甲基丙烯酸甲酯生产工艺及所用贵金属催化剂研究进展

doi:10.16085/j.issn.1000-6613.2020-0540

摘要/Abstract

摘要：

综述了近年来合成甲基丙烯酸甲酯（MMA）主要生产工艺技术及贵金属催化剂在以异丁烯/叔丁醇为原料合成MMA反应的研究进展，重点对负载型金催化剂在氧化酯化合成MMA反应的研究工作进行了介绍。相比于贵金属钯催化剂，金催化剂因反应条件温和，活性、选择性高等优点成为钯催化剂的潜在替代者。然而，金催化剂较低的稳定性限制了其工业化应用。本文对比分析了近年来金催化剂合成MMA的研究结果，阐述了其在提升稳定性方面的相关策略，揭示了金催化体系结构与反应性能之间的关联，并对机理进行了讨论。未来采用特殊手段合成结构可控、尺寸可调的负载型金催化剂以及通过添加助剂或其他金属的方式调变催化剂几何结构、电子结构等将是该领域的研究方向。

关键词: 催化剂, 纳米粒子, 固定床, 氧化, 酯化

Abstract:

The research progresses on the main production technologies and the noble metal catalysts for synthesis of methyl methacrylate (MMA) from isobutylene/tert-butyl alcohol in recent years were systematically reviewed. The researches on the synthesis of MMA with supported gold catalysts by oxidative esterification were mainly introduced. In comparison with the precious metal Pd catalysts, the supported gold catalysts emerge to be potential candidates due to their mild reaction conditions, high activities and selectivities. However, the low stabilities of gold catalysts greatly limit their industrial applications. Herein, the catalytic performances of gold catalysts for synthesis of MMA in recent years were compared and analyzed. The strategies on improving the stabilities of gold catalysts were elaborated. The relevance of the gold catalysts’ structure and their performances was displayed. In addition, the reaction mechanisms of these systems were discussed. In the future, preparation of supported gold catalysts with controllable structures and sizes by special means and modulation of the geometric structure and electronic structure of the catalysts by adding additives or other metals will be the research directions of this field.

Key words: catalyst, nano particle, fixed bed, oxidation, esterification

中图分类号:

TQ426.6

李华胤, 李洁, 谭媛, 丁云杰. 甲基丙烯酸甲酯生产工艺及所用贵金属催化剂研究进展[J]. 化工进展, 2021, 40(1): 183-194.

Huayin LI, Jie LI, Yuan TAN, Yunjie DING. Research progress on production technology and noble metal catalyst for synthesis of methyl methacrylate[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 183-194.

