Selective oxidation of light olefins to aldehydes catalyzed by molybdenum-bismuth composite metal oxides

doi:10.16085/j.issn.1000-6613.2021-0732

Abstract

Abstract:

Selective oxidation of light olefins to produce the corresponding aldehydes and other oxygen-containing compounds is a key step in the production of important organic chemical intermediates and products. Molybdenum bismuth composite metal oxides have attracted wide attentions in industry and academia because of their excellent catalytic performance. However, there is still debate on the selective oxidation mechanism on the catalyst and the nature of the catalytic reaction. This work systematically reviews the research progress of using molybdenum bismuth composite metal oxides as catalyst in selective oxidation of light olefins to aldehydes. It is pointed out that the micro-structure and catalytic performance of molybdenum bismuth composite metal oxides are mainly controlled by three strategies including the phase structure of bismuth molybdate, additives and carriers. And the selective oxidation reaction mechanism over the molybdenum bismuth composite metal oxides is discussed and summarized. Finally, the development of molybdenum-bismuth composite metal oxides in selective oxidation reaction is prospected to provide ideas for their modification and the exploration of efficient catalysts for light olefins to oxygen-containing compounds.

Key words: catalyst, multiphase reaction, activation, propylene, isobutylene, composite metal oxides

摘要：

低碳烯烃选择氧化制备醛类等含氧化合物是生产有机化工中间体及产品的关键步骤，钼铋复合金属氧化物因其优异的催化性能在相关工业界和学术界受到广泛关注，然而目前关于该催化剂上选择氧化反应机制和催化反应本质等科学问题的认识尚未形成统一理论。本文系统综述了钼铋复合金属氧化物在催化低碳烯烃选择氧化制备醛类反应中的研究进展，包括催化剂微观结构的三种调控手段，即主组分钼酸铋物相结构、助剂及载体等对反应性能的影响，并对反应机理进行了深入讨论与总结。最后展望了钼铋复合金属氧化物在该选择氧化反应中的发展前景，为钼铋复合金属氧化物修饰改性及开发高效低碳烯烃选择氧化制含氧化合物催化剂提供思路。

关键词: 催化剂, 多相反应, 活化, 丙烯, 异丁烯, 复合金属氧化物

CLC Number:

O643

LI Qinghui, SONG Huanling, ZHAO Huahua, YANG Jian, ZHAO Jun, YAN Liang, CHOU Lingjun. Selective oxidation of light olefins to aldehydes catalyzed by molybdenum-bismuth composite metal oxides[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1873-1885.

李庆慧, 宋焕玲, 赵华华, 杨建, 赵军, 闫亮, 丑凌军. 钼铋复合金属氧化物催化低碳烯烃选择氧化制备醛类研究进展[J]. 化工进展, 2022, 41(4): 1873-1885.

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催化剂	反应温度/℃	反应空速/h^-1	丙烯转化率%	丙烯醛选择性%	参考专利
MoWBiFeCoNiKSi	310	1400	97.5	85.2	CN101402044A
MoBiFeCoK	320	5000	97.18	81.7	CN1564709A
MoWBiFeCoNiBKSi	310	1565	98.2	81.6	CN1093021A
MoWBiFeCoKSi	320	1800	97.6	90.2	US3825600
MoBiFeCKSi	320	—	99.1	88.8	JP5293389
MoWBiFeCoNiK	315	1200	98.5	82.5	CN93103817
MoBiCoFeNiW	305	850	98.1	85.6	CN102992979A
MoBiCoFeNiWCs	320	1500	98.3	87.4	CN102992979A
MoBiCoFeNiKLa	325	1200	98.3	87.7	CN102992979A
MoBiCoFeNiMgK	310	1100	98.2	85.6	CN102992979A
MoBiCoFeNiKS	367	1000	98.0	86.5	CN102992979A

催化剂	反应温度/℃	反应空速/h^-1	丙烯转化率%	丙烯醛选择性%	参考专利
MoWBiFeCoNiKSi	310	1400	97.5	85.2	CN101402044A
MoBiFeCoK	320	5000	97.18	81.7	CN1564709A
MoWBiFeCoNiBKSi	310	1565	98.2	81.6	CN1093021A
MoWBiFeCoKSi	320	1800	97.6	90.2	US3825600
MoBiFeCKSi	320	—	99.1	88.8	JP5293389
MoWBiFeCoNiK	315	1200	98.5	82.5	CN93103817
MoBiCoFeNiW	305	850	98.1	85.6	CN102992979A
MoBiCoFeNiWCs	320	1500	98.3	87.4	CN102992979A
MoBiCoFeNiKLa	325	1200	98.3	87.7	CN102992979A
MoBiCoFeNiMgK	310	1100	98.2	85.6	CN102992979A
MoBiCoFeNiKS	367	1000	98.0	86.5	CN102992979A

催化剂	反应温度/℃	反应空速/h^-1	异丁烯转化率/%	甲基丙烯醛选择性/%	参考专利
MoBiFeCoCe	300	3600	98.7	97.1	US5138100
MoBiFeCoPr	340	3600	99.0	94.0	US5138100
MoBiFeCoEu	360	3600	99.1	93.0	US5138100
MoBiFeZnCsSb	330	800	95.4	87.7	WO9926912
MoBiFeWCoCsSiZr	330	1600	98.5	88.2	EP685260
MoBiFeNiWCoMgZnBSbCsSi	365	—	97.1	88.2	JP11179206
MoBiFeCoCs	—	750	99.5	83.3	JP2000288396
MoBiFeNiCoZnGeTeCs	340	800	97.6	88.2	JP2000237592
MoWBiFeCoNiKSi	310	1800	98.5	95.1	JP2000325795
MoBiFeNiWCoMgZnBSbCs	365	1000	95.5	88.8	US5532199
MoBiFeCoMnPbPZrCsNa	350	800	98.7	86.0	US5856259

催化剂	反应温度/℃	反应空速/h^-1	异丁烯转化率/%	甲基丙烯醛选择性/%	参考专利
MoBiFeCoCe	300	3600	98.7	97.1	US5138100
MoBiFeCoPr	340	3600	99.0	94.0	US5138100
MoBiFeCoEu	360	3600	99.1	93.0	US5138100
MoBiFeZnCsSb	330	800	95.4	87.7	WO9926912
MoBiFeWCoCsSiZr	330	1600	98.5	88.2	EP685260
MoBiFeNiWCoMgZnBSbCsSi	365	—	97.1	88.2	JP11179206
MoBiFeCoCs	—	750	99.5	83.3	JP2000288396
MoBiFeNiCoZnGeTeCs	340	800	97.6	88.2	JP2000237592
MoWBiFeCoNiKSi	310	1800	98.5	95.1	JP2000325795
MoBiFeNiWCoMgZnBSbCs	365	1000	95.5	88.8	US5532199
MoBiFeCoMnPbPZrCsNa	350	800	98.7	86.0	US5856259

催化剂	比表面积/m²·g^-1
纯α-Bi₂Mo₃O₁₂	2
共沉淀法BiMoO+TiO₂	40
浸渍法BiMoO+TiO₂	39
溶胶-凝胶法BiMoO+TiO₂	108