Fischer–Tropsch synthesis on mono- and bimetallic Co and Fe catalysts supported on carbon nanotubes

An extensive study of Fischer–Tropsch synthesis (FTS) on carbon nanotubes (CNTs)-supported bimetallic cobalt/iron catalysts is reported. Up to 4 wt.% of iron is added to the 10 wt.% Co/CNT catalyst by co-impregnation. The physico-chemical properties, FTS activity and selectivity of the bimetallic catalysts were analyzed and compared with those of 10 wt.% monometallic cobalt and iron catalysts at similar operating conditions (H₂/CO = 2:1 molar ratio, P = 2 MPa and T = 220 °C). The metal particles were distributed inside the tubes and the rest on the outer surface of the CNTs. For iron loadings higher than 2 wt.%, Co–Fe alloy was revealed by X-ray diffraction (XRD) techniques. 0.5 wt.% of Fe enhanced the reducibility and dispersion of the cobalt catalyst by 19 and 32.8%, respectively. Among the catalysts studied, cobalt catalyst with 0.5% Fe showed the highest FTS reaction rate and percentage CO conversion. The monometallic iron catalyst showed the minimum FTS and maximum water–gas shift (WGS) rates. The monometallic cobalt catalyst exhibited high selectivity (85.1%) toward C₅+ liquid hydrocarbons, while addition of small amounts of iron did not significantly change the product selectivity. Monometallic iron catalyst showed the lowest selectivity for 46.7% to C₅+ hydrocarbons. The olefin to paraffin ratio in the FTS products increased with the addition of iron, and monometallic iron catalyst exhibited maximum olefin to paraffin ratio of 1.95. The bimetallic Co–Fe/CNT catalysts proved to be attractive in terms of alcohol formation. The introduction of 4 wt.% iron in the cobalt catalyst increased the alcohol selectivity from 2.3 to 26.3%. The Co–Fe alloys appear to be responsible for the high selectivity toward alcohol formation.     

Fischer–Tropsch synthesis over carbon nanotubes supported cobalt catalysts in a fixed bed reactor: Influence of acid treatment

The influence of acid treatment on carbon nanotubes (CNT) supported cobalt catalysts for Fischer–Tropsch synthesis (FTS) is discussed in this paper. CNTs were first treated with 30 wt.% HNO₃ at 25 and 100 °C for 14 h. Cobalt catalysts supported on fresh and acid treated carbon nanotubes were prepared using the incipient wetness impregnation method with a cobalt loading of 10 wt.%. The catalysts were extensively characterized by BET, XRD, TPR and TEM, and Raman spectroscopy. The TEM analyses of the acid treated support catalysts showed that the major parts of the cobalt particles were homogenously distributed inside the nanotubes. Raman I_D/I_G band intensity ratios as an indication of the quality of carbon nanotubes for catalyst supports, increased with acid treatment. The FTS activity (g HC produced/g cat./h) and selectivity (the percentage of the converted CO that appears as a hydrocarbon product) of the catalysts were assessed and compared with the as-prepared CNT supported 10 wt.% cobalt catalyst using a fixed bed micro-reactor. The acid treatments at 25 and 100 °C respectively, (a) increased the BET surface area by 18% and 25%; (b) decreased the cobalt particle size and increased the cobalt dispersion; (c) increased by 10 and 50% the reducibility of the catalysts and (d) increased the FTS activity and %CO conversion by 36 and 114%. Finally, the product selectivity showed a distinct shift to lower molecular weigh hydrocarbons.     

