Substitution of Co with Ni in Co/Al2O3 Catalysts for Fischer–Tropsch Synthesis

Martinelli, Michela; Karuturi, Sai Charan; Garcia, Richard; Watson, Caleb D.; Shafer, Wilson D.; Cronauer, Donald C.; Kropf, A. Jeremy; Marshall, Christopher L.; Jacobs, Gary

doi:10.3390/catal10030334

Substitution of Co with Ni in Co/Al₂O₃ Catalysts for Fischer–Tropsch Synthesis

Journal Article · Tue Mar 17 04:00:00 EDT 2020 · Catalysts

DOI:https://doi.org/10.3390/catal10030334· OSTI ID:1763653

Martinelli, Michela ^[1]; Karuturi, Sai Charan ^[2]; Garcia, Richard ^[2]; Watson, Caleb D. ^[2]; ^[3]; Cronauer, Donald C. ^[4]; Kropf, A. Jeremy ^[4]; Marshall, Christopher L. ^[4]; Jacobs, Gary ^[5]

Univ. of Kentucky, Lexington, KY (United States). Center for Applied Energy Research
Univ. of Texas at San Antonio, TX (United States)
Asbury Univ., Wilmore, KY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Kentucky, Lexington, KY (United States); Univ. of Texas at San Antonio, TX (United States)

The effect of cobalt substitution with nickel was investigated for the Fischer–Tropsch synthesis reaction. Catalysts having different Ni/Co ratios were prepared by aqueous incipient wetness co-impregnation, characterized, and tested using a continuously stirred tank reactor (CSTR) for more than 200 h. The addition of nickel did not significantly modify the morphological properties measured. XRD, STEM, and TPR-XANES results showed intimate contact between nickel and cobalt, strongly suggesting the formation of a Co-Ni solid oxide solution in each case. Moreover, TPR-XANES indicated that nickel addition improves the cobalt reducibility. This may be due to H₂ dissociation and spillover, but is more likely the results of a chemical effect of intimate contact between Co and Ni resulting in Co-Ni alloying after activation. FTS testing revealed a lower initial activity when nickel was added. However, CO conversion continuously increased with time on-stream until a steady-state value (34%–37% depending on Ni/Co ratio) was achieved, which was very close to the value observed for undoped Co/Al₂O₃. This trend suggests nickel can stabilize cobalt nanoparticles even at a lower weight percentage of Co. Currently, the cobalt price is 2.13 times the price of nickel. Thus, comparing the activity/price, the catalyst with a Ni/Co ratio of 25/75 has better performance than the unpromoted catalyst. Finally, nickel-promoted catalysts exhibited slightly higher initial selectivity for light hydrocarbons, but this difference typically diminished with time on-stream; once leveling off in conversion was achieved, the C₅₊ selectivities were similar (≈ 80%) for Ni/Co ratios up to 10/90, and only slightly lower (≈ 77%) at Ni/Co of 25/75.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); University of Texas – San Antonio; University of Kentucky - Center for Applied Energy Research; U.S. Department of Agriculture (USDA) - National Institute of Food and Agriculture (NIFA)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1763653

Journal Information:: Catalysts, Journal Name: Catalysts Journal Issue: 3 Vol. 10; ISSN 2073-4344

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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