Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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A Review of Domestic Research Trends of Fischer-Tropsch for the Production of Light Hydrocarbons and Middle Distillates From Syngas

합성가스로부터 경질탄화수소 및 중산유분을 생산하기 위한 Fischer-Tropsch의 국내연구동향

  • Kim, Jin-Ho (Plant Engineering Center, Institute for Advances Engineering (IAE)) ;
  • Kim, Hyo-Sik (Plant Engineering Center, Institute for Advances Engineering (IAE)) ;
  • Kim, Ji-Hyeon (Plant Engineering Center, Institute for Advances Engineering (IAE)) ;
  • Ryu, Jae-Hong (Plant Engineering Center, Institute for Advances Engineering (IAE)) ;
  • Kang, Suk-Hwan (Plant Engineering Center, Institute for Advances Engineering (IAE)) ;
  • Park, Myung-June (Department of Chemical Engineering, Ajou University)
  • 김진호 (고등기술연구원 플랜트엔지니어링센터) ;
  • 김효식 (고등기술연구원 플랜트엔지니어링센터) ;
  • 김지현 (고등기술연구원 플랜트엔지니어링센터) ;
  • 류재홍 (고등기술연구원 플랜트엔지니어링센터) ;
  • 강석환 (고등기술연구원 플랜트엔지니어링센터) ;
  • 박명준 (아주대학교 화학공학과)
  • Received : 2019.03.31
  • Accepted : 2019.05.29
  • Published : 2019.08.01
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Abstract

Fischer-Tropsch synthesis process is a typical method for synthesizing hydrocarbons from syngas and is mainly known as iron (Fe) and cobalt (Co) catalysts. Currently, some technologies such as CTL (Coal to Liquid) and GTL (Gas to Liquid) are operated on a commercial scale depending on the products, but the research to produce light hydrocarbons and middle distillates directly has not been commercialized. Therefore, in this study, domestic studies for direct production of light hydrocarbons and middle distillates are summarized and the effect of catalyst preparation, promoter addition, zeolite combination on product selectivity is investigated.

Fischer-Tropsch 합성공정은 합성가스로부터 탄화수소를 합성하는 대표적인 방법이며, 주로 철(Fe)계와 코발트(Co)계 촉매로 알려져 있다. 현재 생성물에 따라 일부 기술(CTL, GTL 등)은 상용 규모로 운전되고 있으나, 경질탄화수소와 중간유분을 직접 생산하는 연구는 아직 상용화되지는 않았다. 그러므로, 본 연구에서는 국내에서 현재까지 경질탄화수소와 중간유분을 직접 생산하기 위한 연구들을 정리하였으며, 촉매의 제조법, 조촉매 첨가, 제올라이트의 조합과 같은 영향이 생성물의 선택도에 미치는 영향을 고찰하였다.

Keywords

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Fig. 1. Application of syngas [1].

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Fig. 2.Type of catalysts and reaction conditions for the heterogeneously catalyzed gas conversion [4].

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Fig. 3. Schematic representation of the morphological and phase change that occur on the α-Fe2O3 catalyst as a result of activation and reaction conditions [5].

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Fig. 4. Product distribution according to the Anderson-Schulz-Flory (ASF) model [6].

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Fig. 5. A correlation between the acidity and the yield of olefins in the range of C2~C4 hydrocarbons [9].

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Fig. 6. CO-TPR profiles of Fe-Cu-K/ZSM5 catalysts [10].

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Fig. 7. Carbon number distribution of hydrocarbon product after FT and cracking reaction. Catalysts: FT = 6K/100Fe-6Cu-16AlOx; cracking = ZSM-5 (SiO2/Al2O3, T = 280 ℃). Reaction conditions-FT synthesis (0.5 g cat.): T = 300 ℃; P = 10 atm; GHSV = 3600 (syngas: 30 cm3/min), cracking reaction (0.15 g cat.) [13].

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Fig. 8. Correlation of catalytic performance with the intensity ratio of C1s, which is the ratio of deposited carbon (I(dep)) and adsorbed carbon (I(ads)) peaks at binding energies of 288.2 and 284.4 eV respectively on the used catalysts [14].

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Fig. 9. The yield to C2-C4 olefin with respect to the superficial gas velocity in FBR and BFBR [15].

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Fig. 10. Carbon conversion and CH4 productivity on NixFe1-x/Al2O3 catalysts according to Fe contents [18].

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Fig. 11. C2-C4 hydrocarbon selectivity as a function of the CO conversion over 5Co-15Fe/γ-Al2O3 at 10 bar and different reaction temperatures and H2/CO ratios [20].

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Fig. 12. Correlation between the surface acidity and the selectivity of hydrocarbons [32].

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Fig. 13. Catalytic performance (CO conversion and product distribution) with respect to the acid site density on the ZSM5-modified Co/SiO2 catalysts [33].

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Fig. 14. Schematic diagram of ZSM5-modified Co/SiO2 and impregnated cobalt-based catalysts [33].

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Fig. 15. Effct of Promoter on the correlation between the surface activity and the selectivity of hydrocarbons [34].

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Fig. 16. Correlation between the Pt content and the yield of hydrocarbons [36].

Table 1. Literatures for middle distillates production by F-T synthesis

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Table 2. CO hydrogenation over Co-Al2O3-promoter/ZSM-5 catalysts (CO hydrogenation was carried out at H2/CO=2, WHSV=4,000 ml/g·h and P=2.0MPa)

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Table 3. Catalytic activity and product distribution on the ordered mesoporous Fe2O3-ZrO2 catalysts (CO hydrogenation was carried out at H2/CO=2, T=300 ℃, WHSV=8,000 L/kg·h and P=2.0MPa)

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Table 4. Catalytic performances on the Fe/KIT-6 catalysts (CO hydrogenation was carried out at H2/CO=2, T=350 ℃, WHSV=4,000 L/kg·h and P=2.0MPa)

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Table 5. Catalytic performances at a steady-state on the P/m-CoAl catalysts (CO hydrogenation was carried out at H2/CO=2, T=230 ℃, WHSV=6,000 L/kg·h and P=2.0MPa)

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Table 6. Catalytic performances at a steady-state on the CoZrP/KIT-6 catalysts (CO hydrogenation was carried out at H2/CO=2, T=230 ℃, WHSV=8,000 L/kg·h and P=2.0MPa)

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