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Citation: Zhi-Bin WANG, Zhi-Feng QIN, Xun HAN, Peng-Cheng SUN, Yi LIU, Li-Ping CHANG, Jun REN, Cong-Ming LI. Highly active and sulfur-tolerant MoO3 modified NiO-Al2O3 catalysts for coke oven gas methanation[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(5): 967-978. doi: 10.11862/CJIC.2023.055 shu

Highly active and sulfur-tolerant MoO3 modified NiO-Al2O3 catalysts for coke oven gas methanation

  • 1.

    State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China

  • 2.

    Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030002, China

  • 3.

    Postdoctoral Research Station, Environmental Planning Institute of Shanxi Province, Taiyuan 030002, China

  • 4.

    Environmental Science and Engineering Postdoctoral Mobile Station, Tsinghua University, Beijing 100084, China

Figures(6)

  • A series of xMoO3/NiO-Al2O3 catalysts (x% represented the mass fraction of MoO3) were prepared by double hydrolytic co-precipitation method combined with impregnation method. The methanation reaction activity and sulfur resistance of catalysts were evaluated using a fixed-bed reactor, and the catalysts were characterized in detail fresh and after deactivation. The results showed that the low-temperature methanation activity of the catalyst decreased with the increase in MoO3 loading, whereas the sulfur resistance of the catalyst was significantly enhanced after MoO3 doping. The decrease in catalyst activity for low-temperature methanation was attributed to the fact that the increase in MoO3 loading reduced the active specific surface area of the catalyst, but the introduction of MoO3 also provided a competitive adsorption site for sulfide, which can delay sulfur poisoning at the active site. The xMoO3/NiO-Al2O3 catalyst with 12.5% MoO3 loading (mass fraction) maintained the highest methanation activity for 7 h in the presence of 143 mg·m-3 H2S/H2 (81.1% CO conversion, 550 ℃). The sulfur chemisorption content of 12.5MoO3/NiO-Al2O3 catalyst reaching 0.71% (mass fraction) was 1.48 times that of NiO-Al2O3 catalyst and further XPS also confirmed that the amount of MoS2 generated was the highest, which indicated that Mo preferentially adsorbs more sulfur and protects the active site. In addition, at a MoO3 loading of 12.5%, MoO3 on the surface of the catalyst reached the threshold of monolayer dispersion, which can provide more adsorption sites for sulfides when competitive adsorption occurs.
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    1. [1]

      Razzaq R, Zhu H W, Jiang L, Muhammad U, Li C S, Zhang S J. Catalytic methanation of CO and CO2 in coke oven gas over Ni-Co/ZrO2-CeO2[J]. Ind. Eng. Chem. Res., 2013,52:2247-2256. doi: 10.1021/ie301399z

    2. [2]

      Portha J F, Uribe-Soto W, Commenge J M, Valentin S, Falk L. Techno-economic and carbon footprint analyses of a coke oven gas reuse process for methanol production[J]. Processes, 2021,91042. doi: 10.3390/pr9061042

    3. [3]

      Hernandez A D, Kaisalo N, Simell P, Scarsella M. Effect of H2S and thiophene on the steam reforming activity of nickel and rhodium catalysts in a simulated coke oven gas stream[J]. Appl. Catal. B-Environ., 2019,258117977. doi: 10.1016/j.apcatb.2019.117977

    4. [4]

      Elbaba I F, Williams P T. Deactivation of nickel catalysts by sulfur and carbon for the pyrolysis-catalytic gasification/reforming of waste tires for hydrogen production[J]. Energy Fuels, 2014,28:2104-2113. doi: 10.1021/ef4023477

    5. [5]

      Jia X Y, Rui N, Zhang X S, Hu X, Liu C J. Ni/ZrO2 by dielectric barrier discharge plasma decomposition with improved activity and enhanced coke resistance for CO methanation[J]. Catal. Today, 2019,334:215-222. doi: 10.1016/j.cattod.2018.11.020

    6. [6]

