丙烯酸催化合成新进展

doi:10.16085/j.issn.1000-6613.2020-2036

摘要/Abstract

摘要：

丙烯酸是一种重要的化工中间体和聚合物单体，需求量巨大。我国丰富的煤炭资源和可再生生物质资源为煤基和生物质基丙烯酸合成路线提供坚实的物质保障。本文将综述这两条主要路线，具体包括以煤基化工原料CO、低碳醇（甲醇和乙醇）、甲醛、乙酸、乙烯等为原料的丙烯酸合成路线；以生物质基平台化合物甘油、3-羟基丙酸、乳酸、富马酸、黏糠酸等为原料的丙烯酸合成路线；并对这些路线进行了比较，为路线的选择提供参考。重点关注了这些过程中的催化问题：反应所需的活性位、副反应分析、催化剂的类型与特点以及催化性能与失活机理，为未来实用煤基和生物质基丙烯酸生产用高效稳定廉价催化剂的设计开发提供理论参考。

关键词: 丙烯酸, 合成, 催化, 煤, 生物质

Abstract:

Acrylic acid (AA) is an important industrial chemical intermediate and polymer monomer, which is in great demand. The rich coal resources and renewable biomass resources in China provide a solid material guarantee for the coal-based and biomass-based synthesis routes of acrylic acid. The two main routes were reviewed, including the synthesis routes of acrylic acid from coal-based chemicals, such as CO, low carbon alcohols (methanol and ethanol), formaldehyde, acetic acid, ethylene, and so on, and the synthesis routes of acrylic acid using glycerol, 3-hydroxypropionic acid, lactic acid, fumaric acid, and muconic acid. These routes are compared to provide a reference for the route selection. In order to provide a theoretical reference to the design and development of efficient, stable, and cheap catalysts for practical coal-based and biomass-based acrylic acid production in the future, the active sites in the catalytic reactions, side reactions analysis, the types and characteristics of catalysts, the catalytic performance and the deactivation mechanism of the catalysts are emphasized.

Key words: acrylic acid, synthesis, catalysis, coal, biomass

中图分类号:

张志鑫, 王业红, 张超锋, 王峰. 丙烯酸催化合成新进展[J]. 化工进展, 2021, 40(4): 2016-2033.

ZHANG Zhixin, WANG Yehong, ZHANG Chaofeng, WANG Feng. New advances in catalytic synthesis of acrylic acid[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2016-2033.

图/表 15

参考文献 106

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催化剂	反应条件	催化性能	参考文献
FeVO(FeO_x/FeVO₄)	O₂,300℃,10h	C=100%,S=14%	[28]
WNbVO	O₂,285℃	C=100%,S=46%	[29]
H₃PO₄/WNbVO	O₂,285℃,1~2h	C=100%,S=59%	[30]
WVO	O₂,318℃,2h	C=100%,S=26%	[40]
WNbVO	O₂,265℃,37h	C=100%,S=51%	[31]
WMoVO	O₂,290℃,69h	C=100%,S=42%	[32]
H_0.1Cs(VO)_0.2(PMo₁₂O₄₀)_0.5(PW₁₂O₄₀)_0.5	O₂,340℃,1h	C=100%,S=60%	[34]
VSiO	O₂,320℃,1h	C=94%,S=85%	[35]
H-Fe-MCM-22	O₂,320℃,10h	Y=53%	[36]
Cs_2.5H_0.5PW₁₂O₄₀/Nb₂O₅+MoVO-SiC	O₂,300℃,70h	C=100%,S=75%	[37]
V-H₃SiW₁₂O₄₀/HZSM-5	H₂O₂,90℃,6h	Y=36%	[38]
Cu/SiO₂-MnO₂	H₂O₂,70℃,30h	C=77%,S=75%	[39]

