Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical prope...Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.展开更多
A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with t...A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with their counterpart Co-impregnated zeolite-based catalysts.Successful transformation of solid raw materials to targeted zeolite was confirmed by XRD,SEM,STEM,and N2 physisorption analysis.An in-depth study of acidic strength and acidic site distribution was conducted by NH3-TPD and Py-IR spectroscopy.Acidic strength showed a pivotal role in defining product range.Co@S1,with the weakest acidic strength of silicalite-1 among three types of zeolites,evaded over-cracking of product and exhibited the highest gasoline and isoparaffin selectivity(≈70%and 30.7%,respectively).Moreover,the solvent-free raw material grinding route for zeolite synthesis accompanies several advantages like the elimination of production of wastewater,high product yield within confined crystallization space,and elimination of safety concerns regarding high pressure due to the absence of the solvent.Facileness and easiness of the solvent-free synthesis route together with promising catalytic performance strongly support its application on the industrial scale.展开更多
Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structu...Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structure characterization indicates that the cobalt‐support interaction has a great influence on the Co2C morphology and catalytic performance.The CNT support facilitates the formation of a CoMn composite oxide during calcination,and Co2C nanoprisms were observed in the spent catalysts,resulting in a product distribution that greatly deviates from the classical Anderson‐Schulz‐Flory(ASF)distribution,where only 2.4 C%methane was generated.The Co3O4 phase for SiO2‐andγ‐Al2O3‐supported catalysts was observed in the calcined sample.After reduction,CoO,MnO,and low‐valence CoMn composite oxide were generated in theγ‐Al2O3‐supported sample,and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst.However,only separated phases of CoO and MnO were found in the reduced sample supported by SiO2,and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms.The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C%and 12.0 C%of theγ‐Al2O3‐and SiO2‐supported catalysts,respectively.These results suggest that a relatively weak cobalt‐support interaction is necessary for the formation of the CoMn composite oxide during calcination,which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.展开更多
Fischer-Tropsch synthesis （FTS） is an increasingly important approach for producing liquid fuels and chemicals via syngas-that is, synthesis gas, a mixture of carbon monoxide and hydrogen-generated from coal, natura...Fischer-Tropsch synthesis （FTS） is an increasingly important approach for producing liquid fuels and chemicals via syngas-that is, synthesis gas, a mixture of carbon monoxide and hydrogen-generated from coal, natural gas, or biomass. In FTS, dispersed transition metal nanoparticles are used to catalyze the reactions underlying the formation of carbon-carbon bonds. Catalytic activity and selectivity are strongly correlated with the electronic and geometric structure of the nanoparticles, which depend on the particle size, morphology, and crystallographic phase of the nanoparticles. In this article, we review recent works dealing with the aspects of bulk and surface sensitivity of the FTS reaction. Understanding the different catalytic behavior in more detail as a function of these parameters may guide the design of more active, selective, and stable FTS catalysts.展开更多
The widespread utilization of fossil fuels has caused an associated increase in CO_(2) emissions over the past few decades,which has resulted in global warming and ocean acidification.CO hydrogenation(Fischer‐Tropsch...The widespread utilization of fossil fuels has caused an associated increase in CO_(2) emissions over the past few decades,which has resulted in global warming and ocean acidification.CO hydrogenation(Fischer‐Tropsch synthesis,FTS)is considered a significant route for the production of liquid fuels and chemicals from nonpetroleum sources to meet worldwide demand.Conversion of CO_(2) with renewable H_(2) into valuable hydrocarbons is beneficial for reducing dependence on fossil fuels and mitigating the negative effects of high CO_(2) concentrations in the atmosphere.Iron‐based catalysts exhibit superior catalytic performance in both FTS and CO_(2) hydrogenation to value‐added hydrocarbons.The abundance and low cost of iron‐based catalysts also promote their wide application in CO_(x) hydrogenation.This paper provides a comprehensive overview of the significant developments in the application of iron‐based catalysts in these two fields.The active phases,promoter effect,and support of iron‐based catalysts are discussed in the present paper.Based on understanding of these three essential aspects,we also cover recent advances in the design and preparation of novel iron‐based catalysts for FTS and CO_(2) hydrogenation.Current challenges and future catalytic applications are also outlined.展开更多
