera Raya, Jakarta 12560, Indonesia hasanah_sariyahoo.com ABSTRACT The objective of this research is to study the archives damage so that the results can support preservation of paper-based archives. The research was conducted on static archives which have historical value and kept permanently in four archival institutions. Archives damage was analyzed based on Archives Damage Atlas and Universal Procedure Archives Assessment. Several damage proiles were shown for each category and were classiied according to severity: slight damage, moderate damage, and serious damage. Damage was divided into the ive categories: Binding and text block damage, chemical damage, mechanical damage, pest infestation, and water damage. The data clearly reveal slight damage in most archives 54-87. For the accessibility issues, 4-28 percent of archives should not be made accessible. It is also discovered that chemical damage was found in most archives. Finally based on these results, both preventive and curative preservation could be improved and archival institution also should endeavour to create more awareness in using archives. Keywords : archives damage; damage atlas; historical value; paper Introduction Archives provide information and evidence of activities. Organizations include Governments create and use archives in their daily activities and relationships with others. Archives have administrative functions so archives produced by organizations have to be managed by archivist to support good governance. The International Council on Archives ICA said that effective records and archives management is an essential precondition for good governance, the rule of law, administrative transparency, the preservation of mankind’s collective memory, and access to information by citizens [1]. The reasons of governments in managing archives are to assist in scrutinizing every decision and activity, to enable communities in transferring knowledge, to learn from the past and to protect the collective interest of society and citizens, and to fulill the interest of society in decision which affect to public [2]. Histories of archives generally start by referring to archives in the ancient world, tracing the record keeping practices of ancient Greece and Egypt, the repositories of the Roman Empire and the links from these written archives to legal and political developments [3]. The history of archival institution in Indonesia was begun on January 28, 1892 when the Dutch government established Landsarchief in Batavia. On May 18, 1971, the Law Number 7 Year 1971 was issued and then celebrated as the National Archives Day. Not all archives produced by the governments should be preserved in archival institution. Governments discard quickly most archives and some are still kept for longer periods because their continuing value to nation. This value is called as secondary value which is the additional historical value to the organization and wider. This can include evidential value derived from the way the record documented the history, structure and functions of an organization, and informational value in providing research material on persons, places and subjects. The opposite of secondary value is primary value which is the value to the organization that created them for administrative, legal and iscal purposes [4]. Law of the Republic of Indonesia Number 43 of 2008 stated that the administration of archives shall be the responsibility of archival institution. Archival institution shall mean an institution that has the functions, duties, and responsibilities in managing static archives and maintaining development in the administration of records and archives [5]. Static archives here mean archives which have historical secondary value. Archives are created in any media like paper, ilm, magnetic tape, optical disk, video, ISBN : 978-602-17761-4-8 74 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech microilm. Today, most archives kept are in paper mediaformat. Paper based archives are vulnerable to deterioration. Paper are subject to intrinsic decay which is degradation that is inherent in the material itself. Patkus called it as ”inherent vice”, a term that describes inherent weaknesses in the chemical or physical structure of an object [6]. There are also external agents of deterioration like water, pests, pollutants, moisture, temperature, light and human agency. In addition to changing environmental conditions, many archives have been exposed to different forms of damage. Careless handling of collections, theft and vandalism also contributes the deterioration of archives. The multitude of preservation research activities being carried out worldwide indicates an international awareness of the need for scientiic tools to tackle the problem of degradation of the world’s cultural heritage. Research is providing new insights into why and how objects deteriorate and is informing the development of new active and passive preventive conservation procedures [7]. Archiving services are required by law, moreover, to pass on archival documents to future generations in good, well-ordered and accessible condition. For this reason it is important to be aware of the condition, not only of the individual documents but also of the archive as a whole. By determining how many archival documents in a piece or a part of it are in poor or even bad condition, a general statement can be made about its quality and accessibility. At the same time, a vision can be developed on the need for future preservation work [8]. The research was conducted on archives stored in four archival institutions. Consideration four archival is based on geographical considerations. It is known that the environment inluences the life of the archives. The objective of this research is to study the archives damage in four archival institutions so that the results can support preservation of paper-based archives. Method Archives damage was analyzed based on Archives Damage Atlas and Universal Procedure Archives Assessment. The Archives Damage Atlas is a tool that can be used to recognize and classify damage to archival documents in order to establish the level of accessibility [8]. The atlas should also provide more insight into the types and causes of damage. Universal Procedure Archives Assessment is a model for calculating the assessment or consultability of archives [9]. Damage was divided into the following categories: 1. Binding and text block damage 2. Chemical damage 3. Mechanical damage 4. Pest infestation 5. Water damage Several damage proiles were shown for each category and were classiied according to severity. This division distinguishes between: 1. Slight damage. The damage to the object is not exacerbated when the archival document is handled when it is moved, for instance, or paged through. 2. Moderate damage The damage to the archival document is not exacerbated when it is calmly and carefully handled. However, if the piece is subjected to handling or treatment that is a bit too rough, there is a good chance that the damage will worsen. 3. Serious damage Even careful and painstaking handling of the archival document for instance, when paging through will result in aggravation of the existing damage. It should also be noted that if there is a danger of information loss, the damage to the archival document should always be regarded as serious. Even if only part of a single leaf of an objectis seriously damaged,the entire object should be considered seriously damaged and therefore should not be made accessible. ISBN : 978-602-17761-4-8 75 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Sampling method was random sampling so that each element has an equal probability of selection. The Sample size was determined using Table of Stephen Isaac and William B. Michael [10]. Population was all collection of paper based archives stored in four archival institutions. The population size and the sample size are shown below: 1. Institution A Population size : 2000 boxes of archives Sample size: 322 boxes of archives 2. Institution B Population size: 1200 boxes of archives Sample size : 304 boxes of archives 3. Institution C Population size: 3500 boxes of archives Sample size : 356 boxes of archives 4. Institution D Population size: 12428 boxes of archives Sample size : 98 boxes of archives In this institution, sample size was not large enough because there was the fumigation process in the time of research. Results and Discussion Level of Archives Damage Identiication of Level of Archives Damage are presented in Table 1, Table 2, Table 3, and Table 4 : Table 1. Level of Archives Damage in Institution A No Level Number 1 Good 63 20 2 Slight damage 219 68 3 Moderate damage 32 10 4 Serious damage 8 2 Total 322 100 According to Universal Procedure Archives Assessment, moderate and serious damage need serious attention. Table 1. shows that 20 of archives are in good condition, 68 of archives are in slight damage, 12 of archives are in damaged condition 10 of archives are in moderate damage and 2 of archives are in serious damage. These mean that most archives stored are accessible to the public and only 12 of archives should not be made accessible. Table 2. Level of Archives Damage in Institution B No Level Number 1 Good 28 9 2 Slight damage 265 87 3 Moderate damage 11 4 4 Serious damage Total 304 100 Table 2. shows that 9 of archives are in good condition, 87 of archives are in slight damage, 4 of archives are in damaged condition. These mean that most archives stored are accessible to the public and only 4 of archives should not be made accessible. ISBN : 978-602-17761-4-8 76 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 3. Level of Archives Damage in Institution C No Level Number 1 Good 64 18 2 Slight damage 193 54 3 Moderate damage 77 22 4 Serious damage 22 6 Total 356 100 Table 3. shows that 18 of archives are in good condition, 54 of archives are in slight damage, 28 of archives are in damaged condition 22 of archives are in moderate damage and 6 of archives are in serious damage. These mean that most archives stored are accessible to the public and only 28 of archives should not be made accessible. Table 4. Level of Archives Damage in Institution D No Level Number 1 Good 7 7 2 Slight damage 70 72 3 Moderate damage 17 17 4 Serious damage 4 4 Total 98 100 Table 4. shows that 7 of archives are in good condition, 72 of archives are in slight damage, 21 of archives are in damaged condition 17 of archives are in moderate damage and 4 of archives are in serious damage. These mean that most archives stored are accessible to the public and only 21 of archives should not be made accessible. Table 5. shows the age of archives. From this data, we can see that most archives are under 100 years of age and it supports the accessibility of archives because the majority of archives are in slight damage. Table 5.Archives’s Age No Institution Year Created Archives’s Age 1 A 1820-2011 197-6 2 B 1958-2005 59-12 3 C 1926-2005 91-12 4 D 1936-1989 81-28 Law of the Republic of Indonesia Number 43 of 2009 Article 36 mandated that Archival institutions shall provide information services on records and archives, consultation, and guidance in managing records and archives of the community. Besides having an obligation to provide information to the community, archival institution shall ensure the protection of archives as the responsibility of the nation in preserving the national identity of the community, the nation and the state. To what extent an object can be accessed is closely connected to how damaged the documents are. These are the kind of damages that were found: Figure 1. a Slight Damage b Moderate Damage c Serious Damage ISBN : 978-602-17761-4-8 77 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Categories of Archives Damage Categories of damage assessed by Universal Procedure Archives Assessment are binding and text block damage, chemical damage, mechanical damage, pest infestation, and water damage. According to Universal Procedure Archives Assessment, moderate and serious damage need serious attention. The percentage of archives damage based on categories of damage in institution A is shown on this Table 5. : Table 6. Categories of Archives Damage in Institution A Categories Number of Moderate Damage Number of Serious Damage Total Binding and text block damage 2 2 3,3 Chemical damage 42 6 48 78,7 Mechanical damage 6 1 7 11,5 Pest infestation 1 2 3 4,9 Water damage 1 1 1,6 61 100 Table 6 shows that the percentage of chemical damage 78.7mechanical damage 11.5pest infestation 4.9binding and text block damage3 water damage 1.6. Moreover, the percentage of archives based on type of archives damage is shown in this Table 7: Table 7.Type of Archives Damage in Institution A Category Type of Damage Number of Moderate and Serious Damage Binding and text block damage Surface Warping Spine damage Loose binding 2 3,3 2 3,3 Chemical damage Fire damage Foxing 17 27,9 Ink corrosion 3 4,9 Rust 18 29,5 Acidiication 9 14,8 Old repairs 1 1,6 48 78,7 Mechanical damage Damage through use 6 9,8 Damage through violence 1 1,6 7 11,5 Pest infestation Damage by insect 3 4,9 Damage by rodents 3 4,9 Water damage Staining 1 1,6 Felting Mould Stuck sheet 1 1,6 Total 61 100 The percentage of archives damage based on categories of damage in institution B is shown on this Table 8: ISBN : 978-602-17761-4-8 78 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 8. Categories of Archives Damage in Institution B Categories Number of Moderate Damage Number of Serious Damage Total Binding and text block damage 1 1 7.7 Chemical damage 6 6 46.2 Mechanical damage 2 2 15.4 Pest infestation 3 3 23.1 Water damage 1 1 7.7 13 100 Table 8 shows that the percentage of chemical damage46.2pest infestation 23.1 mechanical damage 15.4 binding and text block and water damage 7.7. Moreover, the percentage of archives based on type of archives damage is shown in this Table 9. Table 9. Type of Archives Damage in Institution B Category Type of Damage Number of Moderate and Serious Damage Binding and text block damage Surface Warping 1 7.7 Spine damage Loose binding 1 7.7 Chemical damage Fire damage Foxing 2 15.4 Ink corrosion Rust Acidiication 4 30.8 Old repairs 6 46.2 Mechanical damage Damage through use 1 7.7 Damage through violence 1 7.7 2 15.4 Pest infestation Damage by insect 2 15.4 Damage by rodents 1 7.7 3 23.1 Water damage Staining 1 7.7 Felting Mould Stuck sheet 1 7.7 13 100 The percentage of archives damage based on categories of damage in institution C is shown on this Table 10. Table 10 shows that the percentage of chemical damage 48.6 binding and text block damage28.9mechanical damage 11.9water damage 7.8pest infestation2.8. Moreover, the percentage of archives damage based on type of archives damage is shown in this Table 11. The percentage of archives damage based on categories of damage in institution D is shown on this Table 12. ISBN : 978-602-17761-4-8 79 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 10. Categories of Archives Damage in Institution C Categories Number of Moderate Damage Number of Serious Damage Total Binding and text block damage 44 19 63 28.9 Chemical damage 83 23 106 48.6 Mechanical damage 21 5 26 11.9 Pest infestation 6 6 2.8 Water damage 13 4 17 7.8 13 100 Table 11. Type of Archives Damage in Institution C Category Type of Damage Number of Moderate and Serious Damage Binding and text block damage Surface 22 10.1 Warping 3 1.4 Spine damage 22 10.1 Loose binding 16 7.3 63 28.9 Chemical damage Fire damage 0.0 Foxing 25 11.5 Ink corrosion 10 4.6 Rust 11 5.0 Acidiication 52 23.9 Old repairs 8 3.7 106 48.6 Mechanical damage Damage through use 23 10.5 Damage through violence 3 1.4 26 11.9 Pest infestation Damage by insect 5 2.3 Damage by rodents 1 0.5 6 2.8 Water damage Staining 7 3.2 Felting 4 23.5 Mould 4 1.8 Stuck sheet 2 0.9 17 7.8 218 100 Table 12. Categories of Archives Damage in Institution D Categories Number of Moderate Damage Number of Serious Damage Total Binding and text block damage Chemical damage 21 5 26 72.2 Mechanical damage 7 7 19.5 Pest infestation 1 2 3 8,3 Water damage 36 100 ISBN : 978-602-17761-4-8 80 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 12 shows that the percentage of chemical damage 72.2mechanical damage 19.5pest infestation8.3. Moreover, the percentage of archives based on type of archives damage is shown in this Table 13 : Table 13. Type of Archives Damage in Institution D Category Type of Damage Number of Moderate and Serious Damage Binding and text block damage Surface Warping Spine damage Loose binding Chemical damage Fire damage Foxing 7 19.4 Ink corrosion 5 13.9 Rust 4 11.1 Acidiication 10 27.8 Old repairs Mechanical damage Damage through use 7 19.5 Damage through violence Pest infestation Damage by insect 3 8.3 Damage by rodents Water damage Staining Felting Mould Stuck sheet Total 36 100 Based on Table 7, Table 9, Table 11 and Table 13. it can be seen as the following matters: 1. Binding and text block damage Binding and text block damage in institution A was caused by loose binding and in institution B wasonly caused by warping. There were all types of binding and text block damages in institution C and there were not types of binding and text block damage in institution D. Binding and text block damage can be caused by improper and incorrect storage, wear and tear caused by use and transportation, incorrect use of material. 2. Chemical damage In institution A, chemical damage was caused mostly by rust and in institution B, C, and D, chemical damage was caused mostly by acidiication. Besides rust and acidiication, another factor caused chemical damage with big percentage was foxing. 3. Mechanical damage In institution A, C, and D, mechanical damages mostly was caused by damage through use. In institution B, percentage of damage through use and violence is same. 4. Pest damage In institution A and D, pest damage was caused only by insect. In institution B and C, percentage of insect damage is bigger than percentage of rodents damage. 5. Water damage In institution A and B, water damage was caused only by stain. In institution C, water damage was caused by staining, felting, stuck sheet, and mold. In institution D, there was not water damage. Based on above description, moderate and serious damage were caused mostly by chemical factors. Therefore it is necessary to improve preventive and curative preservation programme. The aim of archival preservation is to prolong the usable life of useful research information in two ways. First, preventive preservation seeks to reduce risks of damage and to slow down the rate of ISBN : 978-602-17761-4-8 81 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech deterioration. This aim is usually accomplished by selecting good quality materials and by providing suitable storage environments and safe handling procedures. Secondly, prescriptive preservation is a means of identifying and treating or copying damaged materials to restore useful access to the information [11]. These days, preservation science is a speciality in its own right in which scientists develop an understanding of why and how archive materials deteriorate and then, in co-operation with conservators, research into methods and materials for arresting that deterioration. Most advances in preservation knowledge and practice concentrate on the following three categories decay: cause and mechanism of degradation: treatment: active conservation; storage: passive conservation and damage prevention [12]. Storage plays a successful preventive preservation programme. Proper storage temperature and relative humidity can extend life of archives. The control of temperature and relative humidity is generally accepted as a means to prevent degradation of collections. Observation of temperature and relative humidity in four archival institutions shows that storage doesn’t yet meet requirement of norms for both temperature and relative humidity. If the temperature and humidity are always changing, over time the paper becomes weak because of the disruption of chemical bonds in cellulose polymer. The most common reaction is a hydrolysis reaction. The reaction speed is affected by temperature and moisture content in the paper. The moisture content is inluenced by humidity in the storage room [13]. Archives should be stored in environmental conditions that appropriate to their format. Other preventive preservation programme is reproduction. When paper based archives are in moderate and serious damage, archival institution should reproduce the archives and make the copies available for use. The originals are then kept in safe storage or sent for conservation treatment. According to Moses, reproduction is something that is made in imitation of an earlier style and acces copy is a reproduction of a document created for use by patrons, protecting the original from wear or theft; a use copy [14]. Roper and Millar said that reproduction is a preservation tool [11]. The aim of reproduction is to protect physical archives so the original doesn’t be used for access to public. Paper based archives can be copiedconverted into microilm or digital format [15]. Besides preventive programme, moderate and serious archives also need restoration. Moses deined restoration as the process of rehabilitating an item to return it as nearly as possible to its original condition [14]. Restoration may include fabrication of missing parts with modern materials, but using processes and techniques that are similar to those originally used to create the item. In the restoration, there is acid removal process. Caminiti said that current paper preservation is thus based, overall, on deacidiication- treatments and physical reinforcement [16]. Archival institution also should endeavour to create more awareness in using archives. All element shall participate in utilization of archives by promoting the utilization of archives as a culture in accordance with the appropriate procedure. Handling methods have a direct impact on the useful life of collections and the accessibility of information. Normal use causes wear, but inexpert and rough handling can quickly lead to extensive damage to collections requiring expensive repair. Conclusion Finally based on the above analysis, it can be concluded that The results showed that the biggest damage on paper-based archives was in slight damage 54-87, Percentage of archives which is in moderate and serious damage is vary from 4 until 28 so for archives which are in these levels should not be made accessible, Moderate and serious damage were caused mostly by chemical factors, Both preventive and curative preservation could be improved, Archival institution also should endeavour to create more awareness in using archives. Training and education of staff is crucial to overall preservation of the archives. References 1. The International Council on Archives. About ICA. In: http:www.ica.orgeninternational-council- archives-0. Accessed September 6, 2016. ISBN : 978-602-17761-4-8 82 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 2. Azmi. Reformasi Birokrasi dalam Perspektif Penyelenggaraan Kearsipan. Jurnal Kearsipan 2009 ; Vol 4 1: 1-34. 3. Shepherd, E. Archives and Archivists in 20 th Century England. Surrey England:Ashgate Publishing Limited; 2009. 4. The National Archives. What is Appraisal. Kew UK: The National Archives; 2013. 5. Undang-Undang No. 43 Tahun 2009 tentang Kearsipan. 6. Patkus, B. Assessing Preservation Need, A Self – Survey Guide. Massachusetts: Northeast Document Conservation Centre; 2003. 7. Porck, H.J., Teygeller, R. Preservation Science Survey An Overview of Recent Developments in Research on the Conservation of Selected Analog Library and Archival Materials. Washington D.C: Council on Library and Information Resources; 2003. 8. Van der Most, P., Deize, P., Havermans, J. Archives Damage Atlas A Tool for Assessing Damage. The hague: Metamorfoze; 2010. 9. Nationaal Archief. Universal Procedure Archives Assessment. Den Haag; Workshop Collection Management and Care; 2010. 10. Isaac, S., Michael, W.B. Handbook In Research And Evaluation. In: Silalahi, U. Metode Penelitian Sosial , Bandung: Reika Aditama; 2010. 11. Roper, M., Millar, L., 1999. Managing Public Sector Records: A Study Programme, Preserving Records. International Records Management Trust, London. 12. Teygeller, R. Preserving Paper: Recent Advances. in J.Feather [ed.]: Managing Preservation for Libraries and Archives, Current Practice and Future Developments. Ashgate: Aldershot; 2004, p 83– 112. 13. Porck, H.J. Rate of paper Degradation, the Predictive Value of Artiicial Aging Tests. Amsterdam: European Commission on Preservation and Acces; 2000. 14. Moses, R.P. A Glossary of Records and Terminology. Chicago: The Society of American Archivists; 2005. 15. Arsip Nasional Republik Indonesia. Peraturan Kepala ANRI No. 23 Tahun 2011 Tentang Pedoman Preservasi. Jakarta: ANRI; 2011. 16. Caminiti, R., Campanella, L., Plattner, S.H., Scarpellini, E. Effects of Onnovative Green Chemical Treatments on Paper, Can They Help in Preservation?. International Journal of Conservation science 2016; Vol. 7 1: 247-258. ISBN : 978-602-17761-4-8 83 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ENERGY MANAGEMENT IN PAPER INDUSTRY: A CASE STUDY OF PT X Kholisul Fatikhin Serpong, Banten 15320, Indonesia kfatikhinyahoo.com ABSTRACT The pulp and paper sector is one of the most energy-intensive sectors. Energy is a signiicant production-cost component about 15 – 25 percent, so the sector made efforts to reduce its energy costs by switching the energy sources and or improving energy eficiency. Energy eficiency is a key metric, both in terms of environmental impact and inancial performance of the company. PT X has implemented energy eficiency since 2000s. Some projects to improve its energy performance have been made such as install variable speed drive, improve power factor, ixed steam leakage and other losses. In 2012, PT X implemented Energy Management System ISO 50001. Energy eficiency was carried out better and more systematic using PDCA approach. Energy was managed day to day through daily operating control and involves all the function in the company. After implementing EnMS, PT X achieved about 15.2 energy reduction in 2015 from baseline 2011. Total energy saving is 428,000 GJ. CO 2e reduction is 60,605 tons or reduces about 30 from the baseline. Keyword: energy; energy management; energy conservation, energy eficiency; ISO 50001 Introduction Since the strengthening of the issue of global warming and rising fuel prices, management of PT X decided to implement Energy Management System EnMS. ISO 50001 is an international standard that give a guidelines or a framework for industry which will implement Energy Management System After implementing EnMS ISO 50001, energy eficiency was carried out better and more systematic. Energy was managed day to day through daily operating control and involves all the function in the organization such as design, procurement, operation, maintenance, training, quality assurance and so on. Top management fully support the system by providing the resources needed to establish, implement, maintain and improve the EnMS and energy performance. Commitment from top management has poured into the company policy. Related Work Climate change is one of the driving forces behind a new wave of energy management systems. Most of the currently available energy management systems in domestic environment are concerned with real-time energy consumption monitoring, and display of statistical and real time data of energy consumption. The motivation behind this approach is to provide households effective advice on their energy consumption by enabling them to take focused and effective actions towards eficient energy use [1]. Energy management program is a systematic and scientiic process to identify the potential for improvements in energy eficiency, to recommend the ways with or without inancial investment, to achieve estimated saving energy and energy cost. Thus the need to conserve energy, particularly in industry and commerce is strongly felt as the energy cost takes up substantial share in the overall cost structure of the operation which is relevant to our work [2]. Manufacturing managers need to understand the interrelated links between advanced manufacturing technology, primary and alternative energy choices, energy output values and costs, and energy conservation over the life of a project [3]. ISBN : 978-602-17761-4-8 84 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech EnMS Development and Implementation ISO 50001 give a guidelines or a framework for industry which will implement EnMS. The process to develop and implement the system is described in the diagram below [4], see Fig 1. Fig. 1.EnMS ISO 50001 implementation process Energy Policy Energy policy is a statement to demonstrate that the commitment of top management to improve the energy eficiency continually, ensure the availability of information and of necessary resources to achieve objectives and targets, comply with applicable legal requirements and other requirements, supports the purchase of energy eficient products and services and design for energy performance improvement, provides the framework for setting and reviewing energy objectives and targets and conduct energy review periodically. PT X set the energy policy into the company policy. Top management has decided to communicate about the energy policy, EnMS and energy performance both internally and externally. All the suppliers have been informed about the energy policy and that procurement is partly evaluated on the basis of energy. Top Management has pointed a management representative and energy manager. The energy management team was formed to support the EnMS that consist of representatives of the related department such as Engineering, Production, Quality Assurance, Purchasing, Human Resource and Finance. Main responsibility of the team as follow: 1. Collecting and analyzing the energy data 2. Determine the Signiicant Energy Users SEU 3. Determine the factors that inluence energy consumption 4. Establish baseline and Energy Performance Indicators EnPI 5. Identify the things desired by legal and other requirement 6. Identify opportunities for improvement 7. Identify the people who are responsible for the SEU area 8. Establish energy objectives and targets 9. Establish, implement, and maintain action plans Energy Planning Energy planning is process to analyze energy use and consumption, identify areas of signiicant energy use SEU and consumption, and identify opportunities for improving energy performance. The input of this process is the past and present data of energy use and relevant variable affecting SEU. The output is energy baseline, energy performance indicator EnPI, objectives, targets and action plan. PT X use energy in the form of electricity and steam. Using Pareto Chart was founded that Paper Machine PM and Stock Preparation SP consumes more than 80 of electricity and steam, see Fig 2. Therefore, SP and PM were considered as SEU. EnMS implementation is focused on the SEU. ISBN : 978-602-17761-4-8 85 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 SP PM1 FIN WWT WT 0.0 20.0 40.0 60.0 80.0 100.0 120.0 Percent ACC 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 PM3 PM2 PM1 SPConvChip 0.0 20.0 40.0 60.0 80.0 100.0 120.0 Percent ACC Fig. 2.a Pareto chart of electric consumption; b Pareto chart of steam consumption After determine the SEU than we should identify the relevant variable that affecting to SEU energy drivers. A method to identify the energy driver is a simple regression for single variable or multiple regressions for two or more variables. Correlation test using the past data in PT X, was founded that there are signiicant correlation between production level and energy consumption R-square = 0.865, see Fig 3.Therefore, the regression equation obtained in the test is reliable and able to use as a model to predict the future energy consumption. The equation