固体酸催化高酸值花椒籽油酯化降酸反应

doi:10.16085/j.issn.1000-6613.2016-2116

化工进展 ›› 2017, Vol. 36 ›› Issue (07): 2504-2510.DOI: 10.16085/j.issn.1000-6613.2016-2116

固体酸催化高酸值花椒籽油酯化降酸反应

王伟涛¹, 卢萍¹, 马养民^1,2, 李娜¹, 杨秀芳¹

1 陕西科技大学化学与化工学院, 教育部轻化工助剂化学与技术重点实验室, 陕西西安 710021;
2 陕西农产品加工技术研究院, 陕西西安 710021

收稿日期:2016-11-16 修回日期:2017-03-27 出版日期:2017-07-05 发布日期:2017-07-05
通讯作者: 马养民,教授,主要从事天然产物分离及有机合成研究。
作者简介:王伟涛(1985-),男,博士,讲师,主要从事绿色催化反应研究。E-mail:wwt1806@163.com。
基金资助:
陕西省科技厅重大科技创新计划（2013ZKC（二）07-03）、中国博士后基金（2015M572514）及陕西省科技统筹创新工程计划（2016KTTSNY03-04）项目。

Solid acid catalyst for the esterification of high free fatty acids of Zanthoxylum bungeanum seed oil

WANG Weitao¹, LU Ping¹, MA Yangmin^1,2, LI Na¹, YANG Xiufang¹

1 College of Chemistry & Chemical Engineering, Shaanxi University of Science & Technology, Xi'an 710021, Shaanxi, China;
2 Shaanxi Research Institute of Agricultural Products Processing Technology, Xi'an 710021, Shaanxi, China

Received:2016-11-16 Revised:2017-03-27 Online:2017-07-05 Published:2017-07-05

摘要/Abstract

摘要： 以甘油为碳源，通过直接炭化-磺化制备了炭基固体酸催化剂。采用傅里叶转换红外光谱（FTIR）、扫描电子显微镜（SEM）、X射线光电子能谱分析（XPS）、X射线衍射（XRD）以及Boehm滴定法等方法对催化剂进行了表征，并将其首次应用于花椒籽油的酯化降酸反应。研究了反应条件对酯化反应的影响，并通过正交试验确定了最佳工艺条件：醇油比为40：1，催化剂用量为10.0%，反应温度为75℃，反应3.5h，花椒籽油的酸值可以由最初的73.75mKOH/g降到1.63mgKOH/g，符合后续制备生物柴油的碱催化酯交换反应要求（ < 2mg KOH/g）；并且该催化剂具有较好的重复利用性。

关键词: 花椒籽油, 高酸值, 酯化反应, 炭基固体酸

Abstract: A solid acid catalyst was synthesized by directly carbonization and sulfonation with glycerol.The solid acid catalyst was characterized with FTIR,SEM,XPS,XRD and Boehm titration methods,and was firstly employed as the catalyst for the esterification of Zanthoxylum bungeanum seed oil (ZSO).The effects of different reaction factors were investigated and the optimum conditions for the esterification reaction were obtained by the orthogonal experiment.The optimum conditions were:methanol-to-oil molar ratio,40:1;catalyst amount,10.0%;reaction temperature,75℃;reaction time,3.5h.The acid value of ZSO was reduced from 73.75mgKOH/g to 1.63mgKOH/g,which satisfied the next process of alkali-catalyzed transesterification for biodiesel production.The catalyst possesses desired stability and activity after being used for six cycles without any recovery treatments.

Key words: Zanthoxylum bungeanum seed oil, high free fatty acids, esterification, carbon-based catalyst

中图分类号:

O643.3

王伟涛, 卢萍, 马养民, 李娜, 杨秀芳. 固体酸催化高酸值花椒籽油酯化降酸反应[J]. 化工进展, 2017, 36(07): 2504-2510.

WANG Weitao, LU Ping, MA Yangmin, LI Na, YANG Xiufang. Solid acid catalyst for the esterification of high free fatty acids of Zanthoxylum bungeanum seed oil[J]. Chemical Industry and Engineering Progress, 2017, 36(07): 2504-2510.

