Status of high temperature gas desulfurizer with structural characteristics of molecular sieves

doi:10.16085/j.issn.1000-6613.2022-2317

Abstract

Abstract:

The H₂S gas generated in coal gasification is easy to cause problems such as downstream equipment corrosion, catalyst poisoning and environmental pollution. Molecular sieve supported desulfurizer has been widely used in H₂S purification because it could highly disperse the active components and promote mass transfer during the reaction. Based on the pore size and pore structure characteristics of molecular sieve, this paper introduced the application status of micropore (d<2nm), mesopore (2nm<d<50nm), macropore (d>50nm) and hierarchical porous molecular sieve, as well as the desulfurizer with molecular sieve structural characteristics as the carrier in the adsorption of H₂S gas from high temperature gas. The advantages and disadvantages of different types of molecular sieve-based desulfurizers were analyzed and discussed. Finally, the structural characteristics of different molecular sieve carriers, the research status and performance improvement of molecular sieve-based desulfurizers for H₂S purification, desulfurization functionalization and green preparation processes were concluded and prospected to provide a useful reference for the development and application of molecular sieve-based supported desulfurizer in the future.

Key words: hot coal gas, desulfurization, support, gasification, molecular sieves

摘要：

煤气化过程中产生的H₂S气体易造成下游设备腐蚀、催化剂中毒和环境污染等问题，分子筛负载型脱硫剂由于能够使活性组分高度分散，促进反应传质，在H₂S净化领域应用广泛。本文以分子筛孔径大小和孔道结构特征为依据，分别介绍了微孔（d<2nm）、介孔（2nm<d<50nm）、大孔（d>50nm）和多级孔分子筛及具备分子筛结构特性材料为载体的脱硫剂在高温煤气吸附H₂S气体中的应用现状，分析探讨了不同类型分子筛复合脱硫剂目前存在的优点与不足。最后，从不同分子筛载体的结构特点、分子筛复合脱硫剂净化H₂S现状及性能提升、脱硫功能化和绿色制备工艺等方面进行了总结和展望，以期能够为今后分子筛基负载型脱硫剂的开发与应用提供有益参考。

关键词: 高温煤气, 脱硫, 载体, 气化, 分子筛

CLC Number:

TQ51

LONG Caimei, WU Shuaishan, WANG Jiancheng, MI Jie, FENG Yu. Status of high temperature gas desulfurizer with structural characteristics of molecular sieves[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5943-5955.

龙彩梅, 武帅山, 王建成, 米杰, 冯宇. 基于分子筛结构特性的高温煤气脱硫剂应用现状[J]. 化工进展, 2023, 42(11): 5943-5955.