High growth of SWNTs and MWNTs from C2H2 decomposition over Co-Mo/MgO catalysts

A series of MgO supported catalysts having Co and Mo metals 5-40 wt.% in a ratio of 1:1 was prepared by impregnation method. Carbon nanotubes (CNTs) were grown over the catalysts by decomposition of C₂H₂ at 800 °C for 30 min. It was found that 5 and 10 wt.% Co-Mo/MgO catalysts produced single-wall nanotubes (SWNTs), whereas 20, 30 and 40 wt.% Co-Mo/MgO catalysts produced multi-wall nanotubes (MWNTs). The catalyst Mo/MgO was inactive in growing CNTs. In Co-Mo/MgO catalysts, however Mo generated a favorable environment to grow SWNTs. The growth of SWNTs was strongly dependent on the formation of small clusters of cobalt, which may generate from the decomposition of CoMoO₄ species during the nanotube growth. MWNTs were produced over comparatively larger cobalt clusters generated from Co₃O₄ phase during the nanotube growth stage. The yields of SWNTs were about 6% and 27% over 5 and 10 wt.% Co-Mo/MgO catalysts, respectively. MWNTs yield (576%) was observed over 40 wt.% Co-Mo/MgO catalyst. Carbon yield (%) highly varied with acetylene concentration.     

Cobalt supported on carbon nanotubes — A promising novel Fischer–Tropsch synthesis catalyst

An extensive study of Fischer–Tropsch synthesis (FTS) on carbon nanotubes (CNT) supported and γ–alumina-supported cobalt catalysts with different amounts of cobalt are reported. Up to 40 wt.% of cobalt is added to the supports by the impregnation method. The effect of the support on the reducibility of the cobalt oxide species, dispersion of the cobalt, average cobalt clusters size, water–gas shift (WGS) activity and activity and selectivity of FTS is investigated. Using carbon nanotubes as cobalt catalyst support was found to cause the reduction temperature of cobalt oxide species to shift to lower temperatures. The strong metal-support interactions are reduced to a large extent and the reducibility of the catalysts improved significantly. CNT aided in well dispersion of metal clusters and average cobalt clusters size decreased. Results are presented showing that the hydrocarbon yield obtained by inventive CNT supported cobalt catalyst is surprisingly much larger than that obtained from cobalt on alumina supports. The maximum concentration of active surface Co° sites and FTS activity for alumina and CNT supported catalysts are achieved at 34 wt.% and 40 wt.% cobalt loading respectively. CNT caused a slight decrease in the FTS product distribution to lower molecular weight hydrocarbons.     

Nanotubes and nanofilaments from carbon monoxide disproportionation over Co/MgO catalysts: I. Growth versus catalyst state

A catalyst prepared from the pyrolysis of Co and Mg nitrates and citric acid after their co-dissolution in water was used for carbon deposition from CO. Good yields of nanotubes or nanofilaments were obtained over catalysts which had been reduced by H₂ without preliminary treatment at high temperature. Nanotubes with 10 or more cylindrical carbon layers were obtained from pure CO or from CO+CO₂ mixtures. Nanofilaments with truncated conical layers were obtained from CO+H₂ mixtures in the 500–600 °C range. In both cases, high shape selectivity was obtained and almost all MgO could be eliminated by HCl treatment. The only significant impurities were embedded cobalt particles. This process is therefore suitable for preparing nanotubes or nanofilaments with good shape selectivity and 98 wt% purity. Lowering the Co content of the catalyst produces thinner nanotubes but reduces the yield.     

Kinetic study of carbon nanotube synthesis over Mo/Co/MgO catalysts

The kinetics of carbon nanotube (CNT) synthesis by decomposition of CH₄ over Mo/Co/MgO and Co/MgO catalysts was studied to clarify the role of catalyst component. In the absence of the Mo component, Co/MgO catalysts are active in the synthesis of thick CNT (outer diameter of 7-27 nm) at lower reaction temperatures, 823-923 K, but no CNTs of thin outer diameter are produced. Co/MgO catalysts are significantly deactivated by carbon deposition at temperatures above 923 K. For Mo-including catalysts (Mo/Co/MgO), thin CNT (2-5 walls) formation starts at above 1000 K without deactivation. The significant effects of the addition of Mo are ascribed to the reduction in catalytic activity for dissociation of CH₄, as well as to the formation of Mo₂C during CNT synthesis at high temperatures. On both Co/MgO and Mo/Co/MgO catalysts, the rate of CNT synthesis is proportional to the CH₄ pressure, indicating that the dissociation of CH₄ is the rate-determining step for a catalyst working without deactivation. The deactivation of catalysts by carbon deposition takes place kinetically when the formation rate of the graphene network is smaller than the carbon deposition rate by decomposition of CH₄.     