参考文献

[1] YE B,QIU F X,SUN C J,et al. Biodiesel production from soybean oil using heterogeneous solid base catalyst[J]. Journal of Chemical Technology and Biotechnology,2014,89(7):988-997.
[2] ZHANG Y,DUBE M A,MCLEAN D D,et al. Biodiesel production from waste cooking oil:2. Economic assessment and sensitivity analysis[J]. Bioresource Technology,2003,90(3):229-240.
[3] ZHANG J H,LIU J J,MA H N. Esterification of free fatty acids in zanthoxylum bungeanum seed oil for biodiesel production by stannic chloride[J]. Journal of the American Oil Chemists' Society,2012,89:1647-1653.
[4] WU H T,ZHANG J H,LIU Y P,et al. Biodiesel production from Jatropha oil using mesoporous molecular sieves supporting K₂SiO₃ as catalysts for transesterification[J]. Fuel Processing Technology,2014,119(3):114-120.
[5] ZHANG J H,LIANG L F. Acid-catalyzed esterification of Zanthoxylum bungeanum seed oil with high free fatty acids for biodiesel production[J]. Bioresource Technology,2008,99(18):8995-8998.
[6] LUKIC I,KRSTIC J,JOVANOVIC D,et al. Alumina/silica supported K₂CO₃ as a catalyst for biodiesel synthesis from sunflower oil[J]. Bioresource Technology,2009,100(20):4690-4696.
[7] PRABHAVATHI D B L A,VIJAI K R T,VIJAYA L K,et al. A green recyclable SO₃H-carbon catalyst derived from glycerol for the production of biodiesel from FFA-containing karanja (Pongamia glabra) oil in a single step[J]. Bioresource Technology,2014,153(2):370-373.
[8] NGAOSUWAN K,GOODWIN J G,PRASERTDHAM P. A green sulfonated carbon-based catalyst derived from coffee residue for esterification[J]. Renewable Energy,2016,86:262-269.
[9] DAWODU F A,AYODELE O,XIN J Y,et al. Effective conversion of non-edible oil with high free fatty acid into biodiesel by sulphonated carbon catalyst[J]. Applied Energy,2014,114(s1):819-826.
[10] LIU T T,LI Z L,LI W,et al. Preparation and characterization of biomass carbon-based solid acid catalyst for the esterification of oleic acid with methanol[J]. Bioresource Technology,2013,133(2):618-621.
[11] 赵光辉,杨忠华,齐泮仑, 等. 生物柴油副产甘油的综合利用[J]. 化工中间体,2009,5(4):15-18. ZHAO G H,YANG Z H,QI P L. Comprehensive utilization of glycerol as biodiesel byproduct[J]. Chemical Intermediate,2009,5(4):15-18.
[12] 商红岩,田斐,应学海,等. 生物柴油产业副产甘油利用的研究进展[J]. 化工进展,2012,31(s1):18-24. SHANG H Y,TIAN F,YING X H,et al. Preogress in glycerin (the byproduct from production of biodiesel)[J]. Chemical Industry and Engineering Progress,2012,31(s1):18-24.
[13] 刘群,肖国民,尚倩倩. 生物柴油副产物甘油的开发与利用[J]. 精细与专用化学品,2009,17(17):16-20. LIU Q,XIAO G M,SHANG Q Q. The development and application of glycerin from by-products of biodiesel[J]. Fine and Specialty Chemicals,2009,17(17):16-20.
[14] WANG Y,OU S Y,LIU P Z,et al. Preparation of biodiesel from waste cooking oil via two-step catalyzed process[J]. Energy Conversion and Management,2007,48(1):184-188.
[15] 动植物油脂酸值和酸度测定:GB/T 5530-2005[S]. 北京:中国标准出版社,2005. Animal and vegetable fats and oils-determination of acid value and acidity:GB/T 5530-2005[S]. Beijing:Standards Press of China,2005.
[16] BOEHM H P. Some aspects of the surface chemistry of carbon blacks and other carbons[J]. Carbon,1994,32(5):759-769.
[17] FOAD ADIB A B,BANDOSZ T J. Analysis of the relationship between H₂S removal capacity and surface properties of unimpregnated activated carbons[J]. Environmental Science & Technology,2000,34(4):686-692.
[18] PEJOV L,RISTOVA M,ŠOTRAJANOV B. A gradient-corrected density functional study of structure,harmonic vibrational frequencies and charge distribution of benzenesulfonate anion on the ground-state potential energy surface[J]. Journal of Molecular Structure,2000,555(1):341-349.
[19] SWIDERSKI G,KALINOWASA M,SWISLOCKA R,et al. Spectroscopic (FT-IR,FT-Raman and ¹H and ¹³C NMR) and theoretical in MP2/6-311++G(d,p) and B3LYP/6-311++G(d,p)levels study of benzenesulfonic acid and alkali metal benzenesulfonates[J]. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2013,100:41-50.
[20] PENG L,PHILIPPAERTS A,KE X,et al. Preparation of sulfonated ordered mesoporous carbon and its use for the esterification of fatty acids[J]. Catalysis Today,2010,150(1/2):140-146.
[21] TSUBOUCHI N,XU C,OHTSUKA Y. Carbon crystallization during high-temperature pyrolysis of coals and the enhancement by calcium[J]. Energy & Fuels,2003,17(5):1119-1125.
[22] LIANG X Z,ZENG M F,QI C Z. One-step synthesis of carbon functionalized with sulfonic acid groups using hydrothermal carbonization[J]. Carbon,2010,48(6):1844-1848.
[23] XU L L,WANG Y H,YANG X,et al. Preparation of mesoporous polyoxometalate-tantalum pentoxide composite catalyst and its application for biodiesel production by esterification and transesterification[J]. Green Chemistry,2008,10(7):746-755.

