Deactivation of Activated Alumina Adsorbents Used for H2S Removal from Olefin-containing Streams

Document Type : Research Paper


1 Catalysis Development Technologies Division, Research Institute of Petroleum Industry (RIPI), Tehran, Iran

2 Iran University of Science and Technology, School of Chemical, Petroleum and Gas Engineering, Tehran, Iran


An oligomer produced from unsaturated and reactive components (green oil) is formed when hydrogen sulfide (H2S) is removed from the exhaust stream of the methyl tert-butyl ether (MTBE) plant. A remedy to minimize this contaminant formation is using adsorbents with low reactivity toward the olefinic precursors. Here, the green oil formation on the surface of different types of commercial alumina is studied. Results confirm that the regular commercially activated alumina has low H2S adsorption capacity. Still, the alumina alkalized with 3.98 wt.% of Na2O has a breakthrough time of more than 29 h and stable performance in a cyclic operation. Moreover, the promoted alumina with a wide pore diameter (about 9 nm) and low surface area (about 215 m2/g) is less susceptible to deactivation by forming green oil. It is supposed that the capillary condensation of C3/C4 unsaturated compounds and acidic sites of the alumina intensify the oligomerization inside the pores of an adsorbent.


  1. Aguiar, M. F. & Coelho, L. V. (2017). Adsorption of sulfur compounds from natural gas by different adsorbents and desorption using supercritical CO2, Journal of Environmental Chemical Engineering, 5(5), 4353-4364, ##
  2. Srivastav, A. & Srivastava, V. C. (2009), Adsorptive desulfurization by activated alumina, Journal of Hazardous Materials, 170 (2–3), 1133-1140, ##
  3. Santos, J. P. L., de Carvalho Lima Lobato, A. K., Moraes, C., de Lima Cunha, A., da Silva, G. F. & dos Santos L. C. L. (2016), Comparison of different processes for preventing deposition of elemental sulfur in natural gas pipelines: A review. Journal of Natural Gas Science & Engineering, 32, 364-372, ##
  4. Georgiadis, A. G., Charisiou, N. D. & Goula, M. A. (2020), Removal of hydrogen sulfide from various industrial gases: A review of the most promising adsorbing materials catalysts. Catalysts, 10 (5), 521-557, ##
  5. Silveira, E. B., Veloso, C. O., Costa, A. L. H., Henriques, C. A., Zotin, F. M. Z., Paredes, M. L. I., Reis, R. A. Chiaro, S. X. (2015), Influence of metal oxides impregnated on silica-alumina in the removal of sulphur and nitrogen compounds from a hydrotreated diesel fuel stream. Adsorption Science and Technology, 33(2), 105-116, ##
  6. Mehmood A., Alhasani H., Alamoodi N., Al Wahedi Y. F., Ibrahim S., Abhijeet R. & Nat J. (2020), An evaluation of kinetic models for the simulation of Claus reaction furnaces in sulfur recovery units under different feed conditions. Gas Science and Engineering, 74, 103-06, ##
  7. Al-Degs, Y. S., El-Sheikh, A. H., Al Bakain, R. Z., Newman, A. P. & Al-Ghouti, M. A. (2016), Conventional and upcoming sulfur-cleaning technologies for petroleum fuel: A review. Energy Technology, 4(6):679-99, ##
  8. Fazlollahi, F., Asadizadeh, S., Khoshooei, M. A., Sardashti Birjandi, M. R. & Sarkari, M. (2021), Investigating efficiency improvement in sulfur recovery unit using process simulation and numerical modeling. Oil & Gas Science and Technology, 76, 18-27, ##
  9. Weinlaender, C., Neubauer, R. & Hochenauer, C. (2018), Adsorptive hydrogen chloride and combined hydrogen chloride–hydrogen sulphide removal from biogas for solid oxide fuel cell application. Adsorption Science & Technology, 36(5-6), 1215-1232, ##
  10. Badra J., Alowaid F., Alhussaini A., Alnakhli A. & AlRamadan A. S. (2022), Understanding of the octane response of gasoline/MTBE blends. Fuel, 318, 123647, ##
  11. Liu, J., Zhu, S., Zhang, L., Liu, Z., Cui, Q. & Wang, H. (2020), Study on Characterization and coke compositions of deactivated 5A molecular sieve for adsorption separation of industrial naphtha. Chemistry Select, 5, 12844-12852. Doi. 10.1002/slct.202002741. ##
  12. Sun, H. & Shen, B. (2013), Experimental study on coking, deactivation, and regeneration of binderless 5A zeolite during 1-hexene adsorption. Adsorption, 19, 111-120, doi.10.1007/s10450-012-9426-y. ##
  13. Masoudian, S. K., Sadighi, S., Abbasi, A., Salehrad, F. & Fazlollahi, A. (2013), Regeneration of a commercial catalyst for the dehydrogenation of isobutane to isobutene. Chemical Engineering Technology, 36(9), 1593-1598, ##
