CO2和甲醇直接合成碳酸二甲酯耦合脱水体系研究进展

doi:10.16085/j.issn.1000-6613.2019-0213

摘要/Abstract

摘要：

二氧化碳和甲醇直接合成碳酸二甲酯反应受热力学平衡限制，导致反应物转化率和产物收率较低，极大地阻碍了其工业化应用。耦合脱水体系能够将反应过程中产生的水及时脱除，促进反应正向进行，进而提高产物碳酸二甲酯收率。根据耦合脱水的原理不同，主要可分为物理耦合脱水和化学耦合脱水。本文综合分析了近年来应用于该反应不同物理脱水工艺和化学脱水剂的研究进展，详细论述了不同脱水体系的脱水原理和对反应的促进作用，并对不同脱水体系的优点及局限进行了归纳和分析，提出通过优化反应工艺或设计新的反应工艺大幅降低反应体系的能耗，同时探索更加廉价、低毒且易循环利用的化学脱水剂是耦合脱水体系今后的主要发展趋势。

关键词: 二氧化碳, 催化剂, 反应器, 碳酸二甲酯, 脱水体系

Abstract:

The direct synthesis of dimethyl carbonate from carbon dioxide and methanol is limited by thermodynamic equilibrium, resulting in the lower reactant conversion and product yield, which greatly hinders its industrial application. The coupling of dehydration system can remove the water generated in the reaction process timely, and promote the reaction forward, and then improve the yield of dimethyl carbonate. According to the principle of the coupled dehydration system, it can be mainly divided into physical dehydration system and chemical dehydration system. This paper mainly reviews the recent research progress of various physical dehydration processes and chemical dehydrating agents for the synthesis of dimethyl carbonate from CO₂ and methanol. The dehydration principles of different systems and their promoting effects on the reaction are discussed in detail. The advantages and limitations of different dehydration systems are summarized and analyzed. It is proposed that the reaction process should be optimized or a new design should be made. Exploring the chemical dehydrating agents which are cheaper, less toxic and easy to recycle are the main development trend of the coupled dehydration system in future.

Key words: carbon dioxide, catalyst, reactors, dimethyl carbonate, dehydration systems

中图分类号:

孙宇辰,张国强,刘斌,李忠,上官炬,刘守军,史鹏政. CO₂和甲醇直接合成碳酸二甲酯耦合脱水体系研究进展[J]. 化工进展, 2019, 38(11): 5127-5135.

Yuchen SUN,Guoqiang ZHANG,Bin LIU,Zhong LI,Ju SHANGGUAN,Shoujun LIU,Pengzheng SHI. Progress of the coupled dehydration systems for synthesis of dimethyl carbonate from CO₂and methanol[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 5127-5135.

