Preparation and Characterization of Biopolyol From Liquefied Oil Palm Fruit Waste: Part 1 Shaharuddin Kormin 1,a, Anika Zafiah M.

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1 Preparation and Characterization of Biopolyol From Liquefied Oil Palm Fruit Waste: Part 1 Shaharuddin Kormin 1,a, Anika Zafiah M. Rus 2,b 1,2, Sustainable Polymer Engineering, Advanced Manufacturing and Material Center (SPEN- AMMC), Faculty of Mechanical and Manufacturing Engineering, Universiti Tun Hussein Onn Malaysia, Johor 864, Parit Raja, Batu Pahat, Johor, MALAYSIA a shaharuddin_k@yahoo.com.my, b zafiah@uthm.edu.my Keywords: liquefaction, oil palm fruit wastes, polyhydric alchohol, biopolyol, polyurethane. Abstract. Liquefaction is known to be an effective method for converting biomass into a biopolyol. The biomass liquefaction of oil palm fruit waste (OPFW) in the presence of liquefaction solvent/polyhydric alcohol (PA): Ethylene glycol (EG), polyethylene glycol 4 (PEG4) and glycerol using sulfuric acid as catalyst was studied. For all experiments, the liquefaction was conducted at 15 C and atmospheric pressure. The mass ratio of OPFW to liquefaction solvents used in all the experiments was 1/2, 1/3 and 1/4. The results revealed that almost 5% of the oil palm fruit waste converted into liquid product within 2 hours at 15 C with OPFW/PA ratio of 1/4. Biopolyol produced under different condition showed viscosities from 21 to 65 Pa.s. The result in this study may provide fundamental information on integrated utilization of oil palm fruit waste via biomass liquefaction process. Introduction Nowadays, there has been increased desire for more effective utilization of lignocellulosic biomass waste due to their potential to replace the petroleum based product and aid economic development. Furthermore, the use of biomass as a substitute for fossil fuels can reduce the carbon content in the atmosphere as carbon dioxide is absorbed by pla nt via photosynthesis during growth [1]. In the fields of bioenergy and materials, the catalytic conversion of oil palm waste biomass to produce biopolyol has received sustained attention because of its potential for lower energy consumption, better efficiency, and milder reaction conditions compared with other thermochemical conversions such as pyrolysis [1] or gasification [2]. Malaysia, being a country that actively promotes agricultural activities has abundant biomass wastes, since Malaysia is one of the main palm oil producing and exporting countries in the world. Indiscriminate disposal of these wastes will cause serious environmental problems. Therefore, developing new technologies for converting oil palm biomass to energy sources (liquid or gas) becomes an attractive research area. Lignocellulosic biomass could be liquefied under acid conditions with liquefying reagents, such as ethylene glycol and ethylene carbonate, to produce polyol products [3].The liquefaction can be either acid- or base-catalyzed, with the former being much more commonly used. During the liquefaction processes, biomass is degraded and decomposed into smaller molecules by polyhydric alcohols via solvolytic reactions. Polyols are chemical compounds containing multiple hydroxyl groups. Some polyesters, polyurethanes, and fuels have been prepared from the liquefied polyol product [4]. Thus, the goal of this study was to determine the potential of biomass liquefaction of oil palm fruit waste as the raw material for rigid polyurethane foam. The specific objectives were to determine the effects of oil palm fruit waste/polyhydric alcohol (PA) ratio (w/w) on the properties of oil palm fruit waste polyols. 65

