锆基双金属氧化物催化剂硫中毒的研究

doi:10.19964/j.issn.1006-4990.2022-0162

摘要/Abstract

摘要：

在工业二氧化碳加氢制甲醇过程中，硫化氢气体的引入将对该过程中使用的催化剂活性及稳定性带来负面的影响。基于此，采用微反应合成法成功制备了InZrO _x 和ZnZrO _x 锆基催化剂，并研究了在二氧化碳加氢反应中，硫化氢气体对锆基催化剂的结构性质及其催化性能的影响规律。结果表明，在T=573 K、p=3.0 MPa和GHSV=18 000 mL/（g_cat·h）条件下，仅通入二氧化碳/氢气反应气时，InZrO _x 和ZnZrO _x 催化剂的二氧化碳转化率和甲醇选择性分别为7.2%、9.3%和93%、92%。在二氧化碳/氢气原料气中通入体积分数为5×10^-3硫化氢气体时，InZrO _x 和ZnZrO _x 催化剂的二氧化碳转化率和甲醇选择性都降为0，这主要是因为硫化氢气体占据了氧空位，导致锆基双金属氧化物催化剂硫中毒失活。当停止通硫化氢气体时，InZrO _x 和ZnZrO _x 催化剂的二氧化碳转化率和甲醇选择性分别恢复为5%、8.6%和58%、84%，分析表明停止通硫化氢气体后，氧空位浓度又恢复，锆基双金属氧化物催化剂部分活性恢复。此研究明晰了锆基催化剂硫中毒失活原理，以及为后期开发耐硫性催化剂提供了理论依据。

关键词: 微反应合成, CO₂加氢制甲醇, 锆基双金属氧化物催化剂, 硫中毒, 氧空位

Abstract:

In industrial CO₂ hydrogenation to methanol，the introduction of H₂S gas will have negative impact on the activity and stability of catalyst used in the process.Based on this，InZrO _x and ZnZrO _x zirconium-based catalysts by microreaction synthesis method were successfully prepared Meanwhile，the influence law of H₂S gas on the structural properties and catalytic performance of zirconium-based catalysts in the CO₂ hydrogenation reaction was investigated.The results showed that under the conditions of T=573 K，P=3.0 MPa and GHSV=18 000 mL/（g_cat·h），when only CO₂/H₂ reaction gas was passed，the CO₂ conversion and CH₃OH selectivity of InZrO _x and ZnZrO _x catalysts were 7.2%，9.3% and 93%，92%，respectively.The CO₂ conversion and CH₃OH selectivity of both InZrO _x and ZnZrO _x catalysts were decreased to 0 when H₂S gas at a concentration of 5×10^-3 was introduced into the CO₂/H₂ feed gas.It was mainly due to the occupation of oxygen vacancies by H₂S gas，which led to the sulfur poisoning deactivation of the zirconium-based bimetallic oxide catalysts.When H₂S gas was stopped，the CO₂ conversion and CH₃OH selectivity of InZrO _x and ZnZrO _x catalysts were recovered to 5%，8.6% and 58%，84% respectively.The analysis showed that when the H₂S gas was stopped，the oxygen vacancy concentration was restored and the activity of zirconium-based bimetallic oxide catalysts was partially restored.This study clarified the principle of sulfur poisoning deactivation of zirconium-based catalysts and provided theoretical basis for the later development of sulfur-resistant catalysts.

Key words: microreaction synthesis, CO₂ hydrogenation to methanol, zirconium-based bimetallic oxides catalysts, sulfur poisoning, oxygen vacancy

中图分类号:

TQ426.82

杨庭龙,王富中,刘飞. 锆基双金属氧化物催化剂硫中毒的研究[J]. 无机盐工业, 2023, 55(1): 151-158.

YANG Tinglong,WANG Fuzhong,LIU Fei. Study on sulfur poisoning of zirconium-based bimetallic oxides catalyst[J]. Inorganic Chemicals Industry, 2023, 55(1): 151-158.

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样品	元素质量分数/%							m（S）/m（C）
样品	O	Zr	In	Zn	Mo	S	C	m（S）/m（C）
InZrO _x	25.00	66.63	8.27	—	—	—	—	—
S-InZrO _x	23.01	66.60	8.24	—	—	1.23	0.90	1.37
R-InZrO _x	23.53	66.62	8.25	—	—	0.21	0.89	0.24
ZnZrO _x	25.15	64.41	—	10.45	—	—	—	—
S-ZnZrO _x	23.55	64.39	—	10.43	—	1.61	0.02	80.50
R-ZnZrO _x	25.01	64.40	—	10.44	—	0.21	0.01	21.00

样品	比表面积/（m²?g^-1）			孔容/（cm³?g^-1）
样品	S_BET	S_mic	S_mes	V_t	V_mic	V_mes
InZrO _x	80	12	68	0.22	0.06	0.17
S-InZrO _x	59	3	56	0.07	0.04	0.03
ZnZrO _x	36	2	34	0.1	0.01	0.09
S-ZnZrO _x	35.8	1.8	34	0.09	0.01	0.08

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