DOI: https://doi.org/10.15587/1729-4061.2018.134165

Mathematical model of obtaining a hydrocarbon fuel based on the fischer­tropsch pathway in a stationary layer of the cobalt­based catalyst

Yurii Zakharchuk, Yurii Beznosyk, Liudmyla Bugaieva

Abstract


Studying the kinetics of the Fischer-Tropsch process is a rather important task, since this process is very sensitive to the temperature mode, as well as to the characteristics of the catalyst. In addition, a given process is accompanied by many side reactions that negatively affect the rate and selectivity of the reaction. The Fischer-Tropsch synthesis is an alternative source for obtaining high-quality fuel from coal or biomass rather than petroleum. Therefore, investigating the kinetics of the Fischer-Tropsch reaction, in order to improve the selectivity and activity of catalysts, and to determine the rate constants of chemical reactions, is a relevant problem.

The choice of the catalyst is one of the main factors affecting the quality and product yield for the Fischer-Tropsch synthesis. We fabricated two samples of cobalt catalysts for conducting the experiments. The first sample of the catalyst Со/γ-Al2O3 contains cobalt nanoparticles of the same size. The second sample of the catalyst (Со)/γ-Al2O3 was obtained by the method of impregnating the carrier with a solution of cobalt nitrate. The catalyst, obtained through the method of impregnation of (Со)/γ-Al2O3, demonstrated a higher activity, larger by an order of magnitude than the monodispersed catalysts. However, the monodispersed catalyst showed high selectivity for the lower hydrocarbons.

In order to calculate the kinetics of the Fischer-Tropsch process and to find the reaction rate constants, we developed a software module in the programming environment MS Visual Studio 2017 in the programming language C# using the .NET Framework v4.6 technologies.

By using the developed program module, we calculated reaction rate constants of the Fischer-Tropsch process. After analyzing the data obtained, one can see that the relative error is within 2…3 %, demonstrating the adequacy of the proposed model to solve the inverse problem of chemical kinetics. Therefore, we can state that a given model for the calculation of rate constants could be applied to study the Fischer-Tropsch process.


Keywords


Fischer-Tropsch reaction; cobalt catalyst; inverse problem of kinetics; rate constant

References


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Slivinskiy, E. V., Kuz'min, A. E., Abramova, A. V., Kliger, G. A., Loktev, S. M. (1998). Sintez Fishera-Tropsha: sovremennoe sostoyanie i principy sozdaniya katalizatorov (obzor). Neftekhimiya, 38, 243–268.

Dry, M. E.; Anderson, R. B., Boudard, M. (Eds.) (1981). The Fischer–Tropsch Synthesis. Catalysis, Science and Technology, 1, 159–256.

Schulz, H. (1999). Short history and present trends of Fischer–Tropsch synthesis. Applied Catalysis A: General, 186 (1-2), 3–12. doi: 10.1016/s0926-860x(99)00160-x

Krylov, O. V. (2004). Geterogennyy kataliz. Moscow, 679.

Lapidus, A. L., Krylova, A. Yu. (2000). O mekhanizme obrazovaniya zhidkih uglevodorodov iz CO i H2 na kobal'tovyh katalizatorah. Rossiyskiy himicheskiy zhurnal, 44 (1), 43–56.

Rofer-DePoorter, C. K. (1981). A comprehensive mechanism for the Fischer-Tropsch synthesis. Chemical Reviews, 81 (5), 447–474. doi: 10.1021/cr00045a002

Brunner, K. M., Duncan, J. C., Harrison, L. D., Pratt, K. E., Peguin, R. P. S., Bartholomew, C. H., Hecker, W. C. (2012). A Trickle Fixed-Bed Recycle Reactor Model for the Fischer-Tropsch Synthesis. International Journal of Chemical Reactor Engineering, 10 (1). doi: 10.1515/1542-6580.2840

Tristantini, D., Lögdberg, S., Gevert, B., Borg, Ø., Holmen, A. (2007). The effect of synthesis gas composition on the Fischer–Tropsch synthesis over Co/γ-Al2O3 and Co–Re/γ-Al2O3 catalysts. Fuel Processing Technology, 88 (7), 643–649. doi: 10.1016/j.fuproc.2007.01.012

Davis, B. H. (2007). Fischer−Tropsch Synthesis: Comparison of Performances of Iron and Cobalt Catalysts. Industrial & Engineering Chemistry Research, 46 (26), 8938–8945. doi: 10.1021/ie0712434