is called as energy baseline. Fig. 3. Regression analysis between production level and energy consumption Energy performance can be demonstrated by comparing the actual energy consumption with the prediction. If the actual energy consumption is lower than the prediction, it means that the energy performance improves and vice versa. The energy conservation opportunities ECO is identiied, prioritized and recorded by conducting the energy audits. Action Plan was established and implemented in PT X for achieving their objective and target, see Table 1. Table 1. Energy Conservation Opportunities in PT X Description Annual saving GJ Reduce Air Compressor Pressure 483 Install interlock Auto Off 105 Install Variable Speed Drive 512 Replace V-Belt with Timing Belt 879 Upgrade PM Drive from line shaft to sectional drive3 lines 3,521 Rebuild Steam Condensate System 3 lines 3,600 House keeping - ISBN : 978-602-17761-4-8 86 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Implementation and Operation After implementing EnMS ISO 50001, energy eficiency has been managed better from day to day through daily operation control. All critical parameters for operation and maintenance related to SEU are identiied, monitored, measured and analyzed at planned intervals. Design and procurement process also consider the energy conservation opportunity. All employees related to SEU are trained to improve their competency and awareness. The objectives of the training as follows: • Employees who work especially in the area SEU has adequate competence • Employees care about the importance of EnMS • The employees concerned will beneit from improved energy performance. • Employees concerned that the activities and behavior contribute to the achievement of the objectives and targets companies. All employee especially in SEU areas also involved in the energy eficiency improvement through focused improvement activities such as Small Group Activity SGA and Skill Development Activity SDA. Each employee also may give a suggestion through e-suggestion intranet base. Every year PT X conducts a competition to choose the best project and best suggestion. Some action plan has been established was implemented, monitored and recorded. Some investment has been made to improve energy performance in SEU such as install VSD, upgrade steam and condensate system, upgrade line shaft with sectional drive. Checking PT X ensures that the key characteristics of its operations that determine energy performance are monitored and measured and analyzed. Energy consumption is tracked monthly and compared with predicted energy consumption. Energy team reviews the EnPI to determine the energy performance quarterly. Preventive and corrective action is also reviewed at that time, EnMS audit carried out regularly once a year by internal and external auditors. This audit aims to verify whether the company’s activities are still consistent with the EnMS ISO 50001 requirements, whether the company still meets the legal and other requirements, whether EnMS are carried out effectively. A Technical audit is conducted every 3 years by professional auditor. It is helpful for the company to ind the opportunities for improvement. Management Review Management review is conducted once a year to review if any decisions or actions related to changes in the energy performance of the company, energy policy, EnPI, objective and target, and allocation of the resources. Management review is attended by top management, management representative, energy manager, energy team and all department head. Result and Beneit Energy eficiency improvement gives a positive impact to the company. Production volume increased signiicantly in 2015 compared to baseline. Energy intensity also improves continually. Energy Intensity decreased by 15.2 in 2015 compared to baseline, see Fig 5. ISBN : 978-602-17761-4-8 87 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Fig. 5. a Trend of energy consumption production; b Energy intensity GJTon of product Energy performance can be demonstrated by comparing actual energy consumption with the predicted energy consumption. Actual energy consumption is lower than energy prediction. Gap between actual and prediction is saving. Accumulative energy saving from 2012 – 2015 is about 428,000 GJ, see Fig 6. Fig. 6. a Trend of actual energy consumption prediction; b CUSUM Graph Conclusion Energy is a controllable resource. Therefore, using it eficiently will help the company to improve their inancial performance and increase the company image. EnMS ISO 50001 is an international standard that give a framework for organization which will implement Energy Management System. This standard applies internationally so it can provide added value to the product in the global market Commitment from Top Management is mandatory. Barrier for implementation is if Management just focuses on production and not on energy eficiency. References 1. Kuo-Ming Chao, Shah, N., Farmer, R., Matei, A., Ding-Yuan Chen, Schuster-James, H., Tedd, R., “A Proile Based Energy Management System for Domestic Electrical Appliances”. 2. Irawati Naik, Prof.S.S.More, Himanshu Naik, “Scope of Energy consumption and Energy Conservation in Indian Auto Part Manufacturing Industry”. 3. Jeffrey M. Ulmer, Troy E. Ollison, “Alternative Energy Choices, Conservation, and Management: A Primer for Advanced Manufacturing Managers” 4. Badan Standarisasi Nasional, “Sistem Manajemen Energi – Persyaratan dengan Pedoman Penggunaan”. SNI ISO 50001:2012 ISBN : 978-602-17761-4-8 88 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 89 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech WOOD SUPPLY AND SUSTAINABLE FOREST MANAGEMENT SYSTEM IN APRIL GROUP IN THE PROVINCE OF RIAU Petrus Gunarso 1 , Prayitno Goenarto 2 APRIL, Jl. M.H. Thamrin No.31, Jakarta 10230, Indonesia 1 petrus_gunarsoaprilasia.com 2 prayitno_goenartoaprilasia.com ABSTRACT Indonesia is a rapidly developing country, but millions still live in poverty. Responsible plantation forestry helps the economy grow, creates jobs and improves local livelihoods. Through forest plantations, Indonesia can become a key player in sustainability - meeting the world’s need for wood and iber and at the same time providing jobs, and economic growth. In 2014 APRIL Group - an integrated pulp, paper, and forest plantation introduced an upgraded Sustainable Forest Management Policy that commits the company to implement a moratorium on plantation development in areas where High Conservation Value Forests HCVF assessments have not been completed. The company is also committed to supporting conservation areas through HCVF assessments and has obtained ecosystem restoration concessions with a target of maintaining conservations areas equal in size to its plantation areas. With the implementation of Sustainable Forest Management Policy, the company is guaranteeing sustainable wood supply for the pulp and paper mill with improved quality and eficient mill operation. While most eficiency evaluations focus on mill operations, this paper focuses on the sustainable production of timber and iber, eliminating deforestation from the supply chain, improving environmental conservation to protect and enhance biodiversity within production forests, and addressing the issues of poverty and climate change. Keywords: wood supply; sustainable forest management; HCVF assessment; biodiversity conservation. Introduction Indonesia’s forest cover is decreasing rapidly due to deforestation and illegal logging leading to a shortage of timber resources available for domestic use. Due to current laws and regulations the economic viability for timber plantations other than for pulp and paper to supply domestic markets are questionable. This situation leads most companies to focus on foreign markets and exports, which in turn causes a shortage of timber for domestic consumption and contributes towards a gap between local supply and demand. The large discrepancies between the demand and supply for domestic timber consumption then forces individuals to seek alternative sources to fulil these needs. Discrepancies between domestic market price and estimated price for legally supplied wood suggest that the majority of timber sold domestically does not come from legal sources [1]. The Role of Forest Plantation in Indonesia Deforestation and Illegal Logging Landsat Satellite imagery from 2000, 2005, and 2010 shows the increasing trend in degraded forests [2]. Primary forest cover decreased from 49 million ha Mha, to 44 Mha to 42 Mha ha while degraded forests increased from 28.4 million, to 30.9 million ha, to 31 million ha. The trend in forest degradation is also supported by data from Indonesia’s Ministry of Environment and Forestry indicating a deforested area of about 727,981 ha during the years of 2012-2013[3]. The factors contributing towards the rapid deforestation rates and loss of primary natural forests include historic political, technical and economicmotivations. Before the system of logging permits Hak Pengumutan Hasil Hutan-HPHH and Izin Pemungutan dan Pemanfaatan Kayu-IPPK was stopped early in the irst decade of this century, district governments ISBN : 978-602-17761-4-8 90 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech were issuing numerous logging permits, with various individuals and companies vying for land. A lot of these small-scale district logging licenses were issued because the Ministry of Forestry did not have the capacity to block them under the conditions of decentralization of forest administration that existed at that time[4].Massive land use and land-cover changes occurred as a result of poor governance and law enforcement. Many companies were under pressure to adopt non-sustainable strategies in order to access the timber stock in their concessions before the illegal loggers [5].Under these conditions it has been estimated that less than ten percent of forest was being managed for continuous productivity[6]. The prevalence of illegal logging, and the corruption that ensued following the decentralization of logging permit issuance, was linked to substantial inancial losses into the billions of dollars [7]. The non-sustainable forest management response resulted in land clearing, with no plans to restore or reforest.As a result a majority of licenses were revoked by government leaving open access land vulnerable to encroachment or conversion. The extent of the impact of this process is evident from the fact that of the 560 concessions that existed in 1985 now only around 200 remain. The massive increase in unmanaged forest land has created a potentially enormous pool for conversion to other uses. For example, the projected demand for oil palm land expansion is set to increase by7 annually [8].The expansion and conversion of degraded or unused forest into palm oil plantationshas further reduced the availability of land for timber plantations and has fed a positive-feedback loop.As the gap between demand for timber and potential to supply it under sustainable management widens, the motivation for people to illegally log leaves behind further cleared open access land that is then left unproductive or converted for other purposes. Acknowledging the limit of land availability left for timber, the next most intuitive solution to addressing the gap would be to increase productivity and maximise eficiency of timber production on the already available land through improved plantation productivity. Forest Plantation Productivity Although slow in progress, forest plantations have the potential to sustainably produce large quantity of timber for ibre and wood. Forest plantations Hutan Tanaman in Indonesia produced more than 20 million m 3 of log wood in 2013. Indonesia has the potential to increase this output by a level of magnitude and if managed well, according to scientiic principles, high productivity, intensely managed plantations may also serve the potential to help meet the world’s need for timber [9]. In contrast natural forests Hutan Alam currently produce less than 6 million m 3 of logwood per year [10].The lower yield of timber from natural forests around 1m 3 haannum from a range of species means that this resource should be reserved for high value selective markets and not included in the same market space as that targeted by plantations. April Group APRIL is one of the largest, most technologically advanced and eficient makers of pulp and paper products in the world. It makes products that are used by millions of people every day in liquid packaging, printing and writing paper, tissues, shopping bags, food packaging, magazines and books. APRIL is an integrated Pulp, Paper Mill and Sustainably managed plantation forest - located in Riau Province, Indonesia. In its operation APRIL has shown that forest plantations are capable of reaching 20-25m 3 haannum through a 5 year rotation, allowing for a greater quantity of timber to be harvested more frequently, and providing a stable income base. Certain forest plantations have the potential to restore productivity and rehabilitate degraded tropical production forests[11]. As the forest plantations convert high diversity of forests into monoculture, it is therefore APRIL has initiated a mitigation measures through allocating larger proportion of conservation or protection of its concession with so called one to one. Every one hectare of plantation forest is mitigated with one hectare of protected or conserved natural forests in the concession and implement restoration efforts. Sustainable Forest Management Policy In June 2015 APRIL unveiled its Sustainable Forest Management Policy version 2.0 SFMPv2 [12]. with the objective of “eliminating deforestation from our supply chain and protecting the forest ISBN : 978-602-17761-4-8 91 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech and peat land landscapes in which we operate”. The APRIL Policy is being implemented by ensuring its plantations are developed on areas that are not forested and peatland. APRIL has also placed a moratorium on clearing natural forest pending HCV - High Conservation Value and HCS - High Carbon Stocks assessment. It has no plans to establish further pulp mills or other related infrastructure until plantation ibre self-suficiency is achieved. The SFMPv2 pushes APRIL towards maximising its eficiency and productivity based on the timber resources it has on its existing lands.APRIL is also committed to implementing actions that go beyond legal compliance of micro and macro delineation such as the implementation of HCV assessments since 2005. The purpose of the HCV Assessment is to assess and identify forestsareas which have High Conservation Values, these values pertain to “biological, ecological, social or cultural values which are considered to be outstanding signiicance or critical importance at the national, regional or global scale” [13]. At the landscape level, the Kampar Peninsula, total protected areas that include ERC and HCV areas is greater than 300,000 ha. The current landscape unit of Forest Management -Kesatuan Pengelolaan Hutan Produksi KPHP covers the total area of 513,000 ha. With the current ERC - Ecosystem Restoration Concession and HCV of more than 300,000 ha, the proportion of protected areas in the KPHP - Production Forest Management Unit Tasik Besar Serkap is now more than 58; higher than the APRIL target of 1 to 1. The landscape of Kampar Peninsula is a perfect example for implementation of both one to one principle and ring buffer and core conservation principles. Poverty Alleviation Sustainable Development rests on three related pillars: environmental; social and economic. The irst Goal of the UN Sustainable Development Goals addresses poverty by targeting an end to extreme poverty by 2030[14]. Experience has shown that in order to end poverty those suffering from it need to be engaged and supported in inding solutions.An important element of this approach is to create jobs to reduce unemployment. Rural unemployment has been identiied as an important factor contributing towards local conlict in Indonesia. Unlike local conlict in Java Island, the situation in Sumatra in particular is exacerbated by uncertainty of tenure, so legal assignment of forests land to a company is not necessary perceived and seen by local community as a legal assignment but more seen as legally supported central government of land occupation. This in particular relates to the boundary marking process that each concession has to mark its boundary at own cost. [15]With large populations dependant on land and with no land allocated to them, this will subsequently increased un-employment. Companies operating in this context therefore need to address local un-employment through land sharing and labor force openings. The APRIL Policy supports this approach. Between 1999 and 2014 APRIL has increased employment opportunities in Riau from 42,000 people working in 2000, to 59,000 in 2010 and 58,000 in 2014. The beneits of increased job creation during the study period also translated to a rise in economic output as the agriculture accounted for nearly 70.7 of Pelalawan District economic output.[16] Pelawan is the location of Pulp, Paper and Power Mill of APRL. With household income expected to continue to rise, the economic beneits from the agriculture will hopefully continue and the effects felt by the surrounding communities for generations to come. Past situations where communities were not in a good position to deal and negotiate with companies, and single representatives led negotiations have often resulted in unfavourable gains that did not beneit the community and only beneited a few individuals resulting in confusion and distrust[17].Therefore, it is imperative to provide long term economic support for local community instead of short-term economic ixes and to ensure that beneits are widespread affecting a majority of the communityand not just a few. Conclusion This paper focuses on resource eficiency upstream of the industrial timber process towards the idea of responsible forestry which involves various concepts of sustainability and beneits across environmental, economic and social aspects.As part of responsible plantation forestry, APRIL implements sustainable ISBN : 978-602-17761-4-8 92 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech practices through policies such as the SFMPv2 - Sustainable Forest Management Policy version 2 that ensure no deforestation of forests and legal sources of wood supply. Establishment of pulp mills and sustainable forest plantations also addresses socio-economic issues, with agricultural assistance improving local livelihoods through increased employment opportunities and economic growth. References 1. Klassen AW. Domestic demand: the black hole in Indonesia’s forest policy. European Tropical Forest Research Network News2010; 52: 15-22 2. Gunarso P. Darurat tutupan hutan Indonesia. In: Nugraha A, Santoso H, Ardiansyah I, Imron MI, Sanyoto R, Awang SA, Yuwono T, Istoto YEB, editors. Darurat Hutan Indonesia, Banten; Wana Aksara;2014, p. 235-57 3. Data and Information Centre, Ministry of Environment and Forestry of Indonesia. 2015. Ministry of Environment and Forestry Statistics 2014. Jakarta, Ministry of Environment and Forestry. 4. Barr CM, Resosudarmo IAP, Dermawan A, McCarthy J, Moeliono M, Setiono B. Decentralization of forest administration in Indonesia: Implications for forest sustainability, economic development, and community livelihoods. Center for International Forestry Research 2006: 90-1 5. Jepson P, Jarvie JK, MacKinnon K, Monk, KA. The end of Indonesia’s lowland forests?Science 2001; 292: 859-61 6. Dauvergne P. The politics of deforestation in Indonesia. Paciic Affairs1993;66: 497-518 7. Smith J, Obidziinski K, Subarudi, I. Suramenggala. Illegal logging, collusive corruption and fragmented governments in Kalimantan, Indonesia. International Forestry Review 2003; 5:293-302 8. [8] Gunarso P, Hartoyo ME, Agus F, Killeen TJ.Oil palm and land use change in Indonesia, Malaysia and Papua New Guinea. 2013. Reports from the Technical Panels of the 2 nd Greenhouse Gas Working Group of the Roundtable on Sustainable Palm Oil 2013; 29-64 9. Fox TR. Sustained Productivity in intensively managed forest plantations. Forest Ecology and Management 2000; 138: 187-202 10. Kementerian Kehutanan. 2014. Statistik Kawasan Hutan 2013. 11. Parrotta JA. The role of plantation forests in rehabilitating degraded tropical ecosystems. Agriculture, Ecosystems Environments 1992; 41: 115-33. 12. APRIL. APRIL Group’s Sustainable Forest Management Policy 2.0. 2015: 1-4. 13. Jennings S, Nussbaum R, Judd N, Evans T. The High Conservation Value Forest Toolkit. 2003. Proforest. Edition 1; 1-27 14. United Nations. Transforming our world: the 2030 Agenda for Sustainable Development. 2015. A RES701 15. Barron P, Kaiser K, Pradhan M. Understanding variations in local conlict: Evidence and implications from Indonesia. World Development2009; 37: 698-713 16. Lembaga Penyelidikan Ekonomi dan Masyarakat – Fakultas Ekonomi dan Bisnis Universitas Indonesia. Analisis Dampak Ekonomi Fiskal Analisis Dampak Ekonomi Fiskal APRIL Group Riau Complex AGRC: Update 2014. p. 1-124 17. Obidzinski K, Barr C.The effects decentralisation on forests and forest industries in Berau district, East Kalimantan.In: Case studies on decentralisation and forests in Indonesia. Bogor, Center for International Forestry Research; 2003, p. 1-31 ISBN : 978-602-17761-4-8 93 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech EFFECT OF REYNOLDS NUMBER AT ORIFICE OUTFLOW AND FLOTATION ZONE ON THE FATTY ACID DISPERSION IN CORRELATION WITH DEINKING FLOTATION PERFORMANCE Trismawati a1 , I. N. G. Wardana 2 , Nurkholis Hamidi 3 , Mega Nur Sasongko 4 a Doctoral Student of Mech. Engineering, Univ of Brawijaya, Malang 65144, Indonesia Department of Mechanical Engineering, University of Brawijaya, Malang, 65144, Indonesia, 1 trismawatiupm.ac.id 2 wardanaub.ac.id 3 hamidyub.ac.id 4 megasasongkoub.ac.id ABSTRACT The importance mechanism of bubbling is to generate suitable Reynolds number to create hydrodynamic shear force in lotation. The critical Reynolds number at oriice outlow Re o and in lotation zone Re vt are deined as the maximum Reynolds numbers of luid at some distance from nozzles and in lotation zone to create turbulence without the appearances of proper mixing. The ink and froth is collected at the upper part of the lotation tank, the ibers free of ink are discharged from the bottom part of lotation tank. ONP pulp slurry of 5,0 consistency is poured into the lotation thank that has been illed with water up to 70 of volume so that 1,0 consistency is achieved. From the bottom part of lotation tank, air with difference low rate is injected into the lotation tank through oriice with difference sizes. Fatty acid from Morinda oil is injected into the lotation tank. The Reynolds numbers that are able to disperse the fatty acid is evaluated by the achievable brightness and ERIC. As a benchmark synthetic surfactant is used to evaluate the effectiveness of fatty acid as a surfactant for lotation deinking. From the experiment it is concluded that fatty acid need higher Reynolds number for its dispersion and creates hydrodynamic shear force that able to detach ink from iber surfaces. To high Reynolds number gave proper mixing instead of lotation, results poorer lotation performances and give poor results. Difference lipophilic and hydrophilic character of substance used in the deinking lotation need difference region of turbulence Reynolds number to achieve the proper results. The critical Reynolds number suitable for this deinking lotation is 4,0 – 5,0 x 10 7 at some distance escape from oriice, and 1,0 – 1,3 x 10 7 in lotation zone. Keywords: hydrodynamic shear force, Reynolds number, ink detachment, fatty acid dispersion, oriice outlow, lotation zone Introduction Flotation deinking is a separation process of the detached ink from iber by the use of air that injected into lotation tank. The injected air will create bubbles move upward with the ink particles into the froth zone. For being able to carry up the detach ink, an interaction between ink particles and bubble should be exist. In this case, a substance that has interconnection between ink particles oil based and bubbles bubble - water interface is needed. In order so, the used of surfactant in deinking lotation to assist the separation of ink particles from ibers is unavoidable. Surfactant can be distributed evenly in a lotation medium water because its head has hydrophilic properties, in other side its tail that has lipophilic properties, able to penetrate into the disperse ink particles. This process is apparently simple as long as the surfactant has the appropriate HLB value. Research concerning HLB value of surfactant for deinking lotation has been done. Surfactant with high HLB value is favorable for cellulose activity and low HLB value is favorable for ink removal [1]. HLB value of surfactant is closely relate to the hydrocarbon structure, the longer the hydrocarbon chain and the more the un-saturated structure presence, the better the surfactant performance for deinking lotation [2]. The probability of surfactant and ink interaction is modeled by the probability of ink attachment on bubbles [3]. ISBN : 978-602-17761-4-8 94 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Nomenclature � � �� : ���� ������� �� ������� �� ��� ���� � � �� : ���� ������� �� ������� �� ��������� ���� � � : �������� �� ������� � � � : �������� �� ������ �� ��� ���� � � � : �������� �� ������ �� ��������� ���� � � �� : �������� ������ �� ��� ���� � � �� : �������� ������ �� ��������� ���� � �� : �������� �� ������ �� ��� ���� � �� : �������� �� ������ �� ��������� ���� � � : �������� �� ��� �ℎ����ℎ ������� � ∶ ������� �� ������ � ∶ ��������� �� ������ Numerical code: 20, 40, 60 are orifice diameter of 2, 4, and 6 mm To know the turbulence performance, Reynolds number at oriice outlow and lotation zone is evaluated: In this case: With v fz is the velocity of bubbles at the lotation zone and is measured by dividing the distance of bubble path by the increment of time in 0.25 second by controlling the video of bubbles movement. The bubbles diameter d Bf and d Bj was measured as the average bubbles size using Image J . ISBN : 978-602-17761-4-8 95 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech With Av jz and Av fz is the area covered by bubbles at oriice outlow and lotation zone respectively, and it was measured by Image J. If air is injected continuously through a nozzle into water medium, the air jet immediately breaks up into an array of bubbles which range in diameter from almost zero up to a maximum value. This diameter is depends upon the air discharge and the gravitational acceleration g [4]. The used of surfactant has certain effect on the physical properties of water when it is dissolved on water, such as decreasing water surface tension, decreasing mean diameter of bubbles, increasing gas hold up and gas movement [5, 6, 7]. These all might be related with the hydrogen bonding presence between the hydrophilic part of surfactant and water molecule. In case of fatty acid is used instead of surfactant, hydrogen bonding does not available abundantly. The only interaction is between the fatty acid and fatty ester presence in ink structure. This might be happened when fatty acid can reach contact the fatty ester of ink. In order to disperse fatty acid evenly, turbulences should be created and the hydrodynamic shear forces presence will assisting the separation of ink particle from iber. The critical Reynolds number to create hydrodynamic shear forces is elucidated in this research. The result is compared with the critical Reynolds number when surfactant is used in lotation deinking. Experiment Experiment was performed in the lotation tank as it is depicted in Fig. 1. Air was injected at difference low rate through oriice. The Reynolds number was calculated based on the speed of outlow air through oriice Re o , and based on the average speed of rising bubble Re vt . The oriices used in this experiment were 2, 4, and 6 mm of diameter. Old newspaper pulp was prepared by disintegrate it in a pulper at 5 of consistency for 10 minute. Sodium Lauryl Sulfate was injected as a foaming agent at 0.6 of dosage. fatty acid of Morinda oil FA and synthetic surfactant used for deinking lotation was studied comparatively. The achievable brightness and ERIC was measured with Technidyne – Color Touch 2 models ISO. The maximum Reynolds number that able to create the necessary hydrodynamic shear force for ink liberation without proper mixing was studied to know the lipophilic character of any surfactant or fatty acid for ink liberation. To evaluate the deinking lotation performance, brightness Tappi T 452 and ERIC Tappi T 567 om-04 measurement was performed. Shear force Flotation Zone Fig. 1. Experimental arrangement, ink detachment from ibres and ink attachment on bubble. ISBN : 978-602-17761-4-8 96 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Ink Detachment Analysis It is assumed that the bonding between iber and ink particles has been rupture by the hydrodynamic shear force and friction force during pulping. In deinking lotation hydrodynamic shear force is also presence. When hydrodynamic shear force is created, the ink particle will be pulled out of intact from the iber surface. Hydrodynamic shear force is created by pressurized air escape from nozzles. This force is a function of Reynolds number. In case of synthetic surfactant is used for lotation, the surfactant will distribute easily into lotation medium because of its HLB value is properly designed. In case of fatty acid is used for lotation, the fatty acid does not easily distribute into the lotation medium, because it has higher lipophilic character, and it will easily penetrate into ink particles when they are in touch to each other. The maximum Reynolds number to create hydrodynamic shear force without proper mixing is searched in this experiment. When both synthetic surfactant and fatty acid is able to reach the ink particle, then the ability to detach ink particle is resembles, the created hydrodynamic shear force is suficient to remove ink particle from the iber surface. If the ability to detach ink particle is quite difference, the lipophilic character fatty acid diffusivity into ink particle of fatty acid should be improved. Reynolds number is the property of turbulence. In lotation deinking, there are dead zone, jet zone, lotation zone and froth zone. The ink detachment is mostly happened in jet zone, and the separation of detached ink from iber is mostly happened in lotation zone. Dead zone is dominated by sedimentation of iber. In froth zone, the detached and loated ink particles are collected. When the deinked pulp quality is almost the same, this mean the ink separation in the lotation zone has the necessary Reynolds number to create turbulent for lotation deinking. In other case, when the ability of lotation is resembles, this can be inferred that the hydrophilic character of surfactant and fatty acid is quite strong enough to keep in touch the ink particle from bubbles. Result and Discussion From Fig. 2, it is shown that: a the addition of synthetic surfactant and FAMC result the higher velocity of rising bubbles; b the addition of synthetic surfactant and fatty acid reduces the diameter of rising bubbles. This was happened because the effect of synthetic surfactant and fatty acid addition to the water is reducing its surface tension. This result is supported by other research experiment that the used of surfactant give effect on decreasing of water surface tension, decreasing of mean diameter of bubbles, increasing of gas hold up and gas movement [5, 6, 7, 10]. Fig. 2. Correlation of a bubble velocity and air low rate; b Diameter of bubbles and air low rate - through nozzle; c Image J of bubbles for air low rate of 5 Ls from oriice of 5 mm in lotation zone. From Fig. 3 a it is shown that brightness was increase as the Reynolds number increase but at a certain Reynolds number the brightness was declined. For synthetic surfactant the optimum Reynolds number at oriice outlow is in the range of 2,0 – 4,0 x10 7 and for Fatty acid in the range of 4,0 – 5,0 x10 7 when oriice with diameter of 4 mm and 6 mm was used. If oriice with diameter of 2 mm was used higher Reynolds number is needed. From Fig. 3 b, the ERIC reaches the lowest value at the same Reynolds number as it was performed for brightness. From this result it can be concluded that fatty ISBN : 978-602-17761-4-8 97 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech acid need higher Reynolds number for its dispersion. Fatty acid and water is immiscible, fatty acid has hydrophobic properties so it needs higher turbulence Reynolds number for its dispersion. In other case, synthetic surfactant has a good balance in oil and water properties good HLB value, so synthetic surfactant need lower Reynolds number for its dispersion. When fatty acid has been disperse well, as it was in the above Reynolds number, the brightness and ERIC achievement is approaching of the deinking lotation result using synthetic surfactant, so it can be inferred that the lipophilic properties of fatty acid is almost the same with the lipophilic properties of synthetic surfactant. Fatty acid can reach the best performance as surfactant at Reynolds number of 4,0 X 10 7 . In case of the achievable brightness “and ERIC” of deinking pulp with fatty acid is still lower “higher” than the one with synthetic surfactant, this might be correlated with its hydrophilic properties. Fig. 3. a Brightness of loated pulp; b ERIC of loated pulp vs Reynolds number at oriice outlow From the result presented on Fig. 3 it is clearly seen that Reynolds number of 4,0 x10 7 at the oriice outlow seems the most appropriate for the above system. It gives the best performance for deinking lotation result. At this Reynolds number, the created hydrodynamic shear force gave the best performance for ink particles detachment. From Fig. 2 and Fig. 3, it is clearly seen that oriice with diameter of 4 mm gave the most appropriate bubbles size suitable for deinking lotation. It produces the deinked pulp with highest brightness and lowest ERIC. This may correlates with the ability of suitable bubbles size in lifting the detached ink into froth zone, and the probability of collision between ink particle and bubble [8,9]. Fig. 4. a Brightness and; b ERIC of deinked pulp vs Reynolds number at lotation zone Fig. 4 shows, the correlation of Reynolds number in the lotation zone with the quality of deinked pulp. Bubbles diameter produces from oriice diameter of 4 mm, gave the best performance for deinking lotation. In this case, when synthetic surfactant was used, Reynolds number of 7,5 – 11,5 x 10 6 is the appropriate Reynolds number for deinking lotation to achieve highest brightness and lowest ERIC. When fatty acid was used, the appropriate Reynolds number is higher 1,0 – 1,3 x 10 7 . ISBN : 978-602-17761-4-8 98 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Conclusion From the above experiment, it is conclude that fatty acid need higher Reynolds number for its dispersions, and synthetic surfactant need lower Reynolds number. The Reynolds number needed is 4,0 – 5,0 x 10 7 in the oriice outlow zone and 1,0 – 1,3 x 10 7 in lotation zone for fatty acid dispersion, and 2,0 – 4,0 X 10 7 in the oriice outlow zone and 7,5 – 11,5 x 10 6 in the lotation zone for synthetic surfactant dispersion. Oriice diameter of 4 mm gives the suitable bubbles size for lotation deinking at the above Reynolds number. This could achieve the best performance for both fatty acid and synthetic surfactant dispersion, and for deinking lotation results. It can be inferred that when the disperse fatty acid can reach ink particles, the ability of bubbles to lift the detached ink is still questionable and this could be improved. It may relate with the interaction among air bubbles, bubbles – water interface, and the hydrophilic character of fatty acid. Acknowledgements The authors are grateful for the inancial support of the Indonesian Directorate General of Higher Education DGHE or DIKTI, Grant. No: 1014UN10.14KU2013; PT KAO Indonesia Branch Surabaya for Papyrase enzyme and synthetic surfactant; Darono Wikanaji, M. Eng., Pulp and Paper Technology lecturer and consultant for helpful thinking and educated suggestions. References 1. Mayeli, N., Talaeipour, M. Effect of different HLB value and Enzymatic treatment on the properties of old newspaper deinked pulp. Bioresources 2010; 54, 2520 – 2534. 