KF改性MgAl水滑石催化酯交换合成碳酸乙烯酯

doi:10.16085/j.issn.1000-6613.2019-1657

摘要/Abstract

摘要：

通过简单的共沉淀法制备了MgAl水滑石（Mg₃Al₁-LDH）。随后通过超声法成功合成了KF负载的Mg₃Al₁-LDH（KF/Mg₃Al₁-LDH）前体，并在450℃下煅烧5h，得到一系列KF/Mg₃Al₁-LDO催化剂。使用X射线衍射、热重、红外光谱、N₂-吸脱附、CO₂-程序升温脱附对所制备的催化剂进行表征。表征结果显示样品具有典型的水滑石结构、较好的热稳定性和较高的碱强度。以KF-Mg₃Al₁-LDO作为催化剂用于碳酸二甲酯（DMC）和乙二醇（EG）酯交换合成碳酸乙烯酯（EC）的反应中，考察了反应工艺条件对催化性能的影响。KF/Mg₃Al₁-LDO催化剂表现出良好的催化性能。在酯醇摩尔比为1∶1、催化剂用量占DMC质量2%、反应温度为100℃、反应时间为4h的条件下，EC收率达到最高（54%）。催化剂可循环使用5次以上而催化活性没有显著下降。

关键词: 共沉淀法, 水滑石, 氟化钾（KF）, 酯交换, 碳酸乙烯酯

Abstract:

MgAl hydrotalcite (Mg₃Al₁-LDH) was prepared by a simple coprecipitation method. Then KF-supported Mg₃Al₁-LDH (KF/Mg₃Al₁-LDH) was successfully synthesized by ultrasonic method and was further calcined at 450℃ for 5h to obtain a series of KF/Mg₃Al₁-LDO catalysts. The synthesized catalysts were characterized by means of XRD, TG, FTIR, N₂ adsorption-desorption and CO₂-TPD. The characterization results indicated that the synthesized sample had typical hydrotalcite structure, good thermal stability and relatively high basic strength. The KF/Mg₃Al₁-LDO materials were employed as catalysts for the synthesis of ethylene carbonate (EC) via transesterification between dimethyl carbonate (DMC) and ethylene glycol (EG). The influences of reaction conditions on the catalytic performance have been investigated. Under the reaction conditions of molar ratio of ester to alcohol of 1∶1, 2% weight percentage of catalyst in DMC, reaction temperature of 100℃, and reaction time of 4h, the highest EC yield (54%) was achieved. Furthermore, the catalyst could be reused for at least five times without significant loss of catalytic activity.

Key words: coprecipitation method, hydrotalcite, potassium fluoride, transesterification, ethylene carbonate

中图分类号:

TQ262.2

王军, 赵妍, 邹欣, 柳娜, 许杰, 薛冰. KF改性MgAl水滑石催化酯交换合成碳酸乙烯酯[J]. 化工进展, 2020, 39(7): 2670-2676.

Jun WANG, Yan ZHAO, Xin ZOU, Na LIU, Jie XU, Bing XUE. Synthesis of ethylene carbonate by transesterification over KF modified MgAl hydrotalcite catalyst[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2670-2676.

