费托合成催化剂失活动力学模型的研究进展
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摘要
费托合成催化剂由于自身的化学性质在反应中不可避免会发生失活,为了保证生产的连续稳定,需要建立费托合成催化剂失活的动力学模型来预测催化剂的活性变化,并及时对失活的催化剂进行置换和再生。本文论述了费托合成失活动力学模型的研究进展,讨论了通用型失活动力学模型,根据机理建立的失活动力学模型的特点。通用型失活动力学模型与催化剂种类和失活原因没有直接关联,包括线性模型、简单幂律模型、通用幂律模型、韦伯分布模型、S型分布模型。根据机理建立的失活动力学模型则与催化剂种类和失活发生的机理相关,包括硫中毒失活模型、烧结失活模型、表面氧化失活模型等。通用型失活动力学模型准确性好、容易建立,但比较粗略,适用于费托合成的生产管理、过程模拟。根据机理建立的失活动力学模型建立过程复杂,只适用于特定催化剂,但能够从中研究催化剂的失活机理。费托合成失活动力学模型未来的发展趋势是融合两类模型,从失活机理的角度理解通用型失活动力学模型里参数的含义。
Deactivation is inevitable for Fischer-Tropsch catalysts because of their intrinsic chemical properties. To keep the production stable and consistent, deactivation models should be established in order to replace and regenerate the deactivated catalyst in time. This article summarized the research progress on the catalyst deactivation model for Fischer-Tropsch synthesis. The characteristics of general deactivation model and the reaction mechanism model were discussed. The general deactivation model has no direct correlation to the catalyst type and deactivation mechanism, and consists of linear model,simple power law model, general power law model, Weibull distribution model, and sigmoidal pattern model. On the other hand, the reaction mechanism based deactivation model has correlation to the catalyst type and deactivation cause, which includes sulfur poisoning model, sintering model, surface oxidation model, etc. General deactivation model is accurate and easy to establish, but is relatively rough,which is suitable for production management and process simulation. The reaction mechanism based model is complicated to establish and can only be applied to specific catalyst. The future development of Fischer-Tropsch deactivation model is to combine the two kinds of models together and to investigate the meaning of the parameters in general deactivation models through the view of deactivation mechanism.
Deactivation is inevitable for Fischer-Tropsch catalysts because of their intrinsic chemical properties. To keep the production stable and consistent, deactivation models should be established in order to replace and regenerate the deactivated catalyst in time. This article summarized the research progress on the catalyst deactivation model for Fischer-Tropsch synthesis. The characteristics of general deactivation model and the reaction mechanism model were discussed. The general deactivation model has no direct correlation to the catalyst type and deactivation mechanism, and consists of linear model,simple power law model, general power law model, Weibull distribution model, and sigmoidal pattern model. On the other hand, the reaction mechanism based deactivation model has correlation to the catalyst type and deactivation cause, which includes sulfur poisoning model, sintering model, surface oxidation model, etc. General deactivation model is accurate and easy to establish, but is relatively rough,which is suitable for production management and process simulation. The reaction mechanism based model is complicated to establish and can only be applied to specific catalyst. The future development of Fischer-Tropsch deactivation model is to combine the two kinds of models together and to investigate the meaning of the parameters in general deactivation models through the view of deactivation mechanism.
引文
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[13]MOODLEY D J,VAN DE LOOSDRECHT J,SAIB A M,et al Carbon deposition as a deactivation mechanism of cobalt-based FischerTropsch synthesis catalysts under realistic conditons[J].Applied Catalysis A:General,2009,354:102-110.
[14]CHO W,YU H,AHN W S,et al.Synthesis gas production process for natural gas conversion over Ni-La2O3catalyst[J].Journal of Industrial and Engineering Chemistry,2015,28:229-235.
[15]BECHARA R,BALLOY D,VANHOVE D.Catalytic properties of Co/Al2O3system for hydrocarbon synthesis[J].Applied Catalysis A:General,2001,207:343-353.
[16]LIU Z T,LI Y W,ZHOU J L,et al.Deactivation model of FischerTropsch synthesis over an Fe-Cu-K commercial catalyst[J].Applied Catalysis A:General,1997,161:137-151.
[17]SADEQZADEH M,CHAMBREY S,HONG J P,et al.Effect of different reaction conditions on the deactivation of alumina-supported cobalt Fischer-Tropsch catalysts in a milli-fixed-bed reactor:experiments and modeling[J].Industrial Engineering Chemistry Research,2014,53:6913-6922.
[18]YATES I C,SATTERFIELD C N.Intrinsic kinetics of the FischerTropsch synthesis on a cobalt catalyst[J].Energy Fuels,1991,5(1):168-173.
