ZSM-5催化剂与低温等离子体协同转化H2S-CO2制合成气

doi:10.11949/0438-1157.20211149

化工学报 ›› 2022, Vol. 73 ›› Issue (1): 255-265.DOI: 10.11949/0438-1157.20211149

• 催化、动力学与反应器 • 上一篇下一篇

ZSM-5催化剂与低温等离子体协同转化H₂S-CO₂制合成气

王乾浩^1,²(),赵璐¹(),孙付琳^1,³,房克功¹

^1.中国科学院山西煤炭化学研究所，煤转化国家重点实验室，山西太原 030001
^2.中国科学院大学，北京 100049
^3.东北石油大学化学化工学院，黑龙江大庆 163318

收稿日期:2021-08-12 修回日期:2021-11-10 出版日期:2022-01-05 发布日期:2022-01-18
通讯作者: 赵璐
作者简介:王乾浩（1994—），男，硕士研究生，wangqianhao21@foxmail.com
基金资助:
国家自然科学基金项目(21978313);煤转化国家重点实验室自主研究课题项目(2020BWZ002);中国科学院青年创新促进会人才项目(2020181)

Production of syngas derived from H₂S-CO₂via synergy of ZSM-5 catalyst and non-thermal plasma

Qianhao WANG^1,²(),Lu ZHAO¹(),Fulin SUN^1,³,Kegong FANG¹

^1.State Key Laboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
^2.University of Chinese Academy of Sciences, Beijing 100049, China
^3.College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318, Heilongjiang, China

Received:2021-08-12 Revised:2021-11-10 Online:2022-01-05 Published:2022-01-18
Contact: Lu ZHAO

摘要/Abstract

摘要：

将H₂S和CO₂混合酸气一步转化制合成气，既实现了二者无害化处理，又生产出合成气，是一条理想的废气资源化利用新路线。由于分子结构稳定，在常规条件下因受热力学平衡限制，二者转化率极低。而在低温等离子体中，H₂S和CO₂可被激发为高活性物种来参与反应。研究了具有不同Si/Al摩尔比的ZSM-5催化剂与低温等离子体结合实现H₂S-CO₂一步高选择性制合成气，显著提高了H₂S-CO₂转化性能。考察了ZSM-5催化剂中Si/Al比和低温等离子体放电条件等对反应的影响。其中，当Si/Al比为80时表现出最优催化性能，最高H₂和CO产率分别达到56.1%和10.0%。对常规条件和低温等离子体氛围下的不同ZSM-5催化剂上CO₂、H₂S、CO、H₂等化学吸脱附行为进行了对比研究，发现低温等离子体促进了催化剂对CO₂、H₂及CO分子的吸附活化，进而明显提升了H₂S和CO₂转化。

关键词: 硫化氢, 二氧化碳, 合成气, 低温等离子体, 废物处理

Abstract:

The H₂S and CO₂ mixed acid gas is converted into syngas in one step, which not only realizes the harmless treatment, but also produces syngas, and it is an ideal new route for waste gas resource utilization. Nevertheless, it has not been paid enough attention due to highly thermodynamic stability and kinetic inert of H₂S and CO₂. Non-thermal plasma has an advantage over the thermal processes in enhanced conversion because of its non-equilibrium feature. In this work, we demonstrated a low-temperature and novel non-thermal plasma method aided by ZSM-5 catalysts having different Si/Al molar ratios for syngas production from the simultaneous conversion of H₂S and CO₂ acid gases. The effects of Si/Al molar ratios and discharge conditions were investigated. Especially, the ZSM-5 catalyst with Si/Al molar ratio of 80 showed the best catalytic behavior. The best yields of H₂ and CO were 56.1% and 10.0%, respectively. Meanwhile, comparison of the chemisorption behaviors of CO₂, H₂S, CO and H₂ on various ZSM-5 catalysts in non-thermal plasma with those in conventional conditions were studied. It indicates that non-thermal plasma can enhance the amount of CO₂, CO and H₂ adsorbed on the catalyst surface, thus assisted in the simultaneous conversion of H₂S and CO₂.

Key words: hydrogen sulfide, carbon dioxide, syngas, non-thermal plasma, waste treatment

中图分类号:

TQ110.9

王乾浩, 赵璐, 孙付琳, 房克功. ZSM-5催化剂与低温等离子体协同转化H₂S-CO₂制合成气[J]. 化工学报, 2022, 73(1): 255-265.

Qianhao WANG, Lu ZHAO, Fulin SUN, Kegong FANG. Production of syngas derived from H₂S-CO₂via synergy of ZSM-5 catalyst and non-thermal plasma[J]. CIESC Journal, 2022, 73(1): 255-265.