2. Khalek, M. A. Performance of different surfactants in deinking lotation process. Elixir Appl. Chem. 2012; 46: 8147-8151. 3. Heindel, T. J., Maruvada. K. S. A Methodology for Flotation Deinking Model Validation. Institute of Paper Science and Technology. Profect F00903, Report 7. Atlanta, Gergia. 1998. 4. Kobus, H. Bemessungsrundlagen und Anwendungen fur Luftscheier im Wasserbau. Heft 7. Schriftenreiche “Wasser und Abwasser in Forschung und Praxis”, Erich Schmidt Verlag. Berlin. 1973. 5. Asari, M. Hormozi, F. American Journal of Chemical Engineering, 12, 50 2013. 6. Chaumat, Helene, Billet, Anne Marie, Delmas, Henry. Hydrodynamic and mass transfer in bubbkle column: Inluence of liquid phase surface tension. Un-published. Laboratoire de Genie Chimique, Z. A. Basso Cambo, France. 7. Chaumat, Hélène and Billet, Anne-Marie and Delmas, Henri Hydrodynamics and mass transfer in bubble column: Inluence of liquid phase surface tension. Chemical Engineering Science. 2007 vol. 6 24: 7378-7390. ISSN. 8. Emerson, Z. I., Particle and bubble interactions in lotation systems. Doctor of Philosophy Desertation, Auburn University, Alabama, 2007. 9. Emerson, Z. I., Bonometi, T., Khrishnagopalan, G. A., Duyke, S. R., Visualization of toner ink adsorption at bubble interfaces, Peer Reviewed Deinking, Tappi Journal 2006; 5 4: 10 – 16. 10. Maedeh A., Faramarz H., Effects of Surfactant on Bubble Size Distribution and Gas Hold-up in a Bubble Column, American Journal of Chemical Engineering, Vol. 1 2, 50-58 ISBN : 978-602-17761-4-8 99 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ECO-FRIENDLY MATERIAL SCIENCE AND TECHNOLOGY - PAPER IN THE PAST, PRESENT, AND FUTURE Toshiharu Enomae Faculty of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305-8572, Japan. tenomae.com ABSTRACT Paper is one of the greatest inventions over the course of human history and a multifunctional and ecological material that deserves such an admiration: manufacturing from bio-resources such as plants and animals as well as natural inorganic materials such as calcium carbonate, no need of external energy for manufacturing because black liquor supplies a total energy required, and recycling at a high ratio of recycled pulps as a iber source. Such an environmentally-friendly material should be utilized more broadly for people and societies in the future. However, the demand of printing paper is decreasing in developed countries, due to the replacement of information carrier with digital media. New ields with a large demand are now being explored. In view of this point, we have developed new paper tools such as a power generator from vibration of paper, paper-based sensor to detect copper ions in water, a paper-based bacterial culture system using ink jet printing technology. Also, a new insight for paper conservation to carry over paper-made cultural assets from the past into future by preventing them from oxidation over the lapse of time and inhibiting mold growth after lood damage was obtained. Keywords: bacterial detection, paper sensor, visual awareness Introduction In this article, papermaking technology and paper products will be reviewed from the origin of paper, importance of paper in the present age, and prospective paper-related products under development in our research group. History of Papermaking Technology Origin of Paper Fig. 1 Fangmatan Paper Papermaking technology is considered to be invented in ancient China. The world oldest paper was found and estimated to be buried as a burial good between 179 and 142 BC early Western Han Dynasty This paper was used as a map, where mountains, waterways and roads were drawn as shown in Figure 1. The papermaking technology was summarized by Ts’ai Lun in A.D. 105, and spread all over the world, for example, to Japan in 610, Samarkand, Uzbekistan in the central Asia in 751, Baghdad, Iraq in 793, Fabriano, Italy in 1276, England in 1494, and USA in 1690. The fundamental concept characteristic of this modern papermaking technology is dispersion of ibers into water and the iber slurry is dehydrated to form sheets. Historically, there were many traditional and local paper-like raw-plant-based products by the preceding sheet making technology of beating and spreading out inner bark layers without dispersing ISBN : 978-602-17761-4-8 100 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ibers into water. Included in this category are Hawaiian Tapa, Polynesian Kapa, Mexican Amate Figure 2a, Indonesian bark paper Figure 2b all from various species of mulberry plants, and African tapa Figure 2c. Papyrus is produced from the pith in stems of the papyrus plant. There are recording materials using a part of raw plants that are different from modern paper, bark paper or papyrus. Sastra is a Cambodian document written on leaves of treang trees palm that are tied loosely with strings like a book as shown in Figure 3. Holy texts are recorded as a religious custom. Similar documents were produced in the Southeast Asia. Fig. 2 Bark paper occasionally called “Tapa”; a AD 16-18 c, Mexico, b Batak, Sumatra, Indonesia, c Africa all exhibited in Deutsches Museum, Munich, Germany. Fig. 3 “Sastra”, a document made on tied leaves of treang trees palm that is preserved in temples of Cambodia. Technology of Japanese Paper The history of Japanese paper called “Washi” dates back to A.D. 610 when the papermaking technology was imported. Ancient documents written in the 8 th century are still securely stored in Shosoin, Nara, Japan. The Shosoin documents include a census register written on a sheet of Japanese paper in A.D. 702 at the earliest in Japanese history. Japanese papermaking craftsmen have invented new technology historically. Fiber length is an important factor on paper strength and formation; too short ibers do not realize high strength paper although too long ibers do not realize good formation. Initially since the import, long hemp ibers from Cannabis with a iber length of approximately 100 mm had been widely used partially together with shorter segments of ibers after cutting. Then, Japanese papermaking craftsmen shifted to bast skin ibers extracted from low trees such as paper mulberry Kozo with a iber length of approximately 10 mm to avoid the laborious process “cutting”. Furthermore, they proceeded to Thymelaeaceae Gampi and then, Edgeworthia chrysantha Mitsumata with iber lengths of approximately 5 mm and 4 mm, respectively. The choice for shorter ibers had been improving the writing performance with an ink brush because of less bleeding due to the dense sheet structure, as well as providing comfortable touch feeling of the paper surfaces. Another notable innovation was the discovery and introduction of a iber dispersing agent called “Neri”. This agent is extracted from roots mainly of Abelmoschus manihot and composed of uronic acids[ 1 ] that have negatively charged functional groups on the surface. This negative charge provides repulsive force between ibers in pulp slurry as well as the increased viscosity to prevent a quick dehydration. This effect results in good iber dispersion ISBN : 978-602-17761-4-8 101 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech and therefore good formation of the inished paper in the low sheet-making technique by declining the papermaking wire actually, bamboo splints woven together with silk threads. During dehydration in the static sheet-making process on the contrary, a papermaking wire is commonly allowed to stand and ibers tend to aggregate together in the meanwhile, making the formation worse. Paper Competitive to Digital Media in The Present Age[ 2 ] A Recent Trend in Paper Production in Japan Recently, the amount of paper produced in Japan suddenly decreased immediately after the inancial crisis in 2008 following a stable production period for about 10 years. The depressed economy deinitely still continues to inhibit paper production; however, that is not the only reason for such decreasing paper production. Figure 4 shows the chronological change in the amount of paper production in Japan. Sanitary paper, represented by facial and toilet tissue papers only has increased the amount of production, whereas printing paper, whether coated or uncoated, has severely decreased the production. Newsprint paper decreased less; however, when it is compared to the largest amount of production for these 15 years that was recorded in 2007, the decrease rate is as high as ▲21.5. Although printing paper had been the most suitable material to deliver information publicly, this status is now being replaced with digital media such as tablet computers and smartphones that eliminate on-paper printing processes to obtain information. Fig. 4 Chang in amount of paper production for each category. “▲” denotes a decrease rate from 2000. Comparison Between Paper and Digital Media One problem typical of digital media is visual recognition that might be inferior to that of paper media. People perform proof reading on a computer display and think they have corrected all the errors in their manuscript, but sometimes cannot ind last few errors before additional proof reading on a paper- based document. Such an experience suggests an idea that paper media is more advantageous to visual recognition. On the other hand, ICT Information and Communication Technology-based education has been introducing digital devices even into elementary schools. Therefore, we examined the reading performance between paper and digital tablet media for Indonesian elementary schoolers. Visual Recognition in Reading Texts on Paper Versus Tablet for Indonesian Elementary SchoolErs The objective of this survey is to examine the difference in reading performance between paper and tablet at the elementary school level. However, the overall goal is a consideration on an ideal choice of media for reading at the elementary school level and smooth introduction of digital devices in combination with paper media to achieve the best possible education effect. ISBN : 978-602-17761-4-8 102 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Fig. 5 Paper and tablet containing the same content and dimension. Materials The media used were a tablet Galaxy Tab S 10.5 type SM-T800, Samsung, with a matrix size of 2560 x 1600 pixels and paper Recycle PPC, Daio Paper Corporation, A4 size copy paper containing 70 recycled pulps. The same document containing a proof reading task was displayed or printed practically to the same dimension as shown by Figure 5. Test Method Proofreading of two tasks, that is, texts with purposely misspelled words was assigned to elementary schoolers. Below is a task example including three misspelled words underlined although actual tasks were written in Indonesian language. Table 1 Misspelling patterns set in tasks Misspelling pattern Example 1. Substitution of letters Makan → Makin 2. Adding or eliminating letters Awan → Kawan 3. Change of the order Disalurkan → Disalukran “Once upon a time there was a zebra and a giraffe who were best friend. The giraffe was showing off to the zebra because he had a long deck and he could eat the leaves on the trees. So, the zebra got mad and tried to eat the leaves off the trees, too. But he was too sohrt. Then the zebra remembered that he could do things that the girafe couldn’t do.” Table 1 shows three patterns of misspelling. Each pattern has a sub-pattern in which the misspelled word can be a meaningful word in a different context like “deck” in the task example above. Tasks A and B were edited to the elementary 3rd grade level and both the tasks included each 18 misspelled words in a total of 862 and 870 words, respectively. Every schooler in the 4th n = 31, 5th n = 36, and 6th n = 38 grades in one elementary school in Indonesia answered each task on a different medium on different days: for example, schooler S answered task A on paper on May 5 and task B on tablet on May 7. Prior to the test, they were asked to ind misspelled words simply with check marks without correcting them and read at their own reading paces, but not to read over again. The length of time they spent was also measured. Analytical Method Analysis of variance ANOVA was applied to the proof test results. Dependent variables were set to the total number of misspelled words found Total number of inding ANOVA, Misspelling pattern MANOVA, and sub-misspelling pattern: whether the misspelled words can be a meaningful word in a different context or not Meaningful misspelled word. Independent variables are Task, Grade, and Media. Our focus is especially on Media. ISBN : 978-602-17761-4-8 103 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Fig. 6 Total number of inding and spent time for grades 4, 5, and 6. Results and Discussion Total Number of Finding Figure 6 reveals that the Total number of inding in grades 4 until 6 consecutively increased with the grade, with the differences in spent time decreased also consecutively with the grade. The difference in the number of inding was not observed between the two media F1,198 = 2.38, p= 0.124. Note that p value 0.05 means no signiicant difference between them. Table 2 Effect of media, task and grade on misspelling pattern Variable Wilks’ Ʌ F df Error df p Media 0.953 3.20 3 196 0.025 Task 0.755 21.32 3 196 0.000 Grade 0.790 8.18 6 392 0.000 Table 3 Interaction between misspelling pattern and media Variable F df Error df p Substitute 3.90 1 198 0.050 Add or Eliminate 4.82 1 198 0.029 Order change 0.37 1 198 0.546 Fig. 7 Finding among misspelling patterns. Table 2 shows that the interaction between the misspelling pattern and media appears signiicant because the p value 0.025 is lower than 0.05 suggesting 95 conidence in signiicance. Table 3 shows ISBN : 978-602-17761-4-8 104 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech that signiicant differences appear in substitute and add or eliminate with larger numbers of inding for paper media although it does not appear in order change. Figure 7 graphically shows this tendency. Meaningful Misspelled Word Figure 8 revealed that in task A, grades 5 and 6 schoolers skipped more signiicantly “Meaningless misspelled word” than “Meaningful misspelled word” , but there is no such tendency with signiicance in Task B. Presumably, whether it is meaningful or meaningless is not related to awareness recognition. No signiicant relationship was found between the media and number of inding in the interactions F2, 197 = 1.44, p =0.239. Chapter Conclusion Fig. 8 Finding between ‘Meaningful’ and ‘Meaningless’ words There wa s no signiicant difference in visual awareness performance between paper and digital media. However, after analyzing it on a misspelling pattern basis, paper media help children improve their visual awareness eficiency. Paper Devices in The Future Bioassay System using Paper and Ink-Jet Printing Formation of Hydrogel Medium using a Printer We created an automated bioassay system based on ink-jet printing[ 3 ]. Compared to conventional manual bacterial culture systems, our printing approach improves the quality as well as the processing speed. A hydrophobichydrophilic pattern as a container supporting a culture medium was built on ilter paper using a toluene solution of polystyrene for hydrophobization, followed by toluene printing to create several hydrophilic areas. As culture media we used a standard calcium alginate CA hydrogel. The calcium alginate hydrogel was formed by chemical reaction between sodium alginate and CaCl 2 solutions as shown in Figure 9. A multi-cartridge system MCS printer for color printing equipped with four ink cartridges loadable with four different solutions was applied. Figure 10 shows how to load ink cartridges with all solutions required to compose a hydrogel medium. In addition, the ejected amount of each solution was controlled by specifying CMYK percentages. Together with nutrients, both solutions for forming hydrogel were successfully printed on paper by means of the modiied ink-jet printer. The amount of each solution was demanded simply by outputting CMYK values. ISBN : 978-602-17761-4-8 105 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Bacterial Growth on CA Hydrogel Medium In the last step, bacterial cells were printed. Figure 11 conirms E. coli growth on the printed CA hydrogel medium 6 h after inoculation. Consequently, the average number of colonies per hydrophilic area was consistently approximately 5-6 colonies with low 95 conidence intervals. This low deviation suggests that liquids containing E. coli cells could be dispensed evenly and regularly onto a culture medium. Finally, we achieved a stable bacteria growth which was conirmed by microscopically imaging the growing bacterial colonies. Fig. 9 Reaction Between Sodium Alginate and CaCl2 Fig. 10 Processing of MCS Printer and Procedure of Medium Printing Fig. 11 E. coli Colonies Growing on CA Medium After 6 h ISBN : 978-602-17761-4-8 106 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Electrical Detection of Bacterial Growth on Medium Fig. 12 Setup of Paper-Based Bacterial Sensor. This work is now being applied to an electrical detection system[ 4 ] for acquiring the condition of bacterial growth. Two electrodes were built on ink-jet paper and a cuboid-shpaed Luria-Bertani LB culture medium was placed over them as shown in Figure 12 . When a cyclic electric ield was applied, current-voltage characteristic or I-V curves were measured and assinged to each growth phase of the bacteria. Paper-based Cu 2+ ion sensor Fabrication of Sensor using Ink-Jet Printer Water containing excessive amounts of Cu 2+ is extremely harmful to human health and the biology of other animals. Therefore, we developed a user-friendly, low-cost, sensitive, and ion-species-selective paper-based sensor to inspect drinking water and industrial waste efluent for excessive Cu 2+ levels, for use by people especially in developing countries. A dual-function paper-based sensor was fabricated simply by printing an acetone solution of an anthraquinone derivative onto a ilter paper[ 5 ]. Fig. 13 Paper-based sensors after immersion in Cu2+ aqueous solutions at different concentrations for 10 min. Fig. 14 Fluorescence spectra of paper-based sensors after immersion in Cu2+ aqueous solutions of various concentrations. ISBN : 978-602-17761-4-8 107 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Response of The Sensor In visible detection, the color of the dye on the paper-based sensor changed from yellow to purple with increasing Cu 2+ concentration. Figure 13 shows a photograph of paper-based sensors immersed in Cu 2+ aqueous solutions. This result conirmed that the paper-based sensor was able to detect Cu 2+ at concentration as low as 2 ppm, which is the maximum amount allowed in drinking water according to the World Health Organization. The entire detection process took only 10 min and sensitive detection of Cu 2+ was successfully achieved. In luorescence detection, linear relationships observed between the surface luorescence intensity and Cu 2+ concentration in the dilute solution samples, as shown in Figure 14, indicates successful quantitative detection. Furthermore, the accuracy of the Cu 2+ concentration measurements was proven by comparison with measurements using inductively coupled plasma-optical emission spectroscopy. With regards to detection conditions, pH 7 was optimum and the increase in temperature promoted the detection reaction. Furthermore, although slight color fading of the paper-based sensor was observed with exposure to strong ultra-violet light, protection from light during storage would prevent this photoredox reaction. Acknowledgements Siti Dian Mardiyani, a master candidate is greatly appreciated for research work on “Visual awareness performance in reading texts on paper versus tablet for Indonesian elementary school children” described in Chapter 3. Tithimanan Srimongkon, a post-doctoral research fellow, National Institute of Advanced Industrial Science and Technology is appreciated for the collaborative work on “Bioassay system using paper and ink-jet printing” described in Chapter 4.1. Yinchao Xu, a PhD candidate is appreciated for his pioneering work “Paper-based Cu 2+ ion sensor” described in Chapter 4.2. References 1 Han, Y.-H., Yanagisawa, M., Enomae, T., Isogai, A. and Ishii, T., “Analyses of mucilaginous compounds used in making traditional handmade paper”, Japan Tappi J., 597: 1067-10762005. 2 Mardiyania, S. D., Higuchi, N., Enomae, T., Paper or tablet? - Media effect on visual awareness performance of elementary schoolers-, Ag-ESD symposium, Tsukuba, Japan, Sept., 2016. 3 Srimongkon, T., Mandai, S., Enomae, T., “Application of biomaterials and inkjet printing to develop bacterial culture system”, Advances in Materials Science and Engineering, Vol. 2015, 2907902015. 4 Srimongkon, T., Buerkle, M., Enomae, T., Ushijima, H., Fukuda, N., Study of the electrical response of culture media during bacterial growth on a paper-based device, Proc., ICFPE2016, Yamagata, Japan, Sept., 2016. 5 Xu, Y., Enomae, T., Development of a novel paper-based copper ion sensor using inkjet printing technology, Proc., the 135 th Res. Conf., JSPST, Tokyo, Japan, pp.73-76, May, 2016. ISBN : 978-602-17761-4-8 108 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 109 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech COMPARISON OF WOOD PROPERTIES BY AGE ON EUCALYPTUS PELLITA CLONES USING NEAR INFRARED NIR SPECTROSCOPY Dian Apriyanti a1 , Miho Hatanaka b2 , Ruspandi c3 a Research and Development, Sinarmas Forestry Indonesia b University of Tsukuba, Japan c Research and Development, Sinarmas Forestry Indonesia 1 dian.apriyantisinarmasforestry.com 2 s1521123u.tsukuba.ac.jp 3 ruspandi.ruspandisinarmasforestry.com ABSTRACT Eucalyptus pellita is one of fastest growing trees species for raw material of pulp and paper industries that has received a lot of attention from many researchers. Nevertheless, information on wood properties could enhance additional gains manifesting in the end product. The evolution of wood properties in age 1-5 years was observed in two clones growing at two sites classes named: medium texture SC I and sandy texture SC III. Research was conducted by drilling up to 100 standing trees, collecting the core from clones at different ages. Furthermore, the samples were screened by near infrared NIR spectroscopy. NIR spectroscopy is known as a powerful tool that can provide quantitative information on chemical and physical properties. Thus, NIR predictions of pulp properties were undertaken. NIR was used to evaluate pulp yield and properties of two clones of E. pellita at different ages in two site classes. The results showed that basic wood density and lignin content increase with age. For the particular comparison between clones, wood consumption of the clone EPB is 11 lower than the clone EPA but lignin content 11 higher. Keywoods: Eucalyptus pellita; wood; NIR Introduction Eucalyptus pellita is one of fast growing trees species for raw material of pulp and paper industries that has received a lot of attention from many researchers. Currently, high performing clones in the ield are inally selected by wood properties. 1 Assessing the wood quality is a big challenge for the forest industry, because Eucalyptus wood, as raw material is highly heterogeneous. It is therefore important to have high technology, able to predict wood properties using non-destructive and a rapid analysis method for routine activity. 2 NIR spectroscopy has gained widespread acceptance in recent years because it is a rapid, non- destructive analysis, reliable for determination and the multiplicity of analysis with one operation. Spectra within the NIR region consist of overtone and combination bands of fundamental stretching vibrations of fundamental groups that occur in the middle infrared region, mainly CH, OH and NH, which represent the backbone of all biological compounds. 1 E. pellita is not an exception and NIR was used to evaluate pulp yield and wood properties. This study evaluates by using NIR spectroscopy the variation in wood properties of E. pellita clones according to different site classes from 1 to 5 years of age. Evolution of the wood properties and differences between clones are reviewed based on its characterization as raw material for pulp and paper industry. Materials and Methods Materials The E. pellita clones EPA and EPB were taken from plantations in Riau, Indonesia, district Rasau Kuning, Gelombang and Sorek Table 1. The locations are around latitude 00º46’ N; 100º31’ W, altitude ISBN : 978-602-17761-4-8 110 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 44-57 masl, mean annual rainfall of 2,152 mmyear and average temperature of 30.3 Celsius. There are two site classes of soils represented; one medium texture Site Class I and another sandy texture Site Class III. The samples were taken from 20 trees in each age class 1 to 5 years per clone. A total of 200 samples from site class I were processed and 120 samples from site class III because not all ages were available in the ield. Table 1. Plantation area where samples were taken by site class and age Age year EPA EPB SCI SCIII SCI SCIII 1 Gelombang 208 Gelombang, 197 Sorek, 64 Sorek, 2 Rasau Kuning, 195 Rasau Kuning, 260 Rasau Kuning, 195 Rasau Kuning, 019 3 Rasau Kuning, 96 na Gelombang, 169 na 4 Rasau Kuning, 77 Rasau Kuning, 120 Rasau Kuning, 80 na 5 Rasau Kuning, 63 na Rasau Kuning, 008 Gelombang, 007 Note: SC = site class; na = not available Methods The 320 samples were drilled up from two different clones at different ages. The samples are drilled sample where each tree was drilled at 1.3 m from the ground. Furthermore, the hole made was covered by plugging a tightly-itting wooden peg pasak. Then, tree-cote was applied on the bark surface completely in order to prevent the infection of the sampled tree from outside. The drilled samples were kept in the plastic bag and labeled immediately. Drilled samples were sent to the preparation room to dry and process up to the 40-60 mesh required. Furthermore all the samples were ready to be screened by NIR spectroscopy. NIR Spectroscopy and Data Processing Wood analyses were carried out on the Foss NIRSystems NIR spectroscopy 6500. 3 Absorbance spectra up to 1440 scans were collected at 2.0 nm intervals over the range 400-2500 nm. Basic wood density, cellulose, extractive, lignin, pulp yield were observed. Statistical analysis of the data were undertaking using PLS regression model and software winISI III upgrade to 1.60, a FOSS statistical analysis for predicting wood properties. 4 In addition, wood consumption was estimated as follows: The sig niicance of the main factors clone, site class and age on wood properties such as basic wood density, cellulose, extractive, lignin, pulp yield and wood consumption were estimated by univariate GLM using SPSS program version 20. Results and Discussion There were statistically signiicant differences between clones for basic wood density, lignin, pulp yield and wood consumption; between site classes for basic wood density, extractive and wood consumption; and between ages for all parameters except cellulose content Table 2. A comparitive evaluation of the wood properties between the clones at different ages and site classes is illustated in Fig. 1. ISBN : 978-602-17761-4-8 111 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Probability of a larger value = 0.05 5 4 3 2 1 575 550 525 500 475 450 5 4 3 2 1 I Age year B a si c d e n si ty k g m 3 III 1 2 3 4 5 5 4 3 2 1