2 Experimental procedure Preparation of liquefied oil palm fruits waste (LOPFW) and liquefied oil palm fruits residues. Figure 1 shows the experimental scheme of biomass liquefaction of oil palm fruit waste. Oil palm fruit waste (OPMF, OPS and OPK) was liquefied at different liquefaction condition using 25 ml three-branch flask equipped with thermometer and magnetic stirrer. The liquefied product (polyol) residue content and viscosity were characterized. OPMF/OPS/OPK + Polyhydric alcohol (PA) + Sulfuric acid OPMF/OPS/OPK Temperature: 15 C OPFW/PA ratio: 1/2, 1/3, 1/4 Time: 12 min Acid (catalyst): 5% Liquefied OPFW + residue Characterization Figure 1: Experimental scheme of biomass liquefaction of oil palm fruit waste (a) (b) (c) Figure 2: Liquefied oil palm fruit waste (OPFW) polyol (a) liquefied oil palm mesocarp fibre (OPMF) polyol (b) liquefied oil palm shell (OPS) polyol (c) liquefied oil palm kernel (OPK) polyol. In order to determine the percent of unliquefied oil palm wastes residue, methanol-insoluble residue (R) was calculated by using following equation: Residue content, R (%) = (Wr / Wo ) 1% Liquefaction yield (%) = 1 R (%) Where R is the percentage of residue content; Wo is the initial oven-dried oil palm waste (g); Wr is the oven-dried weight of the solid residue (g) after filtration of the liquefied mixture. 66

3 Viscosity. The viscosity of biopolyols was determined according to ASTM D using a Brookfield DV I Prime viscometer, equipped with a small sample adapter, temperature probe, and temperature control unit. Viscosity was determined at 25 ±.5 C using rotational speeds recommended in the standard. Result and discussion Effect oil palm fruit wastes (OPFW)/polyhydric alcohol (PA) ratio on residue content and viscosity. Liquefaction of oil palm fruit waste with three different liquefaction solvent or polyhydric alcohols (ethylene glycol, polyethylene glycol 4 and glycerol) was studied. The average residue content as function of the OPFW/PA ratio at 15 C are shown in figure 3. Figure 3a shows the effect of OPMF/PA ratio on residue content and viscosity. The residue content for OPMF/EG decreased slightly from 79% to 69% when the ratio decreased from 1/2 to 1/4. The residue content of OPMF/PEG reached 73% to 65% from 1/2 to 1/4 ratios. OPMF/PEG and OPMF/GLY ratio shows decreasing on residues content from 1/2 to 1/4 ratios. OPMF/EG a ratio was the most effective solvent for oil palm mesocarp fiber (OPMF) liquefaction. From figure 3b, the residue content of OPS/EG ratio decreased from 76% to 7% when the ratio decreases from 1/2 to 1/4. It was found that the residue content decreased as the ratio of OPS/GLY decrease from 1/2 to 1/4 which is 75% to 56%. Moreover, when the OPS/PEG ratio decreases from 1/2 to 1/4 the residue content was also decrease from 71% to 67%. Figure 3c present the residue content of OPK/EG reached 7% to 59% from 1/2 to 1/4. The residue content for OPK/PEG slightly decreased from 69% to 66% from 1/2 to 1/4. The residue content of OPK/GLY ratio also show decrease in result from 61% to 51% from 1/2 to 1/4. The decreasing residue content obtained from 1/2 to 1/4 ratio could be attributed to recondensation reactions of the liquefied components due to the high raw material concentration and this would break the liquefaction process [5]. The relatively lower residue content obtained in this study might be explained by the use of a different liquefaction solvent and different lignocellulosic biomass [6][7][8]. Thus, it could be concluded that the effect of different liquefaction solvent on the liquefaction rate of Liquefied oil palm fruit waste is greatly dependent on the oil palm fruit waste/pa ratio. Figure 3a presents the effect of OPFW/PA on viscosity of liquefied OPMF, OPS and OPK. It was observed that with an increase in the liquefaction solvent (PA) amount in the mixture, the viscosity value of the polyols gradually increased. Figure 3a show that liquefied OPMF/PEG increased from 4 to 45 Pa.s when the liquefaction ratio decreased from.5 to.25. The viscosities of liquefied OPS are shown in the figure 3b. Liquefied OPS/PEG show higher viscosity value than liquefied OPS/EG and liquefied OPS/GLY (in the range of 5 to 55 Pa.s. Figure 3c, the viscosity of liquefied OPK also showed an increasing value when amount of liquefaction solvent was increase. Liquefied OPK/PEG show the highest viscosity value compare to liquefied OPK/PEG and OPK/GLY which the viscosity of biopolyols increased from 6 to 65 Pa.s as amount of PA was increased. Previous studies have suggested that an increase in the biomass conversion/liquefaction ratio usually results in a increase in biopoyol viscosity due to the liquefaction of biomass [9]. At the beginning of the liquefaction, oil palm fruit waste is insoluble in the solvent and the viscosity of the reaction system is high. Along with the progress, more and more macro-molecules are dissolved by the solvent, resulting the decrease of the viscosity [6][7][8]. The viscosity of biopolyols continued to increase with further increases in the amount of liquefaction solvent. This might be caused by the fact that the liquefaction process occurred over a short reaction time and additional side reactions (e.g., recondensation of the liquefied components) occurred after liquefaction. 67