图/表 15

图1 低温等离子体系统1—气瓶;2—质量流量控制器;3—高压电极;4—等离子体高压发生器;5—示波器;6—油浴;7—等离子体反应器(填充催化剂);8—接地极;9—积硫槽;10—冷阱;11—气相色谱分析仪;12—碱液处理

Fig.1 Schematic diagram of the non-thermal plasma experimental set-up

图2 介质阻挡放电反应器反应床层截面温度分布

Fig.2 The temperature distribution across the reaction bed under actual reaction conditions

图3 不同Si/Al比ZSM-5催化剂的XRD谱图

Fig.3 XRD patterns of ZSM-5 catalysts with various Si/Al molar ratios

表1 不同Si/Al比ZSM-5催化剂的比表面积及介电常数

Table 1 Specific surface area and dielectric constant of ZSM-5 catalysts with various Si/Al molar ratios

Si/Al比	比表面积/（m²/g）	介电常数ε
25	305	3.15
38	318	3.27
50	324	3.37
80	306	3.42
200	307	3.49

表2 无等离子体下不同Si/Al比ZSM-5催化剂上热转化H2S-CO2反应结果

Table 2 The thermal conversion of H2S-CO2 in the presence of packing various ZSM-5 catalysts without non-thermal plasma

Si/Al比	H₂S转化率/%	CO₂转化率/%
25	5.0	0.9
38	2.9	0.8
50	3.5	1.3
80	5.3	1.4
200	5.9	1.2

图4 不同Si/Al比ZSM-5催化剂上H2S-CO2转化性能随SEI的变化(反应条件:原料气H2S/CO2为1∶4; N2浓度20%; 反应气流量200 ml/min; 填充体积15 ml)

Fig.4 H2S-CO2 conversion as a function of SEI in the presence of packing various ZSM-5 catalysts in non-thermal plasma(feed: H2S/CO2 molar ratio = 1∶4; 20%(vol) N2 in H2S-CO2 gas; feed flow rate 200 ml/min; material bed volume 15 ml)

图5 不同Si/Al比ZSM-5催化剂上H2S-CO2转化反应气相产物分布、H2及CO产率、H2/CO比(反应条件:原料气H2S/CO2为1∶4; N2浓度20%; 反应气流量200 ml/min; 填充体积15 ml)

Fig.5 Gaseous product distributions, H2 and CO yields and H2/CO molar ratios in H2S-CO2 conversion with packing various ZSM-5 catalysts in non-thermal plasma(feed: H2S/CO2 molar ratio = 1∶4; 20%(vol) N2 in H2S-CO2 gas; feed flow rate 200 ml/min; material bed volume 15 ml)

图6 H2S-CO2转化反应中填充不同Si/Al比ZSM-5催化剂的Q-U Lissajous图形、放电功率和有效电容(反应条件:原料气H2S/CO2=1∶4; N2浓度20%; 反应气流量200 ml/min; 填充体积15 ml; 输入功率95 W)

Fig.6 Q-U Lissajous figures, discharge power and effective capacitance in H2S-CO2 conversion with packing various ZSM-5 catalysts in non-thermal plasma(feed: H2S/CO2 molar ratio = 1∶4; 20%(vol) N2 in H2S-CO2 gas; feed flow rate 200 ml/min; material bed volume 15 ml; input power 95 W)

图7 不同Si/Al比ZSM-5催化剂的CO2-TPD谱图

Fig.7 CO2-TPD profiles of ZSM-5 catalysts with various Si/Al molar ratios

图8 不同低温等离子体输入电压下ZSM-5催化剂（Si/Al=80）的CO2-TPD谱图

Fig.8 CO2-TPD profiles of ZSM-5 catalyst with Si/Al molar ratio of 80 at various input voltage

图9 不同Si/Al比ZSM-5催化剂的H2S-TPD谱图

Fig.9 H2S-TPD profiles of ZSM-5 catalysts with various Si/Al molar ratios

图10 不同Si/Al比ZSM-5催化剂的H2-TPD谱图

Fig.10 H2-TPD profiles of ZSM-5 catalysts with various Si/Al molar ratios

图11 不同Si/Al比ZSM-5催化剂的CO-TPD谱图

Fig.11 CO-TPD profiles of ZSM-5 catalysts with various Si/Al molar ratios

图12 ZSM-5催化剂表面吸附CO促进CO2吸附活化示意图

Fig.12 CO adsorption on ZSM-5: improvement for CO2 adsorption

图13 低温等离子体下吸附CO后ZSM-5催化剂（Si/Al比为80）的CO2-TPD谱图

Fig.13 CO2-TPD profiles of ZSM-5 catalyst with Si/Al molar ratio of 80 after CO adsorption in non-thermal plasma

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ZSM-5催化剂与低温等离子体协同转化H₂S-CO₂制合成气

Production of syngas derived from H₂S-CO₂via synergy of ZSM-5 catalyst and non-thermal plasma

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