Advertisement

Activity and selectivity of Co(Ni)Mo sulfides supported on MgO, Al2O3, ZrO2, TiO2, MCM-41 and activated carbon in parallel hydrodeoxygenation of octanoic acid and hydrodesulfurization of 1-benzothiophene

  • Luděk KalužaEmail author
  • Jindřich Karban
  • Daniela Gulková
Article
  • 14 Downloads

Abstract

Mo, CoMo and NiMo sulfide catalysts were prepared using MgO, Al2O3, ZrO2, TiO2, MCM-41 and activated carbon supports. The catalysts were tested in parallel hydrodeoxygenation (HDO) of octanoic acid and hydrodesulfurization (HDS) of 1-benzothiophene. For all supports, NiMo catalysts were more active in both HDO and HDS than Mo and CoMo catalysts. HDO activity of NiMo catalysts decreased with type of support in the following order TiO2 > C > ZrO2 > Al2O3 > MCM-41 > MgO. The products of HDO were linear C7 and C8 hydrocarbons. Some isomerization and cracking activity was observed only with MCM-41 support. HDS activity of NiMo catalysts decreased in the following order C > ZrO2 > TiO2 > Al2O3 > MgO > MCM-41. HDO/HDS selectivity was influenced by the active phase and the support type and it was the highest over the NiMo/TiO2 catalyst.

Keywords

HDO/HDS Octanoic acid Benzothiophene Support effect Co(Ni)Mo sulfides 

Notes

Acknowledgements

Czech Science Foundation (Grant No. 17-22490S) is gratefully acknowledged for the financial support.

Supplementary material

11144_2019_1620_MOESM1_ESM.pdf (278 kb)
Supplementary material 1 (PDF 278 kb)

