Linear α-olefin production with Na-promoted Fe-Zn catalysts via Fischer-Tropsch synthesis

Sunkyu Yang, Sungwoo Lee, Seok Chang Kang, Seung Ju Han, Ki Won Jun, Kwan Young Lee, Yong Tae Kim

Research output: Contribution to journalArticle

Abstract

The production of linear alpha-olefins (α-olefins) is a practical way to increase the economic potential of the Fischer-Tropsch synthesis (FTS) because of their importance as chemical intermediates. Our study aimed to optimize Na-promoted Fe 1 Zn 1.2 O x catalysts such that they selectively converted syngas to linear α-olefins via FTS at 340 °C and 2.0 MPa. The Fe 1 Zn 1.2 O x catalysts were calcined at different temperatures from 350 to 700 °C before Na anchoring. The increase in the size of the ZnFe 2 O 4 crystals comprising the catalyst had a negative effect on the reducibility of Fe oxides and the particle size of Fe 5 C 2 during the reaction. The Na species in the catalyst restrained the reduction of Fe 1 Zn 1.2 O x but facilitated the formation of Fe 5 C 2 . When pure Fe 1 Zn 1.2 O x was calcined at 400 °C, the corresponding catalyst (i.e., Na 0.2 /Fe 1 Zn 1.2 O x (400)) exhibited higher catalytic activity and stability than the other catalysts for a 50 h reaction. Compared to the other catalysts, Na 0.2 /Fe 1 Zn 1.2 O x (400) enabled a higher number of active Fe carbides (Fe 5 C 2 ) to intimately interact with the Na species, even though the catalyst had a lower total surface basicity based on surface area. The Na 0.2 /Fe 1 Zn 1.2 O x (400) showed a maximum hydrocarbon yield of 49.7% with a maximum olefin selectivity of 61.3% in the C1-C32 range. Examination of the reaction product mixture revealed that the Na 0.2 /Fe 1 Zn 1.2 O x catalysts converted α-olefins to branched paraffins (13.9-19.5%) via a series of isomerization, skeletal isomerization, and hydrogenation reactions. The Na 0.2 /Fe 1 Zn 1.2 O x (400) catalyst had a relatively low consumption rate of internal olefins compared to other catalysts, resulting in the lowest selectivity for branched paraffins. The Na 0.2 /Fe 1 Zn 1.2 O x (400) showed a maximum α-olefin yield (26.6%) in the range C2-C32, which was 27.9-50.0% higher than that of other catalysts. The α-olefin selectivity in the C5-C12 range for the Na 0.2 /Fe 1 Zn 1.2 O x (400) was 37.5% relative to the total α-olefins.

Original languageEnglish
Pages (from-to)14176-14187
Number of pages12
JournalRSC Advances
Volume9
Issue number25
DOIs
Publication statusPublished - 2019 Jan 1

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Fischer-Tropsch synthesis
Alkenes
Olefins
Catalysts
Catalyst selectivity
Isomerization
Paraffin
Paraffins
Alkalinity
Hydrocarbons
Reaction products
Oxides
Hydrogenation
Carbides
Catalyst activity
Particle size

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Yang, S., Lee, S., Kang, S. C., Han, S. J., Jun, K. W., Lee, K. Y., & Kim, Y. T. (2019). Linear α-olefin production with Na-promoted Fe-Zn catalysts via Fischer-Tropsch synthesis. RSC Advances, 9(25), 14176-14187. https://doi.org/10.1039/c9ra02471a

Linear α-olefin production with Na-promoted Fe-Zn catalysts via Fischer-Tropsch synthesis. / Yang, Sunkyu; Lee, Sungwoo; Kang, Seok Chang; Han, Seung Ju; Jun, Ki Won; Lee, Kwan Young; Kim, Yong Tae.

In: RSC Advances, Vol. 9, No. 25, 01.01.2019, p. 14176-14187.

