金属氧化物催化CO2与甲醇合成碳酸二甲酯的研究进展

doi:10.16085/j.issn.1000-6613.2019-0391

摘要/Abstract

摘要：

CO₂是主要的温室气体。近年来随着工业的大力发展，CO₂的排放量迅猛增加，严重影响着人类的生存环境。将CO₂转化成有价值的化工产品，受到了研究领域的广泛关注。其中将CO₂与产能过剩的甲醇作为原料，生产碳酸二甲酯（DMC），既能减少CO₂排放，又能产生有价值的绿色产品DMC。本文简述了影响CO₂转化的因素，即受热力学限制和CO₂活化困难；重点介绍了具有酸碱活性中心的金属氧化物ZrO₂、CeO₂以及复合金属氧化物催化剂的催化性能和反应机理，并分析了影响催化活性的主要原因：表面酸碱性能决定了催化活性；进一步分析了催化剂表面的酸碱性来源于Lewis酸碱位和Br?nsted酸性位。对于开发高效的金属氧化物催化剂未来的研究方向提出了展望: 通过调控催化剂的晶相和形貌、增加氧空位和羟基官能团、掺杂碱性或者酸性物种来改变催化剂表面的酸碱性，并且向催化系统中添加脱水剂。最后指出了由于CO₂分子的稳定性很难被活化，需进一步深入研究其活化CO₂的机理，提高CO₂的转化率。

关键词: 二氧化碳, 催化, 合成, 金属氧化物, 活性

Abstract:

CO₂ is main greenhouse gas. In recent years, with the vigorous development of industry, CO₂ emissions are rapidly increasing and seriously affecting our living environment.CO₂ conversion into valuable chemical products has attracted extensive attention in the field of research. The synthesis of dimethyl carbonate (DMC) from CO₂ and methanol can not only reduce CO₂ emissions but also produce valuable green products of DMC. In this paper, the factors effecting on CO₂ conversion are summarized as follows: thermodynamic constraints and difficulty in CO₂ activation. The common metal oxides of ZrO₂, CeO₂ and composite metal oxides with acid-base active centers are significantly introduced from the catalytic performance and reaction mechanism. The main reasons of affecting the catalytic activity are analyzed, which originated from Lewis acid-base sites and Br?nsted acid sites. The future research directions for developing efficient metal oxide catalysts are proposed: adjusting the crystal phase and morphology of catalysts, increasing oxygen vacancies and hydroxyl functional groups, doping alkaline or acidic species, and adding dehydrating agents to the catalytic system. At last, it is pointed out that the stability of CO₂ molecule is difficult to be activated, and the mechanism of activation of CO₂ molecule should be further studied to improve the conversion of CO₂.

Key words: carbon dioxide, catalysis, synthesis, metal oxides, reactivity

中图分类号:

O623.662

王旭慧,赵金仙,裴永丽,任军. 金属氧化物催化CO₂与甲醇合成碳酸二甲酯的研究进展[J]. 化工进展, 2019, 38(11): 4956-4964.

Xuhui WANG,Jinxian ZHAO,Yongli PEI,Jun REN. Research progress in dimethyl carbonate synthesis from carbon dioxide and methanol catalyzed by metal oxides[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4956-4964.

