Study on iron-manganese catalysts for Fischer-Tropsch synthesis

Iron-manganese catalysts were prepared by co-precipitation method.Characterization of catalysts was carried out by using X-ray diffraction(XRD),scanning electron microscopy(SEM),temperature program reduction(TPR),N2 adsorption-desorption measurements.The results from catalytic performance tests in Fischer-Tropsch synthesis showed that the iron-manganese catalysts are supersensitive to catalyst composition and materials source.It was found that C2~4 light olefins increased while CH4 and CO2 decreased by using iron-manganese catalyst prepared from iron(II) sulfate(A catalyst).The activity and selectivity of A catalyst was studied in different operational conditions.The results showed that the best operational conditions for C2~4 light olefins production were H2/CO=1/1(GHSV=2400h-1) at 260℃ under 0.3MPa total pressure.     

Effect of preparation method on halloysite supported cobalt catalysts for Fischer-Tropsch synthesis

Novel cobalt Fischer-Tropsch synthesis(FTS) catalysts were prepared from natural halloysite nanotubes(HNT) by double-solvent and wetimpregnation methods,and characterized by TEM,XRD,TPR and N2 adsorption-desorption.Comparing with the catalyst prepared by wetimpregnation method,the catalyst prepared by double-solvent method reduces Co3O4 particle migration and agglomeration due to size-induced effect,thus showing higher catalytic activity for Fischer-Tropsch synthesis.     

Effects of the ratio of Fe to Co over Fe-Co/SiO2 bimetallic catalysts on their catalytic performance for Fischer-Tropsch synthesis

The Fe-Co/SiO2 bimetallic catalysts with different ratios of Fe to Co were prepared by aqueous incipient wetness impregnation. The catalysts of 10%Fe:0%Co/SiO2, 10%Fe:6%Co/SiO2, 10%Fe:2%Co/SiO2, 10%Fe: 10%Co/SiO2, 6%Fe: 10%Co/SiO2, 2%Fe: 10%Co/SiO2 and 0%Fe: 10%Co/SiO2 by mass were tested in a fixed reactor by the Fischer-Tropsch synthesis. Activity and hydrocarbon distribution were found to be determined by the ratio of iron to cobalt of the catalysts. Higher iron content inhibited the activity, whereas higher cobalt content enhanced the activity of the Fe-Co/SiO2 catalysts. On the other hand, for the catalysts of 10%Fe:6%Co/SiO2, 10%Fe: 10%Co/SiO2, 6%Fe: 10%Co/SiO2, and 2%Fe: 10%Co/SiO2, the total C2-C4 fraction increased (from 10.65% to 26.78%) and C5+ fraction decreased (from 75.75% to 57.63%) at 523 K. Temperature programmed reduction revealed that the addition of cobalt enhanced the reducibility of the Fe-Co/SiO2 catalyst. Metal oxides were present in those catalysts as shown by XRD. The Fe-Co alloy phase was found in the 2%Fe: 10%Co/SiO2, 6%Fe: 10%Co/SiO2, 10%Fe:10%Co/SiO2, 10%Fe:6%Co/SiO2 catalysts and their crystals were perfect.     

Effects of the ratio of Fe to Co over Fe-CO/SiO2 bimetallic catalysts on their catalytic performance for Fischer-Tropsch synthesis

The Fe-Co/SiO2 bimetallic catalysts with different ratios of Fe to Co were prepared by aqueous incipient wetness impregnation. The catalysts of 10%Fe:0%Co/SiO2, 10%Fe:6%Co/SiO2, 10%Fe:2%Co/SiO2, 10%Fe:10%Co/SiO2, 6%Fe:10%Co/SiO2, 2%Fe:10%Co/SiO2 and 0%Fe: 10%Co/SiO2 by mass were tested in a fixed reactor by the Fischer-Tropsch synthesis. Activity and hydrocarbon distribution were found to be determined by the ratio of iron to cobalt of the catalysts. Higher iron content inhibited the activity, whereas higher cobalt content enhanced the activity of the Fe:Co/SiO2 catalysts. On the other hand, for the catalysts of 10%Fe:6%Co/SiO2, 10%Fe:10%Co/SiO2, 6%Fe:10%Co/SiO2, and 2%Fe:10%Co/SiO2, the total C2–C4 fraction increased (from 10.65% to 26.78%) and C5+ fraction decreased (from 75.75% to 57.63%) at 523 K. Temperature programmed reduction revealed that the addition of cobalt enhanced the reducibility of the Fe:Co/SiO2 catalyst. Metal oxides were present in those catalysts as shown by XRD. The Fe-Co alloy phase was found in the 2%Fe:10%Co/SiO2, 6%Fe:10%Co/SiO2, 10%Fe:10%Co/SiO2, 10%Fe:6%Co/SiO2 catalysts and their crystals were perfect.     