Fischer‐Tropsch synthesis(FTS)has the potential to be a powerful strategy for producing liquid fuels from syngas if highly selective catalysts can be developed.Herein,a series of iron nanoparticle catalysts encapsula...Fischer‐Tropsch synthesis(FTS)has the potential to be a powerful strategy for producing liquid fuels from syngas if highly selective catalysts can be developed.Herein,a series of iron nanoparticle catalysts encapsulated by nitrogen‐doped graphitic carbon were prepared by a one‐step pyrolysis of a ferric L‐glutamic acid complex.The FeC‐800 catalyst pyrolyzed at 800°C showed excellent catalytic activity(239.4μmolCO gFe–1 s–1),high C5–C11 selectivity(49%),and good stability in FTS.The high dispersion of ferric species combined with a well‐encapsulated structure can effectively inhibit the migration of iron nanoparticles during the reaction process,which is beneficial for high activity and good stability.The nitrogen‐doped graphitic carbon shell can act as an electron donor to the iron particles,thus promoting CO activation and expediting the formation of Fe5C2,which is the key factor for obtaining high C5–C11 selectivity.展开更多
A bifunctional Co modified Fe3O4-Mn catalyst was prepared for Fischer-Tropsch synthesis (FTS). The influence of Co loading on the synergistic effect of Fe-Co as well as FTS performance over Fe1CoxMn1 catalysts was stu...A bifunctional Co modified Fe3O4-Mn catalyst was prepared for Fischer-Tropsch synthesis (FTS). The influence of Co loading on the synergistic effect of Fe-Co as well as FTS performance over Fe1CoxMn1 catalysts was studied. Incorporation of Co species into the Fe3O4-Mn catalyst promoted the reduction of iron oxides, increasing iron active sites during FTS. Moreover, the adding of Co species enhanced the electron transfer from Fe to Co metal, which strengthened the synergistic effect of Fe-Co, improving the catalytic performance. The Fe1CoxMn1 catalyst with higher Co loading promoted further the hydrogenation ability, favoring the shifting of the product distribution towards shorter hydrocarbons. Under optimized conditions of 280℃, 2.0 MPa and 3000 h-1, the highest yield of liquid fuels was obtained for the Fe1Co1Mn1 catalyst.展开更多
A model for a bubble column slurry reactor is developed based on the experiment of Rhenpreussen Koppers demonstration plant for slurry phase Fischer-Tropsch synthesis reported by Koelble et al. This model is applicabl...A model for a bubble column slurry reactor is developed based on the experiment of Rhenpreussen Koppers demonstration plant for slurry phase Fischer-Tropsch synthesis reported by Koelble et al. This model is applicable to the operation in the churn-turbulent regime and incorporates the information on the bubble size. The axial dispersion model is adopted to describe the flow characteristics of the Fischer-Tropsch slurry reactor. With the model developed, simulations are performed to identify the steady state behavior of a Fischer-Tropsch slurry reactor of commercial size. Predictions of the two-bubble class model is compared with that of the conventional single- bubble class model. The results show that under a variety of conditions, the two-bubble class model gives results different from those for the single-bubble class model.展开更多
The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes,especially eco-friendly and intrinsically safe processes.The idea is to improve the selectivity,activ...The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes,especially eco-friendly and intrinsically safe processes.The idea is to improve the selectivity,activity,and stability of the catalyst in an appropriate reactor.Therefore,it is of great academic and industrial significance to conduct in-situ characterization of a working catalyst while testing its catalytic performance.This is beneficial for a comprehensive study on the dynamic evolution of the catalyst structure under real conditions,deepening the understanding of the structure-performance relationship of catalysts,and providing a scientific basis for the development of future generation catalytic technology.Thus far,it is still a great challenge to realize full life cycle characterization of heterogeneous catalysts from catalyst formation and function to deactivation under real world conditions.In this mini review,we summarize the characterization strategies for heterogeneous catalysts,using zeolite,metal,and metal oxide catalysts as typical examples.The research strategies for the approximation of industrial conditions,multi-scale in-situ characterization devices,and computational modeling of realistic conditions should provide insight for the research and development of industrial catalysis.展开更多