Iron catalyst supported on carbon nanotubes for Fischer-Tropsch synthesis: Effects of Mo promotion

Our studies on the application of carbon nanotubes (CNTs) as support have shown that iron catalysts supported on CNTs are active and selective catalysts for Fischer-Tropsch synthesis (FTS). However, these catalysts experienced deactivation as a result of active site agglomerations. In order to control the agglomeration of active site, which is an important step in developing a novel catalyst supported on carbon-based supports, the effects of Mo promotion on deactivation behavior of iron catalysts supported on CNTs were studied. In this work the properties and catalytic performance of unpromoted iron catalysts were compared with a promoted catalyst with different Mo contents (0.5, 1, 5, and 12 wt%). Based on TEM and XRD analyses, promotion of the catalysts with Mo resulted in production of smaller metal particles compared to the unpromoted iron catalyst. According to XRD analysis, Mo species were deposited in their amorphous structure. TPR analyses showed that addition of Mo increased reduction temperature significantly. Based on TEM and XRD analyses, the particle size of the iron oxides in the unpromoted catalyst increased from 16 to 25 nm under FT operating conditions, while the particle size of the iron oxide in the Mo promoted catalysts (∼12-14 nm) did not change noticeably under the same operating conditions. Activity, selectivity and stability of the unpromoted and Mo promoted catalysts showed that addition of 0.5-1 wt% Mo resulted in a more stable catalyst. Higher contents of Mo (5 and 12 wt%) decreased the activity of the catalysts due to catalytic site coverage and lower extent of reduction. Mo promotion (0.5-12 wt%) increased the selectivity of the catalysts toward lighter hydrocarbons. The promotion of the iron catalyst with 0.5 wt% of Mo stabilized the activity of the catalyst with minimal increase (2%) in methane selectivity.     

Ruthenium promoted cobalt–alumina catalysts for the synthesis of high-molecular-weight solid hydrocarbons from CO and hydrogen

The effect of the ruthenium promotion of Fischer–Tropsch (FT) cobalt–alumina catalysts on the temperature of catalyst activation reduction and catalytic properties in the FT process is studied. The addition of 0.2–1 wt % of ruthenium reduces the temperature of reduction activation from 500 to 330–350°C while preserving the catalytic activity and selectivity toward C₅₊ products in FT synthesis. FT ruthenium-promoted Co–Al catalysts are more selective toward higher hydrocarbons; the experimental value of parameter α_ASF of the distribution of paraffinic products for ruthenium-promoted catalysts is 0.93–0.94, allowing us to estimate the selectivity toward C₂₀₊ synthetic waxes to be 48 wt %, and the selectivity toward C₃₅₊ waxes to be 23 wt %. Ruthenium-promoted catalysts also exhibit high selectivity toward olefins.     

Slurry-Phase Fischer–Tropsch Synthesis Using Co/γ-Al2O3, Co/SiO2 and Co/TiO2: Effect of Support on Catalyst Aggregation

The catalytic performance of Co/γ-Al₂O₃, Co/SiO₂ and Co/TiO₂ catalysts has been investigated in a slurry-phase Fischer–Tropsch Synthesis (FTS). Although Co/SiO₂ catalyst shows higher CO conversion than the other catalysts, the intrinsic activity is much higher on Co/TiO₂ due to large pore size and low deactivation of large cobalt particles by reoxidation mechanism. Co/γ-Al₂O₃ catalyst confirms low formation rate of oxygenates and C₅₊ selectivity because of deactivation of catalyst due to catalyst aggregation and reoxidation by the in situ generated water during the FTS reaction. Long-chain hydrocarbons such as wax formed during FTS reaction generally contains water and trace amount of oxygenate which are conducive to the formation of a macro-emulsion of wax products. Formation of such macro-emulsion on the catalyst suggests that the presence of proper amount of alcohol content derived FTS reaction on large pore of catalyst inhibits the catalyst aggregation. The intrinsic activity (turn-over frequency; TOF) of cobalt-based catalysts, in a slurry-phase FTS reaction, is affected by the average pore size of catalyst, cobalt particle size, degree of reduction of cobalt species and possible reoxidation by in situ generated water.     

