合成气与二甲醚为原料直接制乙醇催化反应研究进展

doi:10.11949/0438-1157.20210079

摘要/Abstract

摘要：

作为一种新型的煤制乙醇工艺，合成气经二甲醚羰基化合成乙酸甲酯，再进一步加氢制备无水乙醇的工艺路径备受市场关注。该工艺反应条件温和，所用分子筛和铜基催化剂价廉且制备方法简单。综述了二甲醚羰基化分子筛催化剂、乙酸甲酯加氢铜基催化剂的研究进展以及两者不同的耦合方式对合成气-二甲醚一步法制备乙醇反应路径的影响。重点介绍了分子筛催化二甲醚羰基化反应和失活机理以及分子筛催化剂设计调控的研究进展。该新型煤制乙醇技术为我国煤炭资源清洁高附加值利用提供了一条重要途径。

关键词: 乙醇, 二甲醚, 羰基化, 乙酸甲酯, 分子筛, 铜基催化剂

Abstract:

As a new method for ethanol synthesis from coal, dimethyl ether carbonylation with CO to methyl acetate and its further hydrogenation to ethanol has attracted much industrial attention. This route requires mild reaction condition and the catalysts can be easily prepared. In this work, we reviewed the advancement of the catalyst in the field of dimethyl ether carbonylation and methyl acetate hydrogenation. In addition, we summarized the effect of proximity of zeolite and Cu-based catalyst for ethanol synthesis. We especially focused on the development of dimethyl ether carbonylation and deactivation mechanism over zeolite as well as the modification methods of zeolite. The new coal-to-ethanol technology provides an important way for the clean and high-value-added utilization of coal resources in China.

Key words: ethanol, dimethyl ether, carbonylation, methyl acetate, zeolite, Cu-based catalyst

中图分类号:

TQ 546.4

冯晓博, 刘天龙, 赵小燕, 曹景沛. 合成气与二甲醚为原料直接制乙醇催化反应研究进展[J]. 化工学报, 2021, 72(8): 3958-3967.

Xiaobo FENG, Tianlong LIU, Xiaoyan ZHAO, Jingpei CAO. Advance in ethanol synthesis from syngas via carbonylation of dimethyl ether and hydrogenation of methyl acetate[J]. CIESC Journal, 2021, 72(8): 3958-3967.

图/表 4

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催化剂（Si/Al）	反应条件	DME转化率/%	产物生成速率/(g/(g_cat·h))	文献
HMOR （10）	190℃, 1.0 MPa, 93% CO/2% DME/5% Ar	—	0.3	[15]
HEU-12（10）	220℃, 1.0 MPa, 4.1% CO/92.8% DME/3.0% Ar	16	0.043	[25]
HSSZ-13（9.2）	165℃ 0.1 MPa, 2% DME, 3% He/5% Ar/95% CO, GHSV = 27000 ml/(g·h)	—	0.009^①	[26]
HSUZ-4（5.1）	220℃, 2.0 MPa, 5% DME/50% CO/2.5Ar, GHSV = 1170 ml/(g·h)	22	0.053	[27]
HZSM-57（17.4）	220℃, 2.0 MPa, 5% DME/50% CO/2.5Ar, GHSV = 1170 ml/(g·h)	10	0.025	[27]
1.74% Cu/HMOR（9）	210℃, 1.8 MPa, 38% CO/2% DME/3% N₂	100	0.62	[31]
1.30% Ni/HMMOR		90	0.4	[31]
1.36% Co/HMOR		100	0.47	[31]
1.67% Zn/HMOR		81	0.35	[31]
1.64% Ag/HMOR		42	0.22	[31]
3.2% Cu/HMOR（7）	210℃, 1 MPa CO, 48 kPa DME, 50.0% CO/2.4% DME/2.9% H₂/44.7% N₂, GHSV=2100 ml/(g·h)	76	0.2	[34]
2% Cu-1% Zn/HMOR		70	0.18	[34]
1.5%Cu-1.5%Zn/HMOR		92	0.24	[34]
0.6%Cu-2.5Zn/HMOR		77	0.2	[34]
HMOR （13.5）	210℃, 1.0 MPa, 5% DME/50% CO/2.5% N₂/42.5% He，GHSV = 1350 ml/ (g·h)	35	0.24	[38]
HMOR	200℃, 2.0 MPa, 5% DME/35% CO/60% H₂, GHSV = 1500 ml/(g·h)	40	0.3	[39]
HMOR（5.5）	210℃, 1.5 MPa, 3% DME/95.5% CO/1.5% N₂, GHSV = 5280 ml/(g·h)	55	0.87	[40]
HMOR （7.7）	200℃, 1% DME/49% CO, 1.5 MPa, GHSV=6000 ml/(g·h)	65	0.35	[41]
HMOR （10.7）	200℃, 1.5 MPa, 10% DME/ 50% CO/40% N₂, GHSV= 2400 ml/(g·h)	45	1.08	[42]
HMOR (12.5)	190℃, 1.5 MPa, 2.0% DME/98.0% CO, GHSV= 2000 ml/(g·h)	92	0.37	[43]
0.9% Fe/HMOR	200℃, 3.0 MPa, 5% DME/ 35% CO/ 60% H₂	82	0.19	[44]
1.8% Fe/HMOR		76	0.18	[44]
3.6% Fe/HMOR		40	0.095	[44]
Ce/HMOR （0）	200℃, 1.5 MPa, 1% DME/49% CO, GHSV= 2000 ml/(g·h)	47	0.16	[45]
Ce/HMOR （1.1）		52	0.17	[45]
Ce/HMOR （2.1）		60	0.2	[45]
Ce/HMOR （4.1）		42	0.14	[45]
HMOR+TEAOH （8.2）	200℃, 1.5 MPa, 1% DME/49% CO,GHSV= 2000 ml/(g·h)	39	0.13	[46]
HMOR+TEAOH （10.2）		47	0.16	[46]
HMOR+TEAOH （11.8）		42	0.14	[46]
HMOR+HMI （11.8）		62	0.20	[46]
FER+PyR （13.2）	200℃, 0.275 MPa, 51.1% DME/48.9% CO/Ar, GHSV= 3600 ml/(g·h)	—	1.3^①	[47]
FER+Pyr+TMA （17.0）		—	0.8^①	[47]
FER+HMI+TMA（17.2）		—	< 0.1^①	[47]
Py/HMOR （6.4）	200℃, 1.0 MPa, 5% DME/50% CO/2.5% N₂/42.5% He, GHSV= 1250 ml/(g·h)	35	0.22	[48]