图/表 2

参考文献 46

1	BALLIVET-TKATCHENKOD, JERPHAGNONT, LIGABUER, et al. The role of distannoxanes in the synthesis of dimethyl carbonate from carbon dioxide[J]. Applied Catalysis A: General, 2003, 255(1):93-99.
2	CHAUGULEA A, BANDHALH A, TAMBOLIA H, et al. Highly efficient synthesis of dimethyl carbonate from methanol and carbon dioxide using IL/DBU/SmOCl as a novel ternary catalytic system[J]. Catalysis Communications, 2016, 75: 87-91.
3	KUMARS, JAINS L. Polyethylene glycol enfolded KBr assisted base catalyzed synthesis of dimethyl carbonate from methanol and carbon dioxide[J]. Industrial & Engineering Chemistry Research, 2014, 53(41):15798-15801.
4	FUZ, YUY, LIZ, et al. Surface reduced CeO₂ nanowires for direct conversion of CO₂ and methanol to dimethyl carbonate: catalytic performance and role of oxygen vacancy[J]. Catalysts, 2018, 8(4): 164.
5	POUNGSOMBATEA, IMYENT, DITTANETP, et al. Direct synthesis of dimethyl carbonate from CO₂ and methanol by supported bimetallic Cu-Ni/ZIF-8 MOF catalysts[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 80: 16-24.
6	ALLAOUIL A, AOUISSIA. Effect of the Brønsted acidity on the behavior of CO₂ methanol reaction[J]. Journal of Molecular Catalysis Chemical, 2006, 259(1/2): 281-285.
7	KUMARS, KUMARP, JAINS L. Graphene oxide immobilized copper phthalocyanine tetrasulphonamide: the first heterogenized homogeneous catalyst for dimethyl carbonate synthesis from CO₂ and methanol[J].Journal of Materials Chemistry A, 2014, 2(44):18861-18866.
8	HOFMANNH J, BRANDNERA, CLAUSP. Direct synthesis of dimethyl carbonate by carboxylation of methanol on ceria-based mixed oxides[J]. Chemical Engineering & Technology, 2012, 35(12):2140-2146.
9	ZHOUY J, XIAOM, WANGS J, et al. Effects of Mo promoters on the Cu-Fe bimetal catalysts for the DMC formation from CO₂ and methanol[J]. Chinese Chemical Letters, 2013, 24(4): 307-310.
10	BIANJ, XIAOM, WANGS, et al. Highly effective synthesis of dimethyl carbonate from methanol and carbon dioxide using a novel copper-nickel/graphite bimetallic nanocomposite catalyst[J]. Chemical Engineering Journal, 2009, 147(2): 287-296.
11	BIANJ, XIAOM, WANGS, et al. Direct synthesis of DMC from CH₃OH and CO₂ over V-doped Cu-Ni/AC catalysts[J]. Catalysis Communications, 2009, 10(8): 1142-1145.
12	BIANJ, XIAOM, WANGS, et al. Carbon nanotubes supported Cu-Ni bimetallic catalysts and their properties for the direct synthesis of dimethyl carbonate from methanol and carbon dioxide[J]. Applied Surface Science, 2009, 255(16): 7188-7196.
13	WANGN, LIUY, HUANGA,et al. Hydrophilic SOD and LTA membranes for membrane-supported methanol dimethyl ether and dimethyl carbonate synthesis[J]. Microporous & Mesoporous Materials, 2015, 207: 33-38.
14	UNNIKRISHNANP, VARHADIP, SRINIVASD. Efficient direct synthesis of dimethyl carbonate from CO₂ using a solid, calcined zirconium phenylphosphonate phosphite catalyst[J]. RSC Advances, 2013, 3(46): 23993-23996.
15	CHOIJ C, HEL N, YASUDAH, et al. Selective and high yield synthesis of dimethyl carbonate directly from carbon dioxide and methanol[J]. Green Chemistry, 2002, 4(3): 230-234.
16	PENGB, DOUH, SHIH, et al. Overcoming thermodynamic limitations in dimethyl carbonate synthesis from methanol and CO₂[J]. Catalysis Letters, 2018, 148(7): 1914-1919.