52.0 51.5

51.0 50.5

50.0 49.5

49.0 5

4 3 2 1 I Age year C e llu lo se III 1 2 3 4 5 5 4 3 2 1 2.4

2.3 2.2

2.1 2.0

1.9 1.8

1.7 1.6

1.5 5

4 3 2 1 I Age year E x tr a ct iv e III 1 2 3 4 5 5 4 3 2 1 35 34 33 32 31 30 29 28 5 4 3 2 1 I Age year Li g n in III 1 2 3 4 5 5 4 3 2 1 53 52 51 50 49 48 47 5 4 3 2 1 I Age year P u lp Y ie ld III 1 2 3 4 5 5 4 3 2 1 4.8

4.6 4.4

4.2 4.0

3.8 3.6

5 4 3 2 1 I Age year W o o d C o n su m p ti o n m 3 III 1 2 3 4 5 Fig. 1 Comparison of EPA dot and EPB cross on a basic wood density, b cellulose, c extractive, d lignin, e pulp yield and f wood consumption along the age in site class I and III. Table 2 Probability of difference within groups clone, site class and age from univariate ANOVAs for each wood property Description Basic wood density Cellulose Extractive Lignin Pulp yield Wood consumption Clone 0.000 0.148 0.557 0.000 0.000 0.000 Site Class 0.000 0.125 0.000 0.061 0.141 0.000 Age 0.000 0.155 0.000 0.000 0.000 0.000 Basic wood density and lignin content trend to increase with age for the two clones in the two site classes, having clone EPB higher values than EPA Fig. 1a and 1d. A similar increasing trend was reported for basic wood density in few Eucalyptus sp. 5 Five years is the current rotation age for comercial plantation of E. pellita in Riau Province, Indonesia. At 5 years of age in site class I, which include the full set of age measurements, clone EPB was 12 higher than clone EPA for basic wood c a ISBN : 978-602-17761-4-8 112 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech density and 11 higher in lignin content. Basic wood density of clones EPB and EPA achieved average values of 560 kgm 3 and 489 kgm 3 , respectively Table 3. In the case of lignin content of EPB and EPA were 34.3 and 30.5 respectively. Table 3 Phenotypic means for all wood properties traits assessed from each clone by site class and age and respective units. Clone Age year SC Basic density kgm 3 Cellulose Extractive Lignin Pulp yield Wood consumption m 3 EPB 5 I 559.9 48.8 2.14 34.3 47.2 3.78 EPB 5 III 529.5 51.3 1.72 33.5 47.9 3.97 EPA 5 I 487.6 50.4 2.10 30.5 48.4 4.24 EPA 4 III 499.0 51.1 1.98 31.3 49.2 4.08 Note: SC= site class; Not signiicant differences between clones was achieved for extractives Table 2 but a trend to incraese with age is shown in Figure 1c. The same trend was explained by Erikson and Arima for Douglas-Fir during the irst 6 years of age. 6 Extractive content of EPB and EPA were 2.14 and 2.10 respectively. Although not completely clear, but still a trend of decreasing values with age occured in pulp yield for clone EPB Fig. 1e. Even the clones showed signiicant differences for pulp yield at the age of 5 years 47.2 and 48.4 for clones EPB EPA, respectively, 1.2 difference is negligible. Cellulose showed not signiicant differences between any of the groups studied Table 2. In case of Douglass-ir wood, the alpha cellulose increased to age 25 years, but there was no signiicant difference between the yields of plot treatment and control trees. 6 Cellulose content of EPB and EPA were 48.8 and 50.4 respectively. The consistent lower wood consumption of clone EPB in site class I does not seem so clear in site class III but still signiicantly different to comment on the performance of clone EPB. According to the results in site class I, this clone is 11 more eficient in the mill Table 3 . Conclusions The results of the study of the wood properties on E. pellita by age demonstrated that there was a clear trend of increasing basic wood density with age. This trend seems to impact in the reduction of wood consuption with age but moderated by the pulp yield. Clone EPB had 11 lower wood consumption than EPA , and on the other hand it had higher lignin content of 11. References 1 Bailleres, H. NIRS Analysis as a tool rapid screening of some major wood characteristics in a Eucalyptus breeding program. Ann. For Sci. 59 479-490. 2002 2 Schimleck LR. Near infrared spectroscopy: a rapid, non-destructive method for measuring wood properties and its application to tree breeding. New Zealand Journal of Forestry Science 38 1: 14- 35. 2008 3 Ndlovu ZTL, Swain TL, Zbonak A, Fossey A. Development of a non-destructive near infrared sampling technique to determine screened pulp yield of Eucalyptus macarthurii. IUFRO Durban 2007 4 Yamada T, Yeh TF, Chang HM, Li L, Kadla JF, Chiang VL. Rapid analysis of transgenic trees using transmittance near-infrared spectroscopy NIR. Hozforschung, Vol. 60, pp 24-28. 2006 5 Backman ME, Leon J. Correlations of pulp and paper properties at an early age and full rotation age of ive Eucalyptus species. Lisboa, EUCEPA, 9, 2003 6 Erickson HD, Arima T. Douglas-Fir Wood quality studies Part II: Effect of age and stimulated growth on ibril angle and chemical constituents. Wood Science and Technology Vol. 8 255-265. 1974 ISBN : 978-602-17761-4-8 113 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech GROWTH OF AGAVE GERMPLASM IN BALITTAS, MALANG EAST JAVA Parnidi 1 , Untung Setyo Budi, Marjani Indonesian Sweetener and Fiber Crops Research Institute Jl. Raya Karangploso Km. 4, Kotak Pos 199, Malang 1 nikicroyahoo.co.id ABSTRACT Agave or sisal is a crop producing non - wood ibers are widely used for textile materials, ropes, paper, craft, building materials and construction. The growth and diverse plant morphology are relection of the wide genetic diversity,which is needed in the Sisal variety assembly program. Until now, the collection of sisal germplasm in Balittas has not been characterized their morphologic characters.Sisal accession characterization was carried out from 2012 to 2015 in Karangploso Experimental Station in Malang is located at an altitude of 515 meters above sea level with the climatic conditions of type D medium Smith Ferguson, rainfall of 1,500 mmyear, and the type of soil GleymosolGleikinceptisol. Each accession was planted in experimental plots, 6 plants for each accession at a spacing of 2 m between plants and 5 m etween accessions. Fertilization was done 2 times at the beginning and end of the rainy season at the following rates: 200 kg Urea 92 kg N + 400 kg Phonska 79.1 P+ 15 tons of manure per hectare. At age 3 years Balittas 15 was the tallest with an average growth rate of 157.34 cm. The highest number of leaves was shown by Balittas 19, with mean increase of 56.33 sheets for 3 years. The greatest length of leaf was shown by Balittas 13 with average growth rate of 87.75 cm for 3 years. The greatest width of leaf was shown by Balittas 14 with average growth rate of 9.20 cm for 3 years. The highest of iber content was shown by Balittas 22 with average 4.59 . Keyword: growth, morphological characteristics, iber yield, germplasm. Introduction Agave is a crop that can grow in tropical and sub-tropical areas. Agave iber is used for textile, cordage, waiver, paper, craft [1], bio-fuel [2], food and beverages [4], medicines [5] and [5] construction materials, synthetic iber manufacture material and as composite material for packaging such as cement bag [6], [7], and [8]. Agave iber has some advantages among others it is renewable, recyclable and also degradable in environment [9]. The agave plant is easy to be cultivated, can be harvested in relatively short time compared with iber from wooden trees. The success of superior excellent variety breeding program is greatly determined by the availability of germplasm, as a source of diversity and genetic resource. The great diversity of genetic resources increases the chances of success in the assembly of new excellent varieties. The role and function of germplasm is important as the plant genetic resources, its presence should be maintained in order to avoid extinction, so that it can meet human needs such as food, clothing and shelter [10]. In addition, it is also necessary to obtain as much as possible genetic information through characterization and evaluation of germplasm. This can be as a source of genetic material in assembling new variety in breeding programs. Sweetener and iber crops research institute Balittas is a national research center applying the mandate to conduct research on iber crops. Balittas has as 23 accessions of agave germplasm collection. The addition of agave germplasm is done by introduction and exploration. This study aims to evaluate the performance of Agave germplasm owned by Balittas. Materials and Methods Agave germplasm was planted in Karangploso Experimental Station, Malang, at an elevation of 515 m asl, D Smith Ferguson climate type, rainfall 1500 mmyear, and soil type Gleymosol GleikInseptisol in 2012-2015. Each accession was planted in a plot of trial with the 6 populations in each accession with ISBN : 978-602-17761-4-8 114 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech the planting distance of 2 m x 2 m and inter-accession distance of 5 m. The fertilization was done twice in the beginning and at the end of rainy season. The rate of fertilizer used was 200 kg Urea 92 kg N + 400 kg Phonska 79.1 kg P + 15 tonnes of manure per hectare. The morphology qualitative characters being assessed were color of leaves, edge leaf color, the present of leaves in the edge and the color of leaves in the tip. This was done when the plant aged 24 months. Meanwhile the quantitative characters includes height of plant, number of leaves, length and width of leaves, fresh weigh of 25 leaves, dried iber weight and iber content. This was done every year. The descriptive statistic analysis was carried out to know the performance of growth and result components. Results and Discussion a. Qualitative Character Performance The agave germplasm in Balittas consists of three groups, namely Agave angustifolia, Agave cantala and Agave sisalana. The qualitative characters of each accession are presented in Figure 1-4 as well as Table 1. Agave cantala has bluish gray leaves, big, sharp and closely spine in the tip of leaves, dark brown thorn in the tip of leaves. A. sisalana has green grayish leaves, big and small prickle in leaves margin and some has no prickle, also dark brown spine in tip of leaves. According to [1] A. cantala is more resistant to drought than A. sisalana . However, the iber production of iber of A. cantala is lower than A. sisalana. The characteristics of A. sisalana which has glaucous leaves with spine in the tip of dark brown [5]. The width of leaves reaches 10 cm and the length of leaves can reach more than 1.5 m. All A. cantala are type of agave with big prickles in the tip of leaves. The prickle in the margin of A. sisalana leaves is catergorized into a number of groups, namely no prickle, small and many prickles and big and rarely prickles as well as big and many prickles. Figure 1. Agave angustifolia Figure 2. Agave cantala Figure 3. Agave sisalanawith green leaves Figure 4. Agave sisalanawith grey leaves ISBN : 978-602-17761-4-8 115 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Agave sisalana has very short basal stems, usually less than 0.5 m tall. Mature plants have relatively large green or greyish-green leaves usually 90-130 cm long that are usually very rigid. These leaves do not have any prickles along their margins [11]. Meanwhile, A. angustifolia has light green leaves, short leaves, great number of leaves, sharp and closed thorny leaves in the edge. A. angustifolia has very short basal stems, usually less than 0.5 m tall. Mature plants have relatively small light green, grayish-green or variegated leaves usually 30-60 cm long that are usually very rigid. These leaves have numerous small prickles 2-5 mm long along their margins. This species produces large capsules and sometimes also develops numerous plantlets i.e. bulbils on the branches of its lower clusters [11]. Table 1. Qualitative Charachters of Agave germplasm in Balittas. Collection name Agave type Leaves color Margin of leaves color Prickle of leaves margin Color of tip spine Balittas 1 A.angustifolia Green Light green Notched, big prickly Dark-brown Balittas 4 A.angustifolia Green Light green Notched, big prickly Dark- brown Balittas 5 A.angustifolia Green Light green Notched, big prickly Dark- brown Balittas 9 A.angustifolia Green Light green Notched, big prickly Dark- brown Balittas 19 A.angustifolia Green Yellowish green Notched, big prickly Dark- brown Balittas 2 A.cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 3 A.cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 6 A.Cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 7 A.Cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 8 A.Cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 11 A.Cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 15 A.Cantala Greyish-green Green Notched, big prickly Dark- brown Balittas 20 A.Cantala Grey Yellowish green Notched, big prickly Dark- brown Balittas 21 A.Cantala Grey Green Notched, big prickly Dark- brown Balittas 22 A.Cantala Grey Grey Notched, big prickly Dark- brown Balittas 26 A.Cantala Grey Green Straight, big prickly Dark- brown Balittas 10 A.Sisalana Dark green Dark green Rare, straight prickly Dark- brown Balittas 12 A.Sisalana Dark green Yellow Straight, Small prickly Dark- brown Balittas 13 A.Sisalana Dark green Yellow Straight, Small prickly Dark- brown Balittas 14 A.Sisalana Green Light green Notched, big prickly Dark- brown Balittas 16 A.Sisalana Grey Grey Without prickly Dark- brown Balittas 24 A.Sisalana Grey Grey Without prickly Dark- brown Balittas 25 A.Sisalana Grey Green Without prickly Dark- brown

