Please wait a minute...
J4  2009, Vol. 43 Issue (5): 926-930    DOI: 10.3785/j.issn.1008-973X.2009.05.027
    
Experimental research on bio-oil catalytic esterification using cation exchange resins
WANG Qi1,2, YAO Yan2, WANG Shu-rong1, LUO Zhong-yang1, CEN Ke-fa1
(1. State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China;
2. College of Metrological Technology and Engineering, China Jiliang University, Hangzhou 310018, China)
Download:   PDF(872KB) HTML
Export: BibTeX | EndNote (RIS)      

Abstract  

 Bio-oil contains a large amount of organic acids, which results in strong corrosion and restrains its application in large scale. Catalytic esterification of bio-oil was carried out in a total reflux mode over strongly acidic cation exchange resins in a glass batch reactor at 60 ℃. The mass ratio of oil/ethanol was 1∶2, and the catalyst mass fraction was 20% of the reaction solution. The results indicated that after esterification, the viscosity and water content of the bio-oil decreased obviously and the gross calorific value increased by 42.7%. The chemical composition of the upgraded bio-oil was different from that of the crude bio-oil, in which most of the organic acids were converted into esters. Besides, the formation mechanism of orthoacetic acid trimethyl ester was proposed.



Published: 18 November 2009
CLC:  TK6  
Cite this article:

WANG Qi, TAO Yan, WANG Shu-Rong, et al. Experimental research on bio-oil catalytic esterification using cation exchange resins. J4, 2009, 43(5): 926-930.

URL:

http://www.zjujournals.com/eng/10.3785/j.issn.1008-973X.2009.05.027     OR     http://www.zjujournals.com/eng/Y2009/V43/I5/926


生物油离子交换树脂催化酯化试验研究

生物油由于含有大量有机酸性物质而具有较强的腐蚀性,不利于其规模化利用.利用间歇式玻璃反应釜,在60 ℃、油醇质量比为1∶2、催化剂质量分数为20%和全回流条件下,研究了强酸型离子交换树脂催化的生物油酯化精制反应,目的是改变生物油的强酸性,提高其品质.结果表明,酯化后生物油的含水量和黏度下降,热值提高了42.7%;生物油中低级羧酸均得到不同程度的转化,产物分布发生较大变化,主要生成乙酸乙酯、原乙酸三乙酯等新成分,并提出了原乙酸三乙酯的生成机理.

[1] OASMAA A, PEACOCKE C. A guide to physical property characterisation of biomass-derived fast pyrolysis liquids [R]. Finland: VTT Publications, 2001: 63.
[2] JAY D C, RANTANEN O, SIPILA K, et al. Wood pyrolysis oil for diesel engines [C]∥ ASME Internal Combustion Engine Division. Alternative Fuels and Natural Gas. New York: ASME, 1995: 5159.
[3] 张琦. 固体酸碱催化剂催化酯化改质提升生物油的研究[D]. 合肥:中国科学技术大学, 2006: 2150.
ZHANG Qi. Upgrading bio-oil over solid acid and base by catalytic esterification [D]. Hefei: University of Science and Technology of China, 2006: 2150.
[4] 杨光,江铁男,赵冬云. 732型强酸性阳离子交换树脂催化合成乙酸苄酯[J]. 高师理科学刊, 2000, 20(4): 3941.
YANG Guang, JIANG Tie-nan, ZHAO Dong-yun. Synthesis of benzyl aoetale with 732 strong acidic cation ion-exchange resin as catalyst [J]. Journal of Science of Teachers College and University, 2000, 20(4): 3941.
[5] 俞善信,张鲁西. 强酸性阳离子交换树脂催化合成丁二酸二丁酯[J]. 工业催化, 2004, 12(3): 3637.
YU Shan-xin, ZHANG Lu-xi. Synthesis of dibutyl succinate catalyzed by strong acid cation exchange resin [J]. Industrial Catalysis, 2004, 12(3): 3637.
[6] 王琦,贺博,姚燕,等. 流化床生物质快速热解制取生物油试验研究[J]. 工程热物理学报, 2008, 29(5): 885888.
WANG Qi, HE Bo, YAO Yan, et al. Experimental research on biomass flash pyrolysis for bio-oil in a fluidized bed reactor [J]. Journal of Engineering Thermophysics, 2008, 29(5): 885888.
[7] 王树荣. 生物质热解制油的试验与机理研究[D].杭州:浙江大学, 1999: 77103.
WANG Shu-rong. Experimental studies on biomass pyrolysis for producing bio-oil and mathematical modeling [D]. Hangzhou: Zhejiang University, 1999: 77103.
[8] 贺博. 生物油的分级分离和初步改性[D]. 杭州:浙江大学, 2006: 2537.
HE Bo. Separation and upgrading of bio-oil [D]. Hangzhou: Zhejiang University, 2006: 2537.
[9] ZHANG Q, CHANG J, WANG T J, et al. Upgrading bio-oil over different solid catalysts [J]. Energy & Fuels, 2006, 20(6): 27172720.
[10] 陈学恒. 载体强酸催化合成柠檬醛二乙缩醛[J]. 现代化工, 2000(6): 3638.
CHEN Xue-heng. Catalytic synthesis of citral diethyl acetal by supported strong acid [J]. Modern Chemical Industry, 2000(6): 3638.

[1] CHEN Ling-Gong, TUN Hua-Cheng, CEN Ge-Fa. Quantitative research of evolved gas rate by TGA-FTIR[J]. J4, 2009, 43(7): 1332-1336.