Patzlaff, J., Liu, Y., Graffmann, C., Gaube, J. (1999). Studies on product distributions of iron and cobalt catalyzed Fischer–Tropsch synthesis. Applied Catalysis A: General, 186 (1-2), 109–119. doi: 10.1016/s0926-860x(99)00167-2

Patzlaff, J., Liu, Y., Graffmann, C., Gaube, J. (2002). Interpretation and kinetic modeling of product distributions of cobalt catalyzed Fischer–Tropsch synthesis. Catalysis Today, 71 (3-4), 381–394. doi: 10.1016/s0920-5861(01)00465-5

Zhou, L., Froment, G. F., Yang, Y., Li, Y. (2016). Advanced fundamental modeling of the kinetics of Fischer-Tropsch synthesis. AIChE Journal, 62 (5), 1668–1682. doi: 10.1002/aic.15141

Sun, Y., Yang, G., Zhang, L., Sun, Z. (2017). Fischer-Tropsch synthesis in a microchannel reactor using mesoporous silica supported bimetallic Co-Ni catalyst: Process optimization and kinetic modeling. Chemical Engineering and Processing: Process Intensification, 119, 44–61. doi: 10.1016/j.cep.2017.05.017

Arsalanfara, M., Mirzaeib, A. A., Bozorgzadehc, H. R., Samimid, A. (2014). A review of Fischer-Tropsch synthesis on the cobalt based catalysts. Phys. Chem. Res., 2 (2), 179–201.

Mosayebi, A., Haghtalab, A. (2015). The comprehensive kinetic modeling of the Fischer–Tropsch synthesis over Co@Ru/γ-Al2O3 core–shell structure catalyst. Chemical Engineering Journal, 259, 191–204. doi: 10.1016/j.cej.2014.07.040

Mosayebi, A., Abedini, R. (2017). Detailed kinetic study of Fischer – Tropsch synthesis for gasoline production over Co Ni/HZSM-5 nano-structure catalyst. International Journal of Hydrogen Energy, 42 (44), 27013–27023. doi: 10.1016/j.ijhydene.2017.09.060

Pyatnickiy, Yu. I., Lunev, N. K. (2001). Kineticheskoe modelirovanie processa Fishera-Tropsha. Kataliz i neftekhimiya, 9-10, 1–4.

Skoretska, I., Beznosyk, Y. (2017). Modeling the heterogeneous catalytic recovery processes of aldehydes and ketones. Eastern-European Journal of Enterprise Technologies, 3 (6 (87)), 36–43. doi: 10.15587/1729-4061.2017.99755

Bezdenezhnyh, A. A. (1973). Inzhenernye metody sostavleniya uravneniy skorostey reakciy i rascheta kineticheskih konstant. Leningrad: Himiya, 256.

Zakharchuk, Y., Beznosyk, Y. (2018). Research and modeling of the heterogeneous process of production the hydrocarbon fuel according to the Fischer-Tropsch scheme. 6th International Scientific-Practical Conference "Modeling and simulation for chemistry, technologies and sustainable development systems – MSCT-6". Kyiv, 139–145.


GOST Style Citations


Chetyre pokoleniya tekhnologii polucheniya sinteticheskogo zhidkogo topliva na osnove sinteza Fishera-Tropsha / Mordkovich V. Z., Sineva L. V., Kul'chakovskaya E. V., Asalieva E. Yu. // Kataliz v neftepererabatyvayushchey promyshlennosti. 2015. Vol. 15, Issue 5. P. 23–45.

Sintez Fishera-Tropsha: sovremennoe sostoyanie i principy sozdaniya katalizatorov (obzor) / Slivinskiy E. V., Kuz'min A. E., Abramova A. V., Kliger G. A., Loktev S. M. // Neftekhimiya. 1998. Vol. 38. P. 243–268.

Dry M. E. The Fischer–Tropsch Synthesis / R. B. Anderson, M. Boudard (Eds.) // Catalysis, Science and Technology. 1981. Vol. 1. P. 159–256.

Schulz H. Short history and present trends of Fischer–Tropsch synthesis // Applied Catalysis A: General. 1999. Vol. 186, Issue 1-2. P. 3–12. doi: 10.1016/s0926-860x(99)00160-x 

Krylov O. V. Geterogennyy kataliz. Moscow, 2004. 679 p.

Lapidus A. L., Krylova A. Yu. O mekhanizme obrazovaniya zhidkih uglevodorodov iz CO i H2 na kobal'tovyh katalizatorah // Rossiyskiy himicheskiy zhurnal. 2000. Vol. 44, Issue 1. P. 43–56.

