离子液体对高酸值油脂的催化酯化降酸效果研究

doi:10.3969/j.issn.1673-5854.2020.04.002

生物质化学工程 ›› 2020, Vol. 54 ›› Issue (4): 9-15.doi: 10.3969/j.issn.1673-5854.2020.04.002

离子液体对高酸值油脂的催化酯化降酸效果研究

李惠文,杨铃梅,吕鹏梅,王忠铭,苗长林*(),袁振宏

中国科学院广州能源研究所; 中国科学院可再生能源重点实验室; 广东省新能源和可再生能源研究开发与应用重点实验室, 广东广州 510640

收稿日期:2019-09-03 出版日期:2020-07-30 发布日期:2020-08-06
通讯作者: 苗长林 E-mail:miaocl@ms.giec.ac.cn
作者简介:李惠文(1979—),男,广东惠州人,高级工程师,硕士,主要从事生物质资源化利用及工程推广方面的研究
基金资助:
国家重点研发计划资助项目(2017YFD0601003);国家自然科学基金资助项目(51606201)

Deacidification Effect of Catalytic Esterification by Ionic Liquid on High Acid Value Oil

Huiwen LI,Lingmei YANG,Pengmei LYU,Zhongming WANG,Changlin MIAO*(),Zhenhong YUAN

Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences; Key Laboratory of Renewable Energy, Chinese Academy of Sciences; Guangdong Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China

Received:2019-09-03 Online:2020-07-30 Published:2020-08-06
Contact: Changlin MIAO E-mail:miaocl@ms.giec.ac.cn

摘要/Abstract

摘要：

以制备的1-丙基磺酸-3-甲基咪唑对甲苯磺酸（[MIMPS][C₇H₇O₃S]）离子液体为催化剂结合自行设计的反应装置，对高酸值酸化油进行酯化降酸试验，考察了甲醇通入量、催化剂用量、反应温度和反应时间等因素对酸化油转化率和预酯化油酸值的影响，并考察了催化剂的重复使用性能。对离子液体的红外光谱分析结果表明制备的离子液体符合反应产物化学结构特征；热稳定性分析表明该离子液体在200℃以下具有较好的稳定性。通过单因素与正交试验确定最佳工艺条件：酸化油50 g、甲醇通入量0.99 mL/min、催化剂用量（以酸化油质量计）2.5%、反应时间3 h、反应温度105℃，在此条件下转化率可达98.42%，酸值由120 mg/g变为1.9 mg/g。油脂酯化降酸后酸值达到后续酯交换制备生物柴油酸值小于4 mg/g的指标要求。催化剂重复使用9次，转化率仍保持在75%以上，说明酸性离子液体催化剂对高酸值原料酯化降酸有很好的催化活性且具有良好的稳定性。

关键词: 生物柴油, 酯化反应, 酸化油, 降酸, 离子液体

Abstract:

Using a self-made 1-propylsulfonic acid-3-methylimidazolium-p-toluenesulfonic acid ionic liquid([MIMPS] [C₇H₇O₃S]) as catalyst, the esterification and deacidification of acidified oil with high acid value was carried out with self-designed equipment as reaction device. The effects of amount of methanol, amount of catalyst, reaction temperature, reaction time on the conversion of acidified oil and acid value of pre-esterified oil were investigated, and then the recyclability of catalyst was studied. The infrared spectrum analysis results showed that the synthesized ionic liquid accorded with its structural characteristics. The ionic liquid had good thermal stability under 200℃. The optimum process conditions determined by single factor and orthogonal tests were as follows:acidified oil 50 g, methanol 0.99 mL/min, catalyst dosage 2.5%, reaction time 3 hours, reaction temperature 105℃. Under these conditions, the conversion rate could reach 98.42%, and the acid value changed from 120 mg/g to 1.9 mg/g. After esterification, the acid value of the acidified oil met the requirement of the acid value for preparing biodiesel (less than 4 mg/g). As the ionic liquid catalyst was reused for 9 times, the conversion rate remained above 75%, indicating that[MIMPS] [C₇H₇O₃S] ionic liquid catalyst had good catalytic activity and good stability for deacidification and esterification of acidified oil with high acid value.

Key words: biodiesel, esterification, acidified oil, deacidification, ionic liquid

中图分类号:

TQ35

李惠文,杨铃梅,吕鹏梅,王忠铭,苗长林,袁振宏. 离子液体对高酸值油脂的催化酯化降酸效果研究[J]. 生物质化学工程, 2020, 54(4): 9-15.

Huiwen LI,Lingmei YANG,Pengmei LYU,Zhongming WANG,Changlin MIAO,Zhenhong YUAN. Deacidification Effect of Catalytic Esterification by Ionic Liquid on High Acid Value Oil[J]. Biomass Chemical Engineering, 2020, 54(4): 9-15.

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序号 No .	A 甲醇通入量/(mL·min^-1) methanol inflow	B 催化剂用量/% catalyst dosage	C 反应温度/℃ reaction temperature	D 反应时间/h reaction time	转化率/% conversion rate
1	0.66	2.5	95	1	61.88
2	0.66	5	105	2	87.96
3	0.66	10	115	3	95.64
4	0.825	2.5	105	3	97.13
5	0.825	5	115	1	64.88
6	0.825	10	95	2	86.61
7	0.99	2.5	115	2	98.42
8	0.99	5	95	3	87.65
9	0.99	10	105	1	73.54
k₁	81.83	85.81	78.71	66.77
k₂	82.87	80.16	86.21	90.99
k₃	86.54	85.26	86.31	93.47
R	4.71	5.65	7.60	26.70

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离子液体对高酸值油脂的催化酯化降酸效果研究

Deacidification Effect of Catalytic Esterification by Ionic Liquid on High Acid Value Oil

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