甲基芳烃液相选择性催化氧化催化剂研究进展

doi:10.16085/j.issn.1000-6613.2022-1429

摘要/Abstract

摘要：

甲基芳烃衍生的芳甲醇、芳甲醛、芳甲酸等高附加值产品作为重要化工中间体，一直在国内外市场处于供不应求状态。其通常以甲基芳烃为原料，通过液相选择性催化氧化技术可控制备。该技术因其转化率高、成本低、安全性好等优点，成为目前工业上该类产品的主要生产方法，而开发高性能催化剂是该技术的关键问题之一。因此，本文在总结甲基芳烃催化氧化机理的基础上，综述了近年来金属盐催化剂、金属络合物催化剂、金属有机框架（MOF）催化剂、金属氧化物催化剂及其他催化剂在甲基芳烃液相选择性催化氧化方面的应用研究进展。研究者从提升催化剂活性、稳定性及降低制备成本出发，对不同种类的催化剂进行改进，发现金属盐及金属络合物催化剂性能的提高在于开发相应载体，而MOFs催化剂在于开发高活性的Co、Mn金属MOFs催化剂，金属氧化物催化剂则需要在现有基础上优化制备工艺。

关键词: 氧化, 催化剂, 芳烃, 选择性

Abstract:

High value-added products such as aromatic methanol, formaldehyde and formic acid that are derived from methyl aromatic hydrocarbons have been always in short supply worldwide. Because of its high conversion rate, low cost, good safety and other advantages, liquid phase selective catalytic oxidation is the main production method of methyl aromatic hydrocarbon derivatives in industry at present, and the high performance catalyst is one of the key factors. Based on the summary of the catalytic oxidation mechanism of methyl aromatic hydrocarbons, the applications of metal salt catalysts, metal complex catalysts, metal-organic framework (MOF) catalysts, metal oxide catalysts and other catalysts are reviewed in this paper. In order to improve the activity and stability of catalysts and reduce the preparation cost, researchers improves different kinds of catalysts, and find that the improvement of the performance of metal salt and metal complex catalysts lies in the development of corresponding support, while that of the MOFs catalyst should develop high activity Co and Mn metal MOFs catalysts. Besides, the development of metal oxide catalyst should optimize the existing preparation process. Finally, the improvement measures and future development directions of catalysts for liquid phase catalytic oxidation of methyl aromatic hydrocarbon are proposed.

Key words: oxidation, catalysts, aromatics, selectivity

中图分类号:

TQ426

殷鹏镇, 吴芹, 黎汉生. 甲基芳烃液相选择性催化氧化催化剂研究进展[J]. 化工进展, 2023, 42(6): 2916-2943.

YIN Pengzhen, WU Qin, LI Hansheng. Advances in catalysts for liquid-phase selective oxidation of methyl aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2916-2943.

图/表 19

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催化剂	反应条件
乙酸钴（Ⅱ）	空气液相氧化，160℃，0.98MPa
硬脂酸钴
钴盐，NaBr	富氧液相氧化，140~170℃，常压
KMnO₄，溴化物>0.03%， CH₃CN>0.05%	原子氧液相氧化
环烷酸钴	90℃，1.47MPa，氧或空气液相氧化
辛酸钴	150~175℃，0.34~0.52MPa
乙酸钴（Ⅱ）苯甲酸钴（Ⅱ）	170℃，0.69MPa
钴	空气液相氧化，>125℃，>0.2MPa
钴盐0.1%~0.3%	空气液相氧化，121~177℃，0.2MPa
可溶性钴盐0.1%~0.3%	空气液相氧化，0.2MPa
月桂酸钴（Ⅱ）月桂酸锰（Ⅱ）	液相氧化，130℃，氧气压力0.49MPa
乙酰丙酮酸钴0.003~0.02mol/L 苯甲醛0.01~0.1mol/L	液相氧化