On the basis of the global CO consumption rate model, the lumped product distribution model and the sedimenta- tion-dispersion model of a catalyst, a steady-state, one-dimensional mathematical model of the slurry bubb...On the basis of the global CO consumption rate model, the lumped product distribution model and the sedimenta- tion-dispersion model of a catalyst, a steady-state, one-dimensional mathematical model of the slurry bubble column reactor for Fischer-Tropsch synthesis were established. The mathematical simulation of the slurry bubble column reactor for Fischer-Tropsch synthesis was carried out under the following typical industrial operating conditions： temperature 230 ℃, pressure 3.0 MPa, gas flow 5x 105 m3/h, catalyst content in slurry phase 30%, reactor diameter 5.0 m and the composition of feed gas： y（H2）=0.60, y（CO）=0.30, y（N2）=0.10. The influences of operating pressure, temperature and re（HE）Ira（CO） in feed gas on the reactor＇s reaction performance were simulated.展开更多
CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the ...CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the alkali metals on the physicochemical properties of the CoCu/TiO_2 catalysts and the catalytic performance for CO_2 hydrogenation to long-chain hydrocarbons（C_（5＋））were investigated in this work. According to the characterization of the catalysts based on X-ray photoelectron spectroscopy, X-ray diffraction, CO_2 temperature-programmed desorption（TPD）, and H_2-TPD, the introduction of alkali metals could increase the CO_2 adsorption and decrease the H_2 chemisorption, which could suppress the formation of CH_4, enhance the production of C_（5＋）, and decrease the hydrogenation activity. Among all the promoters, the Na-modified CoCu/TiO_2 catalyst provided the maximum C_（5＋） yield of 5.4%, with a CO_2 conversion of 18.4% and C_（5＋） selectivity of42.1%, because it showed the strongest basicity and a slight decrease in the amount of H_2 desorption;it also exhibited excellent catalytic stability of more than 200 h.展开更多
Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means...Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means of X-ray diffraction （XRD）, temperature programmed reduction （TPR）, hydrogen temperature programmed desorption （H2-TPD） and O2 titration. Co-support compound formation can be detected in catalyst system by XRD. For the Co/Al2O3 catalysts with low cobalt loading, CoAl2O4 phase appears visibly. Two different reduction regions can be presented for Co/Al2O3 catalysts, which belong to Co3O4 crystallites （reduction at 320 ℃） and cobalt oxide-alumina interaction species （reduction at above 400 ℃）. Increasing Co loading results in the increase of Co3O4 crystallite size. The reduced Co/Al2O3 catalysts have two adsorption sites, and cobalt loading greatly influences the adsorption behavior. With the increase of cobalt loading, the amount of low temperature adsorption is increased, the amount of high temperature adsorption is decreased, and the percentage reduction and cobalt crystallite size are increased.展开更多
The diffusion and reaction phenomenon in a Fe-based catalyst pellet for Fischer-Tropsch synthesis was studied. It was considered that the pores of catalyst pellets were full of liquid wax under Fischer-Tropsch synthes...The diffusion and reaction phenomenon in a Fe-based catalyst pellet for Fischer-Tropsch synthesis was studied. It was considered that the pores of catalyst pellets were full of liquid wax under Fischer-Tropsch synthesis conditions. The re- actants diffused from the bulk gas phase to the external surface of the pellet, and then the reactants diffused through the wax inside the pellet and reacted on the internal surface formed along the pore passages of the pellet. On the basis of reaction kinetics and double a-ASF product distribution model, a diffusion and reaction model of catalyst pellet was established. The effects of diffusion and reaction interaction in a catalyst pellet, the bulk temperature, the reaction pressure and the pellet size on the reactivity were further investigated. The relationship between the internal diffusion effectiveness factor of spherical catalyst pellet and the Thiele modulus were also discussed. The bulk temperature and pellet size have significant effects on the reactivity, while the pressure shows only a slight influence on the reactivity. The internal diffusion effectiveness factor decreases with an increasing Thiele modulus.展开更多