Effect of Addition of Ni metal catalyst onto the Co and Fe supported catalysts for the formation of carbon nanotubes

Production of novel porous material is a major target in current material science research due to its wide applications. As carbon nanotube (CNTs) is a one dimensional hollow structure it is also one of the promising materials in applications ranging from electronics to hydrogen storage medium. Catalytic chemical vapor deposition (CCVD) is a method whereby CNTs can be produced in large amount. Thus, in this work, we have synthesized CNTs via pyrolysis of acetylene using various supported transition-metal catalysts in a fixed-bed reactor. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to investigate the CNTs structure. The structures of nanotubes formed by acetylene pyrolysis were dependent on the catalysts used. It was found that alumina supported Ni/Fe catalyst inhibited the formation of CNTs growth while alumina supported Ni/Co catalyst gave high density of CNTs. However, nanotubes grown over alumina supported Ni/Fe catalyst were less dense due to the deactivation of the catalyst at the early stage of the pyrolysis process.     

Effects of bimetallic catalyst composition and growth parameters on the growth density and diameter of carbon nanotubes

Multi-wall carbon nanotubes (MWNTs) were synthesized by catalytic decomposition of acetylene over Fe, Ni and Fe-Ni bimetallic catalysts supported on alumina under various controlled conditions. The growth density and diameter of CNTs were markedly dependent on the activation time of catalysts in H₂ atmosphere, reaction time, reaction temperature, flow rate of acetylene, and catalyst composition. Bimetallic catalysts were apt to produce narrower diameter of CNTs than single metal catalysts. For the growth of CNTs at 600 ‡C under 10/100 seem flow of C₂H₂/H₂ mixture, the narrowest diameter about 20 nm was observed at the reaction time of 1 h for 20Fe : 20Ni : 60Al₂O₃ catalyst, but at that of 1.5 h for 10Fe : 30Ni : 60Al₂O₃ catalyst. It was considered that the diameter and density of CNTs decreased with the increase of the growth time mainly due to hydrogen etching. The growth of CNTs followed the tip growth mode.     

Simulation Analysis of a GTL Process Using Aspen Plus

Gas‐to‐liquid (GTL) processes are becoming attractive due to the increasing price of crude oil. Process simulation analysis on the integrated GTL process is essential as part of an extended process integration analysis of the research subjects. The two sub‐process models for the GTL process, i.e., the syngas generation process and the Fischer Tropsch synthesis (FTS) process, are analyzed in detail with ASPEN Plus. The autothermal reforming process (ATR) is analyzed using Aspen Plus based on the Gibbs reactor model, while FTS is simulated with ASPEN Plus based on detailed kinetic models for industrial iron and cobalt catalysts. Integrated GTL processes with iron and cobalt‐based catalysts were simulated using ASPEN Plus. The optimal flowsheet structures were selected for each catalyst based on the overall performance in terms of thermal and carbon efficiency and product distributions. For the cobalt‐based catalyst, the full conversion concept without CO₂ removal from the FT tail gas is optimal. On the other hand, the once‐through concept with two series reactors and CO₂ removal from raw syngas is considered optimal for the iron‐based catalyst. The thermal efficiency to crude products is likely to be ca. 60 % for the cobalt‐based catalyst, whereas it is in the range of 49–55 % for the iron‐based catalyst. The carbon efficiency using the water‐gas shift reaction is lower using the iron‐based catalyst (61–68 %) than the cobalt‐based catalyst (73–75 %). As expected, the cobalt‐based catalyst is more active and selective, which offers better selectivity towards C₅+ (75–79 %). The selectivity towards C₅+ for the iron‐based catalyst lies in the range 63–75 %.     

