Product distributions of Fischer-Tropsch synthesis over Co/AC catalyst

The product distributions of Fischer-Tropsch synthesis over Co/AC catalyst are investigated under different reaction conditions in an integral fixed bed reactor.It is found that the product distributions deviate from the ASF distribution.The deviation from ASF distribution is analyzed by taking the readsorption of alkenes and the following secondary reaction into consideration.It is noted that the contents of alcohol,alkene and alkane decline with the increasing carbon number,showing a slighter declining tendency of alkanes than those of alkenes and alcohols.It is also found that high temperature,space velocity,H2/CO in feed gas and low pressure are preferential for light hydrocarbons and alcohols while against the chain propagation.The effect of space velocity on the product distributions especially on the light products is not obvious.It is noticed that low temperature,space velocity,H2/CO and high pressure lead to high contents of alcohols;high temperature,H2/CO and low space velocity lead to high contents of alkanes.The effect of pressure on the amounts of alkanes is not significant;high space velocity and low temperature,pressure,H2/CO are preferential for alkenes.     

浸渍溶液pH值对Co/TiO2催化剂F-T反应性能的影响

Fischer—Tropsch合成（简称F—T合成）是煤和天然气转化制取液体燃料的重要途径,催化剂的研制与开发是该过程实现工业化的关键步骤。钻基催化剂以其较高的加氢反应活性、较高的长链烃选择性和较低的水煤气变换活性而成为F—T合成中最有前途的催化体系之一。钴基催化剂的制备通常采用浸渍法。除了能够提高催化剂的比表面积和分散度,载体可以与金属发生相互作用而改变活性金属组分的结构组成、电子状态等,从而影响催化剂的催化反应性能。TiO2作为F—T合成的载体近年来受到普遍的关注。文献[7,8]是针对TiO2载体的低表面有针对性地添加无机氧化物黏接剂,提高金属钴的负载量,从而改进催化剂的反应性能;或者是添加助剂及第二金属组分以提高催化剂分散与还原性能。本文通过调节浸渍液pH值控制钻钛的相互作用并与催化剂反应性能关联,以期为催化剂制备条件的选择提供参考。     

用于费-托合成的高分散型钴基催化剂*

负载型钴基催化剂是天然气基费托合成的一种重要催化剂,其金属分散度和活性位密度是决定费托合成反应活性和产物选择性（CH4%, C5+%）的关键因素。因此,提高金属钴的分散度和催化剂的还原度是提高金属钴的原子利用率、降低催化剂成本的一条有效途径。本文综述了近年来高分散型钴基催化剂的研究进展,重点探讨了催化剂制备方法、载体类型及贵金属助剂对催化剂分散度和还原性的影响,以及影响高分散型钴基催化剂的费托合成反应活性、产物选择性和反应稳定性的因素,并对负载型钴基催化剂今后的研究发展提出了一些建议。     

Fischer-Tropsch synthesis by nano-structured iron catalyst

Effects of nanoscale iron oxide particles on textural structure, reduction, carburization and catalytic behavior of precipitated iron catalyst in Fischer-Tropsch synthesis (FTS) are investigated. Nanostructured iron catalysts were prepared by microemulsion method in two series. Firstly, Fe2O3, CuO and La2O3 nanoparticles were prepared separately and were mixed to attain Fe/Cu/La nanostructured catalyst (sep-nano catalyst); Secondly nanostructured catalyst was prepared by co-precipitation in a water-in-oil microemulsion method (mix-nano catalyst). Also, conventional iron catalyst was prepared with common co-precipitation method. Structural characterizations of the catalysts were performed by TEM, XRD, H2 and CO-TPR tests. Particle size of iron oxides for sep-nano and mix-nano catalysts, which were determined by XRD pattern (Scherrer equation) and TEM images was about 20 and 21.6 nm, respectively. Catalyst evaluation was conducted in a fixed-bed stainless steel reactor and compared with conventional iron catalyst. The results revealed that FTS reaction increased while WGS reaction and olefin/paraffin ratio decreased in nanostructured iron catalysts.     