参考文献

1	SU W Y, SPERANZA G P. Process for preparing alkylene carbonate：US5003084[P]. 1991-03-26.
2	谭亚南, 何霖, 王凯, 等. 环氧乙烷和二氧化碳合成碳酸乙烯酯催化剂研究进展[J]. 化工进展, 2017, 36(1): 241-246.
2	TAN Y N, HE L, WANG K, et al. Research progress of catalyst for ethylene carbonate synthesis from ethylene oxide and carbon dioxide[J]. Chemical Industry and Engineering Progress, 2017, 36(1): 241-246.
3	程牧曦, 王凯, 何霖, 等. 环氧乙烷和二氧化碳酯化制备碳酸乙烯酯反应催化剂[J]. 化工进展, 2017, 36(1): 274-277.
3	CHENG M X, WANG K, HE L, et al. Catalyst study of the ethylene oxide and carbon dioxide esterification reaction to produce ethylene carbonate[J]. Chemical Industry and Engineering Progress, 2017, 36(1): 274-277.
4	杨超. 碳酸乙烯酯合成及其应用的研究[D]. 西安: 西北大学, 2010.
4	YANG C. Study on synthesis and application of ethylene carbonate[D]. Xi’an: Northwest University, 2010.
5	GOMES C R, FERREIRA D M, VOMSTANTION C J L, et al. Selectivity of the cyclic carbonate formation by fixation of carbon dioxide into epoxides catalyzed by Lewis bases[J]. Tetrahedron Lett., 2008, 49(48): 6879-6881.
6	李杨, 朱培玉, 王延儒. 溴化四乙铵催化合成碳酸乙烯酯反应研究[J]. 南京师范大学学报, 2007, 7(1): 59-62.
6	LI Y, ZHU P Y, WANG Y R. The synthesis of ethylene carbonate using tetraethylammonium bromide(TEAB) as the catalyst[J]. Journal of Nanjing Normal University, 2007, 7(1): 59-62.
7	胡斌, 卓仁禧, 范昌烈. 一种合成环状碳酸酯的新方法[J]. 化学试剂, 1998, 20(6): 355-356.
7	HU B, ZHUO R X, FAN C L. Study on a new synthetic method for cyclic carbonates[J]. Chemical Reagents, 1998, 20(6): 355-356.
8	ZHANG X, MONTEZ R. Process for preparing carbonate and diol products: US8735608[P]. 2014-05-27.
9	GAO B, QI C, LIU Q. Immobilization of quaternary ammonium salts on grafting particle polystyrene/SiO₂ and preliminary study of application performance[J]. Applied Surface Science, 2008, 254 (13): 4159-4165.
10	吴青海, 任天瑞. 固载化离子液体催化环氧乙烷和二氧化碳合成碳酸乙烯酯[J]. 过程工程学报, 2012, 12(2): 302-309.
10	WU Q H, REN T R. Synthesis of ethylene carbonate via carbon dioxide and ethylene oxide catalyzed by immobilized ionic liquid[J]. The Chinese Journal of Process Engineering, 2012, 12(2): 302-309.
11	FATIMAHA I, RUBIYANTOA D, NUGRAHAB J. Preparation, characterization, and modelling activity of potassium flouride modified hydrotalcite for microwave assisted biodiesel conversion[J]. Sustainable Chemistry and Pharmacy, 2018, 8: 63-70.
12	郤谷生. MgAl复合氧化物负载KF固体碱催化剂及其无溶剂条件下CC键形成反应的催化性能[D]. 北京: 北京化工大学, 2010.
12	XI G S. KF-supported MgAl mixed oxide as solid base catalyst for CC bond formation under solven-free conditions[D]. Beijing: Beijing University of Chemical Technology, 2010.
13	PéREZ R J, ABELLó S, PERS N M V D. Influence of the divalent cation on the thermal activation and reconstruction of hydrotalcite-like compounds[J]. J. Phys. Chem. C, 2007,111(9): 3642-3650.
14	王登峰, 张学兰, 柏冬, 等. Mg/Al复合氧化物催化丙酮和碳酸二甲酯合成乙酰乙酸甲酯[J]. 化工进展, 2012, 31(9): 1985-1989.
14	WANG D F, ZHANG X L, BO D, et al. Synthesis of methyl acetoacetate from acetone and dimethyl carbonate over Mg/Al mixed oxides[J]. Chemical Industry and Engineering Progress, 2012, 31(9): 1985-1989.
15	TANG Y, REN H M, CHANG F Q, et al. Nano KF/Al₂O₃ particles as an efficient catalyst for no-glycerol biodiesel production by coupling transesterification[J]. RSC Advances, 2017, 7(10): 5694-5700.
16	LIU N, WU Z M, LI M, et al. A novel strategy for constructing mesoporous solid superbase catalysts: bimetallic Al-La oxides supported on SBA-15 modified with KF[J]. Catalysis Science & Technology, 2017, 7(3): 725-733.
17	SUN J, YANG J Y, LI S P, et al. Preparation and characterization of fluorine modified oxides for transesterification[J]. Catalysis Communications, 2015, 59: 88-91.
18	LI Y, JIANG Y X. Preparation of a palygorskite supported KF/CaO catalyst and its application for biodiesel production via transesterification[J]. RSC Advances, 2018, 8(29): 16013-16018.
19	LOU S, JIA L, GUO X, et al. Synthesis of ethylene glycol monomethyl ether monolaurate catalysed by KF/NaAlO₂as a novel and efficient solid base[J]. RSC Advances, 2016, 6(9): 6921-6931.
20	ABELLO S, MEDINA F, TICHIT D, et al. Aldol condensations over reconstructed Mg-Al hydrotalcites: structure-activity relationships related to the rehydration method[J]. Chem. Eur. J., 2005, 11(2): 728-739.
21	FATIMAH I, ANDIENA R Z, YUDHA S P. Preparation of KF-modified kaolinite as green and reusable catalyst for microwave assisted biodiesel conversion[J]. IOP Conference Series: Materials Science and Engineering, 2017, 172(1): 12-26.
22	陆敏, 刘媛, 李树白，等. 类水滑石催化剂催化合成碳酸二丙酯[J]. 化工进展, 2013, 32(5): 1070-1073.
22	LU M, LIU Y, LI S B, et al. Synthesis of dipropyl carbonate from dimethyl carbonate and propanol catalyzed by hydrotal cite-like catalyst[J]. Chemical Industry and Engineering Progress, 2013, 32(5): 1070-1073.
23	YANG L M, LV P M, WANG Z M, et al. Promotional effect of transition metal doping on the properties of KF/CaO catalyst for biodiesel synthesis[J]. International Journal of Green Energy, 2017, 14(9): 784-791.