b. The Growth, Growth Rate and Fiber Content of Agave Germplasm

At age 3 years the average height and length of A. cantala leaves were, respectively 1.68 m and 1.18 m, while the average height and length of A. sisalana leaves were 1.41 m and 0.97 m respectively. Meanwhile Agave angustifolia has average height of 106.41 cm and average length of leaves of 82.8 cm. For the length of leaves, A. sisalana has 10.46 cm that is wider than A. cantala which is 9.43 cm and also A. angustifolia which is 7.79 cm. According to [12] stating that Agave americana until the lowering phase, the height of Agave plant can reach of 2.4 - 7.6 m with the length of leaves reaches of 1.8 m. in the agave sisala, the height of plant until the lowering phase can reach of 7- 9 m, with the length of leaves reaches 1.5 m [5]. In agave angustifolia, the height of plant ranges from 70 to 90 cm, with mature leaf length ranging from 110 to 130 cm and width from 8 to 10 cm [13]. The number of A. angustifolia leaves reaches 77.18 sheets per year. This shows greater number than A. sisalana 49.77 and A. cantala 53.94. Brown mentioned that during the life until before the lowering phase, the agave can produce 220 sheets of leaves per planting process. The research result by ISBN : 978-602-17761-4-8 116 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech [12] showed that in Agave Americana, the growth of number of leaves each year can reach 40-50 sheets. Based on the data in Table 2, it shows that until the fourth year, the height of plant, length of leaves and width of leaves are still lower than the growth of agave plant in other countries. The coeficient value of agave germplasm in Balittas of for the characters of height of plant, length and width of leaves show the diversity less than 50 . The diversity of genetic of agave germplasm in Balittas is categorized as medium. This is based on the grouping on the diversity coeficient value conducted by [14]. The coeficient of genetic diversity is classiied into 4 criteria, namely: coeficient value of 0 - 25 is categorized as low coeficient value, 25 - 50 is medium coeficient value. The coeficient value of 50 - 75 is categorized as high coeficient value and coeficient value more than 75 is categorized as the highest coeficient value. The Agave germplasm in 2015 has been in the second year of production. The irst harvesting is conducted when the plant has been in the second year. The harvest is conducted for the leaves that have been old and formed angle of 45 o C with the length is not less than 1 meter [15]. Meanwhile, [12] made a limitation that the harvest of agave leaves is conducted after the plant is three years old. The harvest of agave leaves is conducted twice in a year, namely in May and November. The harvest of agave can be conducted until the plant is in lowering phase. The agave plant can produce until it reaches the age of 8-30 years old [12]. Leaves can be harvested after two years of age, which will postpone the “bolting” for 15-20 years. After “bolting”, the plant dies. Based on Table 2. It shows that the growth rate of agave germplasm of Balittas collection keeps increasing. The greatest increase of Agave angustifoliais in accession Balittas 9 and the lowest one is in accession Balittas 1. The growth rate of Agave angustifolia germplasm height of collection Balittas is 61.45 – 107.41 cm for 3 years. The average number of leaves reaches of 29.08 – 56.33 sheets for 3 years. The average of lenght of leaves reaches of 30.79 - 65.53 cm. Meanwhile, the average growth of width of leaves reaches of 2.66 - 4.73 cm for 3 years. Table 2. The Growth rate and iber content of Agave germplasm NamaAksesi Plant height cm Leave number sheet Lenght of leaves cm Width of leaves cm Fibers content Agave angustifolia Balittas 1 61.45 29.08 30.79 2.66 2.95 Balittas 4 77.43 29.67 57.83 3.80 2.82 Balittas 5 106.42 39.00 63.29 4.73 2.32 Balittas 9 107.41 40.17 63.10 4.65 2.50 Balittas 19 82.15 56.33 65.53 4.41 3.81 Agave cantala Balittas 2 114.95 34.34 48.68 3.40 3.64 Balittas 3 138.00 24.50 46.45 5.19 3.99 Balittas 6 106.77 29.42 73.48 4.2 2.93 Balittas 7 110.23 39.92 75.00 4.68 4.13 Balittas 8 118.04 37.17 69.27 4.28 3.50 Balittas 11 137.40 25.50 43.70 6.17 3.76 Balittas 20 141.78 33.09 58.07 6.14 3.51 Balittas 21 150.70 54.75 60.19 6.48 3.55 Balittas 22 141.06 36.75 43.84 6.25 4.59 Balittas 26 93.86 29.50 81.21 4.75 4.42 Agave sisalana Balittas 10 100.25 34.17 25.25 6.75 2.77 Balittas 12 145.89 37.33 56.38 8.33 2.66 Balittas 13 98.00 29.52 87.75 5.20 2.79 Balittas 14 131.29 38.08 74.75 9.20 2.95 Balittas 15 157.34 31.84 61.12 7.48 3.36 Balittas 16 60.96 21.42 28.88 2.88 2.95 Balittas 25 74.91 8.59 51.05 2.82 3.07 Rerata 110.80 35.65 59.04 5.41 3.26 KK 20.90 14.42 5.64 12.01 20.30 ISBN : 978-602-17761-4-8 117 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech The greatest growth rate of Agave cantala is in accession Balittas 21 and the lowest one is in accession Balittas 26. The growth of Agave cantala germplasm height of Balittas collection is 93.86 - 150.70 cm for 3 years. The average growth of number of leaves reaches of 24.50 – 54.75 sheets for 3 years. The average growth of lenght of leaves reaches of 43.84 – 81.21 cm. Meanwhile, the average growth of width of leaves reaches of 3.40 – 6.48 cm for 3 years. Meanwhile, the greatest growth rate of Agave sisalana is in accession Balittas 15 and the smallest one is in accession Balittas 16. The growth of Agave cantala germplas height of Balittas collection is 60.96 – 157.34 cm for 3 years. The average growth of number of leaves reaches of 8.59 – 38.08 sheets for 3 years. The average growth of length of leaves reaches of 25.25 – 87.75 cm. Meanwhile, the average growth of width of leaves reaches of 2.82 – 9.20 cm for 3 years. In general, it shows the normal growth of morphology characters from the three types of agave, namely Agave angustifolia, Agave cantala and Agave sisalana. The growth of Agave germplas is more determined by each genetic. The growth of Agave angustifolia tends to be slower than Agave sisalana and Agave cantala. The greatest average of A. angustifolia iber level is 3.81 , the greatest average of A. cantala iber level is 4.59 and the greatest average of A. sisalana iber level is 3.36 . According to [12] stated that the agave iber level can reach of 4-5. The lenght of leaves, the number of leaves, the width of leaves and weight of leaves are an important determinant of result component for iber producer plants from the leaves. The length of leaves, number of leaves, and weight of leaves have positive correlation on the agave iber results. Meanwhile, according to [16] there was a signiicant interaction between the characters of number of leaves, lenght of leaves, results of dried iber and all parameters of iber quality in the environment. Conclusion Based on the morphology characters of agave germplasm collection in Balittas, it can be divided into 3 types, namely agave angustifolia, agave cantala and agave sisalana. Based on the plant morphology characters, it shows that the agave cantala has greater characters of height of plant and lenght of leaves than sisalana or agave angustifolia. Meanwhile, for the character of number of leaves, the greatest is in agave angustifolia. The agave sisalana has most signiicant character in its width of leaves. The growth of agave cantalagermplasm shows it has faster growth than sisalana or angustifolia. A. Cantala has the highest value of production component than other agave types. References 1. Santoso B. Peluang Pengembangan Agave Sebagai Sumber Serat Alam. Perspektif 2009; 8.2: 84 – 95. 2. Nu~nez, HM. Biofuel Potential in Mexico: Land Use, Economic and Environmental E_ects Work-in-Progress. Department of Economics Centro de Investigaci_on y Docencia Econ_omicas Aguascalientes, Mexico. Agricultural and Applied Economics Association Annual Meeting. Boston, Massachusetts. 2016. 3. Almaraz AN, Amanda EDA, Antonio JÁR, Natividad JUS, Silvia LGV. The Phenols of the Genus Agave Agavaceae. Journal of Biomaterials and Nanobiotechnology 2013; 4: 9-16. 4. Monterrosas BN. Martha LAO, Enrique JF, Antonio RJA, Zamilpa A, Manases GC, Jaime T, and Maribel HR. Anti-Inlammatory Activity of Different Agave Plants and the Compound Cantalasaponin-1. Molecules 2013;18: 8136-8146. 5. Tewari DYC, Tripathi and Anjum N. Agave sislana: a plant with high chemical diversity and medicinal importance. Pharmaceutical Research 2014; 3. 8: 238-249 6. Budiman I, Aulya FS, Subyakto, Subiyanto B, Laporan akhir tahun, UPT BPP Biomaterial LIPI, Penelitian pemanfaatan serat sisal Agave sisalana untuk pembuatan komposit serat semen: hubungan antara temperatur hidrasi dengan kuat tekan. UPT Balai Penelitian dan Pengembangan Biomaterial LIPI. 2006. 7. Subyakto, Hermiati E, Heri DYY, Fitria. Proses pembuatan serat selulosa berukuran nanodari sisal Agave sisalana dan bamboo betung Dendrocalamusasper. Beritaselulosa 2009; 44.2: 57- 65. ISBN : 978-602-17761-4-8 118 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 8. Kusumastuti A, Aplikasi Serat Sisal sebagai Komposit Polimer. .J.KompetensiTeknik 2009; 1.1: 27-32. 9. Zimmermann T, Pohler E, Geiger T. Cellulose Fibrils for Polymer Reinforcement. Advanced Engineering Science 2004; 6.9: 754-761 10. Gajatri SB, Status Pengelolaan Plasma Nutfah Jagung. Plasma Nutfah 2007;13. 1: 11-18. 11. Anonymous, Weeds of Australia - Biosecurity Queensland Edition Fact Sheet. Agave sisalanahttp: www . keyserver.lucidcentral.orgweedsdata...agave_sisalana.pdf. 2016. 12. Hulle A, Kadole P, and Katkar P. Review Agave Americana Leaf Fibers. Fibers 2015; 3: 64-75. 13. Hidalgo MR, Magdaleno CC, Luis HHG and Guillermo UC, 2015. Chemical and morphological characterization of agave angustifolia bagasse ibers. Botanical sciences 2015; 93. 4: 807-817. 14. Rebin RW. and DS Decker W. Cucurbits. Central for Agricultural and Bioscience International. USA. 1995. 15. Brown K. Agave sisalana Perrine. University of Florida, Center for Aquatic and Invasive Plants, 7922 N.W. 71st Street, Gainesville, FL 32653; www.se eppc.org...pdfsummer2002-brown- pp18-21.pdf diaksestanggal 9 September 2016. 16. La-Vina HC. Stability of Yield and iber ineness in ramiBoehmerianivea[L.]Gaud.http:agris.fao. orgagrissearchsearchdisplay.do? F=1994 2FPH2FPH94008.xml3BPH9410635. Diakses 20 Mei 2016. ISBN : 978-602-17761-4-8 119 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech IMPROVED OXYGEN DELIGNIFICATION BY PHOTO PRETREATMENT AND ADDITIVE REINFORCEMENT: A COMPARISON STUDY BETWEEN TROPICAL MIXED HARDWOOD KRAFT PULP AND OIL PALM FIBRE SODA-ANTHRAQUINONE PULP Leh Cheu Peng a1 , Chong Yin Hui, Wan Rosli Wan Daud, Mazlan Ibrahim and Poh Beng Teik a Bioresource, Paper and Coatings Technology, School of Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Pulau Pinang 1 cplehusm.my ABSTRACT Oxygen deligniication O is an important process in pulp and paper industry for enhanced elemental chlorine-free EFC or totally chlorine-free TCF bleaching. The application of an O could remove the residual lignin from unbleached pulp up to 50 percent and therefore, reduce the burden to the bleaching plant. The major drawback of O is its relatively lower selectivity between deligniication and cellulose degradation in comparison to other bleaching agent. For attaining a more eficient chlorine-free ECF or TCF bleaching, as the irst bleaching stage, the selectivity of the O has to be improved. In this study, the selectivity of O was improved through three different modiication approaches—additive reinforcement, pre-treatment and the combination of the two modiications toward two different pulps namely tropical mixed hardwood kraft pulp and oil palm empty fruit bunch EFB soda-anthraquinone pulp. The results obtained showed that all the modiication approaches were capable of improving the bleaching selectivity up to 90 by retaining higher pulp viscosity and achieving better kappa number reduction. The simple photo pretreatment could even eliminate the hexenuronic acid more than 60. These indicated that the beneicial effects of improved Os were repeatable on the two different pulps. Keywords: anthraquinone; bleaching selectivity; hexenuronic acid; oxygen deligniication; photo pretreatment Introduction Among all the chlorine-free bleaching agents, oxygen deligniication O is commonly used as the irst bleaching stage to eliminate residual lignin in bulk from the brown stock. However, in comparison to conventional chlorination C bleaching, O shows relatively lower selectivity in between delignifying power and carbohydrates degradation, and the deligniication is generally limited to no more than 50 to prevent unwarranted carbohydrates degradation[1-2]. As a result, chlorine-free bleached pulps commonly show relatively lower strength properties as well as pulp brightness [3-4]. Hence, the improvement of O is very important as it may alleviate the number of bleaching stage required to avoid undesired degradation of cellulose and increase the brightness of pulp as well. Over the past thirty years, many attempts have been made to improve the selectivity of the O with minor modiications such as additional of additives or implementation of a pre-treatment prior to the process. In 2010, Ng and co-worker 2010 were recommended a higher H 2 O 2 charge 0.5 and small amount of anthraquinone AQ added in the O on oil palm empty fruit bunch EFB soda-AQ pulp. The results of study have proven that the addition of H 2 O 2 and AQ during O generally gives a satisfactory acceleration on the pulp brightness and minimizes cellulose deterioration while retain a rather high degree of deligniication [5-6]. Nevertheless, there is no further modiied O’s research carried out or continued on different chemical pulps even thought the capability of the O pAQ bleaching process is remarkable. On the other hand, some researchers have also found that photo pretreatment can increase the bleaching selectivity due to the generation of reactive radicals during the treatment and they may degrade the lignin into smaller molecules [5-7] and thus, increase the deligniication eficiency in the subsequent bleaching stage. In this study, the improved O by both additive reinforcement and photo pretreatment, and also ISBN : 978-602-17761-4-8 120 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech the combination of two approaches were applied on two different chemical pulps viz. mixed tropical hardwood kraft pulp and oil palm empty fruit bunch EFB soda-anthraquinone pulp. The effectiveness of the three modiication approaches on the two chemical pulps were compared based on pulp properties such as kappa number, viscosity, selectivity, hexenuronic acid content and pulp brightness. Experimental Materials Sabah Forest Industries Sdn. Bhd, Sabah, Malaysia provided the mixed tropical hardwood brown kraft pulp with kappa number of 16.4, pulp viscosity of 30.4 cP, and 36 ISO brightness. The oil palm empty fruit brunch EFB was provided by by Eco Fibre Bhd., Johor, Malaysia. The EFB was soaked in water for one day and washed, in order to remove contaminants such as sand, dust and oil, then it was air-dried and kept in plastic bags prior to pulping. Soda-Anthraquinone Pulp Preparation Pulping of EFB was carried out in a 6 L stainless steel digester. Four hundred gram of oven-dried o.d. EFB was cooked at 160 o C with 25 of sodium hydroxide and 0.1 anthraquinone on the oven dry basic of EFB, material-to-liquor ratio of 1:7, time-to-temperature of 90 min and time-at-temperature of 120 min. After the completion of cooking, the collected EFB soda-AQ pulp was deiberized in a hydro- pulper for 10 min and washed thoroughly with tap water in a stainless steel mesh ilter. The pulp was further disintegrated mechanically in a three bladed disintegrator for 1 minute at a pulp consistency of 2.0 and then screened by Somerville lat-plate screen with 0.15mm slits. The pulp was then spin-dried and kept in the fridge 4 o C before used. Methods Photo Pretreatment Twenty ive grams of hardwood kraft pulp was soaked in the acid solution with pH 5 adjusted by adding 0.5M sulphuric acid solution for 15 min. The pulp stock was then squeezed to remove excess acid solution to reach 10 consistency. After that, the pulp sample was transferred into a polyethylene bag and photo irradiation was carried by placing the pulp sample under ultraviolet, 369 nm 6 watt for a desired duration of time. The distance between the lamp and pulp sample was 3 cm for blue light and 5 cm for the UV light. After the completion, the pulp was washed and spins dried, and then continued with oxygen deligniication. Improved Oxygen Deligniication O with Hydrogen Peroxide O p and Anthraquinone O pAQ Oxygen deligniication O was carried out using a 650-mL stainless steel autoclave equipped with a gas inlet and stirrer, manufactured by the Parr Instrument Company, USA. Twenty-two gram oven- dry basis of pulp sample was mixed with 0.5 magnesium sulfate and 2.5 sodium hydroxide and distilled water was added to adjust the pulp consistency to 10. After the cover was fastened, the air in the autoclave was replaced by oxygen gas through a gas inlet, and the pressure inside the autoclave was kept at 0.55 MPa and 95°C for 30 min. At the end of the deligniication process, the autoclave was cooled and the oxygen pressure was released. The pulp was then washed, spin-dried, and analyzed. The procedures of the improved O, viz. hydrogen peroxide reinforced O O p and anthraquinone AQ aided hydrogen peroxide-reinforced O O pAQ were same as the O, additional hydrogen peroxide and AQ were added according to the amount shown in Table 1. All the chemicals used above were based on oven-dry basis of pulp sample. ISBN : 978-602-17761-4-8 121 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 1. Amount of reinforced additives added to oxygen deligniication. Type of raw material Type of improved O H 2 O 2 , Anthraquinone, SFI hardwood kraft pulp O p 1.4 - O pAQ 1.4 0.04 EFB soda-AQ pulp O p 1.2 - O pAQ 1.2 0.02 Pulp Properties The deligniied pulp was analyzed by the Technical Association of the Pulp and Paper Industry TAPPI T236 2013 to ind the kappa number, TAPPI T230 2008 to establish pulp viscosity, ISO2470 2008 to determine pulp brightness, and TAPPI T282 2013 to determine hexenuronic acid content of the chemical pulp. Bleaching selectivity is deined as the relative reactivity of a bleaching process toward the lignin and carbohydrate components of pulp and it was calculated as the ratio between the difference in kappa number to the difference in pulp viscosity cP before and after the process [5,6]. Analysis of Residual Lignin and Deligniied Pulp by FTIR Absorption Spectroscopy FTIR spectral data were obtained using the potassium bromide KBr pellet technique. Infrared spectra were recorded using a Shimadzu FTIR spectrometer, model 8201PC Japan. Small amounts of sample pulp or lignin were mixed with the KBr powder at a concentration of 1 mg100 mg KBr. The mixture was then ground for 3 to 5 min. The powder was pressed for 2 min to form a KBr pellet. The collar was placed with the pellet onto the sample holder. The spectra were recorded in the absorption band of 4000 to 400 cm−1. Result and Discussion The results demonstrated in Table 1 demonstrated that the kappa number K n reduction of both the hardwood kraft and EFB Soda-AQ pulps by O was not quite impressive, which was limited to not more than 38 and 30 Figure 1, respectively. Hence, it would substantially limit the role of O as the irst bleaching stage in the chlorine-free bleaching sequence. Therefore, to improve the bleaching selectivity of the O, some modiication such as additional of additives or implementation of a pretreatment prior to the deligniication process were carried out. Fig. 1 shows that bleachability of the EFB pulps by O was higher than that of hardwood kraft pulp with the selectivity of 0.63 and 0.53, respectively, even though the latter showed higher kappa number K n reduction Figure 1, it experienced more severe drop in pulp viscosity Table 1. Improved Oxygen Deligniication by Additive Reinforcement As shown in Table 2 and Figure 1, it is quite notably that the additional of hydrogen peroxide into an O, known as H 2 O 2 reinforced O O p , offered a greater improvement on deligniication and brightening effects for both chemical pulps, in which the K n reduction and ISO brightness of hardwood pulp was increased to 55.6 and 52, while those of EFB pulp were increased to 42.1 and 66.8, respectively. The addition of H 2 O 2 in an O causes the generation of more reactive species such as hydropeoxide anion HO 2 -, hydroxyl radical OH· and superoxide anion radical O 2 · - due to the decomposition of H 2 O 2 [2,5]. Since the generated radicals react actively with organic compounds, they would degrade the residual lignin in the pulp and at the same time destroy the chromophoric structures in lignin. As a result, it increased both the kappa number reduction and pulp brightness. However, since the radical reactive species generated in the system attacked both lignin and carbohydrates unselectively, the cellulose degradation was accelerated as well [2,5-7]. Nevertheless, in comparison to deligniication, the effect of ISBN : 978-602-17761-4-8 122 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech hydrogen peroxide on cellulose degradation was relatively smaller, and thus, ended up that the bleaching selectivity of the hardwood kraft and EFB pulps was improved to 0.71 and 0.74, respectively Figure 2. Table 2. Bleaching conditions of oxygen and improved oxygen deligniication Pretreatment Stage Deligniication Stage Responses 360nm UV Exposure time, min Type of Oxygen Deligniication Kappa Number Pulp Viscosity cP Brightness ISO, Hexenuronic acid, μmolg SFI Hardwood Unbleached pulp 16.4±0.4 30.4±0.3 36.0±1.8 55.5±2.3 - O 10.2±0.2 18.7±0.1 43.2±1.5 49.3±3.1 - O p -stage 7.3±0.5 17.5±0.5 52.0±1.8 52.6±5.7 - O pAQ -stage 8.4±0.2 20.4±0.2 52.6±1.8 46.2±6.3 30 O 7.6±0.1 21.7±0.4 47.8±2.3 24.8±2.9 30 O p -stage 6.7 ±0.2 17.1±0.5 60.3±0.9 20.4±3.1 30 O pAQ -stage 7.2±0.5 18.3±0.2 50.9±1.2 28.0±2.0 EFB Soda-AQ Unbleached pulp 11.1±0.3 18.8±0.4 47.5±0.6 47.2±2.3 - O 7.8±0.4 13.6±0.5 55.3±1.2 42.9±3.2 - O p -stage 6.4±0.2 12.5±0.3 66.8±1.1 40.7±3.9 - O pAQ -stage 7.2±0.3 14.2±0.4 65.6±0.9 41.3±4.3 30 O 6.9±0.1 15.1±0.5 56.9±1.3 20.9±4.6 30 O p -stage 5.9±0.3 13.1±0.4 67.0±0.5 18.9±3.6 30 O pAQ -stage 6.3±0.2 14.6±0.3 65.1±0.7 22.6±3.3 On the other hand, the addition of an optimum amount of anthraquinone AQ in an O p , named as AQ- aided H 2 O 2 reinforced O O pAQ , was capable of preserving the cellulose from degradation. As shown in Table 2, the pulp viscosities of both hardwood and EFB pulps were retained even higher than that of the ordinary O one. Different from O p , which its selectivity was increased mainly due to the extended deligniication, the O pAQ improved the bleaching selectivity through both carbohydrate stabilization and extended deligniication. Nevertheless, in comparison to O p , the K n reduction of O pAQ was lesser. Fig. 1. Kappa number reduction of oxygen deligniied pulps with and without modiication According to previous studies, when AQ was added in an alkaline bleaching system, it would reduce to anthrahydroquinone AHQ through oxidizing cellulose reducing end groups to alkali-stale aldonic acid groups. Since AHQ was readily being oxidized by strong oxidants such as hydroxyl radicals, thus, ISBN : 978-602-17761-4-8 123 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech the AQ added in the bleaching system acted as a hydroxyl radical scavenger [5-6,8-9] and therefore might diminish the happening of cellulose degradation caused by hydroxyl radical. However, at the same time the deligniication due to radical attack was also moderated. Even so, there was no signiicant effect of AQ on the pulp brightness as the O pAQ bleached hardwood and EFB pulps remained the same brightness as O p bleached pulped. On the other hand, improved O by O p and O pAQ did not show signiicant effect on the reduction of the hexenuronic acid HexA content for both the pulps used in this study. This indicated that the addition of the additives hydrogen peroxide and AQ in the O did not help in reducing the HexA content. By comparing the hardwood pulp and EFB pulp, it was found that O pAQ gave better improvement on bleaching selectivity to the former 37.7 than the latter 23.8. Nevertheless, due to the initial properties of the unbleached pulp, the EFB Soda-AQ pulp achieved lower K n and higher ISO brightness. Improved Oxygen Deligniication by Photo Pretreatment The application of UV photo pretreatment for only 30 min prior to O on both chemical pulps showed positive effects on deligniication and pulp viscosity preservation. As shown in Table 2, the K n of both hardwood and EFB pulps was reduced to 7.6 and 6.9, hence the K n reduction was enhanced to 57.3 and 37.8 Figure 1, respectively. On the other hand, it was very surprise to see that the increase of deligniication by the photo pretreatment not only did not cause more serious cellulose degradation, it even diminished cellulose degradation during the subsequent O and thus, enhanced the bleaching selectivity of the hardwood and EFB pulps to 1.01 and 1.14 Figure 2, respectively, which accounted to 90 and 80 improvement on selectivity. Moreover, photo pretreatment also showed an overwhelming effect of on eliminating HexA from pulp. The Ph-O was capable of removing more than 55 of HexA from both the unbleached pulps, which was much more effective than the ordinary O or even improved Os Op and O pAQ . As reported by many researchers, HexA groups could be only hydrolysed under drastic acidic condition and which was strongly inluenced by reaction temperature and pH [13,14]. However, in this study, a simple photo pretreatment in mild acidic medium pH5 for 30 min without heating process could easily remove the HexA more than 50. It was believed that the unsaturated double bonds in the HexA could absorb the energyproton released from the irradiation process and subsequently initiated the hydrolysis of the HexA [15,16]. Nevertheless, the Ph-O pulp showed merely a small improvement on pulp brightness in comparison to the O as there was no additional brightening agent such as H 2 O 2 added. Based on the results of the two chemical pulps, it was found that the UV photo-pre-treatment was applicable on different pulps and gave the similar effect as well. Nevertheless, the augmentation of selectivity of EFB pulp was better than that of hardwood pulp. On the other hand, the enhancement of K n reduction of latter was much greater than that of the former. This was possibly due the initial K n of unbleached EFB pulp was rather low and might contain lesser phenolic groups, which are easier to be attacked under alkaline O, it its residual lignin. Fig. 2. Selectivity of oxygen deligniication with and without modiication. ISBN : 978-602-17761-4-8 124 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Improved Oxygen Deligniication by Combination of Photo Pretreatment and Additives Reinforcement Both the additive reinforced O and photo-pre-treatment O were capable of improving the bleaching selectivity of the two chemical pulps with different approaches. Furthermore the former enhanced the brightness increment while the latter increased the removal of HexA. However, based on the results in Table 2, the combination of both approaches offered merely slightly increase in K n reduction but there was no further improvement on the bleaching selectivity. This indicated that single modiication of O might have achieved the asymptotical limit of deligniication, therefore, the extended deligniication become least feasible. Nevertheless, the resultant pulp bleached by combination approaches attained the beneits of higher pulp brightness and low in HexA content, which were never achieved at once by applying only single approach neither via additive reinforcement nor photo pretreatment. Based on selectivity, the combination modiication of O was more workable for EFB pulp than hardwood pulp, wherein the selectivity of the EFB Ph-O p and Ph-O pAQ was still retained considerably high whereas the selectivity of both the hardwood bleached by combination approaches was lower than that of single approach. Conclusion The modiications of oxygen deligniication O by additives reinforcement and pre-treatment were successfully improved the performance of O in all aspects—kappa number reduction, pulp viscosity preservation, brightness increment and removal of hexenuronic acid. Additive reinforcement gave better effect on brightness increment whilst the photo pretreatment enhanced the cellulose stability and removal of hexenuronic acid. In comparison to single approach, modiication of O by combination approaches attained the beneits of both higher pulp brightness and lower in HexA content. The effect of improved O on the hardwood pulp and EFB pulps was basically in similar trend. Based on the improvement of selectivity, the photo-pretreatment and combination modiication of O was more workable for EFB pulp than hardwood pulp Acknowledgment The authors would like to acknowledge the inancial support from grants funded by Universiti Sains Malaysia [FRGS Grant 203-PTEKIND6711327] and USM fellowships scheme and scholarship sponsored by the Ministry of Higher Education MOHE Malaysia Mybrain15 MyPhD to Miss Chong Yin Hui. References 1. Barroca MJMC, Marques PJTS, Seco IM and Castro JAAM. selectivity studies of oxygen and chlorines dioxide in the pre-deligniication stages of a heardwood pulp bleaching plant. Ind Eng Chem Res 2001; 40:5680-5685 2. Suchy M and Argyropoulos DS. Catalysis and activation of oxygen and peroxide deligniication of chemical pulps: A review. TAPPI J 2002; 7854:2-43 3. Ismail D and Guniz G. Dimensionless parameter approach for oxygen deligniication kinetics. Ind Eng Chem Res 2008; 4716: 5871–5878 4. Leh CP, Wan Rosli WD, Zainuddin Z and Tanaka R Optimization of oxygen deligniication in production of totally chlorine-free cellulose pulps from oil palm empty fruit bunch ibre. Ind Crop Prod 2008; 28:260-267 5. Ng SH, Ghazali A, and Leh CP. Anthraquinone-aided hydrogen peroxide reinforced oxygen deligniication of oil palm Elaeis guineensis EFB pulp: A two-level factorial design. Cell Chem Technol 2011; 451-2:77-87 6. Chong YH, Ng SH, and Leh CP. Improved oxygen deligniication selectivity of oil palm EFB Soda- AQ pulp: Effect of photo pre-treatment and AQ-aided H 2 O 2 reinforcement. Cell Chem Technol 2013; 473-4:277-283 ISBN : 978-602-17761-4-8 125 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 7. Sun YP, Kien Loi NY and Wallis AFA. Totally chlorine-free TCF bleaching of radiata pine kraft pulp involving a UV-peroxide stage. APPITA J 1996; 49:96-99 8. Liu Z, Cao Y, Yao H, and Wu S. Oxygen deligniication of wheat straw soda pulp with anthraquinone addition. BioResources 2013; 81:1306-1319 9. Dence CW and Reeve DW. Pulp Bleaching: Principles and Practice. Atlanta, GA: Tappi Press; 1996, pp. 213-239. 10. Hon DNS. Photochemical degradation of lignocellulosic materials. In Grassie, N. Ed. Developments in Polymer Degradation-3. London: Applied Science Ltd; 1983, p 229-281 11. Bikova T and Treimanis A. UV-absorbance of oxidized xylan and monocarboxyl cellulose in alkaline solutions. Carbohyd Polym 2004; 553: 315-322 12. Sjöström E. Wood chemistry: Fundamentals and applications. San Diego: Academic Press Inc; 1993 13. Jiang ZH, Audet A, Sullivan J, Lierop BV and Berry R. A new method for quantifying hexenuronic acid groups in chemical pulps. Pulp Pap Sci 2001; 273:92-97 14. Vuorinen T, Burchet J, Teleman A and Fagerstrom P. Selective hydrolysis of hexenuronic acid groups and its application in ECF and TCF bleaching of krafts pulps. Pulp Pap Sci 1997; 255:155-162 15. Sixta H and Rutkowska EW. Comprehensive kinetic study on kraft pulping of Eucalyptus Globulus Part 2. O Papel 2007; 682: 68-81. 16. Bajpai P. Environmentally Benign Approaches for Pulp Bleaching. Amsterdam, The Netherlands: Elsevier, 1st Edition; 2005 ISBN : 978-602-17761-4-8 126 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 127 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech GREEN TECHNOLOGY IN THE PULP INDUSTRY Dominique Lachenal 1 , Christine Chirat Grenoble INP-Pagora BP 65, 38402 Saint Martin d’Hères Cedex France, 1 dominique.lachenalgrenoble-inp.fr ABSTRACT Kraft cooking and ECF bleaching has become the universal way of producing cellulose pulp ibers from wood. These processes have been so well optimized that impressive progresses have been made in the last decades in reducing the environmental impact of pulp manufacture. However there is still some matter of improvement. Two on-going new developments are presented in this paper. The irst one concerns the conversion of pulping process into a bioreinery operation in which prehydrolysis is performed prior to cooking. Such an approach is already an industrial reality for the production of dissolving pulp. In a near future the prehydrolysis iltrate will be recovered since it represents an important source of hemicellulosic sugars. The main point discussed here is that after prehydrolysis, cooking is much easier. Among the likely reasons are the lower occurrence of lignin carbohydrate linkages, the cleavage of some ether bonds and the better accessibility of the lignin. The change in kinetics is such that the kraft cook could be replaced by a soda cook. In an optimum situation the caustic soda cook is stopped at higher kappa number and is continued by an extensive oxygen deligniication. Using a sulfur free caustic soda cook in place of a kraft cook represents a major process simpliication and a move toward greener technology. The second development deals with the implementation of green bleaching for chemical pulps. Because the common bleaching process uses chlorine dioxide, it remains the cause of signiicant water consumption, release of organic materials in the aqueous efluent and formation of hazardous chlorinated compounds. Replacing chlorine dioxide by ozone is a most straightforward means to develop an environmentally friendly bleaching process. Ozone offers many advantages compared to chlorine dioxide: it is a more powerful oxidant, it produces a chloride-free efluent that can be recovered and burnt. Ozone-based totally chlorine-free sequences are proposed which do not affect pulp quality and are economically attractive. These improvements have been made possible thanks to close examination of the chemistry of ozone with pulp components. It is thought that pulping and bleaching operations will necessarily evolve in a near future because a green product such as cellulose deserves to be produced by the best available technologies. Keywords: sulphur-free cooking; caustic soda cooking; prehydrolysis; totally chlorine-free bleaching; ozone Introduction The kraft process has become the universal way of producing cellulose for paper making. The reason is the unbeatable quality of the extracted cellulose ibres and the overall eficiency of the process which allows for the production of cellulose from wood without any consumption of the cooking chemicals which are entirely recovered, and with a marginal use of fossil fuel, the energy needed being provided by the combustion of the cooking liquor which contains around 50 of the original weight of the processed wood. The energy balance is so favourable that the kraft pulp mills are net producers of energy under the form of green electricity. No other process so far has met such records. However, despite its global performance, the kraft process suffers from several drawbacks: • more than 50 of the wood components lignin and most of the hemicelluloses are burned, which is not the most valuable usage of these sophisticated macromolecules. • methylmercaptan and dimethyl sulphide are released in the atmosphere. Although they do not present any toxicity, their smell is spoiling the environment of a kraft pulp mill over dozens of kilometres. Progress has been made to capture these gases at their point of emission, but the odour problem can only be eficiently tackled in new kraft pulp mills. • bleaching of the kraft cellulosic ibres still uses chlorinated organic chemicals mainly chlorine ISBN : 978-602-17761-4-8 128 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech dioxide. This practice not only generates potentially toxic chlorinated chemicals but also prevents the combustion of the bleaching efluent because it contains chloride ions. As a result, bleaching is by far the main contributor to the water pollution of a kraft pulp mill. This paper summarizes the research efforts which address these problems and will contribute to the development of a sustainable cellulose industry. The Kraft Bioreinery Concept Converting a kraft pulp mill to a bioreinery represents the most realistic mean to develop a sustainable production of chemicals from lignocellulosic biomass. In theory, many other processes may be used to this purpose. They are not described here. For many reasons, it makes more sense and is technically and economically more attractive to take proit of existing cellulose production mills to develop such a chemical platform. The challenges are then to extract the hemicelluloses prior to the deligniication and to recover some of the lignin dissolved in the cooking liquor, which are today industrially feasible. Therefore, many people consider that pulp mills are going to be the future large scale bioreineries. One example will be the start up in 2017 of the new Metsa mill at Aanekoski in Finland which should produce both 1.3 million tons of cellulose per year and a series of bioproducts and biofuels, including sulfuric acid, methanol, textile ibres, lignin derivatives, fertilizers, biogas [1]. Figure 1 gives a general scheme of a kraft bioreinery. In this process the wood is treated at high temperature with vapor prior to kraft cooking. During this step named autohydrolysis, the hemicelluloses are depolymerized and made soluble in water. Part of them is recovered as simple sugars or oligomers which may be the raw material for sugar chemistry [2]. Some of the lignin present in the liquor after cooking is precipitated and recovered as a source of phenolic compounds. However the drawbacks of the kraft process are not addressed. Moreover, the presence of sulfur in the recovered lignin may be a problem for subsequent applications. Our recent work has been devoted to the understanding of the reactions taking place during the autohydrolysis step. Figure 1. Scheme of the kraft bioreinery mill