Rofer-DePoorter C. K. A comprehensive mechanism for the Fischer-Tropsch synthesis // Chemical Reviews. 1981. Vol. 81, Issue 5. P. 447–474. doi: 10.1021/cr00045a002 

A Trickle Fixed-Bed Recycle Reactor Model for the Fischer-Tropsch Synthesis / Brunner K. M., Duncan J. C., Harrison L. D., Pratt K. E., Peguin R. P. S., Bartholomew C. H., Hecker W. C. // International Journal of Chemical Reactor Engineering. 2012. Vol. 10, Issue 1. doi: 10.1515/1542-6580.2840 

The effect of synthesis gas composition on the Fischer–Tropsch synthesis over Co/γ-Al2O3 and Co–Re/γ-Al2O3 catalysts / Tristantini D., Lögdberg S., Gevert B., Borg Ø., Holmen A. // Fuel Processing Technology. 2007. Vol. 88, Issue 7. P. 643–649. doi: 10.1016/j.fuproc.2007.01.012 

Davis B. H. Fischer−Tropsch Synthesis: Comparison of Performances of Iron and Cobalt Catalysts // Industrial & Engineering Chemistry Research. 2007. Vol. 46, Issue 26. P. 8938–8945. doi: 10.1021/ie0712434 

Studies on product distributions of iron and cobalt catalyzed Fischer–Tropsch synthesis / Patzlaff J., Liu Y., Graffmann C., Gaube J. // Applied Catalysis A: General. 1999. Vol. 186, Issue 1-2. P. 109–119. doi: 10.1016/s0926-860x(99)00167-2 

Interpretation and kinetic modeling of product distributions of cobalt catalyzed Fischer–Tropsch synthesis / Patzlaff J., Liu Y., Graffmann C., Gaube J. // Catalysis Today. 2002. Vol. 71, Issue 3-4. P. 381–394. doi: 10.1016/s0920-5861(01)00465-5 

Advanced fundamental modeling of the kinetics of Fischer-Tropsch synthesis / Zhou L., Froment G. F., Yang Y., Li Y. // AIChE Journal. 2016. Vol. 62, Issue 5. P. 1668–1682. doi: 10.1002/aic.15141 

Fischer-Tropsch synthesis in a microchannel reactor using mesoporous silica supported bimetallic Co-Ni catalyst: Process optimization and kinetic modeling / Sun Y., Yang G., Zhang L., Sun Z. // Chemical Engineering and Processing: Process Intensification. 2017. Vol. 119. P. 44–61. doi: 10.1016/j.cep.2017.05.017 

A review of Fischer-Tropsch synthesis on the cobalt based catalysts / Arsalanfara M., Mirzaeib A. A., Bozorgzadehc H. R., Samimid A. // Phys. Chem. Res. 2014. Vol. 2, Issue 2. P. 179–201.

Mosayebi A., Haghtalab A. The comprehensive kinetic modeling of the Fischer–Tropsch synthesis over Co@Ru/γ-Al2O3 core–shell structure catalyst // Chemical Engineering Journal. 2015. Vol. 259. P. 191–204. doi: 10.1016/j.cej.2014.07.040 

Mosayebi A., Abedini R. Detailed kinetic study of Fischer – Tropsch synthesis for gasoline production over Co Ni/HZSM-5 nano-structure catalyst // International Journal of Hydrogen Energy. 2017. Vol. 42, Issue 44. P. 27013–27023. doi: 10.1016/j.ijhydene.2017.09.060 

Pyatnickiy Yu. I., Lunev N. K. Kineticheskoe modelirovanie processa Fishera-Tropsha // Kataliz i neftekhimiya. 2001. Issue 9-10. P. 1–4.

Skoretska I., Beznosyk Y. Modeling the heterogeneous catalytic recovery processes of aldehydes and ketones // Eastern-European Journal of Enterprise Technologies. 2017. Vol. 3, Issue 6 (87). P. 36–43. doi: 10.15587/1729-4061.2017.99755 

Bezdenezhnyh A. A. Inzhenernye metody sostavleniya uravneniy skorostey reakciy i rascheta kineticheskih konstant. Leningrad: Himiya, 1973. 256 p.

Zakharchuk Y., Beznosyk Y. Research and modeling of the heterogeneous process of production the hydrocarbon fuel according to the Fischer-Tropsch scheme // 6th International Scientific-Practical Conference "Modeling and simulation for chemistry, technologies and sustainable development systems – MSCT-6". Kyiv, 2018. P. 139–145.







Copyright (c) 2018 Yurii Zakharchuk, Yurii Beznosyk, Liudmyla Bugaieva

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ISSN (print) 1729-3774, ISSN (on-line) 1729-4061