4 (c) (a) (b) OPMF/PA ratio (w/w, %) OPS/PA ratio (w/w, %) Viscosity (Pa.s) Viscosity (Pa.s) Viscosity (Pa.s) OPMF/EG residue content OPMF/PEG residue content OPMF/GLY residue content OPMF/EG viscosity OPMF/PEG viscosity OPMF/GLY viscosity OPS/EG residue content OPS/PEG residue content OPS/GLY residue content OPS/EG viscosity OPS/PEG viscosity OPS/GLY viscosity OPK/EG residue content OPK/PEG residue content OPK/GLY residue content OPK/EG viscosity OPK/PEG viscosity OPK/GLY viscosity OPK/PA ratio (w/w, %) Figure 3: Effect of OPFW/PA ratio on residue content and viscosity (a) liquefied oil palm mesocarp fibre (OPMF) polyol (b) liquefied oil palm shell (OPS) polyol (c) liquefied oil palm kernel (OPK) polyol. 68

5 Conclusion Oil palm fruit waste (OPFW) has been successfully liquefied in the presence of EG, PEG4 and glycerol as liquefaction solvent at 15 C with sulfuric acid as a catalyst. It was found that liquefied OPFW/PA ratio had great influences on residue content and viscosity. The amount of residue decreases when the ratio of OPFW/PA decreases from 1/2 to 1/4, respectively. Conversely, viscosity increases as the ratio decrease. Biopolyol synthesized via the liquefaction of OPFW would be beneficial for production of targeted rigid polyurethane (PU) foam products. Acknowledgement The author would like to thanks Sustainable Polymer Engineering, Advanced manufacturing and materials Center (SPEN-AMMC), Universiti Tun Hussein Onn Malaysia (UTHM), Johor and Malaysian Government for supporting this research under FRGS vot Reference [1] Demirbas, A., 21. Biomass resource facilities and biomass conversion processing for fuels and chemicals. Energy Convers. Manage. 42, [2] Hosseini SE, Wahid MA, Aghili N. The scenario of greenhouse gases reduction in Malaysia. Renew Sustain Energy Rev 213;28:4 9. [3] Yamada, T., Ono, H. (1999). Rapid liquefaction of lignocellulosic waste by using ethylene carbonate, Bioresource Technology 7(1), [4] Montane, D., Farriol, X., Salvado, J., Jollez, P., and Chornet, E. (1998). Fractionation of wheat straw by steam-explosion pretreatment and alkali delignification. Cellulose pulp and byproducts from hemicellulose and lignin, J. Wood Chem. Technol. 18, [5] Xie, J. L., Huang, X. Y., Qi, J. Q., Hse, C. Y., and Shupe, T. F. (214). Effect of anatomical characteristics and chemical components on microwave-assisted liquefaction of bamboo wastes, BioResources 9(1), [6] Wang, H., & Chen, H. Z. (27). A novel method of utilizing the biomass resource: Rapid liquefaction of wheat straw and preparation of biodegradable polyurethane foam (PUF). Journal of the Chinese Institute of Chemical Engineers, 38(2), [7] Yamada, T., Ono, H. (1999). Rapid liquefaction of lignocellulosic waste by using ethylene carbonate, Bioresource Technology 7(1), [8] Yu, F., Le, Z., Chen, P., Liu, Y., Lin, X., Ruan, R., 28. Atmospheric pressure liquefaction of dried distillers grains (DDG) and making polyurethane foams from liquefied DDG. Appl. Biochem. Biotechnol. 148, [9] Chen, F.G., Lu, Z.M., 29: Liquefaction of wheat straw and preparation of rigid polyurethane foam from the liquefaction products. Journal of Applied Polymer Science 111(1):