[19]SADEQZADEH M,HONG J P,FONGARLAND P,et al.Mechanistic modeling of cobalt based catalyst sintering in a fixed bed reactor under different conditions of Fischer-Tropsch synthesis[J].Industrial Engineering Chemistry Research,2012,51(27):11955-11964.
[2]TAVASOLI A,ABBASLOU R M M,DALAI A K.Deactivation behavior of ruthenium promoted Co/γ-Al2O3catalysts in FischerTropsch synthesis[J].Applied Catalysis A:General,2008,346:58-64.
[3]ELIASON S A,BARTHOLOMEW C H.Catalyst deactivation[M].Elsevier Science Publishers B.V.,1991:211-218.
[4]ARGYLE M D,FROST T S,BARTHOLOMEW C H.Cobalt FischerTropsch catalyst deactivation modeled using generalized power law expressions[J].Topics in Catalysis,2014,57:415-429.
[5]ELIASON S A,BARTHOLOMEW C H.Reaction and deactivation kinetics for Fischer-Tropsch synthesis on unpromoted and potassiumpromoted iron catalysts[J].Applied Catalysis A:General,1999,186:229-243.
[6]POUR A N,HOUSAINDOKHT M R,TAYYARI S F,et al.Deactivation studies of Fischer-Tropsch synthesis on nano-structured iron catalyst[J].Journal of Molecular Catalysis A:Chemical,2010,330:112-120.
[7]POUR A N,HOSAINI E,FEYZI M.Prediction of cobalt particle size during catalyst deactivation in Fischer-Tropsch synthesis[J].Journal of the Iranian Chemical Society,2016,13:139-147.
[8]ATASHI H,VEISKARAMI S.Determination of the deactivation model of iron-potassium/γ-Al2O3catalyst in a fixed bed reactor[J].Physical Chemistry Research,2018,6:365-375.
[9]KHORASHADIZADEH M,ATASHI H.Modeling the kinetics of cobalt Fischer-Tropsch catalyst deactivation trends through an innovative modified Weibull distribution[J].Physical Chemistry Chemical Physics,2017,19:19252-1921.
[10]BAE J W,KIM S M,PARK S J,et al.Deactivation by filamentous carbon formation on Co/aluminum phosphate during Fischer-Tropsch synthesis[J].Industrial Engineering Chemistry Research,2009,48(6):3228-3233.
[11]SAIB A M,BORGNA A,DE LOOSDRECHT J V,et al.XANES study of the susceptibility of nano-sized cobalt crystallites to oxidation during realistic Fischer-Tropsch synthesis[J].Applied Catalysis A:General,2006,312:12-19.
[12]KHORASHADIZADEH M,ATASHI H.Toward the development of a robust kinetic model for the cobalt Fischer-Tropsch catalyst lifetime using a novel sigmoidal pattern[J].Physical Chemistry Research,2018,6(1):173-192.
[13]MOODLEY D J,VAN DE LOOSDRECHT J,SAIB A M,et al Carbon deposition as a deactivation mechanism of cobalt-based FischerTropsch synthesis catalysts under realistic conditons[J].Applied Catalysis A:General,2009,354:102-110.
[14]CHO W,YU H,AHN W S,et al.Synthesis gas production process for natural gas conversion over Ni-La2O3catalyst[J].Journal of Industrial and Engineering Chemistry,2015,28:229-235.
[15]BECHARA R,BALLOY D,VANHOVE D.Catalytic properties of Co/Al2O3system for hydrocarbon synthesis[J].Applied Catalysis A:General,2001,207:343-353.
[16]LIU Z T,LI Y W,ZHOU J L,et al.Deactivation model of FischerTropsch synthesis over an Fe-Cu-K commercial catalyst[J].Applied Catalysis A:General,1997,161:137-151.
[17]SADEQZADEH M,CHAMBREY S,HONG J P,et al.Effect of different reaction conditions on the deactivation of alumina-supported cobalt Fischer-Tropsch catalysts in a milli-fixed-bed reactor:experiments and modeling[J].Industrial Engineering Chemistry Research,2014,53:6913-6922.
[18]YATES I C,SATTERFIELD C N.Intrinsic kinetics of the FischerTropsch synthesis on a cobalt catalyst[J].Energy Fuels,1991,5(1):168-173.
[19]SADEQZADEH M,HONG J P,FONGARLAND P,et al.Mechanistic modeling of cobalt based catalyst sintering in a fixed bed reactor under different conditions of Fischer-Tropsch synthesis[J].Industrial Engineering Chemistry Research,2012,51(27):11955-11964.
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