参考文献 52

1	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.
30	DIAO Yanyan, YAN Ruiyi, ZHANG Suojiang, et al. Effects of Pb and Mg doping in Al₂O₃-supported Pd catalyst on direct oxidative esterification of aldehydes with alcohols to esters[J]. Journal of Molecular Catalysis A: Chemical, 2009, 303(1/2): 35-42.
31	LIU Hongxia, MA Jing, WEI Dongwei, et al. Insight into the effect of Pd and Pd₃Pb surface structure on activation of reactant O₂ and product H₂O in direct oxidative esterification[J]. Applied Surface Science, 2020, 500: 143852-143870.
2	李斌, 解铭, 齐翔, 等. 乙烯路线制备甲基丙烯酸甲酯研究进展[J]. 化工进展, 2019, 38(4): 1739-1745.
	LI Bing, XIE Ming, QI Xiang, et al. Progress in preparation of methyl methacrylate by ethylene route[J]. Chemical Industry and Engineering Progress, 2019, 38(4): 1739-1745.
32	奚彩明, 陈煜, 周益明, 等. 炭载Pd-Pb合金纳米粒子对甲酸电催化氧化的影响[J]. 高等学校化学学报, 2010, 31(7): 1421-1425.
	XI Caiming, CHEN Yu, ZHOU Yiming, et al. Electrocatalytic oxidation of formic acid on carbon supported Pd-Pb alloy nanoparticles[J]. Chemical Journal of Chinese University, 2010, 31(7): 1421-1425.
3	崔小明. 国内外甲基丙烯酸甲酯的供需现状及发展前景分析[J]. 石油化工技术与经济, 2016, 32(4): 27-33.
	CUI Xiaoming. Supply and demand status of methyl methacrylate at home and abroad and its development analysis[J]. Technology & Economics in Petrochemicals, 2016, 32(4): 27-33.
33	MA Jing, YANG Xueqing, NIE Yan, et al. The influence of hydrophobic carrier, reactant and product during H₂O adsorption on Pd surface for the oxidative esterification of methacrolein to methyl methacrylate[J]. Physical Chemistry Chemical Physics, 2018, 20: 9968-9974.
34	DIAO Yanyan, YANG Pu, YAN Ruiyi, et al. Deactivation and regeneration of the supported bimetallic Pd-Pb catalyst in direct oxidative esterification of methacrolein with methanol[J]. Applied Catalysis B: Environmental, 2013, 142/143: 329-336.
4	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 and methyl methacrylate in China[J]. China Elastomerics, 2017, 27(2): 67-71.
5	王邓军, 田延生, 刘升磊, 等. 甲基丙烯酸甲酯国内市场及生产技术进展[J]. 山东化工, 2018, 47(19): 69-70, 74.
	WANG Dengjun, TIAN Yansheng, LIU Shenglei, et al. Progress on market status and production processes of methyl methacrylate[J]. Shandong Chemical Industry, 2018, 47(19): 69-70, 74.
6	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, 7(7): 27-31.
	SHUANG Yue. Processes for the production of MMA and the comparison of technical economy[J]. Chemical Industry, 2014, 7(7): 27-31.
7	MAHBOUB M J D, J-L DUBOIS, CAVANI F, et al. Catalysis for the synthesis of methacrylic acid and methyl methacrylate[J]. Chemical Society Reviews, 2018, 47: 7703-7738.
8	张大洲, 卢文新, 陈风敬, 等. 甲基丙烯酸甲酯生产技术现状及国内发展趋势[J]. 化肥设计, 2018, 56(5): 6-10.
	ZHANG Dazhou, LU Wenxin, CHEN Fengjing, et al. The status quo of production technology of methyl methacrylate and its development trend in China[J]. Chemical Fertilizer Design, 2018, 56(5): 6-10.
9	陈韶辉, 李涛. 甲基叔丁基醚装置技术现状及发展趋势分析[J]. 石油化工技术与经济, 2020, 36(2): 54-57.
	CHEN Shaohui, LI Tao. Analysis of technology status and development trend of methyl tert-butyl ether plant[J]. Technology & Economics in Petrochemicals, 2020, 36(2): 54-57.
10	金联创. MMA: 2020年国内MMA新建产能与终端需求扩充![EB/OL]. 中国石油和化工网: 综合要闻. [2019-12-31]. .
11	SUGIYAMA H, FISCHER U, ANTONIJUAN E, et al. How do different process options and evaluation settings affect economic and environmental assessments? A case study on methyl methacrylate (MMA) production processes[J]. Process Safety and Environmental Protection, 2009, 87(6): 361-370.