图/表 1

参考文献 48

1	UNNIKRISHNAN P , DARBHA S . Direct synthesis of dimethyl carbonate from CO₂ and methanol over CeO₂ catalysts of different morphologies[J]. Journal of Chemical Sciences, 2016,128(6): 957-965.
2	杨盼盼,孙琦,张玉龙,等 .甲醇合成中CO₂作用的研究进展[J].化工进展, 2018,37(1):94-101.
	YANG P P , SUN Q , ZHANG Y L , et al . Research progress of the role of CO₂ in methanol synthesis[J]. Chemical Industry and Engineering Progress, 2018, 37(1):94-101.
3	张成 .CO与CO₂甲烷化反应研究进展[J].化工进展, 2007,26(9):1269-1273.
	ZHANG C . Research progress of methanation of carbon monoxide and carbon dioxide[J]. Chemical Industry and Engineering Progress, 2007, 26(9):1269-1273.
4	TANG Q , HONG Q , LIU Z . CO₂ fixation into methanol at Cu/ZrO₂ interface from first principles kinetic Monte Carlo[J]. Journal of Catalysis, 2009, 263: 114-122.
5	LI C F , ZHONG S 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: 83-90.
6	BIAN J , XIAO M , WANG S J , 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: 287-296.
7	王奔, 陈红萍, 芮玉兰, 等 .甲醇和二氧化碳合成碳酸二甲酯的研究进展[J]. 化工进展, 2010, 29(s1): 305-310.
	WANG B , CHEN H P , RUI Y L ,et al . Research progress in dimethyl carbonate synthesis from carbon dioxide and methanol[J]. Chemical Industry and Engineering Progress, 2010, 29(s1): 305-310.
8	TAMBOLI A H , CHAUGULE A A , KIM H . Catalytic developments in the direct dimethyl carbonate synthesis from carbon dioxide and methanol[J]. Chemical Engineering Journal, 2017, 323: 530-544.
9	KONGPANNA P , PAVARAJARN V , GANI R , et al . Techno-economic evaluation of different CO₂-based processes for dimethyl carbonate production[J]. Chemical Engineering Research and Design, 2015, 93: 496-510.
10	肖雪, 路嫔, 韩媛媛, 等 . 二氧化碳与甲醇合成碳酸二甲酯反应的热力学探讨[J]. 天然气化工，2007, 32(2): 34-37.
	XIAO X , LU B , HAN Y Y , et al . Thermodynamics of dmiethyl carbonate synthesis from carbon dioxide and methanol[J]. Natural Gas Chemical Industry, 2007, 32(2): 34-37.
11	赵天生, 韩怡卓, 孙予罕 . 甲醇和CO₂合成碳酸二甲酯体系的热力学分析[J]. 天然气化工, 1998, 23(5): 52-56.
	ZHAO T S , HAN Y Z , SUN Y H . Thermodynamic estimation of direct synthesis of DMC from CH₃OH and CO₂ [J]. Natural Gas Chemical Industry, 1998, 23(5): 52-56.
12	TAN H Z , WANG Z Q , XU Z N , et al . Review on the synthesis of dimethyl carbonate[J]. Catalysis Today, 2018, 316: 2-12.
13	CAO Y , CHENG H , MA L , et al . Research progress in the direct synthesis of dimethyl carbonate from CO₂ and methanol[J]. Catalysis Surveys from Asia, 2012, 16: 138-147.
14	HUANG S Y , YAN B , WANG S P , et al . Recent advances in dialkyl carbonates synthesis and applications[J].Chemical Society Reviews, 2015, 44(10): 3079-3116.
15	JUNG K T , BELL A T . An in situ infrared study of dimethyl carbonate synthesis from carbon dioxide and methanol over zirconia[J]. Journal of Catalysis, 2001, 204(2): 339-347.
16	PISKORZ W , GRYBOS J , ZASADA F , et al . Periodic DFT and atomistic thermodynamic modeling of thesurface hydration equilibria and morphology of monoclinic ZrO₂nanocrystals[J]. The Journal of Physical Chemistry C, 2011, 115: 24274-24286.
17	SALAVATI-FARD T , VASILIADOU E S , JENNESS G R , et al . Lewis acid site and hydrogen-bond-mediated polarization synergy in the catalysis of Diels-Alder cycloaddition by band-gap transition-metal oxides[J]. ACS Catalysis, 2019, 9: 701-715.
18	MA Z Y , YANG C , WEI W , et al . Surface properties and CO adsorption on zirconia polymorphs[J]. Journal of Molecular Catalysis A: Chemical, 2005, 227: 119-124.