A brief review of Fischer-Tropsch synthesis specially in slurry reactors is presented, covering reaction kinetics, activity and selectivity of catalysts, product distribution, effects of process parameters, mass trans...A brief review of Fischer-Tropsch synthesis specially in slurry reactors is presented, covering reaction kinetics, activity and selectivity of catalysts, product distribution, effects of process parameters, mass transfer and solubility of gas. Some important aspects of further research are proposed for improving both theories and production.展开更多
We first obtained by impregnating of the microsphere magnetic catalyst with salts of Thorium and of Uranium and examined the X-ray thorium-uranium catalyst for Fischer-Tropsch synthesis. Introduction in catalyst addit...We first obtained by impregnating of the microsphere magnetic catalyst with salts of Thorium and of Uranium and examined the X-ray thorium-uranium catalyst for Fischer-Tropsch synthesis. Introduction in catalyst additive thorium and uranium ions and manganese improves the thermal stability of the magnetic microsphere catalyst.展开更多
On August 25,2015 the CFHL technology for hydroupgrading of syncrude obtained from low-temperature Fischer-Tropsch synthesis had been successfully applied on the first in China 1.0 Mt/a indirect coal liquefaction unit.
Photocatalytic reduction of carbon monoxide(CO)is a promising route to the production of high-value chemicals and fuels,as a supplement to high energy-input Fischer-Tropsch synthesis(FTS)and a key step in direct photo...Photocatalytic reduction of carbon monoxide(CO)is a promising route to the production of high-value chemicals and fuels,as a supplement to high energy-input Fischer-Tropsch synthesis(FTS)and a key step in direct photo/electro-reduction CO_(2) to multi-carbon products.However,many current research efforts for high-efficiency FTS/CO_(2) reduction mainly focus on the metal-based catalysts,while metal-free and solar-driven photocatalysts are rarely explored.Here,by means of Lewis acid sites,a metal-free composite photocatalyst for CO reduction,namely boron(B)doped-graphene/g-C_(3)N_(4) heterostructure,is proposed.First-principles calculations show that the dopants(B)as catalytic sites can effectively capture and activate CO molecules and reduce CO to CH_(3)OH and CH_(4) in different doping content.It is worth noting that C_(2) products,i.e.,C_(2)H_(5)OH,can be produced with low free energy barriers on paradoped graphene/g-C_(3)N_(4).Meanwhile,the competitive hydrogen evolution reaction(HER)can be greatly suppressed,leading to the high selectivity of CO reduction.Moreover,the formation of a built-in electric field in heterostructure enhances the separation of photogenerated electrons and holes,which further accelerates the transmission of photogenerated electrons to the catalytic sites and improves the reaction efficiency.Overall,this work not only proposes a new strategy from a new perspective to solve problems of high energy consumption and low selectivity of FTS,but also provides a tandem strategy to solve problems of CO_(2) to multi-carbon products.展开更多
The intrinsic strains at the confinement interface of iron carbide with graphene play important roles in the catalytic Fischer-Tropsch synthesis.In this study,we performed theoretical study of the biaxial strain effec...The intrinsic strains at the confinement interface of iron carbide with graphene play important roles in the catalytic Fischer-Tropsch synthesis.In this study,we performed theoretical study of the biaxial strain effects on the CO adsorption and dissociation on the Fe_(2)C(121)surface covered by graphene(Fe_(2)C@graphene).By varying the lattice strains within a range of±5%,the apparent energy barriers(E_(a,app))correlate with the adsorption energies(E_(ad))in nonlinear scaling relations for the direct and H-assisted CO dissociation at the Fe_(2)C active sites,which is normal Br∅nsted-Evans-Polanyi relation for those at the graphene sites.The nonlinear scaling relations can be interpreted by the strain effects on the confinement distances in the adsorption and transition states.This study provides a deep understanding of the intrinsic strain effects of Fe_(2)C@graphene for CO activation.展开更多
基金supported by the Key Project of Natural Science Foundation of Ningxia(NZ13010)the National Natural Science Foundation of China(21366025)~~
文摘Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.