  14. Ejtemaei, M., Sadighi, S., Rashidzadeh, M., Khorram, S., Back, J., Delir Kheyrollahi Nezhad, P., Penner, S., Noisternig, M. F., Salari, D. & Niaei, A. (2022), Effect of O2/N2 glow discharge plasma on zeolite extrudates as water adsorbent. Chemical Engineering and Processing-Process Intensification, 181, 1-44, ##
  15. Ejtemaei, M., Sadighi, S., Rashidzadeh, M., Khorram, S., Back, J., Penner, S., Noisternig, M. F., Salari, D. & Niaei, A. (2022), Investigating the cold plasma surface modification of kaolin- and attapulgite-bound zeolite A. Journal of Industrial and Engineering Chemistry, 106, 113-127, ##
  16. Siakavelas, G.I., Georgiadis, A.G., Charisiou, N.D., Yentekakis, I.Y., Goula, M.A. (2021), Cost-effective adsorption of oxidative coupling-derived ethylene using a molecular sieve. Chemical Engineering and Technology. 44, 2041-2048, org/10.1002/ceat.202100147. ##
  17. Overjero, G., Romero, M. D., Diez, D., Mestanza, M. & Diez, E. (2020), Bentonite as an alternative adsorbent for the purification of styrene monomer: Adsorption kinetics, equilibrium and process design. Adsorption Science & Technology, 28(2), 101-123, ##
  18. Coelho, A., Caeiro, G., Lemos, M. A. N. D. A., Lemos, F. & Ribeiro, F. R. (2013), 1-Butene oligomerization over ZSM-5 zeolite: Part 1 – Effect of reaction conditions. Fuel, 111, 449-460, ##
  19. Corma, A., Martínez, C. & Doskocil, E. (2013), Designing MFI-based catalysts with improved catalyst life for C3= and C5= oligomerization to high-quality liquid fuels. Journal of Catalysis, 300, 183-196, ##
  20. Rezaei S., Shafaghat H. & Daud W. (2014), Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis: A review. Applied Catalysis A: General, 469, 490-511, ##
  21. Lu, Y., Yan, Q., Han, J., Cao, B., Street, J. & Yu, F. (2017), Fischer–Tropsch synthesis of olefin-rich liquid hydrocarbons from biomass-derived syngas over carbon-encapsulated iron carbide/iron nanoparticles catalyst. Fuel, 193, 369-384, ##
  22. Lamberov, A. A. & Sitnikova, E. Y. (2009), Experience of the industrial use of alumina and KA zeolite in the processes of drying of olefin-containing mixtures in petrochemical industry, Petroleum Chemistry, 49, 184-187, ##
  23. Masoudi-Nejad, M., Fatemi, S. (2014), Thermodynamic adsorption data of CH4, C2H6, C2H4 as the OCM process hydrocarbons on SAPO-34 molecular sieve, Journal of Industrial and Engineering Chemistry. 20, 4045-4053, ##
  24. Elmutasim, O., Basina, G., Al Shami, D., Gaber, D., Gaber, S., Karanikolos, G. N., Al Wahedi, Y. (2020), On the impact of copper local environment on hydrogen sulfide adsorption within microporous AlPO4-5. Journal of Environmental Chemical Engineering, 8 (5), 104245, ##
  25. Amvrosios G.G., Nikolaos D.C, Goula, M.A. (2020), Removal of hydrogen sulfide from various industrial gases: A review of the most promising adsorbing materials. Catalysts, 10, 5, 521-557, ##
  26. De la Osa, A.R., De Lucas, A., Valverde, J.L., Romero, A., Monteagudo, I., Coca, P., Sanchez, P. (2011), Influence of alkali promoters on synthetic diesel production over Co catalyst. Catalysis Today, 167(1), 96-106, ##
  27. Bagreev, A. & Bandosz, T. J. (2002), A Role of sodium hydroxide in the process of hydrogen sulfide adsorption/oxidation on caustic-impregnated activated carbons. Industrial Engineering & Chemical Research, 41, 672-679, ##
  28. Moslempour, Z., Sadighi, S., Dashti, A. & Ahmadpour, A. (2021), Investigating the properties and performance of 3A molecular sieves as an adsorbent to prevent coke formation in olefin dehydration process. International Journal of Chemical Reactor Engineering, 20(8), 833-843, ##
  29. Rezaei, P. S., Shafaghat, H. & Ashri Wan Daud, W. M. (2014), Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis: A review. Applied Catalysis A: General, 469, 490-511, ##
  30. Hashiba, T., Hayashi, D., Katada, N. & Niwa, M. (2004), Decrease of catalytic activity and solid acidity by ion exchange of Na cation on HZSM-5. Catalysis Today, 97(1), 35-39, ##
  31. Gayubo, A. G., Alonso, A., Valle, B., Aguayo, A. T. & Bilbao, J. (2010), Selective production of olefins from bioethanol on HZSM-5 zeolite catalysts treated with NaOH. Applied Catalysis B: Environmental, 97(1–2), 299-306, ##Laperdrix, E., Sahibed-dine, A., Costentin G., Saur O., Bensitel M., Nédez C., Mohamed Saad A. B., Lavalley J. C. (2000), Reduction of sulfate species by H2S on different metal oxides and promoted aluminas. Applied Catalysis B: Environmental. 26(2), 71-80, ##
  32. Mitchell, M.B., Sheinker, V.N. (1996), Adsorption and reaction of sulfur dioxide on alumina and sodium-impregnated alumina. The Journal of Physical Chemistry, 100, 7550-7557, ##