催化剂（Si/Al）	反应条件	DME转化率/%	产物生成速率/(g/(g_cat·h))	文献
HMOR （10）	190℃, 1.0 MPa, 93% CO/2% DME/5% Ar	—	0.3	[15]
HEU-12（10）	220℃, 1.0 MPa, 4.1% CO/92.8% DME/3.0% Ar	16	0.043	[25]
HSSZ-13（9.2）	165℃ 0.1 MPa, 2% DME, 3% He/5% Ar/95% CO, GHSV = 27000 ml/(g·h)	—	0.009^①	[26]
HSUZ-4（5.1）	220℃, 2.0 MPa, 5% DME/50% CO/2.5Ar, GHSV = 1170 ml/(g·h)	22	0.053	[27]
HZSM-57（17.4）	220℃, 2.0 MPa, 5% DME/50% CO/2.5Ar, GHSV = 1170 ml/(g·h)	10	0.025	[27]
1.74% Cu/HMOR（9）	210℃, 1.8 MPa, 38% CO/2% DME/3% N₂	100	0.62	[31]
1.30% Ni/HMMOR		90	0.4	[31]
1.36% Co/HMOR		100	0.47	[31]
1.67% Zn/HMOR		81	0.35	[31]
1.64% Ag/HMOR		42	0.22	[31]
3.2% Cu/HMOR（7）	210℃, 1 MPa CO, 48 kPa DME, 50.0% CO/2.4% DME/2.9% H₂/44.7% N₂, GHSV=2100 ml/(g·h)	76	0.2	[34]
2% Cu-1% Zn/HMOR		70	0.18	[34]
1.5%Cu-1.5%Zn/HMOR		92	0.24	[34]
0.6%Cu-2.5Zn/HMOR		77	0.2	[34]
HMOR （13.5）	210℃, 1.0 MPa, 5% DME/50% CO/2.5% N₂/42.5% He，GHSV = 1350 ml/ (g·h)	35	0.24	[38]
HMOR	200℃, 2.0 MPa, 5% DME/35% CO/60% H₂, GHSV = 1500 ml/(g·h)	40	0.3	[39]
HMOR（5.5）	210℃, 1.5 MPa, 3% DME/95.5% CO/1.5% N₂, GHSV = 5280 ml/(g·h)	55	0.87	[40]
HMOR （7.7）	200℃, 1% DME/49% CO, 1.5 MPa, GHSV=6000 ml/(g·h)	65	0.35	[41]
HMOR （10.7）	200℃, 1.5 MPa, 10% DME/ 50% CO/40% N₂, GHSV= 2400 ml/(g·h)	45	1.08	[42]
HMOR (12.5)	190℃, 1.5 MPa, 2.0% DME/98.0% CO, GHSV= 2000 ml/(g·h)	92	0.37	[43]
0.9% Fe/HMOR	200℃, 3.0 MPa, 5% DME/ 35% CO/ 60% H₂	82	0.19	[44]
1.8% Fe/HMOR		76	0.18	[44]
3.6% Fe/HMOR		40	0.095	[44]
Ce/HMOR （0）	200℃, 1.5 MPa, 1% DME/49% CO, GHSV= 2000 ml/(g·h)	47	0.16	[45]
Ce/HMOR （1.1）		52	0.17	[45]
Ce/HMOR （2.1）		60	0.2	[45]
Ce/HMOR （4.1）		42	0.14	[45]
HMOR+TEAOH （8.2）	200℃, 1.5 MPa, 1% DME/49% CO,GHSV= 2000 ml/(g·h)	39	0.13	[46]
HMOR+TEAOH （10.2）		47	0.16	[46]
HMOR+TEAOH （11.8）		42	0.14	[46]
HMOR+HMI （11.8）		62	0.20	[46]
FER+PyR （13.2）	200℃, 0.275 MPa, 51.1% DME/48.9% CO/Ar, GHSV= 3600 ml/(g·h)	—	1.3^①	[47]
FER+Pyr+TMA （17.0）		—	0.8^①	[47]
FER+HMI+TMA（17.2）		—	< 0.1^①	[47]
Py/HMOR （6.4）	200℃, 1.0 MPa, 5% DME/50% CO/2.5% N₂/42.5% He, GHSV= 1250 ml/(g·h)	35	0.22	[48]

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