基金the financial support from the Zhejiang Province Natural Science Foundation(LY19B060001)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(2018-K25)the Foundation of Zhejiang University of Science and Technology(2019QN18,2019QN23)~~
文摘A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with their counterpart Co-impregnated zeolite-based catalysts.Successful transformation of solid raw materials to targeted zeolite was confirmed by XRD,SEM,STEM,and N2 physisorption analysis.An in-depth study of acidic strength and acidic site distribution was conducted by NH3-TPD and Py-IR spectroscopy.Acidic strength showed a pivotal role in defining product range.Co@S1,with the weakest acidic strength of silicalite-1 among three types of zeolites,evaded over-cracking of product and exhibited the highest gasoline and isoparaffin selectivity(≈70%and 30.7%,respectively).Moreover,the solvent-free raw material grinding route for zeolite synthesis accompanies several advantages like the elimination of production of wastewater,high product yield within confined crystallization space,and elimination of safety concerns regarding high pressure due to the absence of the solvent.Facileness and easiness of the solvent-free synthesis route together with promising catalytic performance strongly support its application on the industrial scale.
文摘Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structure characterization indicates that the cobalt‐support interaction has a great influence on the Co2C morphology and catalytic performance.The CNT support facilitates the formation of a CoMn composite oxide during calcination,and Co2C nanoprisms were observed in the spent catalysts,resulting in a product distribution that greatly deviates from the classical Anderson‐Schulz‐Flory(ASF)distribution,where only 2.4 C%methane was generated.The Co3O4 phase for SiO2‐andγ‐Al2O3‐supported catalysts was observed in the calcined sample.After reduction,CoO,MnO,and low‐valence CoMn composite oxide were generated in theγ‐Al2O3‐supported sample,and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst.However,only separated phases of CoO and MnO were found in the reduced sample supported by SiO2,and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms.The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C%and 12.0 C%of theγ‐Al2O3‐and SiO2‐supported catalysts,respectively.These results suggest that a relatively weak cobalt‐support interaction is necessary for the formation of the CoMn composite oxide during calcination,which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.
基金financial support by NWO-VICI and NWO-TOP grants awarded to Emiel J.M.Hensen
文摘Fischer-Tropsch synthesis （FTS） is an increasingly important approach for producing liquid fuels and chemicals via syngas-that is, synthesis gas, a mixture of carbon monoxide and hydrogen-generated from coal, natural gas, or biomass. In FTS, dispersed transition metal nanoparticles are used to catalyze the reactions underlying the formation of carbon-carbon bonds. Catalytic activity and selectivity are strongly correlated with the electronic and geometric structure of the nanoparticles, which depend on the particle size, morphology, and crystallographic phase of the nanoparticles. In this article, we review recent works dealing with the aspects of bulk and surface sensitivity of the FTS reaction. Understanding the different catalytic behavior in more detail as a function of these parameters may guide the design of more active, selective, and stable FTS catalysts.
