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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
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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]
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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
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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]
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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
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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]
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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.
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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.
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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
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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.
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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
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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.
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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
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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
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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.
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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.
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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
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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.
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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.
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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
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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+
13. Based on Thiocarbonohydrazone System in Aqueous Media. Chem Eur J 2011; 17: 1410–1414.
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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
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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.
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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.
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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].
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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
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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.
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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
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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,
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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
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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.
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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
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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.
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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.
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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,
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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.
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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.
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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
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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:
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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.
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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
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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
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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.
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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.
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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].
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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.
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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 -
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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.
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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
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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
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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
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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
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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
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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].
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Nomenclature
�
�
��
: ���� ������� �� ������� �� ��� ����
�
�
��
: ���� ������� �� ������� �� ��������� ����
�
�
: �������� �� �������
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: �������� �� ������ �� ��� ����
�
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: �������� �� ������ �� ��������� ����
�
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��
: �������� ������ �� ��� ����
�
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: �������� ������ �� ��������� ����
�
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: �������� �� ������ �� ��� ����
�
��
: �������� �� ������ �� ��������� ����
�
�
: �������� �� ��� �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
.
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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.
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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
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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
.
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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
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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
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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
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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.
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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.
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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
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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.
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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
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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.
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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.
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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
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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.
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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
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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
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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
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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
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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
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[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
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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.
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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.
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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
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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.
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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
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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,
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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.
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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
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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
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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
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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
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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
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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
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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.
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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.
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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.
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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.
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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.
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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
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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
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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
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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.
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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
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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.
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Pengaruh Pemanfaatan Limbah Cair Pabrik Pengolahan Kelapa Sawit Sebagai Pupuk Terhadap Biodiversitas Tanah.Jurnal Ilmiah Pertanian
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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–
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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
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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.
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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
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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
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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.
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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
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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.
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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
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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
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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.
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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.
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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.
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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
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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
.
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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].
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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
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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
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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