Research progress on the direct catalytic conversion of syngas to light olefins

doi:10.16085/j.issn.1000-6613.2021-2344

Abstract

Abstract:

The direct conversion of syngas to light olefins such as ethene and propene has become a significant and attractive process in syngas conversion and olefin synthesis due to the abundant resources and its relatively short process. In this review, the direct synthesis of light olefins from syngas via Fischer-Tropsch (FTO) route is introduced at first with the emphasis on the research progress of iron-based and cobalt-based catalysts and the catalytic reaction mechanism. Then the direct conversion based on the recently proposed and developed bifunctional catalytic system consisting of oxides and zeolites (STO) is addressed in detail. The effects of oxide composition and ratio, zeolite acidity and pore structure on the STO catalytic performance are elaborated. The catalytic mechanism for reactions with ketene or methanol/dimethyl ether as key intermediate is also discussed. The directions and challenges on the development of the bifunctional catalysis system are finally proposed.

Key words: syngas, light olefins, catalysis, bifunctional catalyst, Fischer-Tropsch synthesis, reaction mechanism

摘要：

合成气直接催化转化制乙烯、丙烯等低碳烯烃因具有原料来源广泛、流程较短等优点，成为目前合成气催化转化和烯烃制备技术的一个重要发展方向。本文首先介绍了合成气经费托合成直接制备低碳烯烃的路线（FTO），简单概括了铁基和钴基催化剂的研究进展以及催化反应机理。随后重点综述了近年来提出并发展的基于双功能催化体系的合成气直接制低碳烯烃路线（STO），详细阐述了金属氧化物的组成、配比等以及分子筛的酸性、孔道等性质对反应性能的影响，同时讨论了双功能催化体系以乙烯酮或甲醇/二甲醚为关键中间体的催化反应机理。最后对双功能催化体系的研究方向和挑战进行了展望。

关键词: 合成气, 低碳烯烃, 催化（作用）, 双功能催化剂, 费托合成, 反应机理

CLC Number:

O643.3

HU Wende, WANG Yangdong, WANG Chuanming. Research progress on the direct catalytic conversion of syngas to light olefins[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4754-4766.

胡文德, 王仰东, 王传明. 合成气直接催化转化制低碳烯烃研究进展[J]. 化工进展, 2022, 41(9): 4754-4766.

Figures/Tables 9

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CO活化组分	C—C耦合组分	温度/℃	压力/MPa	空速 /mL·g^-1· h^-1	H₂/CO比	CO 转化率/%	CO₂选择性/%	烃类产物选择性/%				参考文献
CO活化组分	C—C耦合组分	温度/℃	压力/MPa	空速 /mL·g^-1· h^-1	H₂/CO比	CO 转化率/%	CO₂选择性/%	CH₄	C₂⁼~C₄⁼	C₂~C₄	C₅₊	参考文献
ZnCrO _x	SAPO-34	400	2.5	4800	2.5	17	41	2	80	14	4	［44］
ZnO-ZrO₂	SAPO-34	400	1.0	3600	2	7	43	4	69	25	2	［45］
Zr-In₂O₃	SAPO-34	400	2.5	3600	1	28	40	4	74	20	2	［56］
Cr-ZnO _x	SAPO-34	400	2.0	1125	1	30	52	16	38	45	—	［46］
ZnAlO _x	SAPO-34	390	4.0	12000	1	7	33	5	78	13	4	［57］
Zr-Zn/Al₂O₃	SAPO-34	400	1.0	3600	2	8	46	13	70	17	—	［52］
Zn/Al₂O₃	SAPO-34	370	1.0	3600	2	5	45	10	77	13	0	［51］
MnGaO _x	SAPO-34	400	2.5	4875	2	14	45	2	88	8	2	［58］
Zn _x Ce_2–_y Zr _y O₄	SAPO-34	300	1.0	5400	2	6	6	5	83	4	9	［64］
ZnGa₂O₄	SAPO-34	400	3.0	3600	2	30	41	5	77	17	2	［62］
ZnAl₂O₄	SAPO-34	400	3.0	3600	2	24	44	4	80	14	2	［62］
Zn-CrO _x	SAPO-34	400	2.0	6480	2	11	36	8	64	25	3	［63］
MnO _x	SAPO-34	400	2.5	4800	2.5	7	43	1	79	15	5	［47］
ZnO	SAPO-34	400	4.0	1600	2.5	32	42	3	77	15	5	［48］
Zn-ZrO₂	SSZ-13	400	3.0	3000	2	29	42	2	77	18	3	［50］
ZnCrO _x	SSZ-13	380	1.0	6000	2	20	49	6	72	15	7.5	［67］
ZnCrO _x	MOR	360	2.0	1600	1	26	48	1	91	4	5	［49］
ZnAl₂O₄	MOR	370	3.0	1500	1	10	44	5	77	12	6	［54］
ZnCrO _x	AlPO-18	390	10.0	3600	1	49	49	2	83	4	11	［59］
ZnAlO _x	SAPO-17	400	3.0	3000	2	23	42	13	66	14	7	［77］
ZnAlO _x	SAPO-18	400	3.0	3000	2	21	44	3	71	16	10	［77］
ZnAlO _x	SAPO-34	400	3.0	3000	2	24	44	4	81	14	1	［77］
ZnCrO _x	SAPO-18/34	390	4.0	6000	1	27	45-48	1	88	2	8	［61］
K-MoS₂	SAPO-34	400	4.0	4000	1	20	50	15	59	22	4	［53］
K-CoMoS	SAPO-34	400	4.0	4000	1	9	45	6	65	26	3	［53］