      Hussain I, Jalil A A, Hassan N S, Hamid M Y S. Recent advances in catalytic systems for CO2 conversion to substitute natural gas (SNG): Perspective and challenges[J]. J. Energy Chem., 2021,62:377-407. doi: 10.1016/j.jechem.2021.03.040

    7. [7]

      Appari S, Janardhanan V M, Bauri R, Jayanti S, Deutschmann O. A detailed kinetic model for biogas steam reforming on Ni and catalyst deactivation due to sulfur poisoning[J]. Appl. Catal. A-Gen., 2014,471:118-125. doi: 10.1016/j.apcata.2013.12.002

    8. [8]

      Ahn J, Chung W, Chang S. Deactivation and regeneration method for Ni catalysts by H2S poisoning in CO2 methanation reaction[J]. Catalysts, 2021,111292. doi: 10.3390/catal11111292

    9. [9]

      Gao J J, Liu Q, Gu F N, Liu B, Zhong Z Y, Su F B. Recent advances in methanation catalysts for the production of synthetic natural gas[J]. RSC Adv., 2015,5:22759-22776. doi: 10.1039/C4RA16114A

    10. [10]

      WANG Y H, BAI S Y, CUI L J, LIU J, YU J, XU G W. Catalytic activity and sulfur resistance stability of Ni-Mo-based catalysts for syngas methanation[J]. CIESC Journal, 2018,69:2063-2072.  

    11. [11]

      Liu X P, Yan J K, Mao J, He D D, Yang S, Mei Y, Luo Y M. Inhibitor, co-catalyst, or intermetallic promoter? Probing the sulfur-tolerance of MoOx surface decoraion on Ni/SiO2 during methane dry reforming[J]. Appl. Surf. Sci., 2021,548149231. doi: 10.1016/j.apsusc.2021.149231

    12. [12]

      HUO X D, WANG Z Q, ZHANG R, SONG S S, HUANG J J, FANG Y T. Preparation of β-Mo2C, Ni3Mo3N/β-Mo2C and its catalytic performance for methanation[J]. Journal of Fuel Chemistry and Technology, 2016,44:457-462.  

    13. [13]

      NIU X P, JIANG Y X. Mo-Ni/γ-formation and function of MoNi4 alloy as Al2O3 methanation catalyst[J]. Journal of Inner Mongolia Agricultural University (Natural Science Edition), 1999,30:709-714.  

    14. [14]

      Mendez-Mateos D, Laura B V, Requies J M, Cambra J F. A study of deactivation by H2S and regeneration of a Ni catalyst supported on Al2O3 during methanation of CO2 effect of the promoters Co, Cr, Fe, and Mo[J]. RSC Adv., 2020,10:16511-16564.

    15. [15]

      Aksoylu A E, Misirli Z, Önsan Z I. Interaction between nickel and molybdenum in Ni-Mo/Al2O3 catalysts: Ⅰ: CO2 methanation and SEM-TEM studies[J]. Appl. Catal. A-Gen., 1998,168:385-397. doi: 10.1016/S0926-860X(97)00369-4

    16. [16]

      Aksoylu A E, Önsan Z I. Interaction between nickel and molybdenum in Ni-Mo/Al2O3 catalysts: Ⅱ: CO hydrogenation[J]. Appl. Catal. A-Gen., 1998,168:399-407. doi: 10.1016/S0926-860X(97)00370-0

    17. [17]

      Aksoylu A E, İşli A I, Önsan Z I. Interaction between nickel and molybdenum in Ni-Mo/Al2O3 catalysts: Ⅲ.: effect of impregnation strategy[J]. Appl. Catal. A-Gen., 1999,183:357-364. doi: 10.1016/S0926-860X(99)00075-7

    18. [18]

      Fowler R W, Bartholomew C H. Activity, adsorption, and sulfur tolerance studies of fluidized bed methanation catalysts[J]. Ind. Eng. Chem. Res., 1979,18:339-347. doi: 10.1021/i360072a022

    19. [19]

