Solvent-free synthesis of alumina supported cobalt catalysts for Fischer–Tropsch synthesis

A novel mechano-synthesis method has been elaborated in this work for the design of efficient cobaltbased Fischer–Tropsch catalysts. The process aims to reduce the total number of steps involved in the synthesis of solid catalysts and thus to avoid relevant toxic solutions generated during the catalyst preparation. The mechano-synthesis of the Co/Al_2O_3 catalyst was processed in a low-energy vibratory micro mill and high energy planetary ball mill. Porous spherical γ-aluminas(1860 μm and 71 μm mean particle diameter) were used in this work as host compounds. Co_3O_4(3 μm mean particle diameter) has provided guest particles for mechano-synthesis. The catalysts were characterized by textural(surface area, porosity and particle size) and structural analyses(X-ray diffraction, TPR, SEM-EDX and microprobe). The microprobe images show deposition of Co_3O_4 on the surface of the alumina and indicated no Co_3O_4 diffusion inside the alumina pores. SEM-EDX mapping illustrated that cobalt coating tended to occur on surface of rounded shape of cracked alumina fragments. After milling, the crystallite size of Co_3O_4 decreased to 15 nm from 30 to 50 nm. The TPR profiles indicated very low concentrations of inactive cobalt aluminate mixed compounds which are usually produced during the catalyst preparation by impregnation.In Fischer–Tropsch synthesis, the catalysts prepared using mechano-synthesis methods showed catalytic performance comparable to the catalysts prepared by impregnation.     

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.     

Synthesis and characterization of Al-modified SBA-15 for Fischer–Tropsch synthesis (FTS) reaction

Research on Chemical Intermediates - In this work, we synthesized a Co-based catalyst supported on modified SBA-15 to obtain the uniform particle size of active metal and selective products with...     

Effects of cobalt carbide on Fischer–Tropsch synthesis with MnO supported Co-based catalysts

Cobalt carbide(Co_2C)was considered as potential catalysts available for large-scale industrialization of transforming syngas(H_2 and CO)to clean fuels.Herein,we successfully synthesized Co-based catalysts with MnO supported,to comprehend the effects of Co_2C for Fischer–Tropsch synthesis(FTS)under ambient conditions.The huge variety of product selectivity which was contained by different active sites(Co and Co_2C)has been found.Furthermore,density functional theory(DFT)shows that Co_2C is efficacious of CO adsorption,whereas is weaker for H adsorption than Co.Combining the advantages of Co and Co_2C,the catalyst herein can not only obtain more C_(5+)products but also suppress methane selectivity.It can be a commendable guide for the design of industrial application products in FTS.     

Industrial catalyst for the selective Fischer–Tropsch synthesis of long-chain hydrocarbons

The results of development of an industrial supported cobalt–silica gel catalyst for the Fischer–Tropsch synthesis are reported. The studies included the selection of a support and the determination of an optimum active component content, a calcination temperature, and the effect of doping with aluminum oxide on the physicochemical and catalytic properties of the Co–SiO₂ system. The catalyst samples were characterized by a set of physicochemical methods. The on-stream stability of the supported cobalt–silica gel catalyst was tested in the continuous mode for 1000 h. In the course of the entire test cycle, the catalyst exhibited stable operation under varied synthesis temperature and gas space velocity, and it can be recommended for industrial applications. The experimental results were used for the preparation of a pilot batch of the catalyst.     

Controlled synthesis of cobalt nanocrystals on the carbon spheres for enhancing Fischer–Tropsch synthesis performance

Non-porous carbon sphere was used as support to synthesize supported cobalt Fischer-Tropsch catalysts with high activity and durability. Strong metal-support interaction was avoided and intrinsic activity of pristine cobalt nano-particles was studied. Thermal decomposition synthesis method was applied to obtain cobalt catalysts with high dispersion and narrow particle size distribution. Furthermore the cobalt size can be controlled by the molar ratio of o-dichlorobenzene/benzylamine. Compared with supported cobalt catalysts prepared by incipient wetness impregnation method and ultrasonic impregnation method,the catalyst prepared by thermal decomposition method showed higher catalytic activity, higher long chain hydrocarbons selectivity and lower methane selectivity.     

Dynamics of carbide formation in iron-supported catalysts of the Fischer–Tropsch process promoted by copper and potassium

The kinetics of the formation of iron carbides during the activation of iron-coated catalyst for Fischer–Tropsch synthesis promoted by copper and potassium, and by carbon monoxide and syngas, is studied. It is established that the presence of copper lowers the initial temperature of hematite reduction to magnetite and leads to the formation of carbide in both CO and СО/Н₂. Potassium slows the rate of magnetite formation, but it accelerates the formation of iron oxide. It is shown that the rate of carbide formation during magnetite reduction for catalysts is half that in the reaction of hematite reduction to magnetite in both CO and СО/Н₂.     

Fischer–Tropsch synthesis on potassium-modified Fe3O4 nanoparticles

Research on Chemical Intermediates - Synthesized magnetite (Fe3O4) nanoparticles, with an average crystallite size of 8 and 22 nm, were investigated for Fischer–Tropsch synthesis...     

Effect of preparation methods on Co/ZrO2 catalysts in Fischer–Tropsch synthesis

Cobalt was incorporated into the zirconia support by different methods. The reducibility and activity of the catalysts was directly related to the preparation methods. Impregnated Co/ZrO₂ catalyst showed the highest reduction degree and the highest CO hydrogenation activity.     