Figures/Tables 9

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脱硫剂种类	合成方法	反应气氛	温度/℃	硫容	参考文献
5Ce5Mn/ZSM-5	溶胶-凝胶法	0.5%H₂S/N₂	750	7653.1µmolS/g	[14]
5La5Mn/ZSM-5	溶胶-凝胶法	0.2%H₂S/N₂	600	1020.0µmolS/g	[15]
CuMn/ZSM-5	湿法浸渍	0.2%H₂S/11%CO₂/12.5%CO/13.8%H₂/1%CH₄/19%H₂O/N₂	871	NA	[16]
Cu@MCM-41/ Cu-MCM-41	浸渍法/水热法	1%H₂S/10%H₂/He	500	23.0gS/100gCuO/ 19.0gS/100gCuO	[20]
LaFeO₃/M41	溶胶-凝胶法	0.33%H₂S/10.5%H₂/17.1%CO₂/N₂	500	3.2gS/100g脱硫剂	[21]
35%ZnO/MCM-41	一步水热法	0.2%~0.3%H₂S/39%H₂/27%CO/12%CO₂/10%H₂O/N₂	500	11.0gS/100g脱硫剂	[22]
40%ZnO/MCM-41	微波水热法	2000μL/L H₂S/39%H₂/27%CO/12%CO₂/N₂	500	11.2gS/100g脱硫剂	[23-24]
Al-ZnO/MCM-41	微波水热法	3000μL/L H₂S/39%H₂/27%CO/12%CO₂/N₂	500	9.1gS/100g脱硫剂	[25]
ZnO/SBA-15 Fe₂O₃/SBA-15	双溶剂法	1.5%H₂S/He	300	5.3gS/100g ZnO 40.1gS/100g Fe₂O₃	[27]
ZnO/DSBA-15 ZnO/Nb₂₀DSBA-15 Zn₅Co/Ti₁₀DSBA-15	溶胶-凝胶法	2787mg/m³H₂S/10.5%H₂/18%CO/5%CO₂/N₂	500	5.7gS/100g脱硫剂 6.7gS/100g脱硫剂 7.1gS/100g脱硫剂	[28]
Zn₂₀Ni₁/SBA-15	溶胶-凝胶法	2000μL/L H₂S/10.5%H₂/18%CO/5%CO₂/N₂	500	16.0gS/100g脱硫剂	[29]
LaFeO₃/SBA-15	溶胶-凝胶法	0.33%H₂S/10.5%H₂/17.1%±0.3%CO₂/72.1%±2%N₂	500	4.9gS/100g脱硫剂	[30]
4Mn1Fe-3%Mo/FSM-16	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	600	18.2gS/100g脱硫剂	[32]
50% Mn/MCM-48	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	550	12.4gS/100g脱硫剂	[34]
Zn/M48 Zn/M41	溶胶-凝胶法	0.2%H₂S/18%CO/10.5%H₂/5%CO₂/N₂	500	NA	[35]
ZnO/KIT-6 La-ZnO/KIT-6	溶胶-凝胶法	0.1%H₂S/2% CO/5% H₂/10%H₂O/N₂	300	5.0gS/100g脱硫剂 7.0gS/100g脱硫剂	[37]
La₃Mn₇/KIT-6	溶胶-凝胶法	0.36%H₂S/13.84%H₂/19.36%CO/N₂	800	11.6gS/100g脱硫剂	[38]
55%5Sm95Mn/MSU-S	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	800	15.2gS/100g脱硫剂	[40]
90Mn10Ca/MSU-H	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	750	18.7gS/100g脱硫剂	[41]
4Mn1Ce/HMS	溶胶-凝胶法	0.33%H₂S/10.6%H₂/18%CO/N₂	600	12.1gS/100g脱硫剂	[43]
90Mn10Mo/KIT-1	溶胶-凝胶法	0.33%H₂S/10.6%H₂/18%CO/N₂	700	16.9gS/100g脱硫剂	[43]
ZnO/SiO₂	胶晶模板法	1mg/m³ H₂S/3.0%H₂O/N₂	500	17.0gS/100g脱硫剂	[45]
ZnCo₂/SS	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	550	13.8gS/100g脱硫剂	[48]
Ca₃Cu₁₀Mn₈₇O_i/MAS-9	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	800	17.2gS/100g脱硫剂	[49]
(8%Ce-Mn)_1.5Al_0.5O _x	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	700	29.0gS/100g脱硫剂	[50]

