乙烯路线制备甲基丙烯酸甲酯研究进展

doi:10.16085/j.issn.1000-6613.2018-0839

摘要/Abstract

摘要：

甲基丙烯酸甲酯（MMA）是一种重要的基础有机化工原料，主要用于生产有机玻璃、塑料改性剂及表面涂料等诸多行业，具有非常广阔的发展前景，MMA 合成路线众多。本文综述了以乙烯为起始原料，经过羰基化反应制备丙醛、丙酸和丙酸甲酯等中间产物，然后经羟醛缩合反应制备MMA的研究进展。概述了乙烯制备MMA的3条工艺路线及其发展趋势，指出中间产物与甲醛的缩合反应是乙烯路线的关键步骤，重点介绍了羟醛缩合反应及其催化剂的研究现状。目前用于气相催化羟醛缩合反应的催化剂主要有V、Si、P酸性催化剂和K、Cs碱性催化剂，其中以Cs为主活性组分的碱性催化剂研究最为广泛，载体种类、助剂、制备方法、反应条件等对催化剂的活性、选择性和寿命等具有较大影响。为进一步改善催化剂的性能，需加强对羟醛缩合反应催化机理的研究，具有酸碱两性的复合催化剂是今后重点研究方向。

关键词: 甲基丙烯酸甲酯, 乙烯, 羟醛缩合, 催化剂

Abstract:

Methyl methacrylate (MMA) is an important raw material in organic industry. It is widely used in the production of organic glass (PMMA), plastic modifier and surface coating and so on. It has a very broad development prospect and many synthetic routes have been adopted for its production. This paper reviews the development of the ethylene route for the preparation MMA. Ethylene is used as the starting material the intermediates such as propionaldehyde, propionic acid and methyl propionate may be obtained through the carboxylation reaction. Therefore, there are three routes to prepare MMA by the aldol condensation reaction based on these intermediates, and their development trend is also summarized. The aldol condensation reaction of these intermediates with formaldehyde is the key step of ethylene route, so the research status of aldol condensation reaction and its catalysts are emphasized in this paper. At present, V, Si, P based acid catalysts and K, Cs based basic catalysts are often used in the gas phase catalytic aldol condensation reaction. Among them, the Cs-based catalysts are the most widely studied. The activity, selectivity, stability of the catalysts are affected by the supports, promoters, preparations and process conditions. To improve the performance of the catalysts, it is necessary to strengthen the basic researches on the mechanism for aldol condensation reaction, and the acid-base composite catalysts are also the key research direction in the future.

Key words: methyl methacrylate, ethylene, aldol condensation, catalyst

中图分类号:

TQ032.4

李斌, 解铭, 齐翔, 张乐, 王光远, 申利红, 王博. 乙烯路线制备甲基丙烯酸甲酯研究进展[J]. 化工进展, 2019, 38(04): 1739-1745.

Bin LI, Ming XIE, Xiang QI, Le ZHANG, Guangyuan WANG, Lihong SHEN, Bo WANG. Progress in preparation of methyl methacrylate by ethylene route[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1739-1745.

