Bioplastic Production from Cellulose of Oil Palm Empty Fruit Bunch | Cellulose

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Isroi1, A. Cifriadi 2, T. Panji1, Nendyo A. Wibowo3 and Khaswar Syamsu4 1 Indonesian Research Institute for Biotechnology and Bioindustri, No.1, Taman Kencana Street, Bogor – Indonesia 16151. isroi93@gmail.com; tri_panji@yahoo.com 2 Indonesian Rubber Research Institute, No.1, Salak Street, Bogor – Indonesia 16151. cifriadi9748@gmail.com 3 Indonesian Industrial and Beverage Crops Research Institute, Pakuwon Main Street Km 2 Parungkuda, Sukabumi – Indonesia 16151. nindya_bios@yahoo.com 4 Department of Agroindustrial Technology, Faculty of Agricultural Engineering and Technology, Bogor Agricultural University, Bogor –Indonesia 16602. khaswars@yahoo.com Abstract. Empty fruit bunch is available abundantly in Indonesia as side product of CPO production. EFB production in Indonesia reached 28.65 million tons in 2015. EFB consist of 36.67% cellulose, 13.50% hemicellulose and 31.16% lignin. By calculation, potential cellulose from EFB is 11.50 million tons. Cellulose could be utilized as source for bioplastic production. This research aims to develop bioplastic production based on cellulose from EFB and to increase added value of EFB. Cellulose fiber has no plastic properties. Molecular modification of cellulose, composite with plasticizer and compatibilizer is a key success for utilization of cellulose for bioplastic. Main steps of bioplastic production from EFB are: 1) isolation and purification of cellulose, 2) cellulose modification and 3) synthesis of bioplastic. Cellulose was isolated by sodium hydroxide methods and bleached using sodium hypochlorite. Purity of obtained cellulose was 97%. Cellulose yield could reach 30% depend on cellulose content of EFB. Cellulose side chain was oxidized to reduce hydroxyl group and increase the carboxyl group. Bioplastic synthesis used glycerol as plasticizer and cassava starch as matrix. This research was successfully producing bioplastic sheet by casting method. In future prospects, bioplastic from EFB cellulose can be developed as plastic bag and food packaging. Keywords: cellulose, oxidation, oil palm empty fruit bunch, composite, film
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  International Conference on Biomass 2016: 10-11t h  October 2016, Bogor, Indonesia 1 Bioplastic Production from Cellulose of Oil Palm Empty Fruit Bunch Isroi 1 , A. Cifriadi  2 , T. Panji 1 , Nendyo A. Wibowo 3  and Khaswar Syamsu 4   1   Indonesian Research Institute for Biotechnology and Bioindustri, No.1, Taman Kencana Street, Bogor – Indonesia 16151. isroi93@gmail.com; tri_panji@yahoo.com  2   Indonesian Rubber Research Institute, No.1, Salak Street, Bogor – Indonesia 16151. cifriadi9748@gmail.com  3   Indonesian Industrial and Beverage Crops Research Institute, Pakuwon Main Street Km 2 Parungkuda, Sukabumi – Indonesia 16151. nindya_bios@yahoo.com 4   Department of Agroindustrial Technology, Faculty of Agricultural Engineering and Technology, Bogor Agricultural University, Bogor –Indonesia 16602. khaswars@yahoo.com  Abstract. Empty fruit bunch is available abundantly in Indonesia as side product of CPO  production. EFB production in Indonesia reached 28.65 million tons in 2015. EFB consist of 36.67% cellulose, 13.50% hemicellulose and 31.16% lignin. By calculation, potential cellulose from EFB is 11.50 million tons. Cellulose could be utilized as source for bioplastic production. This research aims to develop bioplastic production based on cellulose from EFB and to increase added value of EFB. Cellulose fiber has no plastic properties. Molecular modification of cellulose, composite with plasticizer and compatibilizer is a key success for utilization of cellulose for bioplastic. Main steps of bioplastic production from EFB are: 1) isolation and  purification of cellulose, 2) cellulose modification and 3) synthesis of bioplastic. Cellulose was isolated by sodium hydroxide methods and bleached using sodium hypochlorite. Purity of obtained cellulose was 97%. Cellulose yield could reach 30% depend on cellulose content of EFB. Cellulose side chain was oxidized to reduce hydroxyl group and increase the carboxyl group. Bioplastic synthesis used glycerol as plasticizer and cassava starch as matrix. This research was successfully producing bioplastic sheet by casting method. In future prospects, bioplastic from EFB cellulose can be developed as plastic bag and food packaging. Keywords : cellulose, oxidation, oil palm empty fruit bunch, composite, film  1.   