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Title: Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

Abstract

Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of H 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2more » at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation showed that Ni was sulfided faster than Mo and CoMo, and that Mo was sulfided faster when promoted with Ni. Extended X-ray absorption fine structure (EXAFS) results showed the presence of MoS 2 in all sulfided catalysts. Lastly, sulfided CoMo was present as a mixture of CoMoS and Co 9S 8, whereas sulfided NiMo was present as NiMoS.« less

Authors:
 [1];  [2];  [3];  [2];  [1];  [4];  [5];  [6];  [7];  [1]
  1. Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemical and Biochemical Engineering
  2. Karlsruhe Inst. of Technology (KIT) (Germany). Inst. for Chemical Technology and Polymer Chemistry
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
  4. Technical Univ. of Denmark (DTU), Lyngby (Denmark). Center for Electron Nanoscopy
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Karlsruhe Inst. of Technology (KIT) (Germany). Inst. of Catalysis Research and Technology
  6. Haldor Topsoe A/S, Lyngby (Denmark)
  7. Karlsruhe Inst. of Technology (KIT) (Germany). Inst. for Chemical Technology and Polymer Chemistry; Karlsruhe Inst. of Technology (KIT) (Germany). Inst. of Catalysis Research and Technology
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE; Danish Council for Strategic Research
OSTI Identifier:
1425962
Grant/Contract Number:  
AC02-76SF00515; 1377-00025A
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Applied Catalysis. A, General
Additional Journal Information:
Journal Volume: 551; Journal Issue: C; Journal ID: ISSN 0926-860X
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; Hydrodeoxygenation; DFT; Molybdenum sulfide; XAS; Bio-oil

Citation Formats

Dabros, Trine Marie Hartmann, Gaur, Abhijeet, Pintos, Delfina Garcia, Sprenger, Paul, Høj, Martin, Hansen, Thomas Willum, Studt, Felix, Gabrielsen, Jostein, Grunwaldt, Jan-Dierk, and Jensen, Anker Degn. Influence of H2O and H2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl2O4 for hydrodeoxygenation of ethylene glycol. United States: N. p., 2017. Web. doi:10.1016/j.apcata.2017.12.008.
Dabros, Trine Marie Hartmann, Gaur, Abhijeet, Pintos, Delfina Garcia, Sprenger, Paul, Høj, Martin, Hansen, Thomas Willum, Studt, Felix, Gabrielsen, Jostein, Grunwaldt, Jan-Dierk, & Jensen, Anker Degn. Influence of H2O and H2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl2O4 for hydrodeoxygenation of ethylene glycol. United States. doi:10.1016/j.apcata.2017.12.008.
Dabros, Trine Marie Hartmann, Gaur, Abhijeet, Pintos, Delfina Garcia, Sprenger, Paul, Høj, Martin, Hansen, Thomas Willum, Studt, Felix, Gabrielsen, Jostein, Grunwaldt, Jan-Dierk, and Jensen, Anker Degn. Sun . "Influence of H2O and H2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl2O4 for hydrodeoxygenation of ethylene glycol". United States. doi:10.1016/j.apcata.2017.12.008.
@article{osti_1425962,
title = {Influence of H2O and H2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl2O4 for hydrodeoxygenation of ethylene glycol},
author = {Dabros, Trine Marie Hartmann and Gaur, Abhijeet and Pintos, Delfina Garcia and Sprenger, Paul and Høj, Martin and Hansen, Thomas Willum and Studt, Felix and Gabrielsen, Jostein and Grunwaldt, Jan-Dierk and Jensen, Anker Degn},
abstractNote = {Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS2, Ni-MoS2, and Co-MoS2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H2O and H2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H2S level during HDO. DFT calculations unraveled that the active edge of MoS2 could be stabilized against SO exchanges by increasing the partial pressure of H2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H2, and 550–2200 ppm H2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl2O4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C2/C1 ratio of 1.5–2.0 at 550 ppm H2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H2S which also stabilized the activity. Removing H2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation showed that Ni was sulfided faster than Mo and CoMo, and that Mo was sulfided faster when promoted with Ni. Extended X-ray absorption fine structure (EXAFS) results showed the presence of MoS2 in all sulfided catalysts. Lastly, sulfided CoMo was present as a mixture of CoMoS and Co9S8, whereas sulfided NiMo was present as NiMoS.},
doi = {10.1016/j.apcata.2017.12.008},
journal = {Applied Catalysis. A, General},
number = C,
volume = 551,
place = {United States},
year = {Sun Dec 10 00:00:00 EST 2017},
month = {Sun Dec 10 00:00:00 EST 2017}
}

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