References

  1. 1.
    Furimsky E (2000) Catalytic hydrodeoxygenation. Appl Catal A 199:147–190CrossRefGoogle Scholar
  2. 2.
    Mortensen PM, Grunwaldt JD, Jensen PA, Knudsen KG, Jensen AD (2011) A review of catalytic upgrading of bio-oil to engine fuels. Appl Catal A 407:1–19CrossRefGoogle Scholar
  3. 3.
    Furimsky E (2013) Hydroprocessing challenges in biofuels production. Catal Today 217:13–56CrossRefGoogle Scholar
  4. 4.
    Glisic SB, Pajnik JM, Orlovic AM (2016) Process and techno-economic analysis of green diesel production from waste vegetable oil and the comparison with ester type biodiesel production. Appl Eng 170:176–185CrossRefGoogle Scholar
  5. 5.
    Perez-Cisneros ES, Sales-Cruz M, Lobo-Oehmichen R, Viveros-García T (2017) A reactive distillation process for co-hydrotreating of non-ediblevegetable oils and petro-diesel blends to produce green diesel fuel. Comput Chem Eng 105:105–122CrossRefGoogle Scholar
  6. 6.
    Ryymin EM, Honkela ML, Viljava TR, Krause AOI (2010) Competitive reactions and mechanisms in the simultaneous HDO of phenol and methyl heptanoate over sulphided NiMo/γ-Al2O3. Appl Catal A 389:114–121CrossRefGoogle Scholar
  7. 7.
    Gandarias I, Barrio VL, Requies J, Arias PL, Cambra JF, Güemez MB (2008) From biomass to fuels: hydrotreating of oxygenated compounds. Int J Hydrog Eng 33:3485–3488CrossRefGoogle Scholar
  8. 8.
    Viljava TR, Saari ERM, Krause AOI (2001) Simultaneous hydrodesulfurization and hydrodeoxygenation: interactions between mercapto and methoxy groups present in the same or in separate molecules. Appl Catal A 209:33–43CrossRefGoogle Scholar
  9. 9.
    Laurent E, Delmon B (1994) Study of the hydrodeoxygenation of carbonyl, carboxylic and guaiacyl groups over sulfided CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts. I. Catalytic reaction schemes. Appl Catal A 109:77–115CrossRefGoogle Scholar
  10. 10.
    Kaluža L, Kubička D (2017) The comparison of Co, Ni, Mo, CoMo and NiMo sulfided catalysts in rapeseed oil hydrodeoxygenation. React Kinet Mech Catal 122:333–334CrossRefGoogle Scholar
  11. 11.
    Platanitis P, Panagiotou GD, Bourikas K, Kodulis C, Lycourghiotis A (2014) Hydrodeoxygenation of phenol over hydrotreatment catalysts in their reduced and sulfided states. Open Catal J 7:18–25CrossRefGoogle Scholar
  12. 12.
    Xia L, Xia Z, Tang W, Wang H, Fang M (2014) Hydrogenation of model compounds catalyzed by MCM-41-supported nickel phosphide. Adv Mater Res 864–867:366–372CrossRefGoogle Scholar
  13. 13.
    Wang W, Zhu G, Li L, Tan S, Wu K, Zhang X, Yang Y (2016) Facile hydrothermal synthesis of flower-like Co–Mo–S catalysts and their high activities in the hydrodeoxygenation of p-cresol and hydrodesulfurization of benzothiophene. Fuel 174:1–8CrossRefGoogle Scholar
  14. 14.
    Dhandapani B, Clair T, Oyama ST (1998) Simultaneous hydrodesulfurization, hydrodeoxygenation, and hydrogenation with molybdenum carbide. Appl Catal A 168:219–228CrossRefGoogle Scholar
  15. 15.
    Odebunmi EO, Ollis DF (1983) Catalytic hydrodeoxygenation II. Interactions between catalytic hydrodeoxygenation of m-cresol and hydrodesulfurization of benzothiophene and dibenzothiophene. J Catal 80:65–75CrossRefGoogle Scholar
  16. 16.
    Pstrowska K, Walendziewski J, Łuzny R, Stolarski M (2014) Hydroprocessing of rapeseed pyrolysis bio-oil over NiMo/Al2O3 catalyst. Catal Today 223:54–65CrossRefGoogle Scholar
  17. 17.
    Pstrowska K, Walendziewski J, Stolarski M (2014) Hydrorefining of oil from rapeseed cake pyrolysis over NiMo/Al2O3 catalyst. Fuel Process Technol 128:191–198CrossRefGoogle Scholar
  18. 18.
    Pinheiro A, Hudebine D, Dupassieux N, Geantet C (2009) Impact of oxygenated compounds from lignocellulosic biomass pyrolysis oils on gas oil hydrotreatment. Eng Fuel 23:1007–1014CrossRefGoogle Scholar
  19. 19.
