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

doi:10.11949/0438-1157.20211149

Abstract

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

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

CLC Number:

TQ110.9

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.

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.

Figures/Tables 15

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

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

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

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

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

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)

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)

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)

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

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

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

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

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

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

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

ZSM-5催化剂与低温等离子体协同转化H₂S-CO₂制合成气

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References 37

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