图/表 3

参考文献 33

1	谭捷 . 甲基丙烯酸甲酯生产技术研究进展[J]. 精细与专用化学品, 2016, 24(10): 45-47.
	TAN Jie . Research progress on the production technologies of methyl methacrylat[J]. Fine and Specialty Chemicals, 2016, 24(10): 45-47.
2	杨学萍 . 甲基丙烯酸甲酯生产工艺及技术经济比较[J]. 化工进展, 2004, 23(5): 506-510.
	YANG Xueping . Processes for the production of MMA and their techno-economic comparison[J]. Chemical Industry and Engineering Progress, 2004, 23(5): 506-510.
3	谭捷, 吴明杨 . 甲基丙烯酸甲酯生产技术进展及国内市场分析[J]. 弹性体, 2017, 27(2): 67-71.
	TAN Jie , WU Mingyang . Technology progress and market analysis of methyl methacrylate in China[J].China Elastomerics, 2017, 27(2): 67-71.
4	左杰, 田绍友 . 甲基丙烯酸甲酯工业化合成路线及发展现状[J]. 天津化工, 2017, 31(3): 13-16.
	ZUO Jie , TIAN Shaoyou . The industrialization synthetic process of MMA and the current development situation[J]. Tianjin Chemical Industry, 2017, 31(3): 13-16.
5	双玥 . 甲基丙烯酸甲酯生产工艺及其经济性比较[J]. 化学工业, 2014, 32(7): 27-31.
	SHUANG Yue . Processes for the production of MMA and the comparison of technical economy[J]. Chemical Industry, 2014, 32(7): 27-31.
6	NAGAI K . New developments in the production of methyl methacrylate[J]. Applied Catalysis A：General, 2001, 221(1/2): 367-377.
7	MERGER F , FOERSTER H J . Alpha-alkyl-acrolein production from alkanal-by reaction with formaldehyde in presence of amine and carboxylic acid：US 4408079[P]. 1982-01-15.
8	DUEMBGEN G , FOUQUET G , KRABETZ R , et al . Preparation of alpha-alkyl-acrolein derivates-comprises liquid phase reaction of alkanal(s) with formaldehyde in the presence of second amine(s): US 4496770[P]. 1983-03-28.
9	ZHOU Lilong , WANG Lei , ZHANG Suojiang , et al . Effect of vanadyl species in Keggin-type heteropoly catalysts in selective oxidation of methacrolein to methacrylic acid[J]. Journal of Catalsis, 2015, 329：431-440.
10	ZHANG Heng , YAN Ruiyi , YANG Li , et al . Investigation of Cu- and Fe-doped CsH₃PMo₁₁VO₄₀ heteropoly compounds for the selective oxidation of methacrolein to methacrylic acid[J]. Industrial & Engineering Chemistry Research, 2013, 52：4484-4490.
11	陈晓辉, 陈宪, 许锡恩 . 气相羟醛缩合法制MA及MMA研究进展[J]. 工业催化, 1998(5): 3-10.
	CHEN Xiaohui , CHEN Xian , XU Xi’en . Progress in the research on vapor-phase aldol condensation to MA and MMA[J]. Industrial Catalysis, 1998(5): 3-10.
12	SUZUKI K , YAMAGUCHI T , MATSUSHITA K , et al . Aerobic oxidative esterification of aldehydes with alcohols by gold-nickel oxide nanoparticle catalysts with a core-shell structure[J]. ACS Catalysis, 2013, 3(8)：1845-1849.
13	WANG Lianyue , LI Jun , DAI Wen , et al . Facile and efficient gold-catalyzed aerobic oxidative esterification of activated alcohols[J]. Green Chemistry, 2014, 16 (4)：2164-2173.
14	谭露璐, 钱君律, 伍艳辉 . 羟醛缩合催化剂研究进展[J]. 化学工业与工程, 2006, 23(1): 70-77.
	TAN Lulu , QIAN Junlv , WU Yanhui . Advances in catalysts of aldol condensation[J]. Chemical Industry and Engeering, 2006, 23(1): 70-77.
15	NIIZUMA H , KOJIMA S , KATO H , et al . (Meth)Acrylic acid preparation from acetic or propionic acid- and formaldehyde, in gas phase using solid catalyst containing boron or phosphorus oxide having acid site of high acid strength：EP164614[P]. 1985-05-20.
16	GO I, KATSUO B , TAKAYUKI M . Process for producing methyl methacrylate：US 0188151[P]. 2002-12-12.
