Iron-based catalysts encapsulated by nitrogen-doped graphitic carbon for selective synthesis of liquid fuels through the Fischer-Tropsch process

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.

Fischer–Tropsch synthesis over iron catalysts with corncob-derived promoters

A sustainable strategy for Fischer–Tropsch iron catalysts is successfully achieved by embedding of synergistic promoters from a renewable resource, corncob. The iron-based catalysts, named as 'corncob-driven'catalysts, are composed of iron species supported on carbon as primary active components and various minerals(K, Mg, Ca, and Si, etc.) as promoters. The corncob-driven catalysts are facilely synthesized by a one-pot hydrothermal treatment under mild conditions. The characterization results indicate that the formation of iron carbides from humboldtine is clearly enhanced and the morphology of catalyst particles tends to be more regular microspheres after adding corncob. It is observed that the optimized corncob-driven catalyst exhibits a higher conversion than without promoters' catalyst in Fischer–Tropsch synthesis(ca. 73% vs. ca. 49%). More importantly, a synergistic effect exists in multiple promoters from corncob that can enhance heavy hydrocarbons selectivity and lower CO_2 selectivity, obviously different from the catalyst with promoters from chemicals. The proposed synthesis route of corncob-driven catalysts provides new strategies for the utilization of renewable resources and elimination of environmental pollutants from chemical promoters.

Effects of K and Mn promoters over Fe2O3 on Fischer–Tropsch synthesis

Structural and compositional design of core-shell structure is an effective strategy towards enhanced catalysis.Herein,amorphous MnO2 nanosheets and K+-intercalated layered MnO2 nanosheets are controllably assembled over Fe2O3 spindles,in which the MnO2 nanosheets are perpendicularly anchored to the surface of Fe2O3.Such a core shell structure contributes to a high specific surface area and abundant pore channels on the surface of catalysts.In addition,the existence of K+provides large numbers of basic sites and restrains the formation of unpleasant(Fe1-xMnx)3O4.Benefiting from the merits in structure and composition,CO adsorption is enhanced and remaining time of intermediates is prolonged on the surfaces of catalysts during the Fischer–Tropsch synthesis(FTS),facilitating to the formation of active iron carbides and C–C coupling reactions.Resultantly,the Fe2O3@K+-Mn O2 shows both a high CO conversion of 82.3%and a high C5+ selectivity of 73.1%.The present study provides structural and compositional rationales on design high-performance catalysts towards FTS.

Fabrication of K-promoted iron/carbon nanotubes composite catalysts for the Fischer–Tropsch synthesis of lower olefins

K-promoted iron/carbon nanotubes composite（i.e., Fe K-OX） was prepared by a redox reaction between carbon nanotubes and K2FeO4followed by thermal treatments on a purpose as the Fischer–Tropsch catalyst for the direct conversion of syngas to lower olefins. Its catalytic behaviors were compared with those of the other two Fe-IM and Fe K-IM catalysts prepared by impregnation method followed by thermal treatments. The novel Fe K-OX composite catalyst is found to exhibit higher hydrocarbon selectivity,lower olefins selectivity and chain growth probability as well as better stability. The catalyst structureperformance relationship has been established using multiple techniques including XRD, Raman, TEM and EDS elemental mapping. In addition, effects of additional potassium into the Fe K-OX composite catalyst on the FTO performance were also investigated and discussed. Additional potassium promoters further endow the catalysts with higher yield of lower olefins. These results demonstrated that the introduction method of promoters and iron species plays a crucial role in the design and fabrication of highly active,selective and stable iron-based composite catalysts for the FTO reaction.

Cobalt catalysts for Fischer–Tropsch synthesis： The effect of support,precipitant and pH value

In this report,Co-based catalysts supported on ZnO,Al_2O_3 and ZrO_2 as well as the ZrO_2 derived from different precipitants and different pH values were prepared by co-precipitation method.Their catalytic Fischer–Tropsch synthesis(FTS)performance was investigated in a fixed-bed reactor.The results revealed that Co catalyst supported on ZrO_2 exhibited better FTS catalytic performance than that supported on ZnO or Al_2O_3.For the Co/ZrO_2catalyst,different precipitants showed the following an activity order of NaOH>Na_2CO_3>NH_4OH,and the best pH value is 13.The catalysts were characterized by N_2adsorption–desorption,XRF,XRD,H_2-TPR,H_2-TPD and TEM.It was found that the main factor affecting the CO conversion of the catalyst was the amounts of low-temperature active adsorption sites.Moreover,the selectivity of C_5^+hydrocarbons had a positive relationship with the peak temperature of the weak hydrogen adsorption sites.The higher the peak temperature,the higher the C_5^+selectivity is.

Investigation on Supported Iron Catalyst for Fischer-Tropsch Synthesis

The supported iron catalyst Fe 2O 3 La 2O 3 γ Al 2O 3 has been studied by temperature programmed reduction(TPR) and Mssbauer spectroscopy(MES). The results show that this catalyst, in which the carrier γ Al 2O 3 is modified by La 2O 3, exhibits much stronger active component support interaction, stabilizes the ferrous phase and thus is more difficult to reduce to α Fe. Meanwhile no iron carbide can be detected after Fischer Tropsch synthesis accounting for a strong interaction between the active phase and the carrier.