Introduction  Indonesia is the largest oil palm producers in the world, where its production predicted as about 31 million metric tons of oil palm in 2015 (Dirjenbun, 2015). Crude oil palm (CPO) is extracted from the fruits and the lignocellulosic residual remains as oil palm empty fruit bunch (EFB). Accumulation of EFB in the mill is about 28.65 million metric tons per year. EFB has low commercial value and constitutes a disposal problem due to its large quantity. Conventionally, EFB is burned, disposed of in   Isroi, A. Cifriadi and T. Panji    / Bioplastic Production from Oil Palm Empty Fruit Bunch 2 landfills, or composted to organic fertilizer. In order to prevent air pollution and other environmental  problems, burning of EFB is forbidden. It is therefore of importance to optimally utilize EFB in order to solve these problems and at the same time utilize the resource for valuable products. EFB is composed of 40.37% cellulose, 20.06% hemicellulose and 23.89% lignin (Isroi, 2015). Having high cellulose content, EFB has high potential as a source for cellulosic derived products, such as cellulose fiber (Khalid et al. , 2008), nano cellulose (Lani et al. , 2014), glucose (Hamzah, Idris and Shuan, 2011), xylose (Zhang et al. , 2012) and ethanol (Isroi, Mofoluwake and Taherzadeh, 2014). Cellulose also has others potential uses as a source for bioplastic production. Cellulose has no plasticity feature. Uses of cellulose in bioplastic production need some modification. Derivate of the cellulose that has been used in bioplastic synthesis was cellulose nano crystals (CNC) (Arrieta et al. , 2015), nano fiber cellulose (NFC) (Siró and Plackett, 2010), cellulose acetate butyrate (Grunert and Winter, 2002), cellulose acetate (Park et al. , 2004) and bio-PE (Shen, Worrell and Patel, 2010). Cellulose derivate was mixed composed with other biopolymers matrix in order to increase physical properties or as a filler, such as starch and polylactic acid (PLA). The demand for bioplastic increasing along with the rising concern towards environmental problems caused by pretroleum-based plastic. Global production capacity of bioplastic increased by 38% per year during 2003-2007 and predicted will be reach 3.45 million tonnes in 2020. Cellulose and cellulose derivate are about 11% from the global capacity (Shen, Worrell and Patel, 2010). Cellulose from EFB could be used as source for bioplastic production. Potential cellulose from EFB are 11.5 million tonnes in Indonesia making EFB as good source for bioplastic. This research aims to develop bioplastic  production technology from EFB. Cellulose are isolated using sodium hydroxide and sodium hypochlorite. Cellulose obtained from EFB are modified in order to increase physical properties of the  bioplastic. 2.   Material and Methods 1.1.   Oil Palm Empty Fruit Bunches OPEFB was collected from an oil palm mill in Bangka Island, Indonesia. Fresh EFB were chopped and sun dried until the moisture content was less than 10%. Dried EFB chopped into small pieces about 5 cm long and stored in a container at room temperature prior to the experiment. It was analyzed for its lignin, cellulose, and hemicelluloses contents. 1.2.   Cellulose isolation and purification Dried EFB was delignified by sodium hydroxide in the dosage of 1 g NaOH/100 g EFB with consistency 10%. The digester heated until pressure inside the digester was 6 bar for 5 h. Pulp than washed with water to remove NaOH residue and black liquor. The pulp was beaten in laboratory beater to get pulp with freeness level of 300. Sodium hypochlorite (5.25% in water w/w) were used for cellulose  purification. 100 gr of pulp (o.d. basis) was treated in a flask containing 3000ml of deionized water with 33.5 g sodium hypochlorite at 70-75 o C. The addition of sodium hypochlorite was continued at 2 h intervals until the cellulose become white. The cellulose was left in acidified condition for 12 h before washing. Cellulose was washed three times using deionized water. 