富酸油脂无催化快速酯化降酸工艺研究

doi:10.3969/j.issn.0253-2417.2022.03.015

林产化学与工业 ›› 2022, Vol. 42 ›› Issue (3): 111-116.doi: 10.3969/j.issn.0253-2417.2022.03.015

富酸油脂无催化快速酯化降酸工艺研究

李科¹(), 陈洁¹, 聂小安¹^,², 蒋剑春¹^,²

1. 中国林业科学研究院林产化学工业研究所；生物质化学利用国家工程实验室；国家林业和草原局林产化学工程重点实验室；江苏省生物质能源与材料重点实验室；江苏省林业资源高效加工利用协同创新中心，江苏南京 210042
2. 中国林业科学研究院林业新技术研究所，北京 100091

收稿日期:2021-07-19 出版日期:2022-06-28 发布日期:2022-07-04
作者简介:李科(1985—)，男，江苏南京人，助理研究员，博士，主要从事生物质能源与材料方面的开发研究; E-mail: liketaiping@163.com
基金资助:
国家重点研发计划资助项目(2019YFB1504001-02)

Fast Deacidification of Acid-rich Oil by Esterification Without Catalysis

Ke LI¹(), Jie CHEN¹, Xiao'an NIE¹^,², Jianchun JIANG¹^,²

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab.for Biomass Chemical Utilization; Key Lab.of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab.of Biomass Energy and Material, Jiangsu Province; Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing 210042, China
2. Institute of New Technology of Forest, CAF, Beijing 100091, China

Received:2021-07-19 Online:2022-06-28 Published:2022-07-04

摘要/Abstract

摘要：

对富酸油脂进行了甘油无催化酯化降酸的研究，通过实验优化得到了最佳反应条件：甘油与脂肪酸的物质的量比为1.2∶1，反应温度为240 ℃，反应2 h，酸值即可降至1.66 mg/g以下。优化工艺实现了富酸油脂2 h内快速降酸的目的，且所得产品可直接通过酯交换反应制备生物柴油，FT-IR分析确认了羧酸的消失和甘油酯的形成。GPC分析结果表明了降酸后油脂的组成为甘油三酯21.93%、甘油双酯37.93%和甘油单酯40.14%，所得生物柴油组成仅为脂肪酸甲酯。此外，该工艺的完善还直接补全了“不同酸值油脂制备生物柴油的工艺路线图”，对生物柴油行业发展具有一定的借鉴价值。

关键词: 油脂, 脂肪酸, 酯化反应, 生物柴油, 脂肪酸甲酯

Abstract:

Using acid-rich oil as raw materials, the acid value was reduced by esterification with glycerol in the absence of a catalyst. The optimum conditions were obtained as follows: the mole ratio of glycerol to fatty acid was 1.2∶1, the reaction temperature was 240 ℃, and the acid value could be reduced to below 1.66 mg/g for 2 h. The results showed that this process could not only achieve the purpose of fast deacidification within two hours, but also directly produce biodiesel through transesterification. FT-IR analysis confirmed the disappearance of carboxylic acid and the formation of triglyceride. The results of GPC analysis showed that the composition of the oil after deacidification was 21.93% triglyceride, 37.93% diglyceride and 40.14% diglyceride. And the obtained biodiesel was relatively pure fatty acid methyl esters. In addition, the improvement of the process also directly completed the "process roadmap of biodiesel production from oils with different acid values", which had a certain reference value for the development of biodiesel industry.

Key words: oil, fatty acid, transesterification, biodiesel, fatty acid methyl ester

中图分类号:

TQ35
TQ645.8

李科, 陈洁, 聂小安, 蒋剑春. 富酸油脂无催化快速酯化降酸工艺研究[J]. 林产化学与工业, 2022, 42(3): 111-116.

Ke LI, Jie CHEN, Xiao'an NIE, Jianchun JIANG. Fast Deacidification of Acid-rich Oil by Esterification Without Catalysis[J]. Chemistry and Industry of Forest Products, 2022, 42(3): 111-116.