催化剂	反应条件
乙酸钴（Ⅱ）	空气液相氧化，160℃，0.98MPa
硬脂酸钴
钴盐，NaBr	富氧液相氧化，140~170℃，常压
KMnO₄，溴化物>0.03%， CH₃CN>0.05%	原子氧液相氧化
环烷酸钴	90℃，1.47MPa，氧或空气液相氧化
辛酸钴	150~175℃，0.34~0.52MPa
乙酸钴（Ⅱ）苯甲酸钴（Ⅱ）	170℃，0.69MPa
钴	空气液相氧化，>125℃，>0.2MPa
钴盐0.1%~0.3%	空气液相氧化，121~177℃，0.2MPa
可溶性钴盐0.1%~0.3%	空气液相氧化，0.2MPa
月桂酸钴（Ⅱ）月桂酸锰（Ⅱ）	液相氧化，130℃，氧气压力0.49MPa
乙酰丙酮酸钴0.003~0.02mol/L 苯甲醛0.01~0.1mol/L	液相氧化

序号	催化剂	氧化剂	助剂	操作条件	溶剂	产物	时间	转化率/%	选择性/%	参考文献
1	VOSO₄	O₂	氢溴酸	100℃、0.1MPa	乙酸	苯甲酸	20h	99	98	[15]
2	萘酸钴	O₂	无	140℃、2MPa	[Emim]BF₄	苯甲酸	2h	31	60	[16]
3	Co(OAc)₂	O₃	KBr	80℃、0.8L/min	乙酸	对苯二甲酸	6h	96	84	[17]
4	Mn(OAc)₂	O₃	硫酸	60℃、6.0 × 10^-3L/s	乙酸	苯甲酸	75min	27	82.50	[18]
5	CoBr₂/MnBr₂	O₂	无	110℃	乙酸	苯甲酸	10h	16	95	[21]
6	Co(acac)₂/Mn(acac)₂	O₂	苯甲酸	165℃、0.6MPa	无	苯甲醛	4h	45	15	[23]
7	Co(OAc)₂/Mn(OAc)₂	O₂	H₃PW₁₂O₄₀	215℃、3MPa	无	间苯二甲酸	3h	92	31.5	[24]
8	VO(OAc)₂/Zr(OAc)₂	H₂O₂	无	90℃、H₂O₂(30%)5mL	乙酸	苯甲醛	4h	20.3	70.3	[25]
9	Co(OAc)₂/Mn(OAc)₂	O₂	1,1,2,2-四溴乙烷	110℃	乙酸	苯甲醛	8h	67	67.60	[28]
10	Co(OAc)₂	O₂	溴苄/4-二甲氨基吡啶（DMAP）	160℃	无	苯甲酸	80min	42	76	[29]
11	Co(OAc)₂	O₂	NHPI	170~190℃、0.8MPa	无	苯甲酸	20h	84	93	[32]
12	Co(OAc)₂	O₂	NHPI	50℃、1.0MPa	二氯甲烷	苯甲酸	3h	58.7	95	[33]
13	MnCl₂	O₂	NHPI	100℃、0.05L/min	乙酸	苯甲酸	5h	40.4	71.3	[34]
14	MnII1CoII10@MCM-41/HNT	O₂	溴化钾	200~250℃、2.0MPa	乙酸和乙腈	对苯二甲酸	3h	99	93.80	[36]
15	Cu-MCM-41	O₂	溴化十六烷基三甲铵	80℃	无	2,5-二羟基对苯二甲酸	5h	21.70	73.00	[37]
17	Co(NO₃)₂/SiO₂	O₂	NHPI	90℃、2MPa	HFIP	苯甲醛	5h	42.5	52.60	[38]
16	Co(OAc)₂/SiO₂	O₂	NHPI	90℃、2MPa	HFIP	苯甲醛	5h	42.50	73.10	[39]
18	CuBr₂@g-C₃N₄	TBHP	无	120℃	无	苯甲醛	3~6h	55	95	[41]
19	Cu-CNB	TBHP	无	70℃	乙腈	苯甲醛	16h	6.30	99	[44]
20	聚(4-乙烯基吡啶-共二苯基苯）负载Fe（Ⅲ）催化剂	H₂O₂	无	80℃	乙腈	苯甲酸	6h	90	96	[46]