2.1 Impact of Autohydrolysis on Lignin and Lignin-Carbohydrates Complexes

In wood, lignin and carbohydrates are covalently linked. Several types of linkages have been described. Some of them will not be cleaved during the kraft process which means that even though lignin is depolymerized, it may not go into solution. This hinders lignin removal and contributes to the well known fact that residual deligniication has a very slow rate. The quantity of lignin linked to ISBN : 978-602-17761-4-8 129 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech carbohydrates LCC has been investigated for both hardwood mixed and softwood. The procedure for the measurement of LCC was adopted from Due et al 2013 [3]. Table 1 shows that most of the lignin in wood is linked to carbohydrates. After hydrolysis, it is clear that in softwood some lignin carbohydrates linkages are cleaved, since some lignin is left free of carbohydrates. This demonstrates that autohydrolysis has the capability of detaching some lignin from the carbohydrates. In hardwood lignin remains linked to carbohydrates. However it does not mean that no lignin carbohydrates linkages have been cleaved since one lignin molecule may be originally linked to carbohydrates at many locations. The lower proportion of carbohydrates engaged in LCC after autohydrolysis can be consistent with the cleavage of lignin carbohydrates bonds [4]. This should help deligniication. The effect of autohydrolysis on lignin itself is dificult to study. The reason is that, due to the lack of in situ analytical techniques, lignin is usually extracted by acidolysis for analysis. This extraction procedure is known to introduce some modiication to the lignin, which weakens the validity of the conclusions. We have developed an in situ method to measure the phenolic OH groups [5]. The method is based on the fact that at low temperature chlorine dioxide reacts exclusively with the free phenolic groups in lignin. The consumption of chlorine dioxide is then correlated to the content in these groups the higher the ClO 2 consumption, the higher is the phenolic OH content. Some secondary reactions may happen and consume further ClO 2 . However at low temperature 0°C here and appropriate pH phosphate buffer pH 6.7 the extent of these reactions is minimized. Figure 2 compares the consumption of ClO 2 for hardwood chips before and after autohydrolysis. It appears that autohydrolysis introduces new free phenolic groups. Since these groups originate from the cleavage of aryl ether linkages, one may conclude that partial depolymerisation of lignin occurs during autohydrolysis, at least in a irst step, since the possibility of recondensation of lignin fragments cannot be totally excluded. Table 1. Proportion of lignin and carbohydrates engaged in LCC before and after prehydrolysis of softwood and hardwood chips Ratio LCCwood Lignin in LCCs lignin in wood GGM in LCCs GGM in wood Xylans in LCC xylans in wood Cellulose in LCCs cellulose in wood Control softwood 0.98 0.61 0.63 0.83 Prehydrolysed softwood 0.79 0.66 0.41 0.81 Control hardwood 0.92 0.67 1.03 0.83 Prehydrolysed hardwood 0.90 0.47 0.86 0.62 Note: The values do not take into consideration the acetyl and methylglucuronic acid groups in carbohydrates. Figure 2. Consumption of ClO 2 by milled hardwood chips before and after autohydrolysis 0°C, pH 6.7 ISBN : 978-602-17761-4-8 130 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech As a consequence, cooking should be much facilitated after autohydrolysis. Moreover the removal of part of the hemicelluloses which are the main responsible for caustic soda consumption should allow for a substantial decrease in the alkali requirement. Finally, the departure of hemicelluloses must have resulted in a more porous and accessible lignocellulose matrix. This has not been investigated so far but appears logical. Many trials have conirmed that kraft cooking is much easier after autohydrolysis.