17	JACKSON S , JOHNSON D , KELLY D , et al . Catalysts for the production of unsaturated acids or esters：US6544924[P]. 2003-04-08.
18	MAKARAND R G , JAMES J S , JOSEPH R Z . Synthesis of methyl methacrylate by vapor phase condensation of formaldehyde with propionate derivatives[J]. Catallysis Today, 1997, 36：243-254.
19	MAMORU Ai . Vapor-phase adol condensation of formaldehyde with propionic acid on vanadium pentoxide phosphorus pentoxide[J]. Applied Catalysis, 1988, 36：221-230.
20	MAMORU Ai . Reaction of methyl propionate with methylal over V-Si-P ternary oxide catalysts[J]. Bulletin of the Chemical Society of Japan, 1990, 63(12): 3722-3724.
21	SPIVEY J J , GOGATE M R , ZOELLER J R . Acid-base properties of ternary metal oxide catalysts for vapor phase condensation reactions[J]. Proceedings of the International Congress on Catalysis, 1996, 41(1): 233-237.
22	MAMORU Ai, Fujihashi HIDEYUKI , Hosoi SANAE . Production of methacrylic acid by vapor-phase aldol condensation of propionic acid with formaldehyde over silica-supported metal phosphate catalysts[J]. Applied Catalysis A：General, 2003, 252：185-191.
23	PEARSON A . Process for the condensation of formaldehyde with carboxylic acids：US 3840587[P]. 1972-08-03.
24	BAILEY O H , MONTAG R A , YOO J S . Methacrylic acid synthesis: Ⅰ. Condensation of propionic acid with formaldehyde over alkali metal cation on silica catalysts[J]. Applied Catalysis A：General, 1992, 88：163-177.
25	YOO J S . Silica supported metal-doped cesium ion catalyst for methacrylic acid synthesis via condensation of propionic acid with formaldehyde[J]. Applied Catalysis A：General, 1993, 102：215-232.
26	MONTAG R A ， MEKENNA S T . Catalyst and process for production an alpha beta-ethylenically unsaturated monacarboxylic acid: US 4801571[P]. 1989-07-31.
27	OKITA M . Production of methacrylic acid and its ester：JP 05331098[P]. 1983-12-03.
28	TAI J R , DAVIS R J . Synthesis of methacrylic acid by aldol condensation of propionicacid with formaldehyde over acid-base bifunctional catalysts[J]. Catalsis Today, 2007, 123：42-49.
29	GIANCARLO A , PIETRO M . Methyl methacrylate by gas phase catalytic condensation of formaldehyde with methyl propionate[J]. Applied Catalysis, 1983, 6：293-306.
30	冯裕发, 周维友, 刘洋, 等 . K/γ-Al₂O₃ 催化丙酸甲酯合成甲基丙烯酸甲酯[J]. 化工进展, 2015, 34(3): 797-801.
	FENG Yufa , ZHOU Weiyou , LIU Yang , et al . Synthesis of methyl methacrylate from methyl propionate over K/γ-Al₂O₃ catalyst[J]. Chemical Industry and Engineering Progress, 2015, 34(3): 797-801.
31	LI Bin , YAN Ruiyi , WANG Lei , et al . Synthesis of methyl methacrylate by aldol condensationof methyl propionate with formaldehyde over acid–base bifunctional catalysts[J]. Catalysis Letter, 2013, 143：829-838.
32	LI Bin , YAN Ruiyi , WANG Lei , et al . SBA-15 Supported cesium catalyst for methyl methacrylate synthesis via condensation of methyl propionate with formaldehyde[J]. Industrial & Engineering Chemistry Research, 2014, 53：1386-1394.
33	WANG Yanan , YAN Ruiyi , LV Zhaopo , et al . Lanthanum and cesium-loaded SBA-15 catalysts for MMA synthesis by aldol condensation of methyl propionate and formaldehyde[J]. Catalysis Letter, 2016, 146：1808-1818.