文摘The widespread utilization of fossil fuels has caused an associated increase in CO_(2) emissions over the past few decades,which has resulted in global warming and ocean acidification.CO hydrogenation(Fischer‐Tropsch synthesis,FTS)is considered a significant route for the production of liquid fuels and chemicals from nonpetroleum sources to meet worldwide demand.Conversion of CO_(2) with renewable H_(2) into valuable hydrocarbons is beneficial for reducing dependence on fossil fuels and mitigating the negative effects of high CO_(2) concentrations in the atmosphere.Iron‐based catalysts exhibit superior catalytic performance in both FTS and CO_(2) hydrogenation to value‐added hydrocarbons.The abundance and low cost of iron‐based catalysts also promote their wide application in CO_(x) hydrogenation.This paper provides a comprehensive overview of the significant developments in the application of iron‐based catalysts in these two fields.The active phases,promoter effect,and support of iron‐based catalysts are discussed in the present paper.Based on understanding of these three essential aspects,we also cover recent advances in the design and preparation of novel iron‐based catalysts for FTS and CO_(2) hydrogenation.Current challenges and future catalytic applications are also outlined.
文摘Fischer‐Tropsch synthesis(FTS)has the potential to be a powerful strategy for producing liquid fuels from syngas if highly selective catalysts can be developed.Herein,a series of iron nanoparticle catalysts encapsulated by nitrogen‐doped graphitic carbon were prepared by a one‐step pyrolysis of a ferric L‐glutamic acid complex.The FeC‐800 catalyst pyrolyzed at 800°C showed excellent catalytic activity(239.4μmolCO gFe–1 s–1),high C5–C11 selectivity(49%),and good stability in FTS.The high dispersion of ferric species combined with a well‐encapsulated structure can effectively inhibit the migration of iron nanoparticles during the reaction process,which is beneficial for high activity and good stability.The nitrogen‐doped graphitic carbon shell can act as an electron donor to the iron particles,thus promoting CO activation and expediting the formation of Fe5C2,which is the key factor for obtaining high C5–C11 selectivity.
基金supported by International Cooperation and Exchange Program of the National Natural Science Foundation of China(No.51861145102)Science and Technology Program of Shenzhen(No.JCYJ20180302153928437)Fundamental Research Fund for the Central Universities(No.2042019kf0221)
文摘A bifunctional Co modified Fe3O4-Mn catalyst was prepared for Fischer-Tropsch synthesis (FTS). The influence of Co loading on the synergistic effect of Fe-Co as well as FTS performance over Fe1CoxMn1 catalysts was studied. Incorporation of Co species into the Fe3O4-Mn catalyst promoted the reduction of iron oxides, increasing iron active sites during FTS. Moreover, the adding of Co species enhanced the electron transfer from Fe to Co metal, which strengthened the synergistic effect of Fe-Co, improving the catalytic performance. The Fe1CoxMn1 catalyst with higher Co loading promoted further the hydrogenation ability, favoring the shifting of the product distribution towards shorter hydrocarbons. Under optimized conditions of 280℃, 2.0 MPa and 3000 h-1, the highest yield of liquid fuels was obtained for the Fe1Co1Mn1 catalyst.
文摘A model for a bubble column slurry reactor is developed based on the experiment of Rhenpreussen Koppers demonstration plant for slurry phase Fischer-Tropsch synthesis reported by Koelble et al. This model is applicable to the operation in the churn-turbulent regime and incorporates the information on the bubble size. The axial dispersion model is adopted to describe the flow characteristics of the Fischer-Tropsch slurry reactor. With the model developed, simulations are performed to identify the steady state behavior of a Fischer-Tropsch slurry reactor of commercial size. Predictions of the two-bubble class model is compared with that of the conventional single- bubble class model. The results show that under a variety of conditions, the two-bubble class model gives results different from those for the single-bubble class model.