1.3.   Oxidation of Cellulose 5 gr EFB cellulose (o.d. basis) was added into 1000ml Erlenmeyer glass. The cellulose than was impregnated by 500 ml of hydrogen peroxide with various concentrations (0%, 3%, 6% and 9%). The  pH of the solution maintained at 11 using 0.1M NaOH or 0.1M HCl solution, as depending on the  International Conference on Biomass 2016: 10-11t h  October 2016, Bogor, Indonesia 3 condition. The cellulose suspension was continuously shaken with electric shaker for 24 h. In the of reaction, the pulp filtered, washed for at least four time and then dried prior to subsequent treatment and analysis. 1.4 Cellulose-starch bioplastic preparation Bioplastic composite of cellulose-starch composite was prepared by solution casting and evaporation  process using cassava starch as the polymers matrix and glycerol as plasticizer. 30 gr of cassava starch was suspended in 1000 ml distilled water and heated at 60 o C for 15 minutes for gelatinization. Cellulose solution was added slowly to the gelatinized starch and stir until all cellulose mixed well in the gelatinized starch. The amount of cellulose was 0% (C0), 12.5% (C1), 25% (C2), 37.5% (C3), 50% (C4) and 75% (C5). Glycerol addition was 0%, 12.5%, 25%, 37.5% and 50%. The mixture was cooled and cast on acrylic plates and air dried. The film produced was peeled of and kept in zipper bag and stored in desiccator. 1.5 Analytical methods The cellulose, hemicellulose, and lignin of the OPEFB were determined according to the Chesson-Datta Method (Chesson, 1981) and TAPPI Standard. A Fourier transform infrared (FTIR) spectrometer (Impact 410 iS10, Nicolet Instrument Corp.) was used for determining changes in the structure of the EFB, pulp, cellulose and bioplastic film according to the method described in reference (Isroi, Mofoluwake and Taherzadeh, 2014). Each spectrum was obtained with an average of 32 scans and resolution of 4 cm ! 1 from 600–4,000 cm ! 1. The spectrum data was controlled by Nicolet OMNIC 4.1 (Nicolet Instrument Corp.) software and analyzed by eFTIR® (EssentialFTIR, Operant LLC). Bioplastic film micromorphology was visualized using light microscope with 100x – 400x magnification. The carboxylic acid content of all pulp and cellulose samples was determined by a titration technique described elsewhere (Fras and Stana-Kleinschek, 2002). An air-dry cellulose sample equivalent to 0.5-1.0 g was weighted into a 200 ml glass- stopper flask. 100 ml of calcium acetate solution were added. The flasks were shaken overnight, and then the suspension of fibers was filtrated. The color indicator murexide was used as as a metalchromic indicator. The pH value of the filtrate was adjusted to 12 by the addition of 0.1 M sodium hydroxide solution. The decrease in concentration of calcium acetate solution after contact with the fibers was determined by titration technique. Solution of 0.1 M EDTA was used as titrant. Tensile properties which include the tensile strength and Modulus were determined using the ASTM D882-02 method. Films were cut manually into 1.5x10 cm and then stretched using at a crosshead speed of 12.5 mm/min. Testing conditions include relative humidity of 50±5 and temperature of 23±2oC. At least 7 samples per treatment were tested and values were averaged. 3.   Result and Discussion 3.1 Characteristic of empty fruit bunch The initial content of EFB, pulp and cellulose presented in Table 1. EFB used in this research has high lignin content and higher than reported in other references (Law, Daud and Ghazali, 2007). These differences could arise depending on the source of the EFB, the historical treatments of the material  prior to the analysis and the analytical method. Cellulose is the highest constituent of the EFB, then followed by lignin and hemicellulose. EFB will ready to degrade by microbes when exposes to the air on disposal field and lignocellulosic component will be decreased. EFB samples that have already decayed has low hemicellulose and cellulose content.
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