基于不同萃取剂的生物油常压蒸馏研究
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摘要
选用乙酸乙酯、二氯甲烷、乙醚和甲苯四种溶剂,分别与生物油按一定质量比混合萃取。将萃取相蒸馏得到的四种油相层与原始生物油进行对比,研究不同萃取剂对生物油萃取-蒸馏后各馏分的产率、水分及高附加值酚类组分变化的影响。结果表明,经萃取-蒸馏后,生物油残渣比例减少,水分含量降低。在四种溶剂中,甲苯萃取率较低,蒸馏后酚类绝对峰面积较小;乙酸乙酯和乙醚萃取效率较高,但两者萃取相蒸馏后酚类含量低;二氯甲烷萃取酚类能力强,其馏分中愈创木酚及其衍生物相对含量为34.11%,比生物油高出15.52%,富集程度高,更有利于后续进一步提纯愈创木酚及其衍生物等高附加值化学品。
In order to separate and enrich the high value-added chemicals in bio-oil, solvent extraction and distillation methods were combined to separate and purify bio-oil. Ethyl-acetate, dichloromethane, diethyl ether and toluene were elected as extracting agents, which were mixed with bio-oil in a certain mass ratio. The 4 oil phases distilled from four extract phases were compared with bio-oil to study effects of different solvents on the yield, moisture and high value-added components of distillate. The results show that the distillate had higher yield and lower moisture content compared with that of bio-oil after the extraction and distillation. Among the 4 solvents, toluene had the poorest ability to extract high value-added components of bio-oil, achieving the lowest yield of phenols of distillate. The extraction efficiency of ethyl-acetate and diethyl ether was higher than that of toluene, but the contents of high value-added components in their oil phases were lower than those of others. The relative content of guaiacol and its derivatives was 34.11% in the oil phases of dichloromethane, which was 15.52% higher than that of bio-oil, and conducive to further extract for high value-added chemicals such as guaiacol and its derivatives.
In order to separate and enrich the high value-added chemicals in bio-oil, solvent extraction and distillation methods were combined to separate and purify bio-oil. Ethyl-acetate, dichloromethane, diethyl ether and toluene were elected as extracting agents, which were mixed with bio-oil in a certain mass ratio. The 4 oil phases distilled from four extract phases were compared with bio-oil to study effects of different solvents on the yield, moisture and high value-added components of distillate. The results show that the distillate had higher yield and lower moisture content compared with that of bio-oil after the extraction and distillation. Among the 4 solvents, toluene had the poorest ability to extract high value-added components of bio-oil, achieving the lowest yield of phenols of distillate. The extraction efficiency of ethyl-acetate and diethyl ether was higher than that of toluene, but the contents of high value-added components in their oil phases were lower than those of others. The relative content of guaiacol and its derivatives was 34.11% in the oil phases of dichloromethane, which was 15.52% higher than that of bio-oil, and conducive to further extract for high value-added chemicals such as guaiacol and its derivatives.
引文
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[16] 王誉蓉. 基于水萃取和分子蒸馏的生物油分级分离研究[D]. 杭州: 浙江大学, 2016.(WANG Yu-rong. Research on stepwise separation of bio-oil based on water extraction and molecular distillation[D]. Hangzhou: Zhejiang University, 2016.)
[17] 刘绍鹏. 稻壳液化油的选择性分离、分析和酯化[D]. 徐州: 中国矿业大学, 2011.(LIU Shao-peng. Selective isolation, analysis and esterification of the oil from rice husk pyrolysis[D]. Xuzhou: China University of Minning and Technology, 2011.)
[18] 杨潇.水热液化生物油的溶剂萃取与柱层析分离技术[D]. 上海: 复旦大学, 2014.(YANG Xiao. Solvent extraction and column chromatography separation of bio-oil from hvdrothermal liquefaction of biomass residues[D]. Shanghai: Fudan University, 2014.)
[19] TANNERU S K, STEELE P H. Pretreating bio-oil to increase yield and reduce char during hydrodeoxygenation to produce hydrocarbons[J]. Fuel, 2014, 133(133): 326-331.
[20] 刘田元, 刘雄民, 马丽, 赖芳, 张闻扬. 苯甲醚和苯乙醚氧化特性及其产物[J]. 应用化工, 2017, 46(8): 1461-1465.(LIU Tian-yuan, LIU Xiong-min, MA Li, LAI Fang, ZHANG Wen-yang. Oxidation characteristics and products of anisole and phenetole[J]. Appl Chem Ind, 2017, 46(8): 1461-1465.)Atmospheric distillation of bio-oil based on different extractants LI Shi-ying ZHU Xie-fei ZHANG Li-qiang ZHU Xi-feng生物油与二氯甲烷混合萃取结合蒸馏能有效提高生物油馏分产率,降低含水量,富集高附加值酚类组分。J Fuel Chem Technol, 2019, 47(3): 318-322Pt/CeL重整催化剂的制备及其石脑油芳构化性能*张鹏刘坚崔佳杨英胡长禄刘百军
[2] CHEN D Y, GAO A J, CEN K H, ZHANG J, CAO X B, MA Z Q. Investigation of biomass torrefaction based on three major components: Hemicellulose, cellulose, and lignin[J]. Energy Convers Manage, 2018, 169: 228-237.
[3] 徐善宝, 陕永杰.生物质热解油净化及其提纯处理研究[J]. 现代盐化工, 2018, (2): 69-70.(XU Shan-bao, SHAN Yong-jie. Research of purification and purification of biomass pyrolytic oil[J]. Mod Salt Chem Ind, 2018, (2): 69-70.)
[4] CHEN D Y, ZHOU J B, ZHANG Q S, ZHU X F. Evaluation methods and research progresses in bio-oil storage stability[J]. Renewable Sustainable Energy Rev, 2014, 40: 69-79.