Study of activated carbon supported iron catalysts for the Fischer-Tropsch synthesis

Summary Characterization (BET and TPD) and reaction studies were conducted with activated carbon supported iron catalysts (Fe/AC) used for the Fischer-Tropsch synthesis (FTS). The TPD study showed that there existed interactions between metals and the AC surface. Greater association of Cu and K promoters with the AC surface resulted in stronger promoter to surface interaction, which enhanced the H₂ desorption ability of the Cu and K promoted Fe/AC catalyst prepared under vacuum impregnation (VI). Catalytic behavior of a Fe/AC catalyst (VI-15 Fe/2 Cu/2 K/81 AC, in parts per weight) was studied in a 1-liter slurry phase continuous stirred tank reactor. The catalyst presented moderate syngas conversion (44.3-60.6%) and high gaseous selectivity (CH₄, 12.8-15.1% and C₂-C₄, 42.4-46.1%) under 304^oC, 3.0 MPa, 1.1 L(STP)/g-cat/h, and H₂/CO = 2.0 during 166 h of testing. Detectable hydrocarbons up to C₁₈ were formed on the Fe/AC catalyst.     

助剂Cu、K对F-T合成铁基催化剂作用的表征研究

采用连续共沉淀和喷雾干燥技术相结合的方法制备了一组Cu、K助剂单独或同时加入的微球状Fischer-Tropsch（F-T）合成铁基催化剂,借助低温N2吸附、MES、XRD、H2-TPR、CO-TPR研究了Cu和K助剂对催化剂织构、还原性能以及还原和炭化过程中的物相变化的影响。结果表明,K助剂的加入能明显提高催化剂的比表面积和铁物相在催化剂中的分散程度,增加了Fe2O3与SiO2间的相互作用;当催化剂在H2和合成气中还原时,Cu助剂的加入有利于催化剂的还原和Fe3O4的生成,在CO中还原时,Cu助剂的加入则有利于α-Fe的生成和稳定化。在H2和合成气中,单独K助剂的加入会抑制催化剂的还原或炭化,而Cu和K助剂的同时加入在H2、CO和合成气下均可使催化剂的还原或炭化能力明显提高,表明Cu和K助剂间存在一定的协同作用。     

Cu助剂对聚乙烯醇辅助沉淀铁催化剂费托合成反应性能的影响

通过共沉淀法或聚乙烯醇（PVA）辅助共沉淀法分别制备了Fe₂O₃和FeCu催化剂,结合BET、XRD、SEM、H₂-TPR等表征手段,研究了Cu助剂对PVA辅助的沉淀铁催化剂的织构性质、物相结构、形貌特征、还原行为以及F-T合成反应性能的影响。结果表明,Cu助剂的加入增大了铁基催化剂中α-Fe₂O₃的晶粒,减小了催化剂的BET比表面积和孔容,增大了孔径;改变了铁基催化剂的形貌;促进了铁基催化剂在H₂中的还原。反应过程中,在催化剂中只添加Cu助剂时,有利于提高催化剂的反应活性,而当同时加入Cu助剂和PVA时,由于Cu助剂与PVA较强的相互作用,反而降低了催化剂的反应活性,且催化剂的选择性向轻质烃方向偏移。     

Effects of ceria addition and pre-calcination temperature on performance of cobalt catalysts for Fischer-Tropsch synthesis

Summary The effect of ceria addition on the performance of 10 wt.% Co catalysts supported on SiO2 and Al2O3 for Fischer-Tropsch synthesis has been investigated. The catalysts were prepared by impregnation method and characterized by X-ray diffraction technique. The catalytic tests (P = 1 atm, T = 488 K, H2/CO = 2, GHSV=1800 h-1) indicate that with addition of ceria, significant changes in CO conversion and hydrocarbon selectivities are observed. Also, the experiments show that the performance of 10 wt.% Co-CeO2/Al2O3 depends on the ceria concentration as well as on the pre-calcination temperature.     

高温沉淀铁基催化剂上费托合成含氧化合物生成机理的研究

采用漫反射原位红外光谱法及化学捕获方法,考察了费托合成过程中高温沉淀铁基催化剂表面吸附物种的变化,并探讨了含氧化合物的生成机理。结果表明,CO在高温沉淀铁基催化剂上有线式和桥式两种吸附态存在,同时,CO的吸附在催化剂表面生成大量含氧化合物前驱体。费托原位实验捕获到了一些较关键的中间产物:表面乙酸盐、表面酰基、甲氧基等。同时发现高温沉淀铁基催化剂表面具有以下反应共性:醇类可与表面羟基结合生成烷氧基团;催化剂表面的吸附分子具有氧化性;一些基础化学物质如OH^-、晶格氧等可以与甲醇或乙醛分子发生反应。对CH₃OH + CO及CH₃I + CO + H₂两个反应的化学捕获实验表明,酰基是C₂⁺含氧化合物的重要中间产物,酰基加氢是形成C₂⁺含氧化合物的关键步骤。根据表面中间产物及反应特性,得到了高温沉淀铁基催化剂上费托合成含氧化合物的生成机理。     