Online measurement of solids motion in fluidized bed reactor with different distributor for Fischer–Tropsch synthesis

In this paper, the distributions of particle velocity in a gas–solid fluidized bed with branched pipe distributor or circle distributor were measured by using a laser Doppler velocimetry. Our results show that, within a certain range of superficial gas velocity, when using circle distributor, the particle velocity is large and the distribution of the particle velocity is even more compared with the branched pipe distributor. On the basis of the amplitude of tangential movement statistics, the amplitude of tangential movement statistics(AVATMS) decreases with increasing the axial height under the appropriate superficial gas velocity.

Design and construction of size-controlled CoO/CS catalysts for Fischer–Tropsch synthesis

The use of supported Co-based catalysts is widespread in various catalytic reactions due to their unique structures.The structural sensitivity of these catalysts is closely linked to their particle size and crystal form.Consequently,comprehending the structure–activity relationship requires the development of well-defined Co-based catalysts.Herein,we employed a colloidal wet chemical process and a heterogeneous nucleation method to prepare well-defined Co-based catalysts supported by inert carbon nanospheres.The nanospheres’surface possesses abundant functional groups that efficiently capture metal complexes and facilitate the nucleation and growth of CoO nanoparticles.By adjusting the Co source concentration,solvent molar ratio,and nucleation growth kinetics,we successfully prepared CoO/carbon sphere(CS)catalysts with different particle sizes and crystal forms.The influence of metallic face-centered cubic(fcc)-Co^(0) particle size in the range of 6.6–17.6 nm on the performance of Fischer–Tropsch synthesis(FTS)using well-defined CoO/CS catalysts has been investigated.The result demonstrated that the turnover frequency(TOF)remained constant for CoO/CS catalysts with metallic fcc-Co^(0) particle size larger than 7.7 nm.However,both the selectivity and the activity changed for CoO/CS catalysts with smaller particles(<7.7 nm).Significantly,when metallic fcc-Co^(0) particle size was reduced from 17.6 to 7.7 nm,the cobalt time yield increased to 6.7μmolCO·gCo^(-1)·s^(-1),indicating improved catalytic activity.At the same time,the CH_(4) selectivity decreased to 4.9%,suggesting a higher preference for hydrocarbon production.These findings demonstrate the importance of particle size in Co catalyzed Fischer–Tropsch synthesis.The use of well-defined CoO/CS catalysts offers valuable insights into the structure–activity relationship,leading to a better understanding of Co catalyzed Fischer–Tropsch synthesis.

Systematic variation of the sodium/sulfur promoter content on carbon-supported iron catalysts for the Fischer–Tropsch to olefins reaction

The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content（1–3 wt%） leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents（1–3 wt% sodium and 0.5–1 wt% sulfur） but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support（carbide-derived carbon aerogel） shows that the optimum promoter level depends on iron particle size and support pore structure.

Design and control of fraction cutting for the separation of mixed alcohols from the Fischer-Tropsch aqueous by-products

Since the minimum-boiling azeotropes of C2-C8 alcohols with water and high-water content(up to 95%(mass))in the Fischer-Tropsch aqueous by-products,the separation is energy-intensive and challenging.The energy-saving strategy for the complete separation of the Fischer-Tropsch aqueous by-products has received massive attention in recent decades.In this study,a stripper-sidestream decanter process is proposed by exploiting homogeneous azeotropes(C2-C3 alcohols-water)and heterogeneous azeotropes(C4-C8 alcohols-water).The introduction of the stripping column for pre-dehydration avoids the revaporization of the mixture,and energy carried by the overhead vapor is conserved instead of being removed in a condenser.The precise fraction cutting of C1-C3 alcohol-water mixture,C4-C8 alcohols,and water is realized by the sidestream distillation column.The C4-C8 alcohols rich mixture withdrawn from the sidestream flows into the decanter to break the distillation boundary,where the organic phase returns to the sidestream distillation column to obtain the dehydrated C4-C8 alcohols,and the aqueous phase enters the stripping column.Steady-state optimization based on total annual cost(TAC)minimization shows that the stripper-sidestream decanter process reduces TAC by 17.00%and saves energy by 21.27%compared with the conventional three-column distillation process.Further,a control structure of the process is established,and dynamic simulations show that the control structure combining a differential controller with a low-selector exhibits robust co ntrol.This study provides a novel design scheme and deepens the insights into the efficient separation of aqueous by-products of the Fischer-Tropsch synthesis.

