Influence of H<sub>2</sub>S and NH<sub>3</sub> on biogas dry reforming using Ni catalyst: a study on single and synergetic effect

doi:10.1007/s11783-023-1632-1

Front. Environ. Sci. Eng.

2023, Vol. 17

Issue (3) : 32 https://doi.org/10.1007/s11783-023-1632-1

RESEARCH ARTICLE

Influence of H₂S and NH₃ on biogas dry reforming using Ni catalyst: a study on single and synergetic effect

Yuchen Gao¹(

), Jianguo Jiang², Yuan Meng², Tongyao Ju², Siyu Han²

¹. School of Environmental Science and Engineering, Tiangong University, Tianjin 300387, China
². School of Environment, Tsinghua University, Beijing 100084, China

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Abstract

● NH₃ in biogas had a slight inhibitory effect on dry reforming.

● Coexistence of H₂S and NH₃ led to faster decline of biogas conversion.

● Regeneration was effective for catalysts deactivated under synergetic effect.

Biogas is a renewable biomass energy source mainly composed of CH₄ and CO₂. Dry reforming is a promising technology for the high-value utilization of biogas. Some impurity gases in biogas can not be completely removed after pretreatment, which may affect the performance of dry reforming. In this study, the influence of typical impurities H₂S and NH₃ on dry reforming was studied using Ni/MgO catalyst. The results showed that low concentration of H₂S in biogas could cause serious deactivation of catalyst. Characterization results including EDS, XPS and TOF-SIMS confirmed the adsorption of sulfur on the catalyst surface, which was the cause of catalyst poisoning. We used air calcination method to regenerate the sulfur-poisoned catalysts and found that the regeneration temperature higher than 500 °C could help catalyst recover the original activity. NH₃ in the concentration range of 50–10000 ppm showed a slight inhibitory effect on biogas dry reforming. The decline rate of biogas conversion efficiency increased with the increase of NH₃ concentration. This was related to the reduction of oxygen activity on catalyst surface caused by NH₃. The synergetic effect of H₂S and NH₃ in biogas was investigated. The results showed that biogas conversion decreased faster under the coexistence of H₂S and NH₃ than under the effect of H₂S alone, so as the surface oxygen activity of catalyst. Air calcination regeneration could also recover the activity of the deactivated catalyst under the synergetic effect of H₂S and NH₃.

Keywords Biogas Dry reforming Sulfur poisoning Ammonia Synergetic effect Hydrogen

Corresponding Author(s): Yuchen Gao

Issue Date: 27 October 2022

Cite this article:

Yuchen Gao,Jianguo Jiang,Yuan Meng, et al. Influence of H₂S and NH₃ on biogas dry reforming using Ni catalyst: a study on single and synergetic effect[J]. Front. Environ. Sci. Eng., 2023, 17(3): 32.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-023-1632-1
https://academic.hep.com.cn/fese/EN/Y2023/V17/I3/32

Fig.1 CH₄ and CO₂ conversion efficiencies with the presence of H₂S. (a) 700 °C CH₄, (b) 700 °C CO₂, (c) 750 °C CH₄, (d) 750 °C CO₂, (e) 800 °C CH₄, (f) 800 °C CO₂, GHSV=15000 mL/(g_cat·h).

Tab.1 H₂S/H₂ and sulfur coverage values after 12-h reaction under different temperatures and H₂S concentrations

Fig.2 TOF-SIMS sulfur distribution (a) horizontal, (b) vertical, and (c) XPS (S 2p) results for spent catalyst. (12 h, under 750 °C, 20 ppm H₂S).

Tab.2 XPS peak calculation data of sulfur after reaction for 12 h under different concentrations of H₂S at 750 °C

Fig.3 Conversion efficiencies after catalyst regeneration. (a) 700 °C, (b) 750 °C, (c) 800 °C, 20 ppm H₂S, GHSV=15000 mL/(g_cat·h).

Fig.4 CH₄ (a) and CO₂ (b) conversions at 750 °C with catalysts regenerated under different temperatures.

Fig.5 XPS spectrums (S 2p) of regenerated and spent catalysts.

Fig.6 CH₄ and CO₂ conversion efficiencies with the presence of NH₃. (a) 700 °C CH₄, (b) 700 °C CO₂, (c) 750 °C CH₄, (d) 750 °C CO₂, (e) 800 °C CH₄, (f) 800 °C CO₂, GHSV=15000 mL/(g_cat·h).

Tab.3 XPS (O 1s) analysis parameters of spent catalysts with different concentrations of NH₃

Fig.7 XPS spectrums (O 1s) of spent catalysts with the presence of NH₃ (after 12 h, 750 °C).

Fig.8 CH₄ and CO₂ conversion efficiencies with the presence of H₂S and NH₃. (a) 700 °C CH₄, (b) 700 °C CO₂, (c) 750 °C CH₄, (d) 750 °C CO₂, (e) 800 °C CH₄, (f) 800 °C CO₂, GHSV=15000 mL/(g_cat·h).

Fig.9 (a) Biogas conversion at 750 °C of the catalyst after regeneration, (b) XPS spectrums (O 1s) of spent catalyst (deactivated under 1 ppm H₂S + 5000 ppm NH₃) and regenerated catalyst.

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