19	WITOON T , CHALORNGTHAM J , DUMRONGBUNDITKUL P , et al . CO₂ hydrogenation to methanol over Cu/ZrO₂ catalysts: effects of zirconia phases[J]. Chemical Engineering Journal, 2016, 293: 327-336.
20	SATO A G , VOLANTI D P , MEIRA D M , et al . Effect of the ZrO₂ phase on the structure and behavior of supported Cu catalysts for ethanol conversion[J]. Journal of Catalysis, 2013, 307: 1-17.
21	JUNG K T , BELL A T . Effects of catalyst phase structure on the elementary processes involved in the synthesis of dimethyl carbonate from methanol and carbon dioxide over zirconia[J]. Topics in Catalysis, 2002, 20(1/2/3/4): 97-105.
22	TOMISHIGE K , IKEDA Y , SAKAIHORI T , et al . Catalytic properties and structure of zirconia catalysts for direct synthesis of dimethyl carbonate from methanol and carbon dioxide[J]. Journal of Catalysis, 2000, 192(2): 355-362.
23	WANG X H , ZHAO J X , SUN W , et al . A DFT study of dimethyl carbonate synthesis from methanol and CO₂ on zirconia: effect of crystalline phases[J]. Computational Materials Science, 2019,159:210-221.
24	IKEDA Y , ASADULLAH M , FUJIMOTO K , et al . Structure of the active sites on H₃PO₄/ZrO₂ catalysts for dimethyl carbonate synthesis from methanol and carbon dioxide[J]. The Journal of Physical Chemistry B, 2001, 105(43): 10653-10658.
25	JIANG C J , GUO Y H , WANG C G , et al . Synthesis of dimethyl carbonate from methanol and carbon dioxide in the presence of polyoxometalates under mild conditions[J]. Applied Catalysis A: General, 2003, 256: 203-212.
26	WU X L , XIAO M , MENG Y Z , et al . Direct synthesis of dimethyl carbonate on H₃PO₄ modified V₂O₅ [J]. Journal of Molecular Catalysis A: Chemical, 2005, 238: 158-162.
27	LA K L, JUNG J C , KIM H , et al . Effect of acid-base properties of H₃PW₁₂O₄₀/Ce _x Ti_1- _x O₂ catalysts on the direct synthesis of dimethyl carbonate from methanol and carbon dioxide :a TPD study of H₃PW₁₂O₄₀/Ce _x Ti_1- _x O₂ catalysts[J]. Journal of Molecular Catalysis A: Chemical, 2007, 269: 41-45.
28	WANG S P , ZHAO L F , WANG W , et al . Morphology control of ceria nanocrystals for catalytic conversion of CO₂ with methanol[J]. Nanoscale, 2013, 5(12): 5582-5588.
29	ZHAO S Y , WANG S P , ZHAO Y J , et al . An in situ infrared study of dimethyl carbonate synthesis from carbon dioxide and methanol over well-shaped CeO₂ [J]. Chinese Chemical Letters, 2016, 28(1): 1-5.
30	LIU B , LI C M , ZHANG G Q , et al . Direct synthesis of dimethyl carbonate from CO₂ and methanol over CaO-CeO₂ catalysts: the role of acid-base properties and surface oxygen vacancies[J]. New Journal of Chemistry, 2017, 41(20): 12231-12240.
31	CUI Z X , FAN J , DUAN H J , et al . Effect of calcination atmospheres on the catalytic performance of nano-CeO₂ in direct synthesis of DMC from methanol and CO₂ [J]. Korean Journal of Chemical Engineering, 2017, 34(1): 29-36.
32	ARESTA M , DIBENEDETTO A , PASTORE C , et al . Influence of Al₂O₃on the performance of CeO₂ used as catalyst in the direct carboxylation of methanol to dimethylcarbonate and the elucidation of the reaction mechanism[J]. Journal of Catalysis, 2010, 269(1): 44-52.
33	FU Z W , YU Y H , LI Z , 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, 2018,164(8):1-11.
34	ZHANG M , XIAO M , WANG S J , et al . Cerium oxide-based catalysts made by template-precipitation for the dimethyl carbonate synthesis from carbon dioxide and methanol[J]. Journal of Cleaner Production, 2015, 103: 847-853.
