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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.
References
1. Eyrani, K.A,. 2014. Design Alat Sedimentasi dalam Pengolahan Air Limbah Industri Kelapa Sawit.
Laporan Akhir. Jurusan Teknik Kimia. Politeknik Negeri Sriwijaya. Palembang 2. Widhiastuti, R., Suryanto, D., Wahyuningsih, H., 2006
Pengaruh Pemanfaatan Limbah Cair Pabrik Pengolahan Kelapa Sawit Sebagai Pupuk Terhadap Biodiversitas Tanah.Jurnal Ilmiah Pertanian
Kultura Vol. 41, No. 1, 1-6. 3. Ibrahim A.L, Dahlan I., Adlan M.N., dan Dasti A. F. 2013: Characterization of palm oil mill
efluent: a comparative study, Caspian Journal of Applied Sciences Research, 2, 262-268 4. Polprasert, C.1980.
Organic Waste Recycling. John Wiley and Sons, Chicester. 5. Food dan Agriculture Organization. 1997. China:in Agriculture. FAOS oils Bulletin Volume 40.FAO
Rome. 6. Suzuki, K., W.Takeshi, and Lam. 2012.
Consentration and cristalization of phosphate, ammonium and minerals in the efluent of biogas digester in the Mekong Deltha,Vietnam. Jircan and Cantho
University, Cantho Vietnam.Japan Agriculture ResearchQuarter.32 4:271-276. 7. Park, Y.D.1984. Biogas research and utilization in Korea. Procedings of International Symposium,
Alternative Source of Energy for Agriculture.Food and Fertilizer Technology Center for the Asian Pasiic Region.
8. Junus,M.1998. Rekayasa Penggunaan Sludge Limbah Ternak Sebagai Bahan Pakan Dan Pupuk Cair
Tanaman. Jurnal Penelitian Ilmu-ilmu Hayati Life Science. 10 2:93-106. 9. Zhang,Y., L.Yan, L.Chi, X.Long, Z.Mei, and Z.Zhang.2008.Startup and operation ofanaerobic EGSB
reactor treating palm oil efluent.J. Environ.Sci.20: 658-663. 10. Parman, Sarjana. 2007.
Pengaruh Pemberian Pupuk Organik Cair terhadap Pertumbuhan dan Produksi Kentang Solanum tuberosum L.. Buletin Anatomi dan Fisiologi Vol. XV, No. 2.
11. Koh, R. Hyun and H.G. Song, Effects of Application of Rhodopseudomonas sp. On Seed Germination andGrowth of Tomato Under Axenic Conditions, J. Microbiol. Biotechnol. 2007, 1711, 1805–
1810 12. Prawiranata,W.S.H. dan P.Tjondronegoro.1992.
Dasar-dasar Fisiologi Tanaman.Jurusan Biologi, Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor, Bogor.
13. Mugnisjah, W.Q.dan A.Setiawan. 1995. Pengantar Produksi Bersih. PT.Raja GraindoPersada,Jakarta.
14. Prariesta, D dan Winata, R. 2009. Peningkatan Kualitas Pupuk Organik Cair Dari Limbah Cair
Produksi Biogas. Tugas Akhir Jurusan Teknik Kimia. Institut Teknologi Sepuluh Nopember. Surabaya. Tidak diterbitkan
15. Mulyani,S.1994. Pupuk dan Cara Pemupukan. Rineka Cipta,Jakarta. 16. Anwar, Dedy 2015.
Kajian Awal Pembuatan Pupuk Cair Organik dari Efluent Pengolahan Lanjut Limbah Cair Pabrik Kelapa Sawit POME Skala Pilot. Medan: Universitas Sumatera Utara.
17. Winata, L.1998. Budidaya Anggrek. Penebar Swadaya, Jakarta
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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