Effect of Palladium on Iron Fischer–Tropsch Synthesis Catalysts

Studies were conducted to investigate the effect of Pd on the Fischer–Tropsch Synthesis (FTS) selectivity, activity and kinetics as well as on the water–gas shift activity of an iron catalyst. Two palladium promoted catalysts (Pd0.002/Fe100 and Pd0.005/Fe100) were prepared from a base Fe100/Si5.1 (atomic ratio) catalyst. Results of FTS over the two palladium promoted catalysts were compared to those obtained from the K/Fe/Si base catalyst and a Cu/K/Fe/Si catalyst. The results indicate that Pd enhanced the FT activity while the selectivity for CO₂ and CH₄ changed little compared to the results for the base catalyst and the Cu promoted catalyst. Palladium promotion had a negative effect on the C₂—C₄ olefin to paraffin ratio. Pd promotion led to a higher WGS rate than the other two catalysts at high syngas conversions. A higher WGS rate compared to the FTS rate was obtained only for the Pd promoted catalysts. The FTS rate constant for the Pd promoted catalyst is higher than the base catalyst but lower than for the Cu promoted catalyst.     

Co—Mo／MgO作催化剂CVD法制备碳纳米管

研究了催化剂的制备方法对合成碳纳米管的影响,分别采用溶胶凝胶法、浸渍法和燃烧法制备了Co-Mo／MgO催化剂,并以乙炔为碳源,Ar气为保护气,在750-950℃常压下生长碳纳米管。采用TEM对所得产物进行了表征,结果表明,对于Co-Mo／MgO体系,相对浸渍法和燃烧法,溶胶凝胶法是很好的选择,可以得到数量与质量均较好的碳纳米管,并讨论了溶胶凝胶法制备碳纳米管的过程中工艺参数的择优。     

ZSM-5 Supported Cobalt Catalyst for the Direct Production of Gasoline Range Hydrocarbons by Fischer–Tropsch Synthesis

Abstract  

Fischer–Tropsch synthesis (FTS) reaction for the direct production of gasoline range hydrocarbons (C₅–C₉) from syngas was investigated on cobalt-based FTS catalyst supported on the ZSM-5 possessing a four different Si/Al ratio. The FTS catalysts were prepared by impregnation method using cobalt nitrate precursor in a slurry of ZSM-5, and they were characterized by surface area, XRD, H₂-TPR and NH₃-TPD. Cobalt supported catalyst on ZSM-5 having a low Si/Al ratio of 15 was found to be superior to the other catalysts in terms of better C₅–C₉ selectivity due to the formation of small cobalt particle and the presence of larger number of weak acidic sites. It also exhibited the highest catalytic activity because of the higher reducibility and the small cobalt particle size.     

碳纳米管改性对Au/CeO2催化剂乙醇部分氧化制氢的影响

采用沉积沉淀法制备了一系列碳纳米管改性的Au/CeO₂催化剂,以乙醇部分氧化制氢为探针反应,研究了碳纳米管对Au/CeO₂催化剂乙醇部分氧化性能的影响,并运用XRD、TPR、BET等方法对催化剂进行了表征。结果表明,碳纳米管的添加提高了Au/CeO₂催化剂的比表面积、孔容和吸氧量,催化剂的氢气选择性先随碳纳米管添加量的增加而大幅增加,碳纳米管的添加量达6%～10%时,氢气选择性达到43%。进一步提高碳纳米管的含量,氢气选择性增加幅度不大。碳纳米管的添加可以有效抑制副产物CO的产生。     

Formation of bamboo-shape carbon nanotubes by controlled rapid decomposition of picric acid

In the presence of catalysts, carbon nanotubes (CNTs) can efficiently grow in the environment generated by the rapid decomposition of normal explosives. Controlling the reaction parameters of a mixture of picric acid (PA) with cobalt acetate and paraffin can lead to a well-defined morphology of CNTs. The formation of bamboo-shape tubes is favorable at relatively high Co(AC)₂/PA and paraffin/PA ratios. It is found that the bamboo-shape tubes are different in morphology and structure and can be categorized roughly into two types, according to the participation of the catalyst nanoparticles. The formation of the two types is discussed.     