序号	催化剂	氧化剂	助剂	操作条件	溶剂	产物	时间	转化率/%	选择性/%	参考文献
1	VOSO₄	O₂	氢溴酸	100℃、0.1MPa	乙酸	苯甲酸	20h	99	98	[15]
2	萘酸钴	O₂	无	140℃、2MPa	[Emim]BF₄	苯甲酸	2h	31	60	[16]
3	Co(OAc)₂	O₃	KBr	80℃、0.8L/min	乙酸	对苯二甲酸	6h	96	84	[17]
4	Mn(OAc)₂	O₃	硫酸	60℃、6.0 × 10^-3L/s	乙酸	苯甲酸	75min	27	82.50	[18]
5	CoBr₂/MnBr₂	O₂	无	110℃	乙酸	苯甲酸	10h	16	95	[21]
6	Co(acac)₂/Mn(acac)₂	O₂	苯甲酸	165℃、0.6MPa	无	苯甲醛	4h	45	15	[23]
7	Co(OAc)₂/Mn(OAc)₂	O₂	H₃PW₁₂O₄₀	215℃、3MPa	无	间苯二甲酸	3h	92	31.5	[24]
8	VO(OAc)₂/Zr(OAc)₂	H₂O₂	无	90℃、H₂O₂(30%)5mL	乙酸	苯甲醛	4h	20.3	70.3	[25]
9	Co(OAc)₂/Mn(OAc)₂	O₂	1,1,2,2-四溴乙烷	110℃	乙酸	苯甲醛	8h	67	67.60	[28]
10	Co(OAc)₂	O₂	溴苄/4-二甲氨基吡啶（DMAP）	160℃	无	苯甲酸	80min	42	76	[29]
11	Co(OAc)₂	O₂	NHPI	170~190℃、0.8MPa	无	苯甲酸	20h	84	93	[32]
12	Co(OAc)₂	O₂	NHPI	50℃、1.0MPa	二氯甲烷	苯甲酸	3h	58.7	95	[33]
13	MnCl₂	O₂	NHPI	100℃、0.05L/min	乙酸	苯甲酸	5h	40.4	71.3	[34]
14	MnII1CoII10@MCM-41/HNT	O₂	溴化钾	200~250℃、2.0MPa	乙酸和乙腈	对苯二甲酸	3h	99	93.80	[36]
15	Cu-MCM-41	O₂	溴化十六烷基三甲铵	80℃	无	2,5-二羟基对苯二甲酸	5h	21.70	73.00	[37]
17	Co(NO₃)₂/SiO₂	O₂	NHPI	90℃、2MPa	HFIP	苯甲醛	5h	42.5	52.60	[38]
16	Co(OAc)₂/SiO₂	O₂	NHPI	90℃、2MPa	HFIP	苯甲醛	5h	42.50	73.10	[39]
18	CuBr₂@g-C₃N₄	TBHP	无	120℃	无	苯甲醛	3~6h	55	95	[41]
19	Cu-CNB	TBHP	无	70℃	乙腈	苯甲醛	16h	6.30	99	[44]
20	聚(4-乙烯基吡啶-共二苯基苯）负载Fe（Ⅲ）催化剂	H₂O₂	无	80℃	乙腈	苯甲酸	6h	90	96	[46]

序号	催化剂	氧化剂	助剂	操作条件	溶剂	产物	时间	转化率/%	选择性/%	参考文献
1	CoTPP	O₂	乙酰丙酮	165℃	乙腈	苯甲酸	4h	14.6	61.40	[49]
2	VOTPP	O₂	无	145℃、0.8MPa	无	苯甲酸	4h	23.0	86.00	[50]
3	T(p-Cl)PPMnCl	O₂	NHPI、CTAB	100℃，0.05L/min	无	苯甲酸	6h	40.95	65.14	[53]
4	[T(p-Cl)PPFe]₂O	空气	无	190℃、1.0MPa	无	苯甲醛和苯甲醇	90min	8.71	4.20	[54]
5	Schiff碱锰(Ⅲ)配合物	空气	无	120℃、0.05L/h	无	对苯二甲酸	12h	55	90	[55]
6	Co(Ⅱ)TPP/CTS	O₂	无	145℃、0.8MPa	无	苯甲醛和苯甲醇	4.5h	8.93	66	[59]
7	MnTPP/CTS	O₂	无	195℃、0.6MPa	无	苯甲醛和苯甲醇	2h	4.8	95	[60]
8	PS-Fe-NAPA	H₂O₂	无	60℃	乙腈	苯甲醛	7h	78	86	[62]
9	LDH-[NAPABA-M]	TBHP	无	100℃	无	苯甲醛	7h	55.30	86.10	[63]