研究者	催化剂	酸醛摩尔比	转化率/%		选择性/%		收率/%
研究者	催化剂	酸醛摩尔比	PA	HCHO	PA	HCHO	PA	HCHO
Mamoru^[19]	V₂O₂ (P₂O₇)	2∶1		50.0		78.0		39.0
Mamoru^[20]	V/Si₈/P_2.2	2∶1		70.7		82.0		58.0
Spivey等^[21]	Nb₂O₅/SiO₂	5∶1						71.0
Mamoru等^[22]	Sn/Si₈/P_2.3	2∶1		68.6		69		47.2
Pearson^[23]	KOH/SiO₂	4.5∶1		72.0		78.0		56.0
Bailey等^[24]	CsOH/SiO₂	3∶2	30.0		89.0			27.0
Yoo^[25]	Cs/Bi/SiO₂	3∶2	32.3		89.4		28.8
Montag等^[26]	Cs/SiO₂-SnO₂	3∶2	39.0		91.0		35.5
Mitsubish^[27]	Si-Cs-W-Ag-O	2∶1	40.5		98.8		40.0
Tai等^[28]	Cs/SiO₂	3∶2	12.9		96.0		12.4

研究者	催化剂	酸醛摩尔比	转化率/%		选择性/%		收率/%
研究者	催化剂	酸醛摩尔比	PA	HCHO	PA	HCHO	PA	HCHO
Mamoru^[19]	V₂O₂ (P₂O₇)	2∶1		50.0		78.0		39.0
Mamoru^[20]	V/Si₈/P_2.2	2∶1		70.7		82.0		58.0
Spivey等^[21]	Nb₂O₅/SiO₂	5∶1						71.0
Mamoru等^[22]	Sn/Si₈/P_2.3	2∶1		68.6		69		47.2
Pearson^[23]	KOH/SiO₂	4.5∶1		72.0		78.0		56.0
Bailey等^[24]	CsOH/SiO₂	3∶2	30.0		89.0			27.0
Yoo^[25]	Cs/Bi/SiO₂	3∶2	32.3		89.4		28.8
Montag等^[26]	Cs/SiO₂-SnO₂	3∶2	39.0		91.0		35.5
Mitsubish^[27]	Si-Cs-W-Ag-O	2∶1	40.5		98.8		40.0
Tai等^[28]	Cs/SiO₂	3∶2	12.9		96.0		12.4

开发者	催化剂	酯醛摩尔比	转化率/%		选择性/%		收率/%
开发者	催化剂	酯醛摩尔比	MP	HCHO	MP	HCHO	MP	HCHO
Giancarlo等^[29]	Ta₂O₅/SiO₂	6∶1	7.1		39.8		5.1
Mamoru^[19]	V₂O₂ (P₂O₇)	2∶1		29.5		86.4		25.5
Mamoru^[20]	VSi₈P_2.8	2∶1		51.7		81.2		42.0
Pearson^[23]	Cs₂CO₃/SiO₂	4.5∶1		67.1		92.0		61.6
Mamoru^[20]	CsOH/SiO₂	5∶1	14.0		91.5		12.8
冯裕发等^[30]	K/γ-Al₂O₃	1∶1	51.5		76.1		39.2
Li等^[31]	Zr-Mg-Cs/ SiO₂	1∶1	18.0		88.0		15.8
Li等^[32]	Zr-Fe-Cs/SBA-15	1∶1	26.0		93.0		24.2
Wang等^[33]	La-Cs/SBA-15	1∶1	29.2		90.4		26.4

开发者	催化剂	酯醛摩尔比	转化率/%		选择性/%		收率/%
开发者	催化剂	酯醛摩尔比	MP	HCHO	MP	HCHO	MP	HCHO
Giancarlo等^[29]	Ta₂O₅/SiO₂	6∶1	7.1		39.8		5.1
Mamoru^[19]	V₂O₂ (P₂O₇)	2∶1		29.5		86.4		25.5
Mamoru^[20]	VSi₈P_2.8	2∶1		51.7		81.2		42.0
Pearson^[23]	Cs₂CO₃/SiO₂	4.5∶1		67.1		92.0		61.6
Mamoru^[20]	CsOH/SiO₂	5∶1	14.0		91.5		12.8
冯裕发等^[30]	K/γ-Al₂O₃	1∶1	51.5		76.1		39.2
Li等^[31]	Zr-Mg-Cs/ SiO₂	1∶1	18.0		88.0		15.8
Li等^[32]	Zr-Fe-Cs/SBA-15	1∶1	26.0		93.0		24.2
Wang等^[33]	La-Cs/SBA-15	1∶1	29.2		90.4		26.4

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