    Bui VN, Toussaint G, Laurenti D, Mirodatos C, Geantet C (2009) Co-processing of pyrolisis bio oils and gas oil for new generation of bio-fuels: hydrodeoxygenation of guaïacol and SRGO mixed feed. Catal Today 143:172–178CrossRefGoogle Scholar
  20. 20.
    Mercader FM, Groeneveld MJ, Kersten SRA, Geantet C, Toussaint G, Way NWJ, Schaverien CJ, Hogendoorn KJA (2011) Hydrodeoxygenation of pyrolysis oil fractions: process understanding and quality assessment through co-processing in refinery units. Eng Environ Sci 4:985–997Google Scholar
  21. 21.
    Sepúlveda C, Escalona N, García R, Laurenti D, Vrinat M (2012) Hydrodeoxygenation and hydrodesulfurization co-processing over ReS2 supported catalysts. Catal Today 195:101–105CrossRefGoogle Scholar
  22. 22.
    Vonortas A, Papayannakos N (2016) Hydrodesulphurization and hydrodeoxygenation of gasoil–vegetable oil mixtures over a Pt/γ-Al2O3 catalyst. Fuel Process Technol 150:126–131CrossRefGoogle Scholar
  23. 23.
    Vonortas A, Kubicka D, Papayannakos N (2014) Catalytic co-hydroprocessing of gasoil–palm oil/AVO mixtures over a NiMo/γ-Al2O3 catalyst. Fuel 116:49–55CrossRefGoogle Scholar
  24. 24.
    Varakin AN, Salnikov VA, Nikulshina MS, Maslakov KI, Mozhaev AV, Nikulshin PA (2017) Beneficial role of carbon in Co(Ni)MoS catalysts supported on carbon-coated alumina for co-hydrotreating of sunflower oil with straight-run gas oil. Catal Today 292:110–120CrossRefGoogle Scholar
  25. 25.
    Nikulshin PA, Salnikov VA, Pimerzin AA, Eremina YV, Koklyukhin AS, Tsvetkov VS, Pimerzin AA (2016) Co-hydrotreating of straight-run diesel fraction and vegetable oil on Co(Ni)-PMo/Al2O3 catalysts. Petrol Chem 56:56–61CrossRefGoogle Scholar
  26. 26.
    Kaluža L, Gulková D, Vít Z, Zdražil M (2015) High-activity MgO-supported CoMo hydrodesulfurization catalysts prepared by non-aqueous impregnation. Appl Catal B Environ 162:430–436CrossRefGoogle Scholar
  27. 27.
    Schneider P (1995) Adsorption isotherms of microporous-mesoporous solids revisited. Appl Catal A Gen 129:157–165CrossRefGoogle Scholar
  28. 28.
    Kaluža L (2015) Activity of transition metal sulfides supported on Al2O3, TiO2 and ZrO2 in the parallel hydrodesulfurization of 1-benzothiophene and hydrogenation of 1-methyl-cyclohex-1-ene. React Kinet Mech Catal 114:781–794CrossRefGoogle Scholar
  29. 29.
    Moya SA, Escudey M (1994) Use of pH measurements for the characterization of MoO3/Al2O3 catalysts. J Chem Soc Chem Commun 0:1829–1830CrossRefGoogle Scholar
  30. 30.
    Bautista FM, Campelo JM, Garcia A, Luna D, Marinas JM, Romero AA (1994) Fluoride treatment of AlPO4–Al2O3 catalysts. II. Poisoning experiments by bases for cyclohexene conversion and cumene cracking. Catal Lett 24:293–301CrossRefGoogle Scholar
  31. 31.
    Kaluža L, Gulková D, Vít Z, Zdražil M (2013) Water-assisted spreading of MoO3 onto SiO2–Al2O3 supports for preparation of sulfide CoMo hydrodesulfurization catalysts. Fuel 112:272–276CrossRefGoogle Scholar
  32. 32.
    Soják L, Addová G, Kubinec R, Kraus A, Bohác A (2004) Capillary gas chromatography-mass spectrometry of all 93 acyclic octenes and their identification in fluid catalytic cracked gasoline. J Chromatogr A 1025:237–253CrossRefGoogle Scholar
  33. 33.
    Soják L, Addová G, Kubinec R, Kraus A, Hu G (2002) Gas chromatographic-mass spectrometric characterization of all acyclic C5–C7 alkenes from fluid catalytic cracked gasoline using polydimethylsiloxane and squalane stationary phases. J Chromatogr A 947:103–117CrossRefGoogle Scholar
  34. 34.
    Censullo AC, Jones DR, Wills MT (2003) Speciation of the volatile organic compounds (VOCs) in solventborne aerosol coatings by solid phase microextraction-gas chromatography. J Coat Technol 75:47–53CrossRefGoogle Scholar
  35. 35.
    White CM, Hackett J, Anderson RR, Kail S, Spock PS (1992) Linear temperature programmed retention indices of gasoline range hydrocarbons and chlorinated hydrocarbons on cross-linked polydimethylsiloxane. J High Resolut Chromatogr 15:105–120CrossRefGoogle Scholar