Effect of operating conditions and potassium content on Fischer-Tropsch liquid products produced by potassium-promoted iron catalysts

The dependencies of Fischer-Tropsch synthesis liquid hydrocarbon product distribution on operating pressure and temperature have been studied over three potassium-promoted iron catalysts with increasing potassium molar content. The study followed an experimental planning and the results were analyzed based on surface response methodology. The effects of different operating conditions and potassium contents on the liquid product distribution were compared based on number average carbon number and dispersion. Results showed that high pressures （25 to 30 arm） favored the production of waxes that could be converted into liquid fuels through hydrocracking, while greater direct selectivity towards diesel was favored by low pressure （20 arm） using catalysts with low potassium to iron molar ratios. The liquid product distribution produced using an iron catalyst with high potassium content presented higher number-average number of carbons when compared to the distribution obtained using an iron catalyst with low potassium content.     

超临界和近临界条件下Fischer Tropsch合成研究：溶剂的影响

研究了超临界和近临界条件下费托合成过程中溶剂对反应行为的影响。反应在固定床反应器中进行，催化剂为Co/SiO2，所选择的溶剂有两类：纯溶剂（正戊烷和正己烷）和混和溶剂（由正己烷和少量的C5~10烃组成）。结果表明,正己烷分压对CO转化率影响很小，但是产物中1 烯烃含量随正己烷分压增加而增加，超临界条件下1 烯烃含量明显高于非临界条件下。溶剂的种类对CO转化率、CH4和CO2选择性以及产物炭分布影响不大。这一结果表明为了减少溶剂用量，对含有适量轻组分（C5~10）的正己烷溶剂进行循环使用是可行的。结果同时表明与正己烷相比，混和溶剂（25%正己烷和75%正葵烷）具有较高的1 烯烃选择性。     

The sol-gel derived Co-Mn/TiO_2 catalysts for light olefins production

In this research work,two 30%(Co-Mn)/TiO2catalysts were prepared using sol-gel(catalyst A)and coprecipitation(catalyst B)methods.The activity and selectivity to C2~4light olefins in Fischer-Tropsch synthesis(FTS)has been studied in a fixed-bed reactor under different operational conditions.These operational conditions were:temperature220~280℃,and total pressure from0.1~0.6 MPa.The optimum operating conditions were investigated after steady state.As the results shown,the catalyst A was more selective to C2~4olefins(58.7%in 260℃)and catalyst B was more selective to C5+hydrocarbons.Characterization of both catalysts was carried out by using X-ray diffraction(XRD),scanning electron microscopy(SEM)and N2adsorption-desorption measurements methods.     

Cobalt catalysts supported on silica nanotubes for Fischer-Tropsch synthesis

Silica nanotubes(SNT) have been synthesized using carbon nanotubes(CNT) as a template.Silica-coated carbon nanotubes(SNT-CNT) and SNT were loaded with a cobalt catalyst for use in Fischer-Tropsch synthesis(FTS).The catalysts were prepared by incipient wetness impregnation and characterized by N2 physisorption,X-ray diffraction(XRD),hydrogen temperature programmed reduction(H2-TPR) and transmission electron microscopy(TEM).FTS performance was evaluated in a fixed-bed reactor at 493 K and 1.0 MPa.Co/CNT and Co/SNT catalysts showed higher activity than Co/SNT-CNT in FTS because of the smaller cobalt particle size,higher dispersion and stronger reducibility.The results also showed that structure of the support affects the product selectivity in FTS.The synergistic effects of cobalt particle size,catalytic activity and diffusion limitations as a consequence of its small average pore size lead to medium selectivity to C5+ hydrocarbons and CH4 over Co/SNT-CNT.On the other hand,the Co/CNT showed higher CH4 selectivity and lower C5+ selectivity than Co/SNT,due to its smaller average pore size and cobalt particle size.     

Development of niobium-promoted cobalt catalysts on carbon nanotubes for Fischer-Tropsch synthesis

Cobalt-based catalysts were prepared by a wet impregnation method on carbon nanotubes (CNTs) support and promoted with niobium.Samples were characterized by nitrogen adsorption,TEM,XRD,TPR,TPO and H2-TPD.Addition of niobium increased the dispersion of cobalt but decreased the catalysts reducibility.Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K,1 atm and H2/CO=2 for 5 h.Addition of niobium enhanced the C5+ hydrocarbons selectivity by 39% and reduced methane selectivity by 59%.These effects were more pronounced for 0.04%Nb/Co/CNTs catalyst,compared with those observed for other niobium compositions.     