17	LIC F, ZHONGS H. Study on application of membrane reactor in direct synthesis DMC from CO₂ and CH₃OH over Cu-KF/MgSiO catalyst[J]. Catalysis Today, 2003, 82(1): 83-90.
18	KUENENH J, MENGERSH J, NIJMEIJERD C, et al. Techno-economic evaluation of the direct conversion of CO₂ to dimethyl carbonate using catalytic membrane reactors[J]. Computers & Chemical Engineering, 2016, 86: 136-147.
19	SANTOSB A V, SILVAV M T M, LOUREIROJ M, et al. Adsorption of H₂O and dimethyl carbonate at high pressure over zeolite 3A in fixed bed column[J]. Industrial & Engineering Chemistry Research, 2014, 53(6): 2473-2483.
20	SANTOSB A V, PEREIRAC S M, SILVAV M T M, et al. Design of a true moving bed reactor for the direct synthesis of dimethyl carbonate[J]. Chemical Engineering Science, 2015, 123: 406-419.
21	ZHANGZ, LIUS, ZHANGL, et al. Driving dimethyl carbonate synthesis from CO₂ and methanol and production of acetylene simultaneously using CaC₂[J]. Chemical Communications, 2018, 54(35): 4410-4412.
22	ARESTAM, DIBENEDETTOA, FRACCHIOLLAE, et al. Mechanism of formation of organic carbonates from aliphatic alcohols ad carbon dioxide under mild conditions promoted by carbodiimides. DFT calculation and experimental study[J]. Journal of Organic Chemistry, 2005, 70(16): 6177-6186.
23	SHIY, JINX, HUY, et al. Synthesis and characterization of bis[2-(1 H-benzimidazol-2-yl) benzoato] nickel(Ⅱ), and its use for preparation of dimethyl carbonate from methanol and CO₂[J]. Research on Chemical Intermediates, 2014, 40(3): 1179-1186.
24	BALLIVET-TKATCHENKOD, CHAMBREYS, KEISKIR, et al. Direct synthesis of dimethyl carbonate with supercritical carbon dioxide: characterization of a key organotin oxide intermediate[J]. Catalysis Today, 2006, 115(1): 80-87.
25	TOMISHIGEK, KUNIMORIK. Catalytic and direct synthesis of dimethyl carbonate starting from carbon dioxide using CeO₂-ZrO₂ solid solution heterogeneous catalyst: effect of H₂O removal from the reaction system[J]. Applied Catalysis A: General, 2002, 237(1):103-109.
26	WANGS, ZHOUJ, ZHAOS, et al. Enhancement of dimethyl carbonate synthesis with insitu hydrolysis of 2,2-dimethoxy propane[J]. Chemical Engineering & Technology, 2016, 39(4): 723-729.
27	ZHANGZ F, LIUZ W, LUJ, et al. Synthesis of dimethyl carbonate from carbon dioxide and methanol over Ce_xZr_1-_xO₂and [EMIM]Br/Ce_0.5Zr_0.5O₂[J]. Industrial & Engineering Chemistry Research, 2011, 50(4): 1981-1988.
28	SAADAR, KELLICIS, HEILT, et al. Greener synthesis of dimethyl carbonate using a novel ceria-zirconia oxide/graphene nanocomposite catalyst[J]. Applied Catalysis B: Environmental, 2015, 168/169:353-362.
29	HONDAM, SUZUKIA, NOORJAHANB, et al. Low pressure CO₂ to dimethyl carbonate by the reaction with methanol promoted by acetonitrile hydration[J]. Chemical Communications, 2009, 30(30):4596-4598.
30	HONDAM, KUNOS, SONEHARAS, et al. Tandem carboxylation-hydration reaction system from methanol CO₂ and benzonitrile to dimethyl carbonate and benzamide catalyzed by CeO₂[J]. ChemCatChem, 2011, 3(2): 365-370.
31	HONDAM, TAMURAM, NAKAGAWAY, et al. Ceria-catalyzed conversion of carbon dioxide into dimethyl carbonate with 2-cyanopyridine[J]. Chemsuschem, 2013, 6(8): 1341-1344.