Research output: Contribution to journalArticle

Yang, S, Lee, S, Kang, SC, Han, SJ, Jun, KW, Lee, KY & Kim, YT 2019, 'Linear α-olefin production with Na-promoted Fe-Zn catalysts via Fischer-Tropsch synthesis', RSC Advances, vol. 9, no. 25, pp. 14176-14187. https://doi.org/10.1039/c9ra02471a
Yang, Sunkyu ; Lee, Sungwoo ; Kang, Seok Chang ; Han, Seung Ju ; Jun, Ki Won ; Lee, Kwan Young ; Kim, Yong Tae. / Linear α-olefin production with Na-promoted Fe-Zn catalysts via Fischer-Tropsch synthesis. In: RSC Advances. 2019 ; Vol. 9, No. 25. pp. 14176-14187.
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abstract = "The production of linear alpha-olefins (α-olefins) is a practical way to increase the economic potential of the Fischer-Tropsch synthesis (FTS) because of their importance as chemical intermediates. Our study aimed to optimize Na-promoted Fe 1 Zn 1.2 O x catalysts such that they selectively converted syngas to linear α-olefins via FTS at 340 °C and 2.0 MPa. The Fe 1 Zn 1.2 O x catalysts were calcined at different temperatures from 350 to 700 °C before Na anchoring. The increase in the size of the ZnFe 2 O 4 crystals comprising the catalyst had a negative effect on the reducibility of Fe oxides and the particle size of Fe 5 C 2 during the reaction. The Na species in the catalyst restrained the reduction of Fe 1 Zn 1.2 O x but facilitated the formation of Fe 5 C 2 . When pure Fe 1 Zn 1.2 O x was calcined at 400 °C, the corresponding catalyst (i.e., Na 0.2 /Fe 1 Zn 1.2 O x (400)) exhibited higher catalytic activity and stability than the other catalysts for a 50 h reaction. Compared to the other catalysts, Na 0.2 /Fe 1 Zn 1.2 O x (400) enabled a higher number of active Fe carbides (Fe 5 C 2 ) to intimately interact with the Na species, even though the catalyst had a lower total surface basicity based on surface area. The Na 0.2 /Fe 1 Zn 1.2 O x (400) showed a maximum hydrocarbon yield of 49.7{\%} with a maximum olefin selectivity of 61.3{\%} in the C1-C32 range. Examination of the reaction product mixture revealed that the Na 0.2 /Fe 1 Zn 1.2 O x catalysts converted α-olefins to branched paraffins (13.9-19.5{\%}) via a series of isomerization, skeletal isomerization, and hydrogenation reactions. The Na 0.2 /Fe 1 Zn 1.2 O x (400) catalyst had a relatively low consumption rate of internal olefins compared to other catalysts, resulting in the lowest selectivity for branched paraffins. The Na 0.2 /Fe 1 Zn 1.2 O x (400) showed a maximum α-olefin yield (26.6{\%}) in the range C2-C32, which was 27.9-50.0{\%} higher than that of other catalysts. The α-olefin selectivity in the C5-C12 range for the Na 0.2 /Fe 1 Zn 1.2 O x (400) was 37.5{\%} relative to the total α-olefins.",
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N2 - The production of linear alpha-olefins (α-olefins) is a practical way to increase the economic potential of the Fischer-Tropsch synthesis (FTS) because of their importance as chemical intermediates. Our study aimed to optimize Na-promoted Fe 1 Zn 1.2 O x catalysts such that they selectively converted syngas to linear α-olefins via FTS at 340 °C and 2.0 MPa. The Fe 1 Zn 1.2 O x catalysts were calcined at different temperatures from 350 to 700 °C before Na anchoring. The increase in the size of the ZnFe 2 O 4 crystals comprising the catalyst had a negative effect on the reducibility of Fe oxides and the particle size of Fe 5 C 2 during the reaction. The Na species in the catalyst restrained the reduction of Fe 1 Zn 1.2 O x but facilitated the formation of Fe 5 C 2 . When pure Fe 1 Zn 1.2 O x was calcined at 400 °C, the corresponding catalyst (i.e., Na 0.2 /Fe 1 Zn 1.2 O x (400)) exhibited higher catalytic activity and stability than the other catalysts for a 50 h reaction. Compared to the other catalysts, Na 0.2 /Fe 1 Zn 1.2 O x (400) enabled a higher number of active Fe carbides (Fe 5 C 2 ) to intimately interact with the Na species, even though the catalyst had a lower total surface basicity based on surface area. The Na 0.2 /Fe 1 Zn 1.2 O x (400) showed a maximum hydrocarbon yield of 49.7% with a maximum olefin selectivity of 61.3% in the C1-C32 range. Examination of the reaction product mixture revealed that the Na 0.2 /Fe 1 Zn 1.2 O x catalysts converted α-olefins to branched paraffins (13.9-19.5%) via a series of isomerization, skeletal isomerization, and hydrogenation reactions. The Na 0.2 /Fe 1 Zn 1.2 O x (400) catalyst had a relatively low consumption rate of internal olefins compared to other catalysts, resulting in the lowest selectivity for branched paraffins. The Na 0.2 /Fe 1 Zn 1.2 O x (400) showed a maximum α-olefin yield (26.6%) in the range C2-C32, which was 27.9-50.0% higher than that of other catalysts. The α-olefin selectivity in the C5-C12 range for the Na 0.2 /Fe 1 Zn 1.2 O x (400) was 37.5% relative to the total α-olefins.

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