      Zhang Y X, Wang Y D, Xu N N, Zhou X D. A theoretical studies of sulfur poisoning tolerance at the interface of Mo doped Ni/Yttria-stabilized zirconia[J]. Int. J. Hydrog. Energy, 2021,46:21075-21081. doi: 10.1016/j.ijhydene.2021.03.199

    20. [20]

      Zhi C M, Yang W. Improvement of Mo-doping on sulfur-poisoning of Ni catalyst: Activity and selectivity to CO methanation[J]. Comput. Theor. Chem., 2021,1197113140. doi: 10.1016/j.comptc.2020.113140

    21. [21]

      Lv Y H, Xin Z, Meng X, Tao M, Bian Z C, Gu J, Gao W L. Effect of La, Mg and Mo promoters on dispersion and thermostability of Ni species on KIT-6 for CO methanation[J]. Appl. Catal. A-Gen., 2017,534:125-132.

    22. [22]

      Zhang R Y, Wei A L, Zhu M, Wu X X, Wang H, Zhu X L, Ge Q F. Tuning reverse water gas shift and methanation reactions during CO2 reduction on Ni catalysts via surface modification by MoOx[J]. J. CO2 Util., 2021,52101678. doi: 10.1016/j.jcou.2021.101678

    23. [23]

      XU C, WANG X J, HU X H, CHEN X L, WANG F C. Experimental study of nickel-based catalysts for syngas methanation[J]. Journal of Fuel Chemistry and Technology, 2012,40:216-220.

    24. [24]

      Qin Z F, Ban H Y, Wang X Y, Wang Z B, Niu Y X, Yao Y, Ren J, Chang L P, Miao M Q, Xie K C, Li C M. Development of highly stable Ni-Al2O3 catalysts for CO methanation[J]. Catal. Lett., 2021,151:2647-2657. doi: 10.1007/s10562-020-03486-4

    25. [25]

      Qin Z F, Ren J, Miao M Q, Li Z, Lin J Y, Xie K C. The catalytic methanation of coke oven gas over Ni-Ce/Al2O3 catalysts prepared by microwave heating: Effect of amorphous NiO formation[J]. Appl. Catal. B-Environ., 2015,164:18-30. doi: 10.1016/j.apcatb.2014.08.047

    26. [26]

      Ashino T, Takada K, Morimoto Y, Abiko K. Determination of trace amounts of sulfur in high-purity iron by infrared absorption after combustion: Selection and pre-treatment of reaction accelerators[J]. Phys. Status Solidi A-Appl. Mat., 2002,189:123-132. doi: 10.1002/1521-396X(200201)189:1<123::AID-PSSA123>3.0.CO;2-9

    27. [27]

      Hu F F, Wang C H, Li J D, Liu H, Zhang L. Determination of elemental impurities in iron-nickel-based superalloys by glow discharge mass spectrometry[J]. Atom. Spectrosc., 2020,42:25-31.

    28. [28]

      Zhang J Y, Xin Z, Meng X, Lv Y H, Tao M. Effect of MoO3 on structures and properties of Ni-SiO2 methanation catalysts prepared by the hydrothermal synthesis method[J]. Ind. Eng. Chem. Res., 2013,52:14533-14544. doi: 10.1021/ie401708h

    29. [29]

      Chen Y Q, Tian Z W, Liu Q, Bian B. A MoOx-doped Ni/3D-SBA-15 catalyst for CO methanation: The effect of a solvent and a MoOx promoter on the catalytic properties[J]. Sustain. Energ. Fuels, 2020,4:3042-3050. doi: 10.1039/D0SE00269K

    30. [30]

      Zhang Y, Yang H Y, Liu Q, Bian B. MoOx-doped ordered mesoporous Ni/Al2O3 catalyst for CO methanation[J]. Energy Technol., 2020,82000165. doi: 10.1002/ente.202000165

    31. [31]

      Tao M, Zhou C L, Shi Y Q, Meng X, Gu J, Gao W L, Xin Z. Enhanced sintering resistance of bimetal/SBA-15 catalysts with promising activity under a low temperature for CO methanation[J]. RSC Adv., 2020,10:20852-20861. doi: 10.1039/D0RA02168G

    32. [32]

      WANG W H, LI Z H, WANG B W, XU Y, MA X B. Research progress of sulfur-resistant methanation reaction[J]. CIESC Journal, 2015,66:3357-3366.  