CO活化组分	C—C耦合组分	温度/℃	压力/MPa	空速 /mL·g^-1· h^-1	H₂/CO比	CO 转化率/%	CO₂选择性/%	烃类产物选择性/%				参考文献
CO活化组分	C—C耦合组分	温度/℃	压力/MPa	空速 /mL·g^-1· h^-1	H₂/CO比	CO 转化率/%	CO₂选择性/%	CH₄	C₂⁼~C₄⁼	C₂~C₄	C₅₊	参考文献
ZnCrO _x	SAPO-34	400	2.5	4800	2.5	17	41	2	80	14	4	［44］
ZnO-ZrO₂	SAPO-34	400	1.0	3600	2	7	43	4	69	25	2	［45］
Zr-In₂O₃	SAPO-34	400	2.5	3600	1	28	40	4	74	20	2	［56］
Cr-ZnO _x	SAPO-34	400	2.0	1125	1	30	52	16	38	45	—	［46］
ZnAlO _x	SAPO-34	390	4.0	12000	1	7	33	5	78	13	4	［57］
Zr-Zn/Al₂O₃	SAPO-34	400	1.0	3600	2	8	46	13	70	17	—	［52］
Zn/Al₂O₃	SAPO-34	370	1.0	3600	2	5	45	10	77	13	0	［51］
MnGaO _x	SAPO-34	400	2.5	4875	2	14	45	2	88	8	2	［58］
Zn _x Ce_2–_y Zr _y O₄	SAPO-34	300	1.0	5400	2	6	6	5	83	4	9	［64］
ZnGa₂O₄	SAPO-34	400	3.0	3600	2	30	41	5	77	17	2	［62］
ZnAl₂O₄	SAPO-34	400	3.0	3600	2	24	44	4	80	14	2	［62］
Zn-CrO _x	SAPO-34	400	2.0	6480	2	11	36	8	64	25	3	［63］
MnO _x	SAPO-34	400	2.5	4800	2.5	7	43	1	79	15	5	［47］
ZnO	SAPO-34	400	4.0	1600	2.5	32	42	3	77	15	5	［48］
Zn-ZrO₂	SSZ-13	400	3.0	3000	2	29	42	2	77	18	3	［50］
ZnCrO _x	SSZ-13	380	1.0	6000	2	20	49	6	72	15	7.5	［67］
ZnCrO _x	MOR	360	2.0	1600	1	26	48	1	91	4	5	［49］
ZnAl₂O₄	MOR	370	3.0	1500	1	10	44	5	77	12	6	［54］
ZnCrO _x	AlPO-18	390	10.0	3600	1	49	49	2	83	4	11	［59］
ZnAlO _x	SAPO-17	400	3.0	3000	2	23	42	13	66	14	7	［77］
ZnAlO _x	SAPO-18	400	3.0	3000	2	21	44	3	71	16	10	［77］
ZnAlO _x	SAPO-34	400	3.0	3000	2	24	44	4	81	14	1	［77］
ZnCrO _x	SAPO-18/34	390	4.0	6000	1	27	45-48	1	88	2	8	［61］
K-MoS₂	SAPO-34	400	4.0	4000	1	20	50	15	59	22	4	［53］
K-CoMoS	SAPO-34	400	4.0	4000	1	9	45	6	65	26	3	［53］

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