催化剂	反应条件	催化性能	参考文献
FeVO(FeO_x/FeVO₄)	O₂,300℃,10h	C=100%,S=14%	[28]
WNbVO	O₂,285℃	C=100%,S=46%	[29]
H₃PO₄/WNbVO	O₂,285℃,1~2h	C=100%,S=59%	[30]
WVO	O₂,318℃,2h	C=100%,S=26%	[40]
WNbVO	O₂,265℃,37h	C=100%,S=51%	[31]
WMoVO	O₂,290℃,69h	C=100%,S=42%	[32]
H_0.1Cs(VO)_0.2(PMo₁₂O₄₀)_0.5(PW₁₂O₄₀)_0.5	O₂,340℃,1h	C=100%,S=60%	[34]
VSiO	O₂,320℃,1h	C=94%,S=85%	[35]
H-Fe-MCM-22	O₂,320℃,10h	Y=53%	[36]
Cs_2.5H_0.5PW₁₂O₄₀/Nb₂O₅+MoVO-SiC	O₂,300℃,70h	C=100%,S=75%	[37]
V-H₃SiW₁₂O₄₀/HZSM-5	H₂O₂,90℃,6h	Y=36%	[38]
Cu/SiO₂-MnO₂	H₂O₂,70℃,30h	C=77%,S=75%	[39]

催化剂	反应条件	催化性能	参考文献
WO₃/ZrO₂	280℃,10h	C=100%,S=65%	[45]
WO₃/TiO₂	280℃,14h	C=100%,S=73%	[46]
Nb₂O₅	315℃,10h	C=88%,S=51%	[47]
Nb₂O₅/SiO₂-ZrO₂	325℃,8h	C=77%,S=45%	[48]
HY	250℃,10h	C=89%,S=100%	[49]
丝光沸石	250℃,10h	C=92%,S=100%	[50]
FePO₄	280℃,5h	C=100%,S=92%	[51]
VPO	320℃,2h	C=100%,S=70%	[52]
Nd₄(P₂O₇)₃	320℃,7~8h	C=96%,S=83%	[53]
H₃PW₁₂O₄₀/ZrO₂	315℃,10h	C=76%,S=71%	[54]
H₄SiW₁₂O₄₀/SiO₂	275℃,5h	C=98%,S=86%	[55]
Cs_2.5H_0.5PW₁₂O₄₀	275℃,1h	C=100%,S=98%	[56]
CsSiW₁₂O₄₀/Al₂O₃	250℃,3h	Y=96%,S=96%	[57]

催化剂	反应条件	催化性能	参考文献
WO₃/ZrO₂	280℃,10h	C=100%,S=65%	[45]
WO₃/TiO₂	280℃,14h	C=100%,S=73%	[46]
Nb₂O₅	315℃,10h	C=88%,S=51%	[47]
Nb₂O₅/SiO₂-ZrO₂	325℃,8h	C=77%,S=45%	[48]
HY	250℃,10h	C=89%,S=100%	[49]
丝光沸石	250℃,10h	C=92%,S=100%	[50]
FePO₄	280℃,5h	C=100%,S=92%	[51]
VPO	320℃,2h	C=100%,S=70%	[52]
Nd₄(P₂O₇)₃	320℃,7~8h	C=96%,S=83%	[53]
H₃PW₁₂O₄₀/ZrO₂	315℃,10h	C=76%,S=71%	[54]
H₄SiW₁₂O₄₀/SiO₂	275℃,5h	C=98%,S=86%	[55]
Cs_2.5H_0.5PW₁₂O₄₀	275℃,1h	C=100%,S=98%	[56]
CsSiW₁₂O₄₀/Al₂O₃	250℃,3h	Y=96%,S=96%	[57]

催化剂	反应条件	催化性能	参考文献
硅胶	15% 3-HPA水溶液,300℃,WHSV=1h^-1	C=100%,Y>99%	[79]
TiO₂	—	Y=95%	[1]
SiO₂	20% 3-HPA水溶液,250℃	C=100%,Y=97%	[1]
Al₂O₃	60%~80% 3-HPA水溶液,250℃	C=100%,Y=97%	[1]