12	GOGATE M R, SPIVEY J J, ZOELLER J R. Synthesis of methyl methacrylate by vapor phase condensation of formaldehyde with propionate derivatives[J]. Catalysis Today, 1997, 36: 243-254.
13	AI M. Formation of methyl methacrylate by condensation of methyl propionate with formaldehyde over silica-supported cesium hydroxide catalysts[J]. Applied Catalysis A: General, 2005, 288: 211-216.
14	AI M, FUJIHASHI H, HOSOI S, et al. 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.
15	NAGAI K. New developments in the production of methyl methacrylate[J]. Applied Catalysis A: General, 2001, 221: 367-377.
16	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 methacrylate[J]. Fine and Specialty Chemicals, 2016, 24(10): 45-47.
17	EBATA S, HIRAYAMA H, UCHIYAMA T, et al. Process for production of alpha-hydroxycarboxylic acid amide: US4987256[P]. 1991-01-22.
18	KOICHI K. Method of producing a methyl methacrylate: EP0941984A2[P]. 1999-09-15.
19	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.
20	WATZENBERGER O, EMIG G, LYNCH D T. Oxydehydrogenation of isobutyric acid with heteropolyacid catalysts: experimental observations of deactivation[J]. Journal of Catalysis, 1990, 124: 247-258.
21	DRENT E. Process for the carbonylation of acetylenically unsaturated compounds: US4739109[P]. 1988-04-19.
22	KURIMOTO I, HASHIBA H, ONODERA H, et al. Catalyst for the production of methacrylic acid: US5153162[P]. 1992-10-06.
23	王艺森, 任万忠, 王磊. 异丁烯(叔丁醇)选择氧化生产甲基丙烯酸甲酯的催化剂研究进展[J]. 山东化工, 2016, 46(11): 45-48.
	WANG Yisen, REN Wanzhong, WANG Lei. Catalyst research advance in production process of methyl methacrylate from isobutene (tert-butyl alcohol) by selective oxidation method[J]. Shandong Industry, 2016, 46(11): 45-48.
35	DIAO Yanyan, HE Hongyan, YANG Pu, et al. Optimizing the structure of supported Pd catalyst for direct oxidative esterification of methacrolein with methanol[J]. Chemical Engineering Science, 2015, 135: 128-136.
36	WANG Baohe, LIU Hongxia, NIE Yan, et al. Insight into the effect of promoter Pb in Pb-Pd catalyst on methyl methacrylate formation via direct oxidative esterification: a DFT study[J]. Applied Surface Science, 2020, 510: 145320-145237.
37	JIANG Li, DIAO Yanyan, HAN Junxing, et al. MgO-SBA-15 supported Pd-Pb catalysts for oxidative esterification of methacrolein with methanol to methyl methacrylate[J]. Chinese Journal of Chemical Engineering, 2014, 22(10): 1098-1104.
38	HAYASHI T, INAGAKI T, ITAYAMA N, et al. Selective oxidation of alcohol over supported gold catalysts: methyl glycolate formation from ethylene glycol and methanol[J]. Catalysis Today, 2006, 117(1/2/3): 210-213.
39	MIYAMURA H, YASUKAWA T, KOBAYASHI S. Aerobic oxidative esterification of alcohols catalyzed by polymer-incarcerated gold nanoclusters under ambient conditions[J]. Green Chemistry, 2010, 12: 776-778.
40	XU Bingjun, LIU Xiaoying, HAUBRICH J, et al. Vapour-phase gold-surface-mediated coupling of aldehydes with methanol[J]. Nature Chemistry, 2010, 2(1): 61-65.
41	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.
42	HAN Junxing, ZHANG Suojiang, ZHANG Juan, et al. Modified extra-large mesoporous silica supported Au-Ni as a highly efficient catalyst for oxidative coupling of aldehydes with methanol[J]. RSC Advances, 2014, 4(102): 58769-58772.
24	彭程, 唐春, 谢继阳, 等. 甲基丙烯酸甲酯清洁合成及催化剂研究进展[J]. 石油化工, 2019, 48(11): 1180-1187.