[1]	寇佳伟, 程淑艳, 程芳琴. 类水滑石基催化剂光催化二氧化碳还原研究进展[J]. 化工进展, 2022, 41(S1): 190-198.
[2]	陈丹阳, 朱建宇, 吴勤, 王自庆, 张金利. KF/MgO催化甘油和碳酸二甲酯酯交换合成甘油碳酸酯[J]. 化工进展, 2022, 41(4): 2082-2089.
[3]	朱长辉, 朱文超, 罗嘉, 田保河, 孙佳琳, 邹志云. 微波强化酯交换反应制备生物柴油研究进展[J]. 化工进展, 2022, 41(10): 5145-5154.
[4]	岳倩倩, 高李璟, 肖国民, 魏瑞平, 雷严. 生物柴油连续化生产设备及工艺进展[J]. 化工进展, 2021, 40(S2): 81-88.
[5]	王志鸿, 朱华威, 余海峰, 江浩, 李春忠. 共沉淀法制备高镍氧化物正极材料前体研究进展[J]. 化工进展, 2021, 40(9): 5097-5106.
[6]	陶宁, 徐亚津, 冯宇辰, 吕建华, 刘继东. ZrO₂-Al₂O₃复合氧化物催化反应精馏合成碳酸二甲酯[J]. 化工进展, 2021, 40(5): 2603-2612.
[7]	屈亚松, 俞小花, 谢刚, 史春阳, 杨亚刚, 李永刚. Zn-Al-Ce水滑石在Zn-Ni二次电池中的电化学性能[J]. 化工进展, 2021, 40(3): 1558-1564.
[8]	张华成, 孔令奇, 李忠, 郑华艳. 基于CuAl-LDH载体制备高分散Cu/ZnO/Al₂O₃催化剂及其催化性能[J]. 化工进展, 2021, 40(2): 881-889.
[9]	李俏春, 郭恩惠, 李阳, 米杰, 武蒙蒙. 类水滑石衍生锌基复合氧化物的硫化再生行为[J]. 化工进展, 2021, 40(11): 6278-6286.
[10]	褚俊杰, 常洁, 罗志斌, 侯明明, 李谦. 环氧乙烷吸收和转化合成碳酸酯工艺研究进展[J]. 化工进展, 2021, 40(1): 195-204.
[11]	张洁, 贾爱忠, 李芳, 赵新强, 王延吉. 酯交换法合成碳酸甲乙酯催化剂的研究进展[J]. 化工进展, 2020, 39(11): 4435-4445.
[12]	邹建军, 鲁婷, 王家喜. 氨基甲酸酯基丙烯酸酯的合成及其光固化性能[J]. 化工进展, 2019, 38(04): 1947-1952.
[13]	张春光, 谭青峰, 张天琪, 赵愉生. 水滑石法制备渣油加氢催化剂[J]. 化工进展, 2018, 37(11): 4303-4307.
[14]	袁川, 鲁厚芳, 刘长军, 蒋炜, 刘颖颖, 梁斌. 水和游离脂肪酸对DBU催化制备生物柴油的影响[J]. 化工进展, 2018, 37(09): 3386-3392.
[15]	宋孟璐, 杨先贵, 蔡晓东, 王公应. 聚碳酸酯二元醇的合成及应用研究进展[J]. 化工进展, 2018, 37(06): 2295-2301.