脱硫剂种类	合成方法	反应气氛	温度/℃	硫容	参考文献
5Ce5Mn/ZSM-5	溶胶-凝胶法	0.5%H₂S/N₂	750	7653.1µmolS/g	[14]
5La5Mn/ZSM-5	溶胶-凝胶法	0.2%H₂S/N₂	600	1020.0µmolS/g	[15]
CuMn/ZSM-5	湿法浸渍	0.2%H₂S/11%CO₂/12.5%CO/13.8%H₂/1%CH₄/19%H₂O/N₂	871	NA	[16]
Cu@MCM-41/ Cu-MCM-41	浸渍法/水热法	1%H₂S/10%H₂/He	500	23.0gS/100gCuO/ 19.0gS/100gCuO	[20]
LaFeO₃/M41	溶胶-凝胶法	0.33%H₂S/10.5%H₂/17.1%CO₂/N₂	500	3.2gS/100g脱硫剂	[21]
35%ZnO/MCM-41	一步水热法	0.2%~0.3%H₂S/39%H₂/27%CO/12%CO₂/10%H₂O/N₂	500	11.0gS/100g脱硫剂	[22]
40%ZnO/MCM-41	微波水热法	2000μL/L H₂S/39%H₂/27%CO/12%CO₂/N₂	500	11.2gS/100g脱硫剂	[23-24]
Al-ZnO/MCM-41	微波水热法	3000μL/L H₂S/39%H₂/27%CO/12%CO₂/N₂	500	9.1gS/100g脱硫剂	[25]
ZnO/SBA-15 Fe₂O₃/SBA-15	双溶剂法	1.5%H₂S/He	300	5.3gS/100g ZnO 40.1gS/100g Fe₂O₃	[27]
ZnO/DSBA-15 ZnO/Nb₂₀DSBA-15 Zn₅Co/Ti₁₀DSBA-15	溶胶-凝胶法	2787mg/m³H₂S/10.5%H₂/18%CO/5%CO₂/N₂	500	5.7gS/100g脱硫剂 6.7gS/100g脱硫剂 7.1gS/100g脱硫剂	[28]
Zn₂₀Ni₁/SBA-15	溶胶-凝胶法	2000μL/L H₂S/10.5%H₂/18%CO/5%CO₂/N₂	500	16.0gS/100g脱硫剂	[29]
LaFeO₃/SBA-15	溶胶-凝胶法	0.33%H₂S/10.5%H₂/17.1%±0.3%CO₂/72.1%±2%N₂	500	4.9gS/100g脱硫剂	[30]
4Mn1Fe-3%Mo/FSM-16	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	600	18.2gS/100g脱硫剂	[32]
50% Mn/MCM-48	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	550	12.4gS/100g脱硫剂	[34]
Zn/M48 Zn/M41	溶胶-凝胶法	0.2%H₂S/18%CO/10.5%H₂/5%CO₂/N₂	500	NA	[35]
ZnO/KIT-6 La-ZnO/KIT-6	溶胶-凝胶法	0.1%H₂S/2% CO/5% H₂/10%H₂O/N₂	300	5.0gS/100g脱硫剂 7.0gS/100g脱硫剂	[37]
La₃Mn₇/KIT-6	溶胶-凝胶法	0.36%H₂S/13.84%H₂/19.36%CO/N₂	800	11.6gS/100g脱硫剂	[38]
55%5Sm95Mn/MSU-S	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	800	15.2gS/100g脱硫剂	[40]
90Mn10Ca/MSU-H	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	750	18.7gS/100g脱硫剂	[41]
4Mn1Ce/HMS	溶胶-凝胶法	0.33%H₂S/10.6%H₂/18%CO/N₂	600	12.1gS/100g脱硫剂	[43]
90Mn10Mo/KIT-1	溶胶-凝胶法	0.33%H₂S/10.6%H₂/18%CO/N₂	700	16.9gS/100g脱硫剂	[43]
ZnO/SiO₂	胶晶模板法	1mg/m³ H₂S/3.0%H₂O/N₂	500	17.0gS/100g脱硫剂	[45]
ZnCo₂/SS	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	550	13.8gS/100g脱硫剂	[48]
Ca₃Cu₁₀Mn₈₇O_i/MAS-9	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	800	17.2gS/100g脱硫剂	[49]
(8%Ce-Mn)_1.5Al_0.5O _x	溶胶-凝胶法	0.33%H₂S/10.5%H₂/18%CO/N₂	700	29.0gS/100g脱硫剂	[50]

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