固体酸催化高酸值花椒籽油酯化降酸反应

Solid acid catalyst for the esterification of high free fatty acids of Zanthoxylum bungeanum seed oil

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	常耀萍, 官修帅, 郑谦, 靳山彪, 张长明, 张小超. 水热法制备3D花球状Bi₂SiO₅及其光催化油酸酯化反应[J]. 化工进展, 2022, 41(8): 4181-4191.
[2]	刘朋, 蒋剑春, 陈水根, 徐俊明, 李静, 夏海虹. 高酸值废弃油脂制备生物柴油的预酯化[J]. 化工进展, 2015, 34(08): 3015-3018,3064.
[3]	孙洪志，王倩，宋名秀，阿不都拉江?那斯尔，王付燕，朱维群. CO2化学利用的研究进展[J]. 化工进展, 2013, 32(07): 1666-1672.
[4]	王筠翔1，陈慕华1，2，刘准2，曹惠庆2，朱新宝1，2. HZSM-5分子筛催化合成癸二酸二丁氧基乙酯[J]. 化工进展, 2012, 31(12): 2720-2723.
[5]	蒋平平，张书源，冷炎，董玉明，张萍波. 催化合成环保增塑剂的研究及其应用进展[J]. 化工进展, 2012, 31(05): 953-964.
[6]	李工，徐恒，刘维桥，吴非克，佟惠娟. 新型环己亚胺类离子液体的合成及其催化酯化反应性能[J]. 化工进展, 2012, 31(04): 901-906.
[7]	陶维红，杨立荣，徐刚，邰玉蕾，王立，吴坚平. 磁性多孔微粒对脂肪酶的固定化 [J]. 化工进展, 2011, 30(7): 1584-.
[8]	念保义，黄志华，罗菊香，牛玉. 脂肪酶转酯化和水解反应拆分薄荷醇的研究进展 [J]. 化工进展, 2011, 30(6): 1320-.
[9]	张淑新. 酸性离子液体催化合成草酸二乙酯 [J]. 化工进展, 2011, 30(2): 407-.
[10]	万庆梅，金一丰，王胜利 . SO42-/TiO2-Al2O3催化合成双季戊四醇六脂肪酸酯[J]. 化工进展, 2011, 30(12): 2739-.
[11]	赵地顺1，刘猛帅1，徐智策1，付江涛1，任培兵2. 离子液体催化合成酯研究进展[J]. 化工进展, 2011, 30(10): 2287-.
[12]	李柏春，张昌伟，段贵贤. 催化精馏合成乙酸丁酯工业实验 [J]. 化工进展, 2010, 29(9): 1785-.
[13]	李健1，饶小平1，商士斌1，2，高艳清1. 松香多元酸的制备及其应用研究进展 [J]. 化工进展, 2010, 29(11): 2103-.
[14]	王欣，宋航，许超，李江，杜开峰. 响应面法优化离子液体催化合成乳酸乙酯 [J]. 化工进展, 2009, 28(6): 1032-.
[15]	劳锡寮，方岩雄，周蓓蕾，黄宝华，张焜. 溶胶-凝胶法负载离子液体[hnmp]HSO4催化剂在酯化反应中的应用 [J]. 化工进展, 2009, 28(11): 1941-.