Characterization,activity and selectivity of ethylenediamine modified Co/SiO<Subscript>2</Subscript> FT catalyst prepared by sol-gel method

Co/SiO₂ catalysts were prepared by sol-gel method with varied en (ethylenediamine)/Co molar ratios under the same pH. Their physical-chemical properties were compared with those prepared with similar en/Co molar ratios at natural pH or without adding ethylenediamine. Regardless of pH, the catalysts prepared using ethylenediamine possessed high microporosity, which led to a better selectivity to C_5–18 hydrocarbons, versus the catalyst possessing higher mesoporosity which showed slightly higher C₁₈₊ selectivity. As enough positions in the coordination sphere were blocked by ethanediamine ligands, the formation of cobalt silicate disfavored for (en/Co=2) catalysts, which resulted in the higher activity in FT reaction. Whereas the catalysts prepared with lower or higher en/Co molar ratio both showed lower activity due to the formation of [(SiO)Co(en)(EtOH)₃] species or the electronic adsorption of cobalt complexes in the negatively charged silica surface, respectively. However, for the catalyst without using ethylenediamine, the lowest activity and the highest CH₄ selectivity obtained due to its much lower reducibility. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Silica-Supported Cobalt Catalysts for Fischer–Tropsch Synthesis: Effects of Calcination Temperature and Support Surface Area on Cobalt Silicate Formation

Cobalt silicate formation reduces the activity of the catalyst in Fischer–Tropsch synthesis (FTS). In this article, the effects of calcination temperature and support surface area on the formation of cobalt silicate are explored. FTS catalysts were prepared by incipient wetness impregnation of cobalt nitrate precursor into various silica supports. Deionized water was used as preparation medium. The properties of catalysts were characterized at different stages using FTIR, XRD and BET techniques. FTIR-ATR analysis of the synthesized catalyst samples before and after 48 h reaction identified cobalt species formed during the impregnation/calcination stage and after the reduction/reaction stage. It was found that in the reduction/reaction stage, metal-support interaction (MSI) added to the formation of irreducible cobalt silicate phase. Co/silica catalysts with lower surface area (300 m²/g) exhibited higher C₅₊ selectivity which can be attributed to less MSI and higher reducibility and dispersion. The prepared catalysts with different drying and calcination temperatures were also compared. Catalysts dried and calcined at lower temperatures exhibited higher activity and lower cobalt silicate formation. The catalyst sample calcined at 573 K showed the highest CO conversion and the lowest CH₄ selectivity.     

Interplay of interfacial compounds,catalyst thickness and carbon precursor supply in the selectivity of single-walled carbon nanotube growth

This study is devoted to elucidate the interplay of catalyst thickness and growth conditions in the activation and selectivity of single-walled carbon nanotube growth using cobalt deposited on Si/SiO₂ as a model system. In situ Raman studies reveal that thin catalyst layers require a higher pressure of carbon precursor to initiate nanotube growth. However, if the catalysts are pre-reduced, all catalyst thicknesses display the same low threshold pressure and a higher yield of single-walled carbon nanotubes. To explain these results, catalysts formed from a gradient of cobalt thickness are studied. Surface analyses show that during the catalyst preparation, catalyst atoms at the interface with silica form small and hard-to-reduce silicate nanoparticles while the catalyst in excess leads to the formation of large oxide particles. Weakly-reducing conditions of pretreatment or synthesis are sufficient to reduce the large oxide particles and to lead to the growth of large-diameter multi-walled carbon nanostructures. However, highly-reducing conditions are required to reduce the small silicate domains into small cobalt particles able to grow single-walled carbon nanotubes. These results show that reaction of the catalyst with the support to form more refractory compounds greatly impact the nucleation yield and the growth selectivity of single-walled carbon nanotubes.