2.2 Replacing The Kraft Cook by A Caustic Soda Cook

Considering the effect of the autohydrolysis step on lignin-carbohydrate bonds and lignin structures, alkaline deligniication must be much easier, which is actually observed. Then, replacing the kraft cook by the simple sulphur-free caustic soda cook becomes possible. Table 2 illustrates the exceptionally good performance of the caustic soda deligniication after prehydrolysis in the case of Eucalyptus Globulus. Even though the residual lignin content visualized by the corrected kappa number is higher after NaOH cook, its absolute value is quite acceptable. After oxygen deligniication a very low residual lignin is reached. Therefore, in the perspective of bioreinery the caustic soda cooking process associated with autohydrolysis allows for the production of high quality cellulose, sugars monomers and oligomers and for the availability of a sulfur-free lignin. Bleaching may still be an issue. However the next part of this paper will detail the progress which has been made to develop a high performance totally chlorine- free bleaching process. Table 2. NaOH cooking of prehydrolysed PH Eucalyptus chips. Comparison to Kraft cooking of untreated chips. Pretreatment Cooking process Kappa number Kappa number corrected HexA, µmolg DPv Xylans, Cooking Yield Kappa number after O no Kraft 165°C 16.2 9.5 66.4 1460 17.3 51.2 2.4 PH 160°C NaOH AQ 155°C 9.5 9.2 3.1 1500 2.5 52.8 2.9 PH 160°C NaOH 165°C 17.0 16.4 3.6 1580 2.3 51.0 5.0 Kraft: Effective Alkali 23, 30 sulidity, LW ratio 3.5, 45 min NaOH cooking: 18.9 NaOH, LW ratio 3.5, 0.1 AQ NaOH AQ, 45 min PH : 160°C, LW ratio 3, 2 h HexA contribution is substracted 10 µmolg hexA = 1 kappa unit O oxygen deligniication : 100°C, 1 h, 0.3 MgSO 4 , 7H 2 O, 5 bars O 2 , 1 NaOH for Kraft and NaOH AQ pulps, and 1.5 for NaOH pulp AQ: Anthraquinone Green Bleaching Pulp bleaching with oxygen derived reagents green bleaching would offer many advantages for the sustainability of a cellulose production unit: • no AOX formed, • no chloride ions in the bleaching efluent • lower water consumption because of the possible recovery of the bleaching efluent for the washing after oxygen deligniication • possible combustion of the beaching efluent • dramatic reduction of the DBO and DCO charges in the efluent going to the water treatment unit • replacement of caustic soda by oxidized white liquor in the alkaline extraction stages For chemistry reasons green bleaching must include oxygen gas O the cheapest deligniication chemical, ozone Z the most eficient deligniication reagent and hydrogen peroxide P the better whitening agent for the removal of the last chromophores. However some oxidation of the pulp ISBN : 978-602-17761-4-8 131 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech carbohydrates takes place, which results in lower pulp viscosity. Ozone is partly responsible for this drawback. Ozone is a powerful delignifying agent which reacts very readily with unsaturated organic compounds. Applied to the phenolic moieties, this reaction causes lignin degradation and dissolution. The parallel degradation of cellulose during pulp ozonation is generally explained by the formation of hydroxyl radicals when ozone reacts with lignin. We have found that the formation of hydroxyl radicals is much more general than anticipated since it occurs also when non aromatic carbon-carbon double bonds react with ozone [6]. Acetovanillone, maleic acid, and 2,5-dimethyl 2,4-hexadienedioic acid which are models for lignin, HexA and muconic acids respectively Figure 3 were treated by ozone under the conditions of pulp ozone deligniication and the formation of hydroxyl radicals was followed by ESR spectroscopy, using 5,5-dimethyl-pyrrolidine-1-oxyl DMPO as the spin trapping substance. In all cases, OH radicals were observed Figure 4. Several blank experiments, including the addition of H 2 O 2 , one possible product of the Criegee general reaction, indicated that the OH radicals would result from the direct reaction of ozone with the compound. This inding suggests that OH radicals are formed not only when ozone reacts with lignin, but also with hexenuronic acids hexA, and muconic acid derivatives which are the primary oxidation products of lignin. Therefore, the key to improved selectivity of ozone deligniication would be to minimize the reaction of ozone with carbon-carbon double bond structures. One way is to reduce the amount of HexA prior to ozone application e.g. by hot acid treatment A. Another way is to limit the presence of muconic acids as much as possible. This can be achieved by splitting the ozone charge and applying an alkaline extraction after each ozonation phase. Some of the muconic acid derivatives formed by the ozone are made soluble and are eliminated in the next washing stage before addition of the new ozone charge. Both ways must be taken in the case of hardwood paper pulp. For softwood paper pulp and dissolving pulps, the content in HexA is generally too small to justify the implementation of A stage. Selective TCF bleaching sequences were designed based on these principles. One promising approach is the AZEZEZE type sequence in which the Z stages are carried out with 1-2 kg O 3 o.d. t pulp in a mixer at 70°C for a very short time, immediately followed by an alkaline extraction at the same temperature. O HOOC OXyl OH OH COOH COOH Acetovanillone Maleic acid HexA COOH COOH HOOC COOH Muconic acid derivative 2,5-dimethyl 2,4-hexadienedioic acid Figure 3. Models used for the detection of OH radicals during ozonation. Structures of HexA and muconic acid derivative are given for comparison. ISBN : 978-602-17761-4-8 132 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Figure 4. ESR signal given by a solution of maleic acid MA during ozonation in the presence of DMPO An example of bleaching line lowsheet is given in Figure 5. The whole sequence is carried out at medium consistency. The A Q stage is a high temperature 90°C acid pH 3.0 treatment 2h. Q stands for chelating agent like EDTA. Q is optional. The A efluent is released to the water treatment plant. This efluent contains most of the metal ions present in the pulp before bleaching. Countercurrent washing of the 3-stage ZEZEP sequence is proposed here with fresh water added at the P wash press. The corresponding alkaline efluent is used to wash the pulp after oxygen deligniication in combination with fresh water. One drawback of the sequence is the higher consumption of caustic soda. In theory oxidized white liquor might be used since the alkaline efluents are ultimately burned in the recovery furnace of the mill. Then extensive oxidation should be performed to be able to use oxidized white liquor in P. If not, some other efluent recycling strategies will have to be looked for. Figure 5. Flowsheet of the AZEZEP sequence for the bleaching of eucalyptus kraft paper pulp Two sequences are proposed where the alkaline extraction stages are reinforced with oxygen and where hydrogen peroxide is added at the end to destroy the last colored chromophores and improve brightness stability: AZEoZEoP for paper pulp Table 3 and ZEoZEoZP for dissolving pulp Table 4 [7]. We have shown that they lead to pulp qualities equivalent to their ECF counterparts. ISBN : 978-602-17761-4-8 133 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 3. Chlorine-free bleaching sequence for eucalyptus kraft paper pulp Kappa number 9 after oxygen deligniication Treatment ClO 3 on pulp O 3 on pulp H 2 O 2 on pulp NaOH on pulp Brightness DP No - 60 1350 D hot EpDP 0.55+0.25 0.35+0.2 1+0.8 90.5 1180 ZEoP 0.8 0.6 1+1 86 800 A Q ZE o ZE o P - 0.25+0.18 0.6 1.1+1.1+0.8 90.5 1000 Table 4. Chlorine-free bleaching sequence for eucalyptus prehydrolysis- Kraft dissolving pulp Kappa number 3.0 after oxygen deligniication Treatment ClO 2 on pulp O 3 on pulp H 2 O 2 on pulp NaOH on pulp Brightness DP No - 57 920 D E o pDP 0.4+0.4 0.1+0.1 1+0.5 89 740 ZP - 0.4 0.6 0.8 86 400 ZE o ZE o ZP - 0.1+0.1+0.1 0.2 1+1+1 90 620 Conclusion Although cellulose manufacture has already reached a high degree of sustainability, some improvements are still possible. Among them, the recovery of sugars and oligomers from the wood hemicelluloses prior to cooking by autohydrolysis allows for the conversion of the kaft process to caustic soda process. This change is possible because deligniication is made easier by the effect of the acidic conditions and the removal of hemicelluloses. Sulfur-free cooking will simplfy the mill operations, reduce the impact on the air in the vicinity of the mill and improve the potential quality of the lignin which may be extracted from the black liquor. Another progress would be the development of a new generation of chlorine-free bleaching process based on the implementation of multi-stage ozonation. Because most of the washing iltrates can be recovered and ultimately burned, this change may reduce the impact of bleaching on water consumption and efluent quality. References 1. http:bioproductmill.comarticlesmetsa-group-to-build-next-generation-bioproduct-mill-in- aanekoski 2. Boucher et al . Extraction of hemicelluloses from wood in a pulp bioreinery, and subsequent fermentation into ethanol, Energy Conversion and Management 2014; 88:1120–1126. 3. Due et al. Universal fractionation of lignin–carbohydrate complexes LCCs from lignocellulosic biomass: an example using spruce wood, Plant J. 2013;74:328-338. 4. Claire Monot et al. Characterisation of lignin and lignin-carbohydrate complexes in control and prehydrolysed wood chips, Holzforschung, 2017 to be published. 5. Delmas et al. Titration of free phenolic groups in pulps, Holzforschung 2009;63:705-710. 6. Pouyet et al. On the origin of cellulose depolymerization during ozone treatment of hardwood kraft pulp, Bioresources 2013;84:5289-5298. 7. Perrin et al. New chlorine-free bleaching for dissolving pulp production presented at 18 th ISWFPC. Vienna; 2015. ISBN : 978-602-17761-4-8 134 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 135 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech EFFECT OF RATIO LIQUID WASTE OF OUTPUT SEDIMENTATION AND FERMENTATION BIOGAS FROM PALM OIL MILL EFFLUENT POME ON BIOFERTILIZER PRODUCTION Martha Aznury 1 , Robert Junaidi, Jaksen M. Amin, Victor Alberto Valentino Department of Chemical Engineering, Politeknik Negeri Sriwijaya, Palembang Jl. Srijaya Negara Bukit Besar,Palembang 30139, Indonesia 1 martha_aznurypolsri.ac.id ABSTRACT Palm oil mill efluent POME can pollute the waters because of high organic matter content, low acidity levels, and contain macro nutrients such as nitrogen N, phosphorus P and potassium K that need treatment before being discharged to the river. Palm oil mill efluent when processed exactly it will produce biogas. Palm oil mill efluent is processed into biogas will produce of liquid waste from output sedimentation and fermentation biogas digester. This study aims to determine effect ratio of output sedimentation and fermentation biogas digester for liquid organic to biofertilizer. The method used is anaerobic fermentation process in two stages from two outputs biogas digester. Variables measured are the ratio of liquid waste volume percent of the output of biogas and bio-activator additions. The results of ratio 10:0 sedimitation: fermentation with bio-activator showed nitrogen, phosphorus, potassium 2.66, 0.07, 1.11, approximately. The highest result without the addition of bio-activator with ratio 10:0 had2.44, 0.07 and 1.03, nitrogen, phosphorus, and potassium, approximately Keywords: Palm oil mill efluent, biogas, sedimentation, fermentation, biofertilizer Introduction Palm oil mill efluent POME from palm oil industries contained substances high organic and macro nutrients such as nitrogen N, phosphorus P and potassium K. POME needs treatment before being discharged in the bank of river Eyrani, 2014. If the waste is not managed well and just directly discharged waters it will be very disturbing the surrounding environment. Most industries would dispose of waste are required to process them beforehand to prevent contamination of the surrounding environment Widhiastuti et al, 2006. POME cannot be directly discharged to the river n because it has a concentration of Chemical Oxygen Demand COD is high to 50,000 mg Ibrahim et al., 2013. POME can generate on biogas production and waste. Waste biogas was through from sedimentation and fermentation could be used as bio fertilizer, which contains organic substances. POME due process in bioreactors is methanogenesis fermentation which will also produce organic substances. The rest of the biogas output has undergone anaerobic fermentation so that it can be directly used to fertilize crops. Organic fertilizers including compound fertilizer because it contains nutrient more than one element and micronutrients. The content of nutrients in bio fertilizer was not high when compared to inorganic fertilizer but bio fertilizer could to improve the nature of physical and biological soil, loosening soil surface layer, increase the number of microorganisms, as well as increase the absorption and store water so that the whole can improve soil fertility. Bio fertilizers produced from waste biogas output is organic fertilizer as the main material is organic waste. Waste output in the form of biogas and liquid slurry. The waste can be processed into liquid bio fertilizer. Bio fertilizer itself has several advantages over solid organic fertilizer for application more easily and nutrients contained therein more easily absorbed by plants. Processing biogas output is expected to reduce the waste from the biogas output resulting in lower levels of pollution to the environment. The process of composting or anaerobic decay of organic material is carried by the microorganisms in the fermentation process Polprasert, 1980. The nutrient content of the waste contained biogas can be seen in Table 1. ISBN : 978-602-17761-4-8 136 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 1. Nutrient Content of Waste Biogas Material N P 2 O 5 K 2 O Solid 0.64 0.22 0.24 Liquid 1.00 0.02 1.08 Junus, 1998 Table 1 shows the nutrient content of the output from biogas installations which are a by-product of anaerobic composting system that is free of pathogenic bacteria and can be used as fertilizer to maintain soil fertility and increase crop production Food and Agriculture Organization, 1997. Efluent contains macro elements that are essential for plant growth as an element of N, P, K, and micro elements, namely Cu, Fe, Mg, S, and Zn Suzuki et al ., 2001. Park 1984 stated that the efluent from biogas if used as fertilizer for crops can improve agricultural yields and improve soil fertility. Fermentation is a process in which the chemical components generated as a result of the growth and metabolism of microbes. Bio fertilizer production process can be accelerated by the addition of bio- activator that is a source of microorganisms. Microorganism activity is inluenced by concentration of sugar as sucrose contained in the sugar solution is the substrate that is easily digested and utilized for growth of microorganisms. Bio fertilizer production by the fermentation of success marked by a white coating on the surface, a characteristic odour, and colour changes from green to brown and fertilizer produced brownish yellow. White coating on the surface of the fertilizer is actinomycetes, which kinds of mushrooms grow after bio fertilizer production [6]. Based on this, the authors conducted a study of POME by utilizing the output of the digester sedimentation and fermentation biogas production. The output of the sedimentation and fermentation is directly discharged into the environment can damage the soil and pollute the environment. It is necessary for the processing of these outputs by anaerobic fermentation process using gallons media to be more effective and eficient. Bio fertilizer as a product can be applied to oil palm plantations for itself and other plants. Output processing using gallons media this is an effective and eficient in terms of place, time, and cost of processing. The purposes of this study include: 1. Utilize a byproduct of sedimentation and fermentation digester output into bio fertilizer. 2. Obtain appropriate concentration variation between the byproduct of the digester output sedimentation and fermentation digester to be used as organic manure. 3. Determine the inluence of bio-activator to the content of N, P, and K are produced from bio fertilizer. Methodology Palm oil mill efluent POME from PT. Mitra Ogan Tbk was fermented with activator microorganism activator from cow manure obtained from slaughter houses in Gandus area, as well as the chemicals used are available in the laboratory of Chemical Engineering Department of the Polytechnic of Sriwijaya. In the output processing efluent from sedimentation and fermentation biogas digester uses advanced anaerobic fermentation methods using such media gallon. Both liquid waste digester biogas output will be used as organic manure by using anaerobic fermentation in the media about a gallon for 10 days. Production of bio fertilizer will be the effect of comparisons percent bio-activator volume and also inluence the nutrient content contained in the organic fertilizer will be produced. Process Preparation of raw materials 1. Tools a. Funnel b. Jerry can c. Bucket 2. Procedure: a. Opening the pipeline that is below bioreactors biogas. b. Accommodate the output from the digester sedimentation and fermentation into jerry cans and return pipe shut bioreactor. ISBN : 978-602-17761-4-8 137 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Output from Fermentation Digester Output from Sedimentation Digester Figure 1.Output from Sedimentation and Fermentation Digester. Fermentation Process 1. Materials and Equipment a. Materials • Materials from output sedimentation and fermentation biogas digester • bio-activator EM 4 • Brown sugar • Water b. Tools • Gallons of water 2.5 liter • Hose • Plasticine • Measure Iwaki glass 500 mL • Cutter • Knife • Plastic bottles of 600 mL • Former syrup bottles 2. Procedure: a. Prepared materials as follows: the liquid waste digester output sedimentation and fermentation that has been accommodated, 54 grams sugar, 27 mL of bio-activator and water at a certain ratio. b. Gallons of water prepared as media fertilizer, 1 meter transparent aerator hose diameter approximately 0.5 cm, and plastic bottles of 600 mL size. Close gallon sized perforated hose aerator. c. The second output of the biogas digester was added to a gallon by comparison as follows: Ratio of output of sedimentation and fermentation digesters in sample 1, 2, 3, 4, 5, and 6 can be seen in Table 2. Table 2. Ratio of output of sedimentation and fermentation digester with number of sample Output Digester vv Sample 1 2 3 4 5 6 Sedimentation 20 40 60 20 Fermentation 100 80 60 40 80 100 ISBN : 978-602-17761-4-8 138 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Analysis Procedures Having obtained a bio fertilizer through a fermentation process, then did the analysis procedure. The analysis includes the determination of macro and micro levels of bio fertilizer by using Atomic Absorption Spectroscopic AAS and UV Spectrophotometer for Chemical Oxygen Demand COD and Biological Oxygen Demand BOD. Procedure BOD and COD used SNI 6989.2-2009 Determination of concentration nitrogen in bio fertilizer used ISO 2803: 2010. Analysis of levels Phosphorus used ISO 2803: 2010 and concentration potassium used SNI 2803:2010. Results Preliminary Analysis of Bio fertilizer In the initial analysis of bio fertilizer from output of sedimentation and fermentation digesters add bio- activator and without bio-activator. Results samples with the addition of bio-activator, nitrogen obtained ranged from 1.0211 to 1.4150, while the sample without the addition of bio-activator have 0.9981 to 1.3878 nitrogen. In a phosphorus element analysis for samples with the addition of bio-activator have ranged from 0.0352 to 0.0488, and without bio-activator phosphorus have ranged from 0.0352 to 0.0439. The content of phosphorus is very small because it is based on Junus 1998 mentions that are element phosphorus contain in the waste liquid biogas that is equal to 0.02. The content of the element potassium in bio fertilizer in the initial analysis for samples with the addition of bio-activator ranged from 0.8341 to 0.8843, and without the addition of bio-activator ranges from 0.8172 to 0.8743. The content contained in the initial organic liquid fertilizer that has not actually meet the standards fermented bio fertilizer based on the Minister of Agriculture No.28 Permentan OT.140 22009 is 2. But the elements of value Nitrogen, phosphorus, and potassium need to be improved in order to produce a bio fertilizer which has a better quality. That was why a process of anaerobic fermentation to enhance the existing content in the liquid organic fertilizer. Anaerobic fermentation processing is preferred because it carried the potential for handling POME because it has the characteristics of organic matter Zhang et al. 2008. Nitrogen Analysis Nitrogen N is an essential macro nutrient that is needed for growth in the bio fertilizer plant. Nitrogen serves to prepare proteins that function in the metabolism of plants which will further stimulate cell division and elongation Parman, 2007. The results of the analysis of the nitrogen content can be seen in Figure 2. Figure 2. Concentration Nitrogen after Fermentation Anaerobic Treatment ISBN : 978-602-17761-4-8 139 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech From Figure 2 it can be seen that the nitrogen content after the process of anaerobic fermentation ranged from 1.7853 to 2.6625 of the samples with the addition of bio-activator, while for the samples without the addition of bio-activator obtained nitrogen levels ranged from 1.5257 to 2.4373. From these data it is seen that the samples with the addition of bio-activator tend to have a greater nitrogen content compared to samples without bio-activator. This is because there is a bio-activator in the nitrogen- ixing bacteria, namely Rhodopseudomonas sp. According Koh.et al, 2007, Rhodopseudomonassp bacteria capable of increasing the content of nitrogen in organic fertilizer. The analysis of this study showed that the nitrogen content obtained in this study is still much to exceed the standard liquid organic fertilizer, deined by the Minister of Agriculture No.28 Permentan OT.140 22009 where the required standards, i.e. 2, Provision of excess nitrogen will result in very rapid vegetative growth, leaf colour to dark green, and more fertile, inducing the plant to be susceptible to pests and diseases Prawiranata and Tjondronegoro, 1992. From Figure 2 can also be seen that the nitrogen content was lowest for the irst sample where sample 1 is a sample that contains only the output of the digester fermentation alone. Levels of nitrogen will increase concurrently with increasingly smaller percent volume of fermentation digester. This is because the fermentation digester contains little organic materials compared to the digester sedimentation so that if the mixture contains more fertilizer output from the digester fermentation, the levels of nitrogen obtained will be smaller too. Phosphorous Analysis The element phosphorus P on the plant be functioning in the formation of lowers, fruits, and seeds as well as accelerate the ripening of fruit. Provision of P in adequate amounts can improve the quality of seeds that include the potential for germination and seedling vigour Mugnisjah and Setiawan, 1995. Results of analysis of phosphorus levels after treatment in the anaerobic fermentation can be seen in Figure 3. Figure 3. Concentration Phosphorus after Fermentation Anaerobic Treatment Figure 3 the levels of phosphorus to the sample with the addition of bio-activator ranged from 0.0579 to 0.0701, while for the samples without the addition of bio-activator obtained phosphorus levels ranged from 0.0527 to 0.0689. Phosphorus levels were highest in the study contained in the sample 6 with the addition of bio-activator, is equal to 0.0701, while the lowest levels of phosphorus are present in the sample 1 without the addition of bio-activator. From Figure 3 can also be seen that the addition of bio-activator has a role in increasing the content of phosphorus in bio fertilizer. Phosphorous levels will also increase concurrently with the decrease in percent volume fermentation digester. Levels of phosphorus in liquid organic fertilizer in this study are now eligible liquid organic fertilizer quality standards based on the Minister of Agriculture No.28 Permentan OT.140 22009 is 2. Phosphorus content value is worth very little by Junus 1998 biogas output has value only phosphorus content of 0.02. From the data obtained it was not much different when compared to the research conducted Anwar 2015 mentions that the phosphor obtained by 0.07. According to Manan 2006 P ISBN : 978-602-17761-4-8 140 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech element is also a very important substance, but always in a state of less deep. P element is very important as a source of energy ATP. Therefore, P deiciency can inhibit the growth and reactions of plant metabolism. To increase the content of P fertilizer, during the process of making organic fertilizer can be added-rich material P such as bone meal Prariesta and Winata, 2009. Potassium Levels Potassium K plays a role in the formation of proteins and carbohydrates, hardening of the wooden parts of the plant, increase plant resistance to disease, and improving the quality of seeds and fruits Mulyani, 1994. Results of analysis of potassium levels after processing performed by the anaerobic fermentation can be seen in Figure 4. Figure 4. Concentration Potassium after Fermentation Anaerobic Treatment From Figure 4, the levels of potassium to the sample with the addition of bio-activator ranged from 0.8693 to 1.1055, while for the samples without the addition of bio-activator obtained potassium levels ranged from 0.8574 to 1.0335. Potassium levels were highest in the study contained in the sample 6 with the addition of bio-activator, in the amount of 1.1055, while the lowest potassium levels found in sample 1 without the addition of bio-activator, in the amount of 0.8574. From Figure 4, it can also be seen that the addition of bio-activator has a role in increasing the content of potassium in liquid organic fertilizer. Potassium levels will also increase concurrently with the decrease in percent volume fermentation digester. Potassium levels obtained in this study is greater than the levels of potassium in the research conducted by Anwar 2015 is only 0.07. This is due to the addition of bio-activator that helps in increasing the nutrient content contained in a liquid organic fertilizer. Potassium levels obtained in this study also have to meet the standards set by the Minister of Agriculture No.28PermentanOT.140 22009 is 2. The element potassium is needed by plants because plants that lack the element of K will experience symptoms of dryness at the end of the leaves, especially older leaves. Dry end will increasingly spread to the leaf base. Sometimes it seems like the plants that lack of water. K element deiciencies in fruit trees, affecting the sweet taste of fruit Winata. 1998. Analysis of Chemical Oxygen Demand COD and Biological Oxygen Demand BOD 5 COD value indicates the amount of oxygen needs is equivalent to the content of organic substances in wastewater efluent that can be oxidized by a strong chemical oxidant. Oxidation of organic material produces CO 2 and H 2 O. High COD value in waste biogas output is directly discharged into the water can contaminate the environment. If the waste is directly discharged into the water, then some will sink, decompose slowly, consume dissolved oxygen, causing turbidity, emit a pungent smell and can damage aquatic ecosystems. For the analysis of COD liquid organic fertilizer after processing performed by the anaerobic fermentation can be seen in Figure 5. ISBN : 978-602-17761-4-8 141 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech with without Figure 5. Concentration COD from Bio fertilizer after Fermentation Anaerobic Treatment Figure 5 shows that COD value increases with the addition of bio-activator and the COD value will decrease without a bio-activator. This can be seen in the sample 5 and sample 6 with a bio-activator COD value increased by 310 mgL and 325 mgL approaching the maximum allowed by the government. Viewed from the South Sumatra Governor Regulation No. 08 of 2012 About Liquid Waste Quality Standard for Palm Oil Industry maximum limit that is collected is equal to 350 mgL to be discharged directly into the environment. Bio fertilizer thus generated good COD value is without the use of bio-activator. Bio-activator has a function as change materials - organic materials and accelerates the fermentation time. This case can causes fermentation in the COD value by using bio-activator increases. As for the BOD value of POME can be seen in Figure 6. with without Figure 6. Concentration of BOD from Bio fertilizer after Fermentation Anaerobic Treatment Figure 6 show that BOD values increase with the addition of bio-activator, but when no bio-activator addition, BOD value will decrease. This can be seen in the sample 5 and sample 6 with a bio-activator BOD value increased by 103.5 mgL and 104.6 mgL has passed the maximum allowed by the government whereas without bio-activator decreasing. The maximum allowed by the government in the amount of 100 mgL. This causes Liquid Organic Fertilizer produced viewed from the BOD i.e. without using a bio-activator. Conclusion Production bio fertilizer with bio-activator plays an important role in increasing the nutrient content. This can be seen in the sample with the addition of bio-activator has the nutrient content greater than that of samples without the addition of bio-activator. This is because in a bio-activator there are microorganisms that contribute in decomposition of organic matter ISBN : 978-602-17761-4-8 142 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Acknowledgements 1. The authors would like to acknowledge the inancial suport of Penelitian Stategis Nasional, Directorate General of Higher Education provides funding research project grants NOMOR SPPK : 189SP211LTDRPMIII2016, Date: 7 Desember 2015, entitled Rancang Alat Biodigester Untuk Pengolahan Air Limbah Industri Minyak Kelapa Sawit Untuk Memproduksi Biometan Dan Pupuk 2. PT. Perkebunan Mitra Ogan was a suport of POME. References 1. Eyrani, K.A,. 2014. Design Alat Sedimentasi dalam Pengolahan Air Limbah Industri Kelapa Sawit. Laporan Akhir. Jurusan Teknik Kimia. Politeknik Negeri Sriwijaya. Palembang 2. Widhiastuti, R., Suryanto, D., Wahyuningsih, H., 2006 Pengaruh Pemanfaatan Limbah Cair Pabrik Pengolahan Kelapa Sawit Sebagai Pupuk Terhadap Biodiversitas Tanah.Jurnal Ilmiah Pertanian Kultura Vol. 41, No. 1, 1-6. 3. Ibrahim A.L, Dahlan I., Adlan M.N., dan Dasti A. F. 2013: Characterization of palm oil mill efluent: a comparative study, Caspian Journal of Applied Sciences Research, 2, 262-268 4. Polprasert, C.1980. Organic Waste Recycling. John Wiley and Sons, Chicester. 5. Food dan Agriculture Organization. 1997. China:in Agriculture. FAOS oils Bulletin Volume 40.FAO Rome. 6. Suzuki, K., W.Takeshi, and Lam. 2012. Consentration and cristalization of phosphate, ammonium and minerals in the efluent of biogas digester in the Mekong Deltha,Vietnam. Jircan and Cantho University, Cantho Vietnam.Japan Agriculture ResearchQuarter.32 4:271-276. 7. Park, Y.D.1984. Biogas research and utilization in Korea. Procedings of International Symposium, Alternative Source of Energy for Agriculture.Food and Fertilizer Technology Center for the Asian Pasiic Region. 8. Junus,M.1998. Rekayasa Penggunaan Sludge Limbah Ternak Sebagai Bahan Pakan Dan Pupuk Cair Tanaman. Jurnal Penelitian Ilmu-ilmu Hayati Life Science. 10 2:93-106. 9. Zhang,Y., L.Yan, L.Chi, X.Long, Z.Mei, and Z.Zhang.2008.Startup and operation ofanaerobic EGSB reactor treating palm oil efluent.J. Environ.Sci.20: 658-663. 10. Parman, Sarjana. 2007. Pengaruh Pemberian Pupuk Organik Cair terhadap Pertumbuhan dan Produksi Kentang Solanum tuberosum L.. Buletin Anatomi dan Fisiologi Vol. XV, No. 2. 11. Koh, R. Hyun and H.G. Song, Effects of Application of Rhodopseudomonas sp. On Seed Germination andGrowth of Tomato Under Axenic Conditions, J. Microbiol. Biotechnol. 2007, 1711, 1805– 1810 12. Prawiranata,W.S.H. dan P.Tjondronegoro.1992. Dasar-dasar Fisiologi Tanaman.Jurusan Biologi, Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor, Bogor. 13. Mugnisjah, W.Q.dan A.Setiawan. 1995. Pengantar Produksi Bersih. PT.Raja GraindoPersada,Jakarta. 14. Prariesta, D dan Winata, R. 2009. Peningkatan Kualitas Pupuk Organik Cair Dari Limbah Cair Produksi Biogas. Tugas Akhir Jurusan Teknik Kimia. Institut Teknologi Sepuluh Nopember. Surabaya. Tidak diterbitkan 15. Mulyani,S.1994. Pupuk dan Cara Pemupukan. Rineka Cipta,Jakarta. 16. Anwar, Dedy 2015. Kajian Awal Pembuatan Pupuk Cair Organik dari Efluent Pengolahan Lanjut Limbah Cair Pabrik Kelapa Sawit POME Skala Pilot. Medan: Universitas Sumatera Utara. 17. Winata, L.1998. Budidaya Anggrek. Penebar Swadaya, Jakarta ISBN : 978-602-17761-4-8 143 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech PREPARATION OF POLYPYRROLE GRAPHITE COMPOSITE ANODE MATERIALS FOR LITHIUM BATTERY BY SOLUTION CASTING METHOD Jadigia Ginting a1 , Sri Yatmani b2 , Yustinus Purwamargapratala c3 a,c Pusat Sains dan Teknologi Bahan Maju-BATAN PUSPIPTEK, Serpong, Tangerang Selatan 15314 b Teknik Elektro ITI , Jl Raya Puspiptek Serpong Tangerang Selatan 15320 1 jadigia.gintingyahoo.com 2 sri_yatyahoo.com 3 pratalabatan.go.id ABSTRACT Preparation of Polypyrrole Graphite Composite Anode Materials For Lithium Battery By Solution Casting Method. Preparation and characterization measurement have been practisized recently in our anode study progression. The research was focused to observ the effect of the composition polypyrrole to graphite composite that proposed could increase the anode performance. Sample composition were 0 ; 2 ; 4 ; 6 and 8 of polypyrrole. Identiication of the polymeric electrolyte composite forming were realisized using FTIR spectroscopy, the optical instrument and XRD diffractometer. Homogenity was observed with SEM. The conductivity measured using LCR apparatus. The result indicated the conductivity of the graphite polymeric composite decreased after the addition of polypyrrole respectively : for 0 ppy was 10 -0.3 ; 2 was 10 -0.55 ; 4 was 10 -0.62 ; 6 was 10 -0.8 ; and for 8 polypyrrole added the conductivity was 10 -0.7 SCm -1 . All measurements operated at frequency of 40 - 105 Hz. Microscopies observation data showed the homogeneous particles distribution. No interesting result was found by thiese method experiment. Keywords : anode, polypyrrole, lithium batteries, solution casting Preliminary Pyrrole is a natural material that can be polymerized with commercial graphite SFG10 by polymerization technique.[1] . This materials can be made to produce gellic electrolyte that having speciic charge capacity of the cathode or an anode and could discharge the system to have 0.4 Volt and showing no less capacity when cycled to 100 cycles [2]. The electronically conducting polymers ECPs like polypyrrole ppy are known to give unusually high electrical conductivity especially in doping process.[3] Conducting polymers like this can be processized either chemically or electrochemically. The electrochemical synthesis is the most common method as it is simpler, quick and perfectly controllable.[3-4]. Polypyrrole are applicable to make anode and cathode materials for ion lithium battery. [2]. This experiment propose to ind an easier and productable result for material anode preparation with solution casting technique. Methodology Materials and Instruments All materials used in this workis coming from commercials grade like MTI and Aldrich Catalog. The instruments used in the study is a spatula, micro balance, measuring cups, glass beaker, magnetic stirrer hotplate, mortar, ultrasonic, vacuum ilter, compacting, furnace, X-ray diffraction XRD, FTIR spectroscopy, impedance capasitance resistance LCR meter, optical microscopy. ISBN : 978-602-17761-4-8 144 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Experimental Methods To ix the mixture forming composite, treatment was applied by hand made using the mortar tools. After a certain amounts of polypyrrole and graphite weighted with hyphothetic composition for every 2 grams sample graphite was added polypyrrole of 0; 2; 4; 6 and 8 , the materials were treated to make smoothing in size with hand made and solved with acetone. Then dried at room temperature and continued in the oven at 50 o C. The powder samples was compacted with 4000 psi for 1 minute to form pellets for conductivity measurements. Results and Discussion Microscope Optic Analysis Figure 1. Observation the morphology of polymers composite polypyrrolegraphite composized: 0; 2; 4; 6; and 8 ppy Microscopy igure above indicate the morphology of distribution of polypyrrole unto graphite, seemed the best distribution is the concentration of 8 ppy that should have better conductivity. Diffractometric Analysis Figure 2. The pattern of X-Ray Diffractionintensity for ppygra in divers composition of ppy ISBN : 978-602-17761-4-8 145 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech After this difgfraction we consider that at the angel of 2Ɵ at 12 has formed polymeric composite of polypyrrolygraphite, considering that no bulk peak formed Conductivity Measurements Figure3. Conductivity of polypyrrolegraphite composite of divers composition of ppy. LCR meter measurements showed that the conductivity graphite decrease by addition the ppy, respectively as follow: 0, 2, 4, 6, and 8 PPY are 10 -0,3 , 10 -0,55 , 10 -6,2 , 10 -0,8 , dan 10 -0,7 S.cm -1 at frequency measurement range 40-105 Hz . Conclusion No satisfaction result found after these experiments according to Powder Metallurgical Technique and even with Solution Casting Technique. More detail and serious study needed to explore these materials development and its application. Solution Casting Technique not worthy in preparation of anode and cathode materials using polypyrrole polymers. Acknowledgements The writers would like to thank to all those who have participated helping this research, especially to Head of Advanced Materials Science And Technology, PSTBM Batan Serpong. References 1. Basker Veeraraghavan, et.al, “ Study of polypyrrole graphite composite as anode material for secondary lithium-ion batteries”, Journal of Power Sources 109 2002 377-387. 2002 2. J.G. Killian, et.al . “Polypyrrole Composite Electrodes in an All-Polymer Battery System”,Journal of The Electrochemical Society, 1996 volume 143, issue3, 936-942. 1996 3. R.N. Singh, Madhu and R. Awasthi, “ Polypyrrole Composite : Electrochemical,Synthesis, Characterization and Application “, Banaras Hindu University, India. www.intechopen.com 4. C.M. Li, C.Q.Sun, W. Chen, L. Pan , “ Electrochemical thin ilm deposition of polypyrrole on different substrates”, Surface and coating Technology 198 2005 474-477. 2005 5. A. Manuel Stephan, K.S. Nahm, “ Review on Composite Polymer Electrolytes for Lithium Batteries,”Polymer 47 2006 5952-5964. 2006 6. L. Yu, D. Cai, H. Wang, M.M. Titirici, “Synthesis of Microspherical LiFePO 4 -Carbon Composites for Lithium Ion Batteries”, Nanomaterials, Vol. 3, pp. 443-452, 2013 7. Wang J,Chen y and Qi L, The Development of Silicon Nanocomposite Materials for Li-ion Secondary Batteries, The Open Materials Journal, 2011, 5, Suppl 1:M5 228-235 ISBN : 978-602-17761-4-8 146 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 8. I.S. Kim and P.N. Kumta, High Capacity SiC nanocomposite anodea for Li-ion batteries, Journal Of Power Sources, Vol 136, Issue1, 10 Sept 2004,pages 145-149. 9. J.M. Tarascon, M. Armand, “Issues and challenges facing rechargeable lithium batteries”, Nature, Vol. 414, pp. 359-367, 2001. 10. Y.P. Wu, E. Rahm, R. Holze, “Carbon anode materials for lithium ion batteries”, J. Power Sources, Vol. 114, pp. 228-236, 2003 11. H. Azuma, H. Imoto, S. Yamada, K. Sekai, “Advanced carbon anode materials for lithium ion cells”, J. Power Sources, Vol. 81- 82, pp. 1-7, 1999 12. Z.X. Chen, J.F. Qian, X.P. Ai, “Preparation and electrochemical performance of Sn-Co-C composite as anode material for Li-ion batteries”, J. Power Sources, Vol. 189, pp. 730-732, 2009 13. E. Kendrick, A. Swiatek, J. Barker, “Synthesis and characterization of iron tungstate anode materials”, J. Power Sources, Vol. 189, pp. 611-615, 2009. 14. F. Sauvage, J.M. Tarascon, E. Baudrin, “In Situ Measurements of Li ion Battery Electrode Material Conductivity: Application to Li x CoO 2 and Conversion Reaction”, J. Phys. Chem. C., Vol. 111, pp. 9264-9269, 2007 15. J.Y. Luo, Y.G. Wang, H.M. Xiong, Y.Y. Xia,”Ordered Mesoporous Spinel LiMn 2 O 4 by a Soft Chemical Process as a Cathode Material for Lithium Ion Batteries”, Chem. Mater., Vol. 19, pp. 4791-4795, 2007. ISBN : 978-602-17761-4-8 147 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech DEVELOPMENT OF RECOMBINANT MICROBIAL ENZYMES FOR APPLICATION IN PULP AND PAPER INDUSTRY Is Helianti Center for Bioindustrial Technology, Agency for Assessment and Application of Technology BPPT Building No 611, LAPTIAB-BPPT, Puspiptek-Serpong, Tangerang Selatan, Banten, INDONESIA isheliantibppt.go.id ABSTRACT Enzyme is protein that catalyzes the biochemical reaction in living cells. Because of their speciicity and high eficiency, many microbial enzymes are applied in the various ields, from pulp and paper industries to food industries. The use of enzymes in the pulp and paper industry started in the late 1980’s. Although enzyme usage leads to better and greener processes in industries, its use is still relatively insigniicant. This presentation will discuss the development of recombinant enzymes to increase their productivity in different microbial hosts, using our own experience in the improvement of the production of xylanase, lipase, and cellulase, three enzymes commonly used in pulp and paper application. Keywords: enzymes; bleaching; deinking; pulp and paper industries Introduction The paper and pulp production and consumption increase annually. Globally, paper and paper board production exceed 270 million metric tons; while in North America, more than 50 million metric tons of paper is produced every year https:www.greenamerica.orgPDFPaperFacts.pdf. In Indonesia, as 7 th rank of the ten largest paper producer in the world Table 1, in 2015 the amount of pulp export reached 3.5 million tons, worth USD 1.72 billion, whereas paper export reached 4.35 million tons, worth US3.74 billion. It is predicted that the global paper demand will increase from 394 million to 490 million tons by 2020 http:tempo.co.id. Table 1 Paper and Paper Broad Producer in the World in 2011 Rank 2014 Country Production in 2014 1,000 ton Share 2014 1 China 107,579 26.5 2 United States 73,188 18.0 3 Japan 26,471 6.5 4 Germany 22,540 5.5 5 South Korea 11,702 2.9 6 Canada 11,076 2.7 7 Indonesia 10,943 2.7 8 India 10,866 2.7 9 Sweden 10,419 2.6 10 Finland 10,409 2.6 Total 295,193 72.6 11 Others 111,298 27.4 World Total 406.491 100.0 Source: http:www.jpa.gr.jpstatesglobal-viewindex.htmltopic01 However, actually, the pulp and paper industry has been held responsible as one of the causes of several environmental problems, from deforestation to the environmental pollution. For these problem, enzyme is a smart solution. Enzyme-based processes could gradually replace the chemical processes in ISBN : 978-602-17761-4-8 148 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech this industry, since they can save energy, reduce water, chemicals, prevent environmental pollution, and improve the product quality Kenealy and Jeffries 2003. In Indonesia, only 15 of the domestic pulp and paper industry uses enzymes in the process BPPT 2006. Even if only a fraction of all pulp and paper production in Indonesia or globally uses enzymatical processes, , it could mean a great expansion of the existing enzyme industry. The development of enzymes and their application also support the sustainability of industry in economical, environmental, and social aspects. In this short review, we will discuss the enzymes that have potential application in pulp and paper industry, their production, and the technology advancement related to the production such as recombinant DNA technology. We discuss them based on our own experience combined with information gathered from various reports. Potential Enzymes in Pulp and Paper Industries Several enzymes are known for their potential application in pulp and paper industries, such as xylanases, lipases, cellulase, amylase, etc. The majority of these enzymes come from microorgainisms. For instance, amylase has been applied in modiications of raw starch in paper industry for a long time; however, other enzymes application only emerged from the late of 1980’s. Xylanases could be applied in bleaching of pulp and reduce the amount of chemicals required for bleaching, it also enhances deinking process Sunna and Antranikian 1997. Cellulases can smooth ibers, enhance drainage, and promote ink removal, so that it can also be used in deinking process. Whereas, lipases reduce pitch; laccases and lignin-degrading enzymes reduce color in efluents, and promote lignin removal Kenealy and Jeffries 2003. The prominent enzymes used in pulp and paper industry were summarize in Table 2. Table 2 Types of Enzymes in Pulp and Paper Industry, Respective Substrates, and the Applications Enzymes Substrates Application References Amylase Starch • Reduce viscosity by cleaving starch molecules • Used for surface sizing and for starch in coatings Venditti http:www4.ncsu. edu~richardvdocumentscs irEnzymeApplicationsinPul pandPaperrav.pdf Cellulase Cellulose ibers Deinking process of waste paper • Cellulase enzymes hydrolyze the microibrils that stuck with ink, releasing the adhesives • Enzyme assisted deinking reported to remove 30-60 more toners and improve brightness by 4-5 points • Cellulase could improve softness becauses its partial depolymerization of cellulose and swelling of ibers to becoming more lexible ibers •Reduction of ines Venditti http:www4.ncsu. edu~richardvdocumentscs irEnzymeApplicationsinPul pandPaperrav.pdf Kenealy and Jeffries 2003. ISBN : 978-602-17761-4-8 149 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Xylanase Hemicellulose Bleaching process • Used to cleave hemicelluloses in iber, making the bleaching process more effective • May be able to reduce bleaching chemicals by up to 30 • Can improve brightness Deinking of waste paper • Xylanase enzymes hydrolyze the microibrils that stuck with ink, releasing the adhesives • Enzyme assisted deinking reported to remove 30-60 more toners and improve brightness by 4-5 points Venditti http:www4.ncsu. edu~richardvdocumentscs irEnzymeApplicationsinPul pandPaperrav.pdf Kenealy and Jeffries 2003; Helianti et al. 2014a; Viikari 1994; Bajpai 2012 Lipase Glycerol backbone, pitch Pitch treatment • Used to control pitch in pulping processes • Converts tri-glycerides to fatty acids which are more stable in water, so it will not be accumulated http:www4.ncsu. edu~richardvdocuments csirEnzymeApplicationsin PulpandPaperrav.pdf Esterase Ester, stickies Stickies treatment • Used to break ester bonds in polymers used in toners and adhesives • Improved paper cleanliness http:www4.ncsu. edu~richardvdocuments csirEnzymeApplicationsin PulpandPaperrav.pdf Lacasse Lignin • Used in deligniication and brightening of the pulp • To remove the lipophilic extractives responsible for pitch deposition from both wood and nonwood paper pulps • Improving properties of pulp by forming reactive radicals with lignin or by functionalizing lignocellulosic ibers • Degrade coloured and toxic compounds released as efluents from pulp and paper industry Virk et al. 2012; Upadhyay et al. 2016 Nowadays, the most signiicant application of enzymes from economical and environmental aspects in pulp and paper industry is in bleaching process. Xylanase treatment can improve lignin extraction, change carbohydrate and lignin associations linkage, or cleave reaccumulated xylan Viikari et al. 1994. It is the most effective enzymes for the prebleaching of kraft paper, and now used in several mills in the world Viikari et al . 1994, Bajpai 2012. Xylanases hydrolize the xylan of the pulp iber structures, so that ibres more permeable. Hence, the xylan hydrolysis in inner iber layer also enhance ISBN : 978-602-17761-4-8 150 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech the bleachability. However, the main target of the enzymes usage in the bleaching is to counteract the environmental issue, namely the reduction of chlorine chemicals and inally lowering the adsorbable organic halides AOX in the efluents. Another important application of xylanase is in the process of deinking waste paper. Deinking waste paper is the prefered paper processing to counter the deforestation and global warming issues. One of the main applications of enzymes in iber recycling is to remove print. Waste paper usually consists of uncoated papers printed with copy and laser printer toners that are often dificult to remove by conventional, alkaline deinking processes. With xylanase, cellulase also plays signiicant roles in deinking process. Enzyme assisted deinking reported to remove 30-60 more toners, and also reported improve brightness by 4-5 points http:www4.ncsu.edu~richardvdocumentscsirEnzymeApplicationsinPulpandPaperrav. pdf. From our own experience, the xylanase usage in deinking process could improve the whiteness and brightness of recycled paper Helianti et al. 2014a.