    33. [33]

      Bian Z C, Meng X, Tao M, Lv Y H, Xin Z. Effect of MoO3 on catalytic performance and stability of the SBA-16 supported Ni-catalyst for CO methanation[J]. Fuel, 2016,179:193-201. doi: 10.1016/j.fuel.2016.03.091

    34. [34]

      Fan X Q, Liu D D, Zhao Z, Li J M, Liu J. Influence of Ni/Mo ratio on the structure-performance of ordered mesoporous Ni-Mo-O catalysts for oxidative dehydrogenation of propane[J]. Catal. Today, 2020,339:67-78. doi: 10.1016/j.cattod.2019.02.036

    35. [35]

      ZHOU T N, YIN H L, HAN S N, CAI Y M, LIU Y Q, LIU C G. Influences of different phosphorus contents on NiMoP/Al2O3 hydrotreating catalysts[J]. Journal of Fuel Chemistry and Technology, 2009,37:330-334.

    36. [36]

      Domínguez-Crespo M A, Díaz-García L, Arce-Estrada E M, Torres-Huerta A M, Cortéz-De la Paz M T. Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al2O3 catalysts[J]. Appl. Surf. Sci., 2006,253:1205-1214. doi: 10.1016/j.apsusc.2006.01.061

    37. [37]

      Alihosseinzadeh A, Nematollahi B, Rezaei M, Lay E N. CO methanation over Ni catalysts supported on high surface area mesoporous nanocrystalline γ-Al2O3 for CO removal in H2-rich stream[J]. Int. J. Hydrog. Energy, 2015,40:1809-1819. doi: 10.1016/j.ijhydene.2014.11.138

    38. [38]

      Zhang K, Zhang H T, Ma H F, Ying W Y, Fang D Y. The effect of preparation method on the performance of Pt Sn/Al2O3 catalysts for acetic acid hydrogenation[J]. Pol. J. Chem. Technol., 2015,17:11-17.

    39. [39]

      Fang L, Shu Y Y, Wang A Q, Zhang T. Green synthesis and characterization of anisotropic uniform single-crystal α-MoO3 nanostructures[J]. J. Phys. Chem. C, 2007,111:2401-2408. doi: 10.1021/jp065791r

    40. [40]

      Weber T, Muijsers J C, Van Wolput J H M C, Verhagen C P J, Niemantsverdriet J W. Basic reaction steps in the sulfidation of crystalline MoO3 to MoS2, as studied by X-ray photoelectron and infrared emission spectroscopy[J]. J. Phys. Chem., 1996,100:14144-14150. doi: 10.1021/jp961204y

    41. [41]

      Ninh T K T, Massin L, Laurenti D, Vrinat M. A new approach in the evaluation of the support effect for NiMo hydrodesulfurization catalysts[J]. Appl. Catal. A-Gen., 2011,407:29-39. doi: 10.1016/j.apcata.2011.08.019

    42. [42]

      Hernández-Huesca R, Mérida-Robles J, Maireles-Torres P, Rodríguez-Castellón E, Jiménez-López A. Hydrogenation and ring-opening of tetralin on Ni and NiMo supported on alumina-pillared α-zirconium phosphate catalysts. A thiotolerance study[J]. J. Catal., 2001,203:122-132. doi: 10.1006/jcat.2001.3321

    43. [43]

      Galtayries A, Wisniewski S, Grimblot J. Formation of thin oxide and sulphide films on polycrystalline molybdenum foils: Characterization by XPS and surface potential variations[J]. J. Electron. Spectrosc., 1997,87:31-44. doi: 10.1016/S0368-2048(97)00071-6

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