Controllable Fe/HCS catalysts in the Fischer-Tropsch synthesis: Effects of crystallization time

The Fischer--Tropsch synthesis(FTS)con-tinues to be an attractive alternative for producing a broad range of fuels and chemicals through the conversion of syngas(H2 and CO),which can be derived from various sources,such as coal,natural gas,and biomass.Among iron carbides,Fe2C,as an active phase,has barely been studied due to its thermodynamic instability.Here,we fabricated a series of Fe2C embedded in hollow carbon sphere(HCS)catalysts.By varying the crystallization time,the shell thickness of the HCS was manipulated,which significantly influenced the catalytic performance in the FTS.To investigate the relationship between the geometric structure of the HCS and the physic-chemical properties of Fe species,transmission electron microscopy,X-ray diffraction,N2 physical adsorption,X-ray photo-electron spectroscopy,hydrogen temperature-programmed reduction,Raman spectroscopy,and Mossbauer spectro-scopy techniques were employed to characterize the catalysts before and after the reaction.Evidently,a suitable thickness of the carbon layer was beneficial for enhancing the catalytic activity in the FTS due to its high porosity,appropriate electronic environment,and relatively high Fe2C content.

Size dependence of carbon-encapsulated iron-based nanocatalysts for Fischer–Trposch synthesis

The conversion from syngas derived from non-petroleum recourses to liquid fuels and chemicals via Fischer–Tropsch synthesis(FTS)is regarded as an alternative and potential route.Developing catalyst with controllable particle size and clarifying size effect are of significance to promote the process.Herein,we engineered carbon-encapsulation structure to restrict particle growth but avoid strong metal–support interactions.The prepared carbon-encapsulated nanoparticles(Fe@C)showed a superior catalytic activity compared with conventional carbon-supported nanoparticles(Fe/C).By tuning particle size from 3.0 to 9.1 nm,a volcano-like trend of iron time yield(FTY)peaked at 2659μmol·gFe^(−1)·s^(−1)is obtained with an optimum particle size of 5.3 nm.According to temperature-programmed reduction and desorption results,a linear relationship between apparent turnover frequency and CO dissociation capacity was established.The enhanced CO dissociative adsorption along with weakened H_(2)activation on larger nanoparticles resulted in higher C_(5+)selectivity.This study provides a strategy to synthesize carbon supported metal catalysts with controllable particle size and insight into size effect on Fe-based catalytic FTS.

Recent advances in application of iron‐based catalysts for CO_(x) hydrogenation to value‐added hydrocarbons

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.

A new kinetic model for direct CO2 hydrogenation to higher hydrocarbons on a precipitated iron catalyst:Effect of catalyst particle size

The kinetic of the direct COhydrogenation to higher hydrocarbons via Fischer–Tropsch synthesis（FTS）and reverse water-gas shift reaction（RWGS） mechanisms over a series of precipitated Fe/Cu/K catalysts with various particle sizes was studied in a well mixed, continuous spinning basket reactor. The iron catalysts promoted with copper and potassium were prepared via precipitation technique in various alcohol/water mixtures to achieve a series of catalyst particle sizes between 38 and 14 nm. A new kinetic model for direct COhydrogenation was developed with combination of kinetic model for FTS reaction and RWGS equilibrium condition. For estimate of structure sensitivity of indirect COhydrogenation to higher hydrocarbons, the kinetic parameters of developed model are evaluated for a series of iron catalysts with various particle sizes. For kinetic study a wide range of syngas conversions have been obtained by varying experimental conditions. The results show that the new developed model fits favorably with experimental data. The values of activation energies for indirect COhydrogenation reaction are fall within the narrow range of 23–16 kJ/mol.

Production of synthetic hydrocarbons from coal through its underground gasification

The problem of the high-level processing of coal into synthetic motor fuels assumes worldwide actual meaning nowadays. Thereat, it is important especially for countries and regions which possess extensive coal resources and are forced to be guided by the import of liquid and gas hydrocarbons. However, a greater emphasis is paid to the given issue in Russia-The development of the federal program for highlevel processing of coal into synthetic motor fuels was initiated. This article describes options of underground coal gasification (UCG) use for the generation of hydrocarbons from UCG gas in the process of the Fischer-Tropsch synthesis (FTS). The technical and economic analysis of the integrated UCG-FTS powerchemical factories has detected their investment attractiveness and practicability of experimental-industrial testing at coal deposits of the Russian Federation.

The modification of titanium in mesoporous silica for Co-based Fischer–Tropsch catalysts

Ordered SBA-15 mesoporous silica with incorporated titanium was successfully synthesized via a onepot hydrothermal crystallization method.The characterization including powder X-ray diffraction,Brunauer–Emmett–Teller,transmission electron microscope,temperatureprogrammed reduction,temperature-programmed desorption,Fourier transform infrared and ultraviolet-visible-near infrared spectrometer was performed to explore the physical and chemical structures of both the supports and the catalysts.The results showed that titanium was successfully incorporated into the mesoporous silica framework with a limited amount of titanium(Si/Ti>20),and the mesoporous structure was retained.However,the increased titanium content inevitably resulted in the formation of anatase TiO2 particles on the support surface.The increased incorporated titanium strengthened the interactions between cobalt species and supports,which was favorable for the cobalt species dispersion,despite the limited cobalt oxide reducibility.The enhanced metalsupport interactions were beneficial for the CO/H2 ratio at the active cobalt sites,which facilitated the formation of more C5+hydrocarbons.This study provides a promising method for support modification with incorporatedheteroatoms for the rational development of Fischer–Tropsch catalysts.