Fischer–Tropsch synthesis using zeolitic imidazolate framework (ZIF-7 and ZIF-8)-supported cobalt catalysts

The Fischer–Tropsch synthesis using cobalt catalysts supported on zeolitic imidazolate frameworks (ZIFs), ZIF-7 and ZIF-8, has been investigated. ZIF-7, ZIF-8 and corresponding cobalt-containing catalysts, after preparation, were characterized using various techniques. Thermogravimetric analysis results show that ZIF-7 and ZIF-8 supports have good thermal stability for the Fischer–Tropsch synthesis reaction, and weaker interaction between cobalt and zinc in the ZIF-7 and ZIF-8 supports results in more cobalt reduction. The catalytic performance was evaluated in Fischer–Tropsch synthesis and compared with that of a cobalt catalyst supported on SBA-15 promoted with zinc. The pore structure of the ZIF supports plays an essential role in product selectivity for the prepared catalysts. The carbon number in hydrocarbon products and olefin selectivity depend on cobalt dispersion and support structure owing to the impacts of site density and carrier skeleton on the speed of diffusion-enhanced olefin re-adsorption reactions.     

Promotion of cobalt catalyst for Fischer–Tropsch synthesis by molybdenum as protection against sulfur poisoning

Molybdenum promotion was used to increase the resistance of a cobalt catalyst for the Fischer–Tropsch synthesis to sulfur poisoning. A series of experiments on adding 1,3,5-trithiane to synthesis gas (sulfur content of 1 ppm) showed that the Co–Mo /Al₂O₃ catalyst regained its initial activity after 8 h of operation. In comparison, catalysts not containing molybdenum experienced a significant irreversible loss of activity that was not recovered after stopping the addition of 1,3,5-trithiane to the feed.     

Participation of Water in the Secondary Transformations of Hydrocarbons on Cobalt–Zeolite Catalysts for the Fischer–Tropsch Synthesis

This review is dedicated to the effect of water as the main by-product of the Fischer–Tropsch synthesis on the process. The reasons for the negative effect of water are analyzed and the possible versions of the control of its participation in the process are considered. As an optimal solution to the problem, the use of zeolites in the H form as the constituents of cobalt catalysts for the Fischer–Tropsch synthesis is proposed. Bibliography: 148 references.     

The Influence of Alkali Treatment for Synthesizing Hierarchical Zeolite on Behavior of Cobalt Fischer–Tropsch Synthesis Catalysts

Hierarchical zeolites were synthesized by alkali treatment and their applications in Fischer–Tropsch (FT) synthesis were studied. It was found that alkali treatment not only created hierarchical structure but also could tune cobalt-support interaction. The dissolution of Si by alkali treatment became easier with the increase of Si/Al ratio, and thus the amount of mesopority increased. An optimal Si/Al molar ratio was identified over the zeolite with Si/Al ratio of 80, which was found to be superior to other catalysts in terms of better diesel selectivity and lower CH₄ selectivity due to its relatively narrow bimodal pore size distribution and moderate cobalt-support interaction. Meanwhile alkali treatment could enhance cobalt-support interaction via the formation of ɑ-SiO_2, Co/MZ-120 catalyst showed the lowest FT activity and higher CH₄ selectivity due to the increase of such new phase.     

Fischer–Tropsch synthesis on impregnated cobalt-based catalysts:New insights into the effect of impregnation solutions and pH value

The Co-based catalysts were prepared with different cobalt acetate solutions. Effects of p H value were studied deeply on Fischer–Tropsch synthesis(FTS) through a semi-batch reactor. Among all impregnation solutions(water, butanol, amyl alcohol, acetic acid, nitric acid and ammonium nitrate), the catalyst prepared by NH_4NO_3 solution showed the highest catalytic activity due to its small particle size and high reduction degree. However, the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS. According to FT-IR spectra results, the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity. Whereas, the high activity of catalysts prepared from NH_4NO_3 solution could be explained by the high intensity of absorbed CO on the catalysts.The cobalt species on the catalysts prepared under lower p H conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher p H value.     

Fischer–Tropsch Synthesis on Bifunctional Cobalt Catalysts with the Use of Hierarchical Zeolite HBeta

Kinetics and Catalysis - The production of fuel components in the integrated Fischer–Tropsch synthesis on bifunctional cobalt catalysts in the form of a mixture of the cobalt catalyst...     

Effects of glow discharge plasma on Cu–Co–Al-based supported catalysts for higher alcohol synthesis

The novel plasma assisted Cu–Co/γ-Al₂O₃ catalysts were prepared by incipient impregnation method for CO hydrogenation to higher alcohols and characterized by means of scanning electron microscopy (SEM), N₂ adsorption, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. It was found that introduction of plasma significantly improved the specific surface area, dispersion of catalyst and the enrichment of active species on the surface of catalysts. Under the conditions of P = 5.0 MPa, GHSV = 6,000 h⁻¹, V(H₂)/V(CO) = 2, T = 573 K, the conversion of carbon monoxide over the plasma enhanced catalyst increased by 41.9% compared with that of the conventional sample, and the space time yield reached 337.1 g kg⁻¹ h⁻¹.     

General and highly efficient fluorinated-N-heterocyclic carbene–based catalysts for the palladium-catalyzed Suzuki–Miyaura reaction

A general and highly efficient trifluoromethylated-N-heterocyclic carbene (NHC)-based catalyst for the palladium-catalyzed Suzuki–Miyaura reaction was reported. In the presence of the catalyst, reactions of non-activated aryl chlorides and triflates with aryl boronic acids occurred at room temperature with good to excellent yields (63–98%). In addition, catalysts generated from a combination of Pd(OAc)₂/imidazolium salt 6a is not only effective for the coupling of heteroaryl boronic acid with aryl halides and heteroaryl halides, but also efficient for coupling of other heteroaryl halides and heteroaryl boronic acids. Finally, the catalyst is highly effective for Suzuki–Miyaura reaction of aryl bromides and chlorides with 0.01–0.1 mol % loading if the temperature was raised at refluxed THF/H₂O.