35	WADA S , OKA K, WATANABE K , et al . Catalytic conversion of carbon dioxide into dimethyl carbonate using reduced copper-cerium oxide catalysts as low as 353K and 1.3MPa and the reaction mechanism[J]. Frontiers in Chemistry, 2013, 1: 1-8.
36	TOMISHIGE K , KUNIMORI K . 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: 103-109.
37	KUMAR P , WITH P , SRIVASTAVA V C , et al . Efficient ceria-zirconium oxide catalyst for carbon dioxide conversions: characterization, catalytic activity and thermodynamic study[J]. Journal of Alloys and Compounds, 2017, 696: 718-726.
38	HOFMANN H J , BRANDNER A , CLAUS P . Direct synthesis of dimethyl carbonate by carboxylation of methanol on ceria-based mixed oxides[J]. Chemical Engineering and Technology, 2012, 35(12):2140-2146.
39	LIU H , ZOU W J , XU X L , et al . The proportion of Ce⁴⁺ in surface of Ce _x Zr_1- _x O₂ catalysts: the key parameter for direct carboxylation of methanol to dimethyl carbonate[J]. Journal of CO₂ Utilization, 2017, 17: 43-49.
40	LEE H J, JOE W, SONG I K . Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over transition metal oxide/Ce_0.6Zr_0.4O₂ catalysts: effect of acidity and basicity of the catalysts[J]. Korean Journal of Chemical Engineering, 2012, 29(3): 317-322.
41	陈红萍, 梁英华, 郑小满, 等 .铁锆复合氧化物催化甲醇与CO₂直接合成DMC反应性能[J].分子催化, 2013, 27(6): 556-565.
	CHEN H P , LIANG Y H , ZHENG X M , et al . Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over Fe-Zr-O catalyst[J]. Journal of Molecular Catalysis, 2013, 27(6): 556-565.
42	KUMAR P , SRIVASTAVA V C , GLÄSER R , et al . Active ceria-calcium oxide catalysts for dimethyl carbonate synthesis by conversion of CO₂ [J]. Powder Technology, 2017, 309: 13-21.
43	TOMISHIGE K , FURUSAWA Y , IKEDA Y , et al . CeO₂-ZrO₂ solid solution catalyst for selective synthesis of dimethyl carbonate from methanol and carbon dioxide[J]. Catalysis Letters, 2001, 76(1): 71-74.
44	SAADA R , KELLICI S , HEIL T , et al . Greener synthesis of dimethyl carbonate using a novel ceria-zirconia/graphene nanocomposite catalyst[J]. Applied Catalysis B: Environmental, 2015,168/169:353-362.
45	ZHANG Z F , LIU Z W , LU J , et al . Synthesis of dimethyl carbonate from carbon dioxide and methanol over Ce _x Zr_1- _x O₂ and [EMIM]Br/Ce_0.5Zr_0.5O₂ [J]. Industrial & Engineering Chemistry Research, 2011,50:1981-1988.
46	STOIAN D , MEDINA F , URAKAWA A . Improving the stability of CeO₂ catalyst by rare earth metal promotion and molecular insights in the dimethyl carbonate synthesis from CO₂and methanol with 2-cyanopyridine[J]. ACS Catalysis, 2018, 8(4): 3181-3193.
47	ETA V, MÄKI-ARVELA P , WÄRNÅ J , et al . Kinetics of dimethyl carbonate synthesis from methanol and carbon dioxide over ZrO₂-MgO catalyst in the presence of butylene oxide as additive[J]. Applied Catalysis A: General, 2011, 404: 39-46.
48	BANSODE A , URAKAWA A . Continuous DMC synthesis from CO₂and methanol over a CeO₂ catalyst in a fixed bed reactor in the presence of a dehydrating agent[J]. ACS Catalysis, 2014, 4: 3877-3880.

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金属氧化物催化CO₂与甲醇合成碳酸二甲酯的研究进展

Research progress in dimethyl carbonate synthesis from carbon dioxide and methanol catalyzed by metal oxides

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