Catalytic behaviors of Co-Mn/TiO2 catalysts for Fischer-Tropsch synthesis

The 15%(Co-Mn)/TiO₂,(Co/Mn=1/6) catalyst was prepared using fusion procedure and studied for the conversion of synthesis gas to C_2~4 olefins. The effects of calcination conditions and operation conditions such as the H₂/CO molar feed ratio at different temperatures, gas hourly space velocity (GHSV) and total reaction pressure on the catalytic performance of catalyst were investigated. The stability of the catalyst during 150 h at optimal operation conditions (t=250 ℃ H₂/CO=2/1, GHSV=1 500 h^-1 and p=0.3 MPa) has been investigated. It is found that this catalyst is high stable for production C_2~4 olefins. Characterizations of both precursors and calcined catalysts by powder X-ray diffraction, scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) specific surface area measurement and thermal analysis methods such as thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) show that the different preparation method influences the catalyst precursor structure and morphology.     

Silylated Co/SBA-15 catalysts for Fischer-Tropsch synthesis

A series of silylated Co/SBA-15 catalysts were prepared via the reaction of surface Si-OH of SBA-15 with hexamethyldisilazane (HMDS) under anhydrous, vapor-phase conditions, and then characterized by FT-IR, N₂ physisorption, TG, XRD, and TPR-MS. The results showed that organic modification led to a silylated SBA-15 surface composed of stable hydrophobic Si-(CH₃)₃ species even after calcinations and H₂ reduction at 673 K. Furthermore, the hydrophobic surface strongly influenced both metal dispersion and reducibility. Compared with non-silylated Co/SBA, Co/S-SBA (impregnation after silylation) showed a high activity, due to the better cobalt reducibility on the hydrophobic support. However, S-Co/SBA (silylation after impregnation) had the lowest FT activity among all the catalysts, due to the lower cobalt reducibility along with the steric hindrance of grafted -Si(CH₃)₃ for the re-adsorption of α-olefins.     

Kinetics of the water-gas shift reaction in Fischer-Tropsch synthesis over a nano-structured iron catalyst

Based on formate and direct oxidation mechanisms, three Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic models of the water-gasshift (WGS) reaction over a nano-structured iron catalyst under Fischer-Tropsch synthesis (FTS) reaction conditions were derived and compared with those over the conventional catalyst. The conventional and nanostructured Fe/Cu/La/Si catalysts were prepared by co-precipitation of Fe and Cu nitrates in aqueous media and water-oil micro-emulsion, respectively. The WGS kinetic data were measured by experiments over a wide range of reaction conditions and comparisons were also made for various rate equations. WGS rate expressions based on the formate mechanism with the assumption that the formation of formate is rate determining step were found to be the best.     

Effect of barium on reducibility and activity for cobalt-based Fischer-Tropsch synthesis catalysts

Barium modified Co/Al2O3 catalysts were prepared by incipient wetness impregnation. The catalysts were characterized by XRD, TPD and DRIFTS. The catalytic activity for Fischer-Tropsch synthesis was measured in a continuously stirred tank reactor. It was found that small amounts of BaO (≤ 2 wt%) improved the cobalt reducibility, which led to more cobalt active sites on the catalyst surface, and then resulted in higher CO conversion and C5+ selectivity. However, for the catalysts with high BaO loadings negative effects on the catalytic activity and selectivity for high hydrocarbons were observed because of low cobalt reducibility.     

以钴羰基簇合物为前驱体制备的钴基催化剂上F-T反应性能简

以含羧酸配体的钴羰基簇合物Co₂（CO）₆HCCCOOH,Co₃（CO）₉CCH₂COOH,Co₄（CO）₁₀HCCCOOH 为前驱体,γ-Al₂O₃为载体,通过浸渍法制备了一系列催化剂;同时以Co（NO₃）₂作为前驱体制备了参比催化剂. 对制备的催化剂进行了费托反应性能评价,并用透射电子显微镜、氨程序升温脱附和傅里叶变换红外光谱等手段对催化剂进行了表征. 结果发现,不同前驱体制备的催化剂对载体上Co的分布具有明显影响,进而影响催化剂活性. 反应结果表明,不同前驱体制备的催化剂上CO转化率及C₅₊选择性顺序为Co₃（CO）₉CCH₂COOH > Co₂（CO）₆HCCCOOH > Co₄（CO）₁₀HCCCOOH > Co（NO₃）₂.     

Selectivity of Fischer-Tropsch synthesis on supported nickel catalysts

Alumina supported Ni as well as Ni²⁺ exchanged CaNaX zeolites were used to study Fischer-Tropsch synthesis. Two significant selectivity effects can be distinguished, which are related to the different structures and acidities of the catalysts.

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CaNaX, Ni, Ni⁺² , -. , .