Issue
Korean Journal of Chemical Engineering,
Vol.35, No.6, 1263-1273, 2018
Kinetic models of Fischer-Tropsch synthesis reaction over granule-type Pt-promoted Co/Al2O3 catalyst
Kinetic models of CO hydrogenation to paraffinic hydrocarbons through Fischer-Tropsch synthesis (FTS) reaction were studied by using Langmuir-Hinshelwood Hougen-Watson (LHHW) model of 16 different reaction steps with a pseudo steady-state assumption (PSSA) on the prototype Pt-promoted Co/Al2O3 catalyst having a granule size of ~1 mm of spherical γ-Al2O3 support (surface area of 149m2/g). The derived kinetic models from ten sets of experimental data by altering the reaction conditions such as temperatures, pressures, space velocities and H2/CO molar ratios were found to be well fitted with reasonable kinetic parameters and small errors of conversion of CO and hydrocarbon distributions in terms of mean absolute relative residual (MARR) and relative standard deviation error (RSDE). The derived reaction rates and CO activation energy of ?86 kJ/mol well correspond to the our previously reported results using power-type catalysts. Based on the LHHW model with PSSA, the possible chemical intermediates on the granule ball-type Co-Pt/Al2O3 surfaces were precisely considered to explain the typical adsorption, initiation, propagation and termination steps of FTS reaction as well as to derive elementary reaction rates with their kinetic parameters and hydrocarbon distributions. The derived kinetic models were further used to verify temperature-profiles in a pilot-scale fixed-bed tubular FTS reactor with a packing depth of 100 cm catalyst, and it confirmed that the temperature gradients were less than 10 °C in a length of reactor by effectively removing the generated heat by an exothermic FTS reaction.
[References]
  1. Khodakov AY, Chu W, Fongarland P, Chem. Rev., 107(5), 1692, 2007
  2. Davis BH, Top. Catal., 32, 143, 2005
  3. Iglesia E, Appl. Catal. A: Gen., 161(1-2), 59, 1997
  4. Dry ME, Catal. Today, 71(3-4), 227, 2002
  5. Tsubaki N, Sun SL, Fujimoto K, J. Catal., 199(2), 236, 2001
  6. Song SH, Lee BS, Bae JW, Sai Prasad PS, Jun KW, Catal. Commun., 9, 2282, 2008
  7. Woo MH, Cho JM, Jun KW, Lee YJ, Bae JW, ChemCatChem, 7, 1460, 2015
  8. Kwack SH, Park MJ, Bae JW, Park SJ, Ha KS, Jun KW, Fuel Process. Technol., 92(12), 2264, 2011
  9. Park SJ, Kim SM, Woo MH, Bae JW, Jun KW, Ha KS, Appl. Catal. A: Gen., 419-420, 148, 2012
  10. Lee BS, Jang IH, Bae JW, Um SH, Yoo PJ, Park MJ, Lee YC, Jun KW, Catal. Surv. Asia, 16, 121, 2012
  11. Kwack SH, Bae JW, Park MJ, Kim SM, Ha KS, Jun KW, Fuel, 90(4), 1383, 2011
  12. Kwack SH, Park MJ, Bae JW, Ha KS, Jun KW, Reac. Kinet. Mech. Catal., 104, 483, 2011
  13. Yang G, Gao D, Zhang J, Zhang J, Shi Z, Zhu Z, Xue D, RSC Adv., 3, 508, 2013
  14. Ahn CI, Koo HM, Jo JM, Roh HS, Lee JB, Lee YJ, Jang EJ, Bae JW, Appl. Catal. B: Environ., 180, 139, 2016
  15. Zhu H, Razzaq R, Jiang L, Li C, Catal. Commun., 23, 43, 2012
  16. Sexton BA, Hughes AE, Turney TW, J. Catal., 97, 390, 1986
  17. Madon RJ, Iglesia E, J. Catal., 139, 576, 1993
  18. Lapidus A, Krulova A, Kazanskii V, Borovkov V, Zaitsev Z, Rathousky J, Zukal A, Jancalkova M, Appl. Catal. A: Gen., 73, 65, 1991
  19. Cats KH, Weckhuysen BM, ChemCatChem, 8, 1531, 2016
  20. Ahn CI, Koo HM, Jin M, Kim JM, Kim TG, Suh YW, Yoon KJ, Bae JW, Microporous Mesoporous Mater., 188, 196, 2014
  21. Ponec V, van Barneveld WA, Ind. Eng. Chem. Prod. Res. Dev., 18, 268, 1979
  22. Rofer-DePoorter CK, Chem. Rev., 81, 447, 1981
  23. Ernst KH, Schwarz E, Christmann K, J. Chem. Phys., 101(6), 5388, 1994
  24. Kummer JT, DeWitt TW, Emmett PH, J. Am. Chem. Soc., 70, 3632, 1948
  25. van Steen E, Schulz H, Appl. Catal. A: Gen., 186(1-2), 309, 1999
  26. Bell AT, Catal. Rev.-Sci. Eng., 23, 203, 1980
  27. Kellner CS, Bell AT, J. Catal., 70, 418, 1981
  28. Hovi JP, Lahtinen J, Liu ZS, Nieminen RM, J. Chem. Phys., 102(19), 7674, 1995
  29. van Barneveld WAA, Ponec V, J. Catal., 88, 382, 1984
  30. Joyner RW, Catal. Lett., 1, 307, 1988
  31. Schulz H, Beck K, Erich E, Fuel. Process. Technol., 18, 293, 1988
  32. Visconti CG, Tronconi E, Lietti L, Zennaro R, Forzatti P, Chem. Eng. Sci., 62(18-20), 5338, 2007
  33. Jun HJ, Park MJ, Baek SC, Bae JW, Ha KS, Jun KW, J. Natural Gas Chem., 20, 9, 2011