  36. 36.
    California Environmental Protection Agency (1997) Procedure for the detailed hydrocarbon analysis of gasolines by single column high efficiency (capillary) column gas chromatography. https://www.arb.ca.gov/testmeth/slb/slb118.pdf. Accessed Aug 1997
  37. 37.
    Senol OI, Ryymin EM, Viljava TR, Krause AOI (2007) Reactions of methyl heptanoate hydrodeoxygenation on sulphided catalysts. J Mol Catal A 268:1–8CrossRefGoogle Scholar
  38. 38.
    Pinheiro A, Dupassieux N, Hudebine D, Geantet C (2011) Impact of the presence of carbon monoxide and carbon dioxide on gas oil hydrotreatment: investigation on liquids from biomass cotreatment with petroleum cuts. Eng Fuel 25:804–812CrossRefGoogle Scholar
  39. 39.
    Abotsi GMK, Scarconi AW (1989) A review of carbon-supported hydrodesulfurization catalysts. Fuel Process Technol 22:107–133CrossRefGoogle Scholar
  40. 40.
    Robinson WRAM, Van Veen JAR, De Beer VHJ, Van Santen RA (1999) Development of deep hydrodesulfurization catalyst. I. CoMo and NiMo catalysts tested with (substituted) dibenzothiophene. Fuel Process Technol 61:89–101CrossRefGoogle Scholar
  41. 41.
    Farag H, Whitehurst DD, Sakanishi K, Mochida I (1999) Carbon versus alumina as a support for Co–Mo catalysts reactivity towards HDS of dibenzothiophenes and diesel fuel. Catal Today 50:9–17CrossRefGoogle Scholar
  42. 42.
    Saleh TA, Al-Hammadi SA, Abdullahi IM, Mustaqeem M (2018) Synthesis of molybdenum cobalt nanocatalysts supported on carbon for hydrodesulfurization of liquid fuels. J Mol Liq 272:715–721CrossRefGoogle Scholar
  43. 43.
    Nikulshin PA, Salnikov VA, Varakin AN, Kogan VM (2016) The use of CoMoS catalysts supported on carbon-coated alumina for hydrodeoxygenation of guaiacol and oleic acid. Catal Today 271:45–55CrossRefGoogle Scholar
  44. 44.
    Al-Hammadi SA, Al-Amer AM, Saleh TA (2018) Alumina-carbon nanofiber composite as a support for MoCo catalysts in hydrodesulfurization reactions. Chem Eng J 345:242–251CrossRefGoogle Scholar
  45. 45.
    Escobar J, Barrera MC, Gutiérrez AW, Cortés-Jacome MA, Angeles-Chávez C, Toledo JA, Solís-Casados DA (2018) Highly active P-doped sulfided NiMo/alumina HDS catalysts from Mo-blue by using saccharose as reducing agents precursor. Appl Catal B 237:708–720CrossRefGoogle Scholar
  46. 46.
    Venderbosch RH, Ardiyanti AR, Wildschut J, Oasmaa A, Heeres HJ (2010) Stabilization of biomass-derived pyrolysis oils. Chem Technol Biotechnol 85:674–686CrossRefGoogle Scholar
  47. 47.
    Elliott DC (2007) Historical developments in hydroprocessing bio-oils. Eng Fuel 21:1792–1815CrossRefGoogle Scholar
  48. 48.
    Laurent E, Delmon B (1994) Influence of water in the deactivation of a sulfided NiMo/γ-Al2O3 catalyst during hydrodeoxygenation. J Catal 146:281–291CrossRefGoogle Scholar
  49. 49.
    Blackmond DG (2005) Reaction progress kinetic analysis: a powerful methodology for mechanistic studies of complex catalytic reactions. Angew Chem Int Ed 44:4302–4320CrossRefGoogle Scholar
  50. 50.
    Vít Z, Nondek L (1984) Determination of the surface hydroxyl groups on alumina and silica-alumina catalysts by dimethylzinc. React Kinet Catal Lett 24:137–139CrossRefGoogle Scholar
  51. 51.
    Gervasini A, Wahba L, Finol MD, Lamonier JF (2012) Property and activity of molybdates dispersed on silica obtained from various synthetic procedures. Mater Sci Appl 3:195–212Google Scholar
  52. 52.
    Topsøe NY, Topsøe H (1993) FTIR studies of Mo/Al2O3-based catalysts. II. Evidence for the presence of SH groups and their role in acidity and activity. J Catal 139:641–651CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.Institute of Chemical Process Fundamentals of CAS, v. v. iPrague 6Czech Republic

Personalised recommendations