图/表 6

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参考文献 17

1	VASUDEVAN P T , BRIGGS M . Biodiesel production: Current state of the art and challenges[J]. Journal of Industrial Microbiol & Biotechnology, 2008, 35 (5): 421- 430.
2	忻耀年, SONDERMANNB, EMERSLEBENB. 生物柴油的生产和应用[J]. 中国油脂, 2001, 26 (5): 72- 77.
	XIN Y N , SONDERMANN B , EMERSLEBEN B . Production and application of bio diesel fuel[J]. China Oils and Fats, 2001, 26 (5): 72- 77.
3	袁银南, 江清阳, 孙平, 等. 柴油机燃用生物柴油的排放特性研究[J]. 内燃机学报, 2003, 21 (6): 423- 427. doi: 10.3321/j.issn:1000-0909.2003.06.008
	YUAN Y N , JIANG Q Y , SUN P , et al. Study of emission characteristics of diesel engine fueled with biodiesel[J]. Transactions of Csice, 2003, 21 (6): 423- 427. doi: 10.3321/j.issn:1000-0909.2003.06.008
4	张恬, 袁银南. 生物柴油的环境效益与社会经济效益[J]. 能源环境保护, 2005, 19 (2): 16- 19.
	ZHANG T , YUAN Y N . Environmentai and economic benefit of biodiesel[J]. Energy Environmental Protection, 2005, 19 (2): 16- 19.
5	XUE J , GRIFT T E , HANSEN A C . Effect of biodiesel on engine performances and emissions[J]. Renewable & Sustainable Energy Reviews, 2011, 15 (2): 1098- 1116.
6	ATADASHI I M , AROUA M K , AZIZ A A . High quality biodiesel and its diesel engine application: A review[J]. Renewable & Sustainable Energy Reviews, 2010, 14 (7): 1999- 2008.
7	AGARWAL A K , BIJWE J , DAS L M . Wear assessment in a biodiesel fueled compression ignition engine[J]. Journal of Engineering for Gas Turbines & Power, 2003, 125 (3): 820- 826.
8	AGARWAL A K . Biofuels(alcohols and biodiesel) applications as fuels for internal combustion engines[J]. Progress in Energy & Combustion Science, 2007, 33 (3): 233- 271.
9	AYOUB M , ABDULLAH A Z . Critical review on the current scenario and significance of crude glycerol resulting from biodiesel industry towards more sustainable renewable energy industry[J]. Renewable and Sustainable Energy Reviews, 2012, 16 (5): 2671- 2686. doi: 10.1016/j.rser.2012.01.054
10	BABU P S , MAMILLA V R . Significance of biodiesel use as I.C.engine fuels[J]. International Journal of Advanced Engineering Research and Studies, 2012, 1 (2): 40- 43.
11	赵宗保, 华艳艳, 刘波. 中国如何突破生物柴油产业的原料瓶颈[J]. 中国生物工程杂志, 2005, (11): 1- 6.
	ZHAO Z B , HUA Y Y , LIU B . How to secure triacylglycerol supply for Chinese biodiesel industry[J]. Progress in Biotechnology, 2005, (11): 1- 6.
12	DEMIRBAS A . Biodiesel from waste cooking oil via base-catalytic and supercritical methanol transesterification[J]. Energy Conversion & Management, 2009, 50 (4): 923- 927.
13	ZHENG S , KATES M , DUBÉ M A , et al. Acid-catalyzed production of biodiesel from waste frying oil[J]. Biomass and Bioenergy, 2006, 30 (3): 267- 272. doi: 10.1016/j.biombioe.2005.10.004
14	张勇. 利用地沟油制备生物柴油[J]. 中国油脂, 2008, 33 (11): 48- 50.
	ZHANG Y . Preparation of biodiesel with hogwash oil[J]. China Oils and Fats, 2008, 33 (11): 48- 50.
15	何寿林, 黄奠坤, 张红丽. 多不饱和脂肪酸甘油酯的合成工艺研究[J]. 武汉理工大学学报, 2012, 34 (3): 34- 37.
	HE S L , HUANG D K , ZHANG H L . Research on synthesis technology of PUFAs glyceride[J]. Journal of Wuhan University of Technology, 2012, 34 (3): 34- 37.
16	刘朋, 蒋剑春, 陈水根, 等. 高酸值废弃油脂甘油酯化脱酸研究[J]. 应用化工, 2016, 45 (7): 1242- 1245.
	LIU P , JIANG J C , CHEN S G , et al. Deacidification of high acid value waste oil by esterification with glycerol[J]. Applied Chemical Industry, 2016, 45 (7): 1242- 1245.
17	李科, 李翔宇, 蒋剑春, 等. 质量法——一种计算油脂甲酯化转化率的新方法研究[J]. 林产化学与工业, 2011, 31 (2): 43- 47.
	LI K , LI X Y , JIANG J C , et al. A new approach to calculate conversion rate of methyl ester ification of fatty oil by mass-change method[J]. Chemistry and Industry of Forest Products, 2011, 31 (2): 43- 47.

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富酸油脂无催化快速酯化降酸工艺研究

Fast Deacidification of Acid-rich Oil by Esterification Without Catalysis

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