32	STOIAND, MEDINAF, URAKAWAA. Improving the stability of CeO₂ catalyst by rare earth metal promotion and molecular insights in the dimethyl carbonate synthesis from CO₂ and methanol with 2-cyanopyridine[J]. ACS Catalysis, 2018, 8(4): 3181-3193.
33	MARCINIAKA A,ALVESO C, APPELL G, et al. Synthesis of dimethyl carbonate from CO₂ and methanol over CeO₂: role of copper as dopant and the use of methyl trichloroacetate as dehydrating agent[J]. Journal of Catalysis, 2019, 371: 88-95.
34	WESTF B, MONTONNAR E. The free energies of reactions of calcium carbide[J]. Journal of Physical Chemistry, 1941, 45(8):1179-1194.
35	刘青, 刘清雅, 王仁醒,等. 电石与醇的反应行为[J]. 化工学报, 2013, 64(7): 2573-2579.
	LIUQ, LIUQ Y, WANGR X, et al. Reaction behavior of calcium carbide with alcohols[J]. CIESC Journal, 2013, 64(7): 2573-2579.
36	王伟, 李文峰, 杨玉琼,等. 缩合剂1,3-二环己基碳二亚胺（DCC）在有机合成中的应用[J]. 化学试剂, 2008, 30(3): 185-190.
	WANGW, LIW F, YANGY Q, et al. The application of 1,3-dicyclohexyl carbodiimide(DCC) used as condensation agent in organic synthesis[J]. Chemical Reagents, 2008, 30(3): 185-190.
37	SAKAKURAT, SAIYOY, OKANOM, et al. Selective conversion of carbon dioxide to dimethyl carbonate by molecular catalysis[J]. Journal of Organic Chemistry, 1998, 63(20): 7095-7096.
38	KORNBLUMN, SINGARAMS. The conversion of nitriles to amides and esters to acids by the action of sodium superoxide[J]. Chemischer Informationsdienst, 1980, 11(14): 289-303.
39	徐粉, 康位粉, 孟彦羽, 等. 金属催化腈水解反应制备伯酰胺衍生物的研究进展[J]. 轻工学报, 2017, 32(1): 72-81.
	XUF, KANGW F, MENGY Y, et al. Research progress of hydrdysis reaction of nitriles to form amide derivatives catalyzed by metal catalyst[J]. Journal of Light Industy, 2017, 32(1): 72-81.
40	DOWNSE L, TYLERD R. Nanoparticle catalysts for nitrile hydration[J]. Coordination Chemistry Reviews, 2014, 280: 28-37.
41	赵晓甫, 张月成, 张宏宇, 等. 过渡金属氧化物催化腈水合生成酰胺的研究进展[J]. 化工进展, 2016, 35(7): 2071-2080.
	ZHAOX P, ZHANGY C, ZHANGH Y, et al. Progress on hydration of nitriles to amides catalyzed by transitionmetal oxides[J]. Chemical Industry and Engineering Progress, 2016, 35(7): 2071-2080.
42	TAMURAM, WAKASUGIH, SHIMIZUK I, et al. Efficient and substrate-specific hydration of nitriles to amides in water by using a CeO₂ catalyst[J]. Chemistry, 2011, 17(41): 11428-11431.
43	TAMURAM, SATSUMAA, SHIMIZUK. CeO₂-catalyzed nitrile hydration to amide: reaction mechanism and active sites[J]. Catalysis Science & Technology, 2013, 3(5): 1386-1393.
44	HONDAM, TAMURAM, NAKAGAWAY, et al. Organic carbonate synthesis from CO₂ and alcohol over CeO₂ with 2-cyanopyridine: scope and mechanistic studies[J]. Journal of Catalysis, 2014, 318:95-107.
45	WANGS P, ZHOUJ J, ZHAOS Y, et al. Enhancements of dimethyl carbonate synthesis from methanol and carbon dioxide: the insitu hydrolysis of 2-cyanopyridine and crystal face effect of ceria[J]. Chinese Chemical Letters, 2015, 26(9): 1096-1100.
46	STOIAND, BANSODEA, MEDINAF, et al. Catalysis under microscope: unraveling the mechanism of catalyst de- and re-activation in the continuous dimethyl carbonate synthesis from CO₂ and methanol in the presence of a dehydrating agent[J]. Catalysis Today, 2017, 283: 2-10.

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CO₂和甲醇直接合成碳酸二甲酯耦合脱水体系研究进展

Progress of the coupled dehydration systems for synthesis of dimethyl carbonate from CO₂and methanol

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