	PENG Cheng, TANG Chun, XIE Jiyang, et al. Research progress in methyl methacrylate clean synthesis and catalysts[J]. Petrochemical Technology, 2019, 48(11): 1180-1187.
25	CIRIMINNA R, FALLETTA E, PINA C D, et al. Industrial applications of gold catalysis[J]. Angewandte Chemie International Edition, 2016, 55: 14210-14217
26	XU Bingjun, HAUBRICH J, FREYSCHLAG C G, et al. Oxygen-assisted cross-coupling of methanol with alkyl alcohols on metallic gold[J]. Chemical Science, 2010, 1(3): 310-314.
27	ZHAO Wei, CHENG Weiguo, LI Zengxi, et al. Oxidative esterification of methacrolein to methyl methacrylate over supported palladium catalyst[J]. Chinese Chemical Letters, 2006, 17(6): 739-742.
28	WANG Baohe, SUN Wenjuan, ZHU Jin, et al. Pd-Pb/SDB bimetallic catalysts for the direct oxidative esterification of methacrolein to methyl methacrylate[J]. Industrial & Engineering Chemistry Research, 2012, 51: 15004-15010.
29	WANG Baohe, LI Hui, ZHU Jing, et al. Preparation and characterization of mono-/multi-metallic hydrophobic catalysts for the oxidative esterification of methacrolein to methyl methacrylate[J]. Journal of Molecular Catalysis A: Chemical, 2013, 379: 322-326.
43	TRIMPALIS A, GIANNAKAKIS G, CAO S F, et al. NiAu single atom alloys for the selective oxidation of methacrolein with methanol to methyl methacrylate[J]. Catalysis Today, 2020, 355: 804-814.
44	WAN Xiaoyue, DENG Weiping, ZHANG Qinghong, et al. Magnesia-supported gold nanoparticles as efficient catalysts for oxidative esterification of aldehydes or alcohols with methanol to methyl esters[J]. Catalysis Today, 2014, 233: 147-154.
45	LI Yuchao, WANG Lei, YAN Ruiyi, et al. Gold nanoparticles supported on Ce-Zr oxides for the oxidative esterification of aldehydes to esters[J]. Catalysis Science & Technology, 2015, 5: 3682-3692.
46	LI Yuchao, WANG Lei, YAN Ruiyi, et al. Promoting effects of MgO, (NH₄)₂SO₄ or MoO₃ modification in oxidative esterification of methacrolein over Au/Ce_0.6Zr_0.4O₂-based catalysts[J]. Catalysis Science & Technology, 2016, 6(14): 5453-5463.
47	LI Yuchao, ZHENG Yanxia, WANG Lei, et al. Oxidative esterification of methacrolein to methyl methacrylate over supported gold catalysts prepared by colloid deposition[J]. ChemCatChem, 2017, 9(11): 1960-1968.
48	ZUO Cuncun, TIAN Yun, ZHENG Yanxia, et al. One step oxidative esterification of methacrolein with methanol over Au-CeO₂/γ-Al₂O₃ catalysts[J]. Catalysis Communications, 2019, 124: 51-55.
49	TIAN Yun, LI Yuchao, ZUO Cuncun, et al. Ionic-liquid-modified porous Au/CeMnO_x nanorods for methyl methacrylate (MMA) synthesis via direct oxidative esterification[J]. Chemnanomat, 2019, 5(11): 1361-1366.
50	GAO Jun, FAN Guoli, YANG Lan, et al. Oxidative esterification of methacrolein to methyl methacrylate over gold nanoparticles on hydroxyapatite[J]. ChemCatChem, 2017, 9(7): 1230-1241.
51	PAUL B, KHATUN Ra, SHARMA S K, et al. Fabrication of Au nanoparticles supported on one-dimensional La₂O₃ nanorods for selective esterification of methacrolein to methyl methacrylate with molecular oxygen[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(4): 3982-3994.
52	李国松, 王连月, 张毅, 等. 纳米 Au-CoO_x催化剂的制备及其催化甲基酯化法制备甲基丙烯酸甲酯动力学研究[J]. 石油化工, 2018, 46(9): 969-975.
	LI Guosong, WANG Lianyue, ZHANG Yi, et al. Preparation of nanometer Au-CoO_x catalyst and kinetic study on catalytic methyl esterification over it to prepare methyl methacrylate[J]. Petrochemical Technology, 2018, 46(9): 969-975.

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