文摘The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes,especially eco-friendly and intrinsically safe processes.The idea is to improve the selectivity,activity,and stability of the catalyst in an appropriate reactor.Therefore,it is of great academic and industrial significance to conduct in-situ characterization of a working catalyst while testing its catalytic performance.This is beneficial for a comprehensive study on the dynamic evolution of the catalyst structure under real conditions,deepening the understanding of the structure-performance relationship of catalysts,and providing a scientific basis for the development of future generation catalytic technology.Thus far,it is still a great challenge to realize full life cycle characterization of heterogeneous catalysts from catalyst formation and function to deactivation under real world conditions.In this mini review,we summarize the characterization strategies for heterogeneous catalysts,using zeolite,metal,and metal oxide catalysts as typical examples.The research strategies for the approximation of industrial conditions,multi-scale in-situ characterization devices,and computational modeling of realistic conditions should provide insight for the research and development of industrial catalysis.
文摘On the basis of the global CO consumption rate model, the lumped product distribution model and the sedimenta- tion-dispersion model of a catalyst, a steady-state, one-dimensional mathematical model of the slurry bubble column reactor for Fischer-Tropsch synthesis were established. The mathematical simulation of the slurry bubble column reactor for Fischer-Tropsch synthesis was carried out under the following typical industrial operating conditions： temperature 230 ℃, pressure 3.0 MPa, gas flow 5x 105 m3/h, catalyst content in slurry phase 30%, reactor diameter 5.0 m and the composition of feed gas： y（H2）=0.60, y（CO）=0.30, y（N2）=0.10. The influences of operating pressure, temperature and re（HE）Ira（CO） in feed gas on the reactor＇s reaction performance were simulated.
文摘CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the alkali metals on the physicochemical properties of the CoCu/TiO_2 catalysts and the catalytic performance for CO_2 hydrogenation to long-chain hydrocarbons（C_（5＋））were investigated in this work. According to the characterization of the catalysts based on X-ray photoelectron spectroscopy, X-ray diffraction, CO_2 temperature-programmed desorption（TPD）, and H_2-TPD, the introduction of alkali metals could increase the CO_2 adsorption and decrease the H_2 chemisorption, which could suppress the formation of CH_4, enhance the production of C_（5＋）, and decrease the hydrogenation activity. Among all the promoters, the Na-modified CoCu/TiO_2 catalyst provided the maximum C_（5＋） yield of 5.4%, with a CO_2 conversion of 18.4% and C_（5＋） selectivity of42.1%, because it showed the strongest basicity and a slight decrease in the amount of H_2 desorption;it also exhibited excellent catalytic stability of more than 200 h.
文摘Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means of X-ray diffraction （XRD）, temperature programmed reduction （TPR）, hydrogen temperature programmed desorption （H2-TPD） and O2 titration. Co-support compound formation can be detected in catalyst system by XRD. For the Co/Al2O3 catalysts with low cobalt loading, CoAl2O4 phase appears visibly. Two different reduction regions can be presented for Co/Al2O3 catalysts, which belong to Co3O4 crystallites （reduction at 320 ℃） and cobalt oxide-alumina interaction species （reduction at above 400 ℃）. Increasing Co loading results in the increase of Co3O4 crystallite size. The reduced Co/Al2O3 catalysts have two adsorption sites, and cobalt loading greatly influences the adsorption behavior. With the increase of cobalt loading, the amount of low temperature adsorption is increased, the amount of high temperature adsorption is decreased, and the percentage reduction and cobalt crystallite size are increased.
基金Financial support from the National Basic Research Program of China(973 Program,2010CB736203)
文摘The diffusion and reaction phenomenon in a Fe-based catalyst pellet for Fischer-Tropsch synthesis was studied. It was considered that the pores of catalyst pellets were full of liquid wax under Fischer-Tropsch synthesis conditions. The re- actants diffused from the bulk gas phase to the external surface of the pellet, and then the reactants diffused through the wax inside the pellet and reacted on the internal surface formed along the pore passages of the pellet. On the basis of reaction kinetics and double a-ASF product distribution model, a diffusion and reaction model of catalyst pellet was established. The effects of diffusion and reaction interaction in a catalyst pellet, the bulk temperature, the reaction pressure and the pellet size on the reactivity were further investigated. The relationship between the internal diffusion effectiveness factor of spherical catalyst pellet and the Thiele modulus were also discussed. The bulk temperature and pellet size have significant effects on the reactivity, while the pressure shows only a slight influence on the reactivity. The internal diffusion effectiveness factor decreases with an increasing Thiele modulus.