[5] CHEN D Y, ZHENG Z C, FU K X, ZENG Z, WANG J J, LU M T. Torrefaction of biomass stalk and its effect on the yield and quality of pyrolysis products[J]. Fuel, 2015, 159: 27-32.
[6] 张瑾, 李小华, 董良秀, 王嘉骏, 刘莎, 蔡忆昔, 邵珊珊, 张小雷, 胡超. 碱处理HZSM-5分子筛在线催化提质生物油[J].燃料化学学报, 2017, 45(7): 828-836.(ZHANG Jin, LI Xiao-hua, DONG Liang-xiu, WANG Jia-jun, LIU Sha, CAI Yi-xi, SHAO Shan-shan, ZHANG Xiao-lei, HU Chao. Online upgrading of bio-oil with alkali-treated HZSM-5 zeolites[J]. J Fuel Chem Technol, 2017, 45(7): 828-836.)
[7] 方丽娜, 陈宇, 刘娅, 吴可荆, 吴玉龙, 杨明德. 藻类水热液化产物生物油分离纯化及组分分析[J]. 化工学报, 2015, 66(9): 3640-3648.(FANG Li-na, CHEN Yu, LIU Ya, WU Ke-jing, WU Yu-long, YANG Ming-de. Separation, purification and composition analysis of bio-oil from hydrothermal liquefaction of microalgae[J]. J Chem Ind Eng, 2015, 66(9): 3640-3648.)
[8] KIM J S. Production, separation and applications of phenolic-rich bio-oil-A review[J]. Bioresour Technol, 2015, 178 : 90-98.
[9] PEDERSEN T H, JENSEN C U, SANDSTR?M L, ROSENDAHLA L A. Full characterization of compounds obtained from fractional distillation and upgrading of a HTL biocrude[J]. Appl Energy, 2017, 202: 408-419.
[10] HASSAN E B, EL-GIAR E M, STEELE P. Evaluation of the antioxidant activities of different bio-oils and their phenolic distilled fractions for wood preservation[J]. Int Biodeterior Biodegrad, 2016, 110: 121-128.
[11] WANG S R, WANG Y R, CAI Q J, WANG, X Y, JIN H, LUO Z Y. Multi-step separation of monophenols and pyrolytic lignins from the water-insoluble phase of bio-oil[J]. Sep Purif Technol, 2014, 122(3): 248-255.
[12] HU X, WANG Y, MOURANT D, GUNAWAN R, LIEVENS C, CHAIWAT W, GHOLIZADEH M, WU L P, LI X, LI C Z. Polymerization on heating up of bio-oil: A model compound study[J]. AIChE J, 2013, 59(3): 888-900.
[13] ZHANG X S, YANG G X, JIANG H, LIU W J, DING H S. Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis[J]. Sci Rep, 2013, 3: 1120.
[14] 秦菲, 崔洪友, 王传波, 王丽红, 易维明. 萃取耦合化学转化法提质生物油油溶相的研究[J]. 燃料化学学报, 2014, 42(7): 805-812.(QIN Fei, CUI Hong-you, WANG Chuan-bo, WANG Li-hong, YI Wei-ming. Upgrading the oil-soluble fraction of bio-oil by solvent extraction coupling with chemical conversion[J]. J Fuel Chem Technol, 2014, 42(7): 805-812.)
[15] WEI Y, LEI H W, WANG L, ZHU L, ZHANG X S, LIU Y P, CHEN S L , BIRGITTE A. Liquid-liquid extraction of biomass pyrolysis bio-oil[J]. Energy Fuels, 2014, 28(2): 1207-1212.
[16] 王誉蓉. 基于水萃取和分子蒸馏的生物油分级分离研究[D]. 杭州: 浙江大学, 2016.(WANG Yu-rong. Research on stepwise separation of bio-oil based on water extraction and molecular distillation[D]. Hangzhou: Zhejiang University, 2016.)
[17] 刘绍鹏. 稻壳液化油的选择性分离、分析和酯化[D]. 徐州: 中国矿业大学, 2011.(LIU Shao-peng. Selective isolation, analysis and esterification of the oil from rice husk pyrolysis[D]. Xuzhou: China University of Minning and Technology, 2011.)
[18] 杨潇.水热液化生物油的溶剂萃取与柱层析分离技术[D]. 上海: 复旦大学, 2014.(YANG Xiao. Solvent extraction and column chromatography separation of bio-oil from hvdrothermal liquefaction of biomass residues[D]. Shanghai: Fudan University, 2014.)
[19] TANNERU S K, STEELE P H. Pretreating bio-oil to increase yield and reduce char during hydrodeoxygenation to produce hydrocarbons[J]. Fuel, 2014, 133(133): 326-331.
[20] 刘田元, 刘雄民, 马丽, 赖芳, 张闻扬. 苯甲醚和苯乙醚氧化特性及其产物[J]. 应用化工, 2017, 46(8): 1461-1465.(LIU Tian-yuan, LIU Xiong-min, MA Li, LAI Fang, ZHANG Wen-yang. Oxidation characteristics and products of anisole and phenetole[J]. Appl Chem Ind, 2017, 46(8): 1461-1465.)Atmospheric distillation of bio-oil based on different extractants LI Shi-ying ZHU Xie-fei ZHANG Li-qiang ZHU Xi-feng生物油与二氯甲烷混合萃取结合蒸馏能有效提高生物油馏分产率,降低含水量,富集高附加值酚类组分。J Fuel Chem Technol, 2019, 47(3): 318-322Pt/CeL重整催化剂的制备及其石脑油芳构化性能*张鹏刘坚崔佳杨英胡长禄刘百军
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