3. Recombinant Enzyme Production for Pulp and Paper Industry and Its Prospect in Indonesia

From the above description, we know that enzymes are green chemicals that can improve the process and the product quality in pulp and paper industry, as well as support the sustainability of the industry through energy saving, environmentally friendly process, etc. Although enzymes are very important for domestic pulp and paper industry, Indonesia depends on imported enzymes to meet its domestic demand. Indonesia imports almost 100 of its demand in industrial enzymes BPPT 2006. The demand of industrial enzymes is shown in table 3, where it is also shown that the enzyme demand for pulp and paper industry is signiicant. Only 15 of total pulp and paper industry uses enzymes in their processes, because imported enzymes are expensive. Therefore, it is high time to produce affordable enzymes for domestic market. Table 3 The Demand of Industrial Enzymes in Indonesia at 2006 Industry Total production tonyear User enzymes Enzymes needed in 1 kg product Prediction of total enzymes needed kg Detergent 372,285,536 53 1.80 354,766,217 Feed 9,442,303 46 0.04 174,319 Textile 1,098,776 n.a 219,848 Leather 71,800 76 38.52 2,114,975 Pulp and paper 12,781,730 15 26.18 50,921,301 Source: BPPT 2006 To meet the pulp and paper industry’s requirements, the most important characteristics are the optimum pH and temperature of the enzyme, high speciic activity, and strong resistance to metal cations and chemicals. Other speciications include cost-effectiveness, eco-friendliness, and ease of use. Therefore, most of the reported xylanases do not possess all of the characteristics required by this industry Motta et al. 2013. The discovery of ideal enzyme for pulp and paper industry is still required. Three decades ago, there is only one approach to produce enzyme namely to ind new organisms and new enzymes. However, nowadays, besides this conventional method we have recombinant DNA technology that can clone the enzyme-encoding gene of from known producer, dificult to culture microbes, unculturable microbes, or even just the DNA sequence and based on it we can synthesize DNA. Using this recombinant DNA technology, we can increase the productivity of enzymes and eficiency of production, for instance by cloning the enzyme genes into microbe with faster growth or do not need expensive medium, etc. Using similar technology, modiication of optimum temperature, pH, and stability of the cloned enzymes might be performed, for instance by random mutagenesis, gene shufling, directed evolution, and site-directed mtagenesis. It is also possible to design and create ISBN : 978-602-17761-4-8 151 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech enzymes that are not presently found in nature. Thus, recombinant DNA technology make the ideal enzymes for pulp and paper industry available and accessible. Today, by combining the recombinant DNA technology, bioprocess engineering, and large scale fermentation, several enzymes needed by the pulp and paper industry are manufactured http:www.novozymes.comensolutionspulp-and-paper. When we want to produce recombinant enzymes, the productivity of the enzymes the production rate and yield is the main consideration. We have to choose which microbial host is the most appropriate for the cloning. Recombinant enzymes have been expressed in bacteria e.g., Escherichia coli, Bacillus, ilamentous fungi e.g., Aspergillus and yeasts e.g., Pichia pastoris, Saccharomyces cerevisiae. Prokaryotic system or bacterial hosts such as E. coli and Bacillus can be used to quickly and easily overexpress recombinant enzymes; however, the bacterial systems cannot express very large proteins more than 100 kD and proteins that require post-translational modiications. Large proteins 100 kD are usually expressed in eukaryotic systems, such as yeast or ilamentous fungi. Indeed, E. coli expression system continues to dominate the bacterial expression systems, however, if we want to express the extracellular enzymes, E. coli is not the best choice. Rather than E. coli, Bacillus systems are better choices, since the bacteria is a high secretors and, thus, mainly preferred for the homologous expression of recombinant extracllular enzymes. For larger proteins and those need translational modiication, yeast and ilamentous fungi are good choices. However, compared to yeast, the relatively less understanding of the basic knowledge about fungi still hinders the development of the fungal host. Yeast can be grown rapidly to high density, and the level of product expression can be regulated by simple manipulation of the medium Motta et al. 2013. We BPPT team have isolated, identiied, and characterized an alkalothermophilic xylanase producer from local hot spring Ulfah et al. 2011. A native alkalothermophilic xylanase have been produced from this bacterial strain and characterized. We designated this bacterial strain Bacillus halodurans CM1. The native xylanase of this bacterial strain and the recombinant xylanase from E. coli have been produced and applied in deinking process, and proven to increase the brightness and whiteness of the paper Helianti et al. 2014a. Currently, we are still establishing this native xylanase production in pilot scale using corncobs and ish lour as the main medium component Helianti et al. 2015. Since the Bacillus halodurans CM1 is thermophilic, its fermentation is conducted at 50 °C, which, although reduces contamination, need higher energy for fermentation. Therefore, the cloning and expression into more economically feasible microbial host must be considered. Previously, we have cloned and expressed family 11 xylanase from Bacillus subtilis AQ1 in both E. coli and B. subtilis DB104 Helianti et al. 2010; Helianti et al. 2016. The high level expression of this gene in these bacterial host seemed regulated constitutively by the promoter. At present, we have isolated and cloned an alkalotermophilic xylanase gene from the B. halodurans CM1 in three microbial hosts, namely E. coli, Bacillus subtilis, and Pichia pastoris. This alkalothermophilic xylanase is family 10 glycosyl hydrolase and the expression is induced greatly by the presence of xylan. We found the expression of this gene in E. coli was very low, therefore we we continue the cloning and expression procedure into Bacillus and yeast Pichia pastoris not published yet. Expression via plasmid in Bacillus subtilis gave higher extracellular alkalothermophilic xylanase. Expression of the gene in Pichia pastoris gave the highest activity, however, the production time was longer table 4. In this Pichia system, the xylanase productivity was induced by methanol not xylan since the xylanase gene was integrated in alcohol oxidase locus. These recombinant xylanases are produced in lab scale, and still need further bioprocess engineering before continuing into pilot production. We also cloned the cellulase gene from Bacillus licheniformis F11 in E. coli and Bacillus megaterium. The cellulase gene expressed well both in E. coli and Bacillus megaterium. The characteristics of the enzyme was good, however, the level of the intrinsic activity must be increased for pulp and paper process application Helianti et al. 2014b. The synthetic gene encoding of Thermomyces lanuginosus lipase has also been cloned and expressed in E. coli and Bacillus Haniyya et al. 2016. The lipase gene expresion was very faint as we expected, as these prokaryotic bacteria were not the the proper choice for eukaryotic lipase gene expression. Therefore, we continued to clone and express of the gene in Pichia pastoris, and now still on progress. Based on our experience in producing recombinant microbial enzymes we can conclude that, the wild type bacterial strain must have excellent characters to be used in large scale enzymes production. ISBN : 978-602-17761-4-8 152 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech To ind this kind of strain is not easy, and it took several years to isolate the best one. Hence, recombinan DNA technology must be applied to obtain more feasible condition for enzyme production. The choice of microbial host and the inding the most suitable promoter for the gene expression are the keys to achieve good level of recombinant enzymes production. Table 4 Comparison of alkalothermophilic xylanase, lipase, and cellulase gene expression in E.coli, Bacillus subtilis DB104, and Pichia pastoris in our laboratory Host Expression Time of production Actvity Recombinan xylanase E.coli Via plasmid 24 h Low, extracellular and intracellular Bacillus subtilis Via plasmid 24 h Good, extracellular Pichia pastoris Integrated into DNA chromosom 5 days Better than in Bacillus, extracellular Recombinant lipase E.coli Via plasmid 24 h Low Bacillus subtilis Via plasmid 24 h Low Pichia pastoris Integrated into DNA chromosom Under development Under development Recombinant cellulase E.coli Via plasmid 24 h Low, intracellular and extracellular Bacillus subtilis Via plasmid 24 h Moderate, extracellular References 1. Bajpai P. 2012. Biotechnology for pulp and paper processing. Springer US, Boston, MA; 2012. 2. BPPT.2006. Kajian prospek pasar enzim-enzim industri. 3. Haniyya. 2016. Karakterisasi produk gen sintetik lipase Thermomyces lanuginosus yang diekspresikan oleh Bacillus subtilis DB104 rekombinan yang mengandung pSKE194-lip skripsi, Universitas Indonesia. 4. Helianti I, Nurhayati N, Ulfah M, Wahyuntari B, Setyahadi S. 2010. High level of constitutive expression of endoxylanase gene from newly isolated Bacillus subtilis strain AQ1 cloned in Escherichia coli. J Biomed Biotechnol. http: dx.doi.org10.11552010980567. 5. Helianti I a , Ulfah M, Wahyuntari B, Nurhayati N, Wahjono E, Vitianingrum DF. 2014. Properties of Native and Recombinant Thermoalkalophilic Xylanases from Bacillus halodurans CM1, and Application of the Enzymes in Waste Paper Deinking Process. The 1 st ASEAN Microbial Biotechnology Conference 2014 AMBC2014, Bangkok, 19-21 Februari 2014. 6. Helianti I b , Ulfah M, Nurhayati N, Mulyawati L. 2014. Cloning, sequencing,and expression of the gene encoding a family 9 cellulase from Bacillus licheniformis F11 in Escherichia coli and Bacillus megaterium, and characterization of the recombinant enzymes. Microbiol Indones 84: 147-160. Doi DOI: 10.5454mi.8.4.2. 7. Helianti I, Ulfah M, Nurhayati N, Wahyuntari B, Nurhasanah A, Suhendar D, Wahjono E. 2015. Proses produksi xilanase yang bersifat tahan panas dan tahan basa untuk diaplikasikan pada industri kertas. Paten terdaftar Oktober 2015. 8. Helianti I, Ulfah M, Nurhayati N, Finalissari AK, Wardhani AK. 2016. Production of Xylanase by Recombinant Bacillus subtilis DB104 Cultivated in Agro-Industrial Waste Medium. Hayati “Journal of Life Science” accepted. ISBN : 978-602-17761-4-8 153 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 9. Kenealy WR, Jeffries TW. 2003. Enzyme processes for pulp and paper: A Review of Recent Developments. US Government work. 10. Motta FL, Andrade CCP, Santana MHA. 2013. A review of xylanase production by the fermentation of xylan: classiication, , characterization and applications. Intech: 251e75. http:dx.doi. org10.577253544. 11. Sunna A, Antranikian G. 1997. Xylanolytic enzymes from fungi and bacteria. Critical Reviews in Biotechnology 1997;17: 39–67. 12. Ulfah M, Helianti I, Wahyuntari B, Nurhayati N. 2011. Characterization of a new thermoalkalophilic xylanase-producing bacterial strain isolated from Cimanggu Hot Spring, West Java, Indonesia. Microbiol Indones 53: 139-143. doi: 10.5454mi.5.3.7. 13. Upadhyay P, Shrivastava R, Agrawa PK. 2016. Bioprospecting and biotechnological applications of fungal laccase. 3 Biotech. 61: 15. 14. Viikari L, Kantelinen A, Sundquist J, Linko M. 1994. Xylanases in bleaching: From an idea to the industry. FEMS Microbiology Reviews 13: 335–350. 15. Virk AP, Sharma P, Capalash N. 2012. Use of laccase in pulp and paper industry. Biotechnol Prog. 2012 Jan-Feb;281:21-32. doi: 10.1002btpr.727. Epub 2011 Oct 19. ISBN : 978-602-17761-4-8 154 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 155 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech THE MANUFACTURE OF BAMBOO FIBRE COMPOSITE Theresia Mutia a1 , Hendro Risdianto b , Susi Sugesty b , Teddy Kardiansyah b , Henggar Hardiani b a Center for Textile, Ministry of Industry Jl. Ahmad Yani, Bandung, Indonesia b Center for Pulp and Paper, Ministry of Industry Jl. Raya Dayeuhkolot 132, Bandung, Indonesia 1 theresia.mutiayahoo.com ABSTRACT Fiber and bamboo pulp have not been used optimally as a substitute for wood in wood manufacture industry, whereas bamboo planting period is much shorter. Therefore, study of three bamboo species from West Java, namely Gigantochloa apus Tali bamboo, Gigantochloa pseudoarundinacea Temen bamboo and Bambusa vulgaris v. green Haur bamboo have been conducted as raw material for composite. The objective of this study was to manufacture bamboo composite for sound absorber material which is expected can be used as a iberboard too, using bamboo iber and pulp from selected bamboo. Bamboo cooking chemicals for G. apus require the least, so it was chosen to make pulp by Kraft cooking process and to get its iber by soda cooking process, than be made for composite. The composite was made with Hot Press Machine at a pressure of 60 kgcm2, using epoxy resin and bamboo ibers or pulp with a certain ratio. From the test results was known that composite of bamboo iber and pulp at 5000 Hz reference frequency can reduce noise 28 and 77 consecutively, so it can be used as sound absorber material ISO 11654:1997. The quality of bamboo iber composite was higher than bamboo pulp composite and at 2500 Hz can reduce noise up to 97. Furthermore, bamboo iber composite also comply with the physical properties of the applicable standards as iberboard SNI 01 – 4449 - 2006. Keywords : bamboo iber, bamboo pulp, iberboard, natural iber, sound absorber composite Introduction Manufactured wood plywood, chipboard and iberboard is all wood derived products are made in factories by binding ibers, particles with an adhesive to form a composite material [1, 2 in 3]. Fiberboard is classiied by types of raw materials, production methods and density, but the best way to classify is based on density [4 in 5]. Manufactured wood made of wood iber and plastic primarily used in outdoor use such as park bench, deck boats and can also be used for indoor use, such as furniture, sound absorber materials, automotive purposes, etc. [6, 7]. The advantage of manufactured wood compared with natural wood is consistent and uniform shape, not rotten and cannot be eaten by insects, does not absorb water and does not require periodic painting. Nowadays, wood products having problems, because the availability of raw material is limited [8]. This causes inequality between the availability of wood production with the needs of national timber. One solution to overcome this problem, i.e. by utilizing materials containing lignocellulose as wood substitute in the manufacture of composite boards [9]. There are many choices for alternative raw materials and available in large quantities, such as bamboo of various types species. Bamboo ibers is a long iber with shorter planting period 3 - 5 years compared to wood 8 – 20 years [10, 11]. In addition, bamboo produces cellulose per hectare 2 - 6 times greater than pine and increased biomass per day is higher 10 - 30 than wood 2.5 [12]. The content of cellulose in bamboo is also quite high, between 40 - 54 [13 in 14]. Bamboo is widely used as home building materials, household appliances, paper pulp, composites, and others [15, 16]. Composite is a material formed from a combination of two or more different components, for example, resinplastic and reinforcing materials such as iberswebbing or other [17, 18, 19, 20 in 21]. Plastics are widely used for composite products, because it has advantages compared with other materials, are easily molded, lightweight, and inexpensive [22 in 23 ]. Fibers function in the composite is to strengthen the ISBN : 978-602-17761-4-8 156 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech product, so the product will be strong and sturdy [6, 9, 14, 21]. Besides it can reduce the use of resin and synthetic ibers [15]. In an effort to get the appropriate raw materials, various materials have been used for composites, but up to this moment, bamboo iber or bamboo pulp have not been optimally used as a substitute for synthetic ibers, and other materials, such as glass, plastic, metal or other conventional materials; which is used to make composite for various products, such as iberboard or sound absorber material. In addition, composite bamboo iber, as well as composites from natural ibers are expected to have better characteristics, i.e. easily available, cheaper, lighter, environmentally friendly and can reduce the use of synthetic ibers and resins. Therefore, study has been done on three types of bamboo plants that are endemic in West Java, namely Tali bamboo G. apus, Temen bamboo G. pseudoarundinacea and Haur bamboo B. vulgaris v. Green in order to know the characteristics of pulp and bamboo iber that can be used as composite raw material. This initial study focused on getting the method of pulp and iber processes of some species of bamboo and then selected types of bamboo that use minimal chemicals. The objective of this study was to manufacture bamboo composite for sound absorber material which is expected can be used as a iberboard too, using bamboo iber and pulp from selected bamboo. Materials and Method Raw Materials and Chemicals The raw material used come from three types of bamboo plants that are endemic in West Java, namely Tali bamboo G. apus, Temen bamboo G. pseudoarundinacea and Haur bamboo B. vulgaris v. Green Equipment Wood chipper, glassware, Rotary Digester, Mechanical Softening Brushing Machine, Hot Press Machine. Method Pulping Process Bamboo was cut into small pieces chip by wood chipper, then made into pulp by Kraft process with a solid to liquor ratio of 1 : 5, at 165°C for 2 hours with various concentrations of active alkali and sulidity, and followed by 2 times of reining process and soda process for selected bamboo with a solid to liquor ratio of 1 : 5, at 165°C for 2 hours with caustic soda 12, and followed by 2 times of reining process. Decomposition Bamboo Fiber For getting unravel iber bamboo of pieces of bamboo for selected bamboo, the bamboo is cut along approximately 25 cm and then digested to remove most lignin by soda process caustic soda 12, with a solid to liquor ratio of 1 : 5, at 165°C for 2 hours, then combed and leveled through Mechanical Softening and Brushing equipment. Composite Making In this study, the process of making composites was performed by epoxy resin matrix. Natural ibers as reinforcement composites used in this study were pulp and bamboo iber from selected bamboo. The composite was made using epoxy resin and pulp or ibers with a certain ratio with Hot Press Machine at a pressure of 60 kgcm 2 . ISBN : 978-602-17761-4-8 157 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Testing Bamboo a. Bamboo iber morphology b. Chemical components analysis • The water content, in accordance with SNI 08-7070-2005, Determination of the moisture content of pulp and wood by heating in oven method • Levels of ash and silicate levels, in accordance with ISO 776: 2010, Pulp- determination of acid insoluble ash • Lignin, in accordance with SNI 0492-2008, Pulp and wood – Determination of lignin – Klaxon method • Pentose, in accordance with SNI 14-1304-1989, Determination of pentose content in wood pulp • Extractive Extract Alcohol-Benzene, in accordance with SNI 14-1032-1989, Determination of extractive alcohol-benzene extract in wood and pulp • Hollocellulose, in accordance with SNI 01-1303-1989, Determination of holo cellulose in wood • Alpha Cellulose, in accordance with SNI 0444:2009, Determination of alpha, beta and gamma cellulose • Solubility in cold water and hot and cold water, according to SNI 01-1305-1989, Determination of wood solubility in cold water and hot water c. Microstructure analysis SEM d. Functional groups analysis FTIR Spectroscopy Composite a. Microstructure analysis SEM b. Functional groups analysis FTIR Spectroscopy c. Sound absorption coeficient determination [24] Results and Discussion Raw Material Fiber Dimension Fiber dimension of these bamboo ibers can be seen at Table 1.a., while iber dimension of seven wood species as a comparison, can be seen at in Table 1.b. [25]. Table 1.a. Dimension of Bamboo Fiber Parameter Species of bamboo Haur Tali Temen Fiber length, mm 3.24 3.14 3.76 Outer diameter, µm 20.32 25.62 27.58 Inner diameter, µm 11.13 13.71 15.43 Wall thickness , µm 4.60 5.96 6.08 Fiber dimension is one of the important properties of raw materials that can be used as the basis for selecting raw materials for the production of pulp and paper. From Table 1.a. and Table 1.b. [25], known that the length of the bamboo iber is generally above 3 millimeters and higher than wood iber. According to the classiication IAWA, bamboo iber including to a long iber grade that is at least 1.6 mm, maximum 4.4 mm and an average of 2.7 mm [26]. ISBN : 978-602-17761-4-8 158 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech From previous studies known that the longer the wood ibers, the pulp produced will have high strength [26, 27]. This is due to the long ibers provide a wider ield of contiguity and better webbing between one iber to another, which allows more occur hydrogen bonds between the ibers. Furthermore, long-iber pulp is more dificult to pass the ilter, so it is easily washable. Fiber length affects certain properties of pulp and paper, including tear resistance, tensile strength and folding endurance. Haur bamboo iber diameter is smaller than Temen and Tali bamboo. Similarly, lumen diameter of Haur bamboo is smaller than Temen and Tali bamboo. Haur bamboo iber wall thickness is thinner than the Tali dan Haur bamboo. From Table 1.a. and Table 1.b. it’s known that the wall thickness of bamboo ibers are higher than wood ibers, but the inner diameter are smaller. Thin-walled iber will more easily be lattened, resulting in pulp and paper sheet denser and better bursting strength compared to thick- walled ibers. Instead, thick-walled ibers produce sheet that has high tear strength, but low bursting strength. To obtain bursting strength and high tear, thick-walled ibers need to be mixed with long and thin-walled ibers [26, 28]. Chemical Components Chemical components of bamboo iber can be seen at Figure 1. 10 20 30 40 50 60 70 80 Tali Temen Haur Lignin Pentosan Alpha cellulose Hollocellulose 0.5 1 1.5 2 2.5 3 3.5 Tali Temen Haur Ash content Extractive Figure 1. Chemical Components of Bamboo Fiber There are two major chemical components in wood, i.e. lignin 18 – 35 and carbohydrate 65– 75 comprises of 40 to 50 cellulose and 25 to 35 hemicelluloses, and minor amounts of extraneous materials usually 4– 10, mostly in the form of organic extractives and inorganic minerals ash [29]. From the chemical components analysis of the iber Figure 1. is known that the iber used in this study contains alpha cellulose, hemicellulose and lignin of about 44 - 53, 21 - 23 and 21 - 23 respectively. Lignin and extractives contain of tali bamboo relatively lower than temen and haur bamboo. As for the contents of cellulose, temen bamboo is the highest, while the lowest is haur bamboo. Therefore it is necessary for cooking by using caustic soda solution to reduceeliminate the content of Table 1.b. Fiber Dimension of Seven Wood Species [26] No. Species Fiber length µm Fiber diameter µm Fiber wall thickness µ Lumen diameter µm 1. Anthocephalus cadamba jabon 1.561 23.956 2.788 18.380 2. Octomeles sumatraa binuang 1.427 27.058 1.976 23.108 3. Macaranga hypoleuca mahang putih 1.455 36.822 2.277 32.267 4. Macaranga pruinosa mahang keriting 1.607 33.810 3.071 27.667 5. Macaranga tanarius setutup 1.207 20.164 2.627 14.909 6. Macaranga conifera Bodi 1.053 21.515 2.591 16.333 7. Macaranga gigantea sekubung 1.598 26.344 2.363 18.039 ISBN : 978-602-17761-4-8 159 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech these substances, especially lignin so that the surface roughness of iber increased and iber has better adhesion with the matrix resin, because it is so critical in composite manufacture [30]. Compare to wood ibers, bamboo contains lignocelluloses whose levels are relatively equal and can be used as an alternative raw material for particleboard or iberboard [9], but as wood iber also contains extractive substances, hemicellulose and other impurities [31, 32]. These substances can hinder the adhesive to react with cellulose, especially extractive substances which affect the consumption of adhesive and durability of iber board. In addition extractive materials that evaporate can cause blowing or delaminating at the compression process [2 in 3]. From Figures 1 and the results of evaluation of iber dimension is known that the three types of bamboo potential to produce good pulp [28, 33]. Bamboo Pulp In this study, the cooking process is done with Kraft process by varying the concentration of active alkali and sulidity, in order to determine the inluence of the process variation to the Kappa number and yield of bamboo pulp. From the preliminary study found that variations condition of cooking process for Tali bamboo will generate Kappa numbers smaller than the Temen and Haur bamboo. This might be due to the levels of lignin and extractives of Tali bamboo is the lowest. It found that the total yield of Temen bamboo is relatively higher compared to Tali and Haur bamboo. This might be due to alpha cellulose content of Temen bamboo is the highest. In the manufacture of composites, lignin in natural ibers as reinforcement is necessary, because of its nature as an adhesive, so that the ibers do not easily break or has a lower tensile strength. Therefore, the experiment was continued to obtain pulp with Kappa number of about 30 lignin content + 5 , using different concentration of alkali active and sulidity, based on the results of the cooking at preliminary study. The results of the test are presented in Figure 2. 15 30 45 60 Tali Temen Haur Kappa Number Total Yied 5 10 15 20 25 Tali Temen Haur Fiber length mm Diameter μm Fines Figure 2a. Cooking Results to Get Kappa Number 30 Figure 2b. Pulp Morphologi at Kappa Number 30 1 2 3 4 5 Tali Temen Haur Ash content Extractive Lignin 30 60 90 Tali Temen Haur Pentosan Alpha cellulose Figure 2c. Pulp Chemical Components at Kappa Number 30 Figure 2d. Pulp Chemical Components at Kappa Number 30 ISBN : 978-602-17761-4-8 160 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech From the previous research knew that to produce bamboo pulp with a certain lignin content or have a certain Kappa number, it is necessary to use active alkali and sulidity with different concentrations. Furthermore, from the test result knew that to produce pulp with a lignin content of about 5 or have a Kappa number of about 30, it is necessary to use active alkali and sulidity with different concentrations. Cooking of Tali, Temen and Haur bamboo require active alkali and sulidity consecutive ie, 16 and 25, 18 and 25 and 22 and 32. Thus it is known that Tali bamboo requires the lowest chemicals concentration, while Temen bamboo and especially Haur bamboo require chemicals that are relatively higher. This is due to the levels of lignin and extractives of Tali bamboo is the lowest. The use of chemicals is higher on haur bamboo caused by several factors, including ash, extractive and lignin content. From Figure 2. it is known that the cooking conditions as above will produce pulp with Kappa Number and total yield at range between 30.43 - 32.71 and 44.13 - 53.82. Note also that the value of Tali bamboo pulp relatively better than the two other bamboo. All the pulp has iber length between 2 mm - 2.3 mm, diameter of 18.9 μm - 20.8 μm and ines between 5.1 - 6.65, while the lignin content of about 4.21 - 4.89; alpha cellulose 83.86 - 84.82; and hemicellulose between 14.07 - 15.59. Cooking Tali bamboo requires the lowest chemicals, so the it was chosen to be the raw material for reinforcing composites by mixing with a resin. Characteristics of Fiber and Bamboo Pulp {Tali Bamboo G. apus} Fiber and bamboo pulp characteristics after cooking are presented in Figure 3, while the microstructure test results of pulp and bamboo iber by SEM analysis are presented in Figure 4. From Figure 3 known that the levels of lignin, ash and extractive of bamboo pulp from Kraft Process is smaller than bamboo iber, whereas higher levels of cellulose. As has been described above, that it is caused by the cooking process for bamboo iber using lower caustic soda concentration than pulp cooking by Kraft process, so that lignin, ash and extractive in the ibers can not be degradeddissolved entirely. It is known also, that the iber length is about 2 - 4.5 mm, and iber from soda cooking process is longer than pulp, especially than pulp from Kraft cooking process. It may be caused by the concentration of chemicals in Kraft cooking process is higher than the soda cooking process, thus it can partially degrade cellulose ibers. From the test results it is known that the water content of iber and pulp is still below 10, so it is expected does not affect the quality of the composite; because the optimum water content in the manufacture of composites is about 10 - 14 if it is too high, then the lexural rigidity and internal bonding strength of the particle board will decrease [9]. From Figure 4. can be seen that the microstructure of specimen material at a vertical and horizontal position, the material making up the specimen pulp in a vertical position seem their air cavities between the ibers in the pulp, while the bamboo iber specimen at the position appears more compact than pulp. 15 30 45 60 75 90 1 2 3 1. Fiber 2 Pulp Soda

3. Pulp Kraft Hemi cellulose