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

Highlights

● 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.

Abstract

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.

Graphical abstract

Keywords

Biogas / Dry reforming / Sulfur poisoning / Ammonia / Synergetic effect / Hydrogen

References

[1] Abdullah B , Abd Ghani N A , Vo D V N . (2017). Recent advances in dry reforming of methane over Ni-based catalysts. Journal of Cleaner Production, 162: 170–185

[2] Alstrup I , Rostrup-Nielsen J R , Røen S . (1981). High temperature hydrogen sulfide chemisorption on nickel catalysts. Applied Catalysis, 1(5): 303–314

[3] Bian Z , Suryawinata I Y , Kawi S . (2016). Highly carbon resistant multi core-shell catalyst derived from Ni-Mg phyllosilicate nanotubes@silica for dry reforming of methane. Applied Catalysis B: Environmental, 195: 1–8

[4] Chattanathan S A , Adhikari S , McVey M , Fasina O . (2014). Hydrogen production from biogas reforming and the effect of H₂S on CH₄ conversion. International Journal of Hydrogen Energy, 39(35): 19905–19911

[5] Chein R Y , Chen Y C , Chen W H . (2021). Experimental study on sulfur deactivation and regeneration of Ni-based catalyst in dry reforming of biogas. Catalysts, 11: 777

[6] Chen X , Jiang J , Yan F , Li K , Tian S , Gao Y , Zhou H . (2017). Dry reforming of model biogas on a Ni/SiO₂ catalyst: overall performance and mechanisms of sulfur poisoning and regeneration. ACS Sustainable Chemistry & Engineering, 5(11): 10248–10257

[7] Elsayed N H , Elwell A , Joseph B , Kuhn J N . (2017). Effect of silicon poisoning on catalytic dry reforming of simulated biogas. Applied Catalysis A: General, 538: 157–164

[8] Finocchio E , Montanari T , Garuti G , Pistarino C , Federici F , Cugino M , Busca G . (2009). Purification of biogases from siloxanes by adsorption: on the regenerability of activated carbon sorbents. Energy & Fuels, 23(8): 4156–4159

[9] Gao Y , Aihemaiti A , Jiang J , Meng Y , Ju T , Han S , Chen X , Liu J . (2020). Inspection over carbon deposition features of various nickel catalysts during simulated biogas dry reforming. Journal of Cleaner Production, 260: 120944

[10] Gao Y , Jiang J , Meng Y , Yan F , Aihemaiti A . (2018). A review of recent developments in hydrogen production via biogas dry reforming. Energy Conversion and Management, 171: 133–155

[11] Hernandez A D , Kaisalo N , Simell P , Scarsella M . (2019). Effect of H₂S and thiophene on the steam reforming activity of nickel andrhodium catalysts in a simulated coke oven gas stream. Applied Catalysis B: Environmental, 258: 117977

[12] Hou Z , Chen P , Fang H , Zheng X , Yashima T . (2006). Production of synthesis gas via methane reforming with CO₂ on noble metals and small amount of noble-(Rh-) promoted Ni catalysts. International Journal of Hydrogen Energy, 31(5): 555–561

[13] Kurkela E, Laatikainen-Luntama J, Ståhlberg P, Moilanen A (1996). Pressurised fluidised-bed gasification experiments with biomass, peat and coal at VTT in 1991–1994: Part 3. Gasification of Danish wheat straw and coal. Espoo: VTT Publications

[14] Li T S , Xu M , Gao C , Wang B , Liu X , Li B , Wang W G . (2014). Investigation into the effects of sulfur on syngas reforming inside a solid oxide fuel cell. Journal of Power Sources, 258: 1–4

[15] Liu X P , Yan J K , Mao J , He D D , Yang S , Mei Y , Luo Y M . (2021). Inhibitor, co-catalyst, or intermetallic promoter? Probing the sulfur-tolerance of MoO_x surface decoration on Ni/SiO₂ during methane dry reforming. Applied Surface Science, 548: 149231

[16] Mancino G , Cimino S , Lisi L . (2016). Sulphur poisoning of alumina supported Rh catalyst during dry reforming of methane. Catalysis Today, 277: 126–132

[17] Marschelke C , Fery A , Synytska A . (2020). Janus particles: from concepts to environmentally friendly materials and sustainable applications. Colloid & Polymer Science, 298(7): 841–865

[18] Pakhare D , Spivey J . (2014). A review of dry (CO₂) reforming of methane over noble metal catalysts. Chemical Society Reviews, 43(22): 7813–7837

[19] Pawar V , Appari S , Monder D S , Janardhanan V M . (2017). Study of the combined deactivation due to sulfur poisoning and carbon deposition during biogas dry reforming on supported Ni catalyst. Industrial & Engineering Chemistry Research, 56(30): 8448–8455

[20] Rasi S , Lantela J , Rintala J . (2011). Trace compounds affecting biogas energy utilization: a review. Energy Conversion and Management, 52(12): 3369–3375

[21] Struis R P W J, Schildhauer T J, Czekaj I, Janousch M, Biollaz S M A, Ludwig C (2009). Sulphur poisoning of Ni catalysts in the SNG production from biomass: a TPO/XPS/XAS study. Applied Catalysis A:General, 362(1–2): 121–128

[22] Theofanidis S A , Pieterse J A Z , Poelman H , Longo A , Sabbe M K , Virginie M , Detavernier C , Marin G B , Galvita V V . (2020). Effect of Rh in Ni-based catalysts on sulfur impurities during methane reforming. Applied Catalysis B: Environmental, 267: 118691

[23] Xu Y , Gong H , Dai X . (2021). High-solid anaerobic digestion of sewage sludge: achievements and perspectives. Frontiers of Environmental Science & Engineering, 15(4): 71

[24] Yan X , Hu T , Liu P , Li S , Zhao B , Zhang Q , Jiao W , Chen S , Wang P , Lu J , Fan L , Deng X , Pan Y X . (2019). Highly efficient and stable Ni/CeO₂-SiO₂ catalyst for dry reforming of methane: effect of interfacial structure of Ni/CeO₂ on SiO₂. Applied Catalysis B: Environmental, 246: 221–231

[25] Yentekakis I V , Panagiotopoulou P , Artemakis G . (2021). A review of recent efforts to promote dry reforming of methane (DRM) to syngas production via bimetallic catalyst formulations. Applied Catalysis B: Environmental, 296: 120210

[26] Yeo T Y , Ashok J , Kawi S . (2019). Recent developments in sulphur-resilient catalytic systems for syngas production. Renewable & Sustainable Energy Reviews, 100: 52–70

[27] Zhang J, Li F (2015). Coke-resistant Ni@SiO₂ catalyst for dry reforming of methane. Applied Catalysis B: Environmental, 176–177: 513–521

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-023-1632-1 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2023 Higher Education Press