文摘A brief review of Fischer-Tropsch synthesis specially in slurry reactors is presented, covering reaction kinetics, activity and selectivity of catalysts, product distribution, effects of process parameters, mass transfer and solubility of gas. Some important aspects of further research are proposed for improving both theories and production.
文摘We first obtained by impregnating of the microsphere magnetic catalyst with salts of Thorium and of Uranium and examined the X-ray thorium-uranium catalyst for Fischer-Tropsch synthesis. Introduction in catalyst additive thorium and uranium ions and manganese improves the thermal stability of the magnetic microsphere catalyst.
文摘On August 25,2015 the CFHL technology for hydroupgrading of syncrude obtained from low-temperature Fischer-Tropsch synthesis had been successfully applied on the first in China 1.0 Mt/a indirect coal liquefaction unit.
基金supported by the National Natural Science Foundation of China(22033002,21525311,21773027,21703032,and 21973011)the China Postdoctoral Science Foundation(2020M681450)。
文摘Photocatalytic reduction of carbon monoxide(CO)is a promising route to the production of high-value chemicals and fuels,as a supplement to high energy-input Fischer-Tropsch synthesis(FTS)and a key step in direct photo/electro-reduction CO_(2) to multi-carbon products.However,many current research efforts for high-efficiency FTS/CO_(2) reduction mainly focus on the metal-based catalysts,while metal-free and solar-driven photocatalysts are rarely explored.Here,by means of Lewis acid sites,a metal-free composite photocatalyst for CO reduction,namely boron(B)doped-graphene/g-C_(3)N_(4) heterostructure,is proposed.First-principles calculations show that the dopants(B)as catalytic sites can effectively capture and activate CO molecules and reduce CO to CH_(3)OH and CH_(4) in different doping content.It is worth noting that C_(2) products,i.e.,C_(2)H_(5)OH,can be produced with low free energy barriers on paradoped graphene/g-C_(3)N_(4).Meanwhile,the competitive hydrogen evolution reaction(HER)can be greatly suppressed,leading to the high selectivity of CO reduction.Moreover,the formation of a built-in electric field in heterostructure enhances the separation of photogenerated electrons and holes,which further accelerates the transmission of photogenerated electrons to the catalytic sites and improves the reaction efficiency.Overall,this work not only proposes a new strategy from a new perspective to solve problems of high energy consumption and low selectivity of FTS,but also provides a tandem strategy to solve problems of CO_(2) to multi-carbon products.
基金supported by the National Natural Science Foundation of China(21972170,22072184)the Fund for Academic Innovation Teams of South-Central Minzu University(XTZ24013)
文摘The intrinsic strains at the confinement interface of iron carbide with graphene play important roles in the catalytic Fischer-Tropsch synthesis.In this study,we performed theoretical study of the biaxial strain effects on the CO adsorption and dissociation on the Fe_(2)C(121)surface covered by graphene(Fe_(2)C@graphene).By varying the lattice strains within a range of±5%,the apparent energy barriers(E_(a,app))correlate with the adsorption energies(E_(ad))in nonlinear scaling relations for the direct and H-assisted CO dissociation at the Fe_(2)C active sites,which is normal Br∅nsted-Evans-Polanyi relation for those at the graphene sites.The nonlinear scaling relations can be interpreted by the strain effects on the confinement distances in the adsorption and transition states.This study provides a deep understanding of the intrinsic strain effects of Fe_(2)C@graphene for CO activation.