单相Co_2C的制备及其费-托合成催化性能研究

采用CO与金属钴在温度280℃,压力2 MPa的条件下反应48 h后制备得到单相Co_2C催化剂。通过XRD、H2-TPR、TEM和XAS对催化剂的结构和组成进行表征并考察了单相Co_2C催化剂在费-托合成反应中的稳定性与催化性能。结果表明,随着费-托合成反应的进行,Co_2C催化剂的活性缓慢上升,同时伴随着产物中甲烷的选择性逐渐降低,C5+的选择性逐渐升高。对比反应前后催化剂发现,反应后的催化剂为Co_2C和少量金属Co的混合相,表明在费-托合成反应条件下,单相Co_2C会发生部分分解,生成的金属Co会导致CO的转化率和产物的选择性发生变化。     

Particle size effects in Fischer-Tropsch synthesis by Co catalyst supported on carbon nanotubes

The effect of Co particle size on the Fischer-Tropsch synthesis (FTS) activity of carbon nanotube (CNT)-supported Co catalysts was investigated. Microemulsion (using water-to-surfactant molar ratios of 2 to12) and impregnation techniques were used to prepare catalysts with different Co particle sizes. Kinetic studies were performed to understand the effect of Co particle size on catalytic activity. Size-dependent kinetic parameters were developed using a thermodynamic method, to evaluate the structural sensitivity of the CNT-supported Co catalysts. The size-independent FTS reaction rate constant and size-independent adsorption parameter increased with increasing reac-tion temperature. The Polani parameter also depended on catalyst particle size, because of changes in the catalyst surface coverage.     

Activation pressure studies with an iron-based catalyst for slurry Fischer-Tropsch synthesis

Fischer-Tropsch synthesis (FTS) was carried out with an industrial iron-based catalyst (100Fe/5Cu/6K/16SiO2, by weight) under the baseline conditions in a stirred tank slurry reactor (STSR). The effects of activation pressure on the catalyst activity and selectivity were investigated. It was found that iron phase compositions, textural properties, and FTS performances of the catalysts were strongly dependent on activation pressure. The high activation pressure retards the carburization. Møssbauer effect spectroscopy (MES) results indicated that the contents of the iron carbides clearly decrease with the increase of activation pressure, especially for the activation pressure increasing from 1.0 MPa to 1.5 MPa, and the reverse trend is observed for superparamagnetic Fe3+ (spm). The higher content of Fe3+ (spm) results in the higher amount of CO2 in tail gas when the catalyst is reduced at higher pressure. The catalyst activity decreases with the increase of activation pressure. The high quantity of iron carbides is necessary to obtain high FTS activity. However, the activity of the catalyst activated in syngas can not be predicted solely from the fraction of the carbides. It is concluded that activation with syngas at the lower pressure would be the most desirable for the better activity and stability on the iron-based catalyst.     

Deactivation studies of nano-structured iron catalyst in Fischer-Tropsch synthesis

A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis (FTS) was prepared by micro-emulsion method. Compositions of bulk iron phase and phase transformations of carbonaceous species during catalyst deactivation in FTS reaction were characterized by temperature-programmed surface reaction with hydrogen (TPSR-H2), and XRD techniques. Many carbonaceous species on surface and bulk of the nano-structured iron catalysts were completely identified by combined TPSR-H2 and XRD spectra and which were compared with those recorded on conventional co-precipitated iron catalyst. The results reveal that the catalyst deactivation results from the formation of inactive carbide phases and surface carbonaceous species like graphite, and it will be increased when the particle size of iron oxides was reduced in FTS iron catalyst.     

Recent advances in understanding the key catalyst factors for Fischer-Tropsch synthesis

Catalytic conversion of synthesis gas (CO+H₂) into hydrocarbons, also known as Fischer-Tropsch (FT) synthesis, is a crucial reaction for the transformation of non-petroleum carbon resources such as coal, natural gas, shale gas, coal-bed gas and biogas, as well as biomass into liquid fuels and chemicals. Many factors can influence the catalytic behavior of a FT catalyst. This review highlights recent advances in understanding some key catalyst factors, including the chemical state of active phases, the promoters, the size and the microenvironment of active phase, which determine the CO conversion activity and the product selectivity, particularly the selectivity to C₅₊ hydrocarbons.     

Studies on product distribution of alkali promoted iron catalyst in Fischer-Tropsch synthesis

The dependencies of hydrocarbon product distributions of alkali promoted iron catalyst in Fischer-Tropsch synthesis have been studied. The concept of two superimposed Anderson-Schulz-Flory distributions has been applied for the representation of the effects of Mg, La and Ca promoters on product distributions. The FTS performance of the catalysts was tested in a fixed bed reactor under the conditions 563 K, 1.7 MPa, H2/CO = 1 and space velocities 4.86 and 13.28 nl h-1 gFe-1 . The results indicate that approp...     

Chain termination mechanism in the Fischer-Tropsch synthesis on a Co/SiO<Subscript>2</Subscript>Zr(IV) catalyst at elevated pressure

The mechanism for the formation of C₂₊ paraffins differs from the mechanism for the formation of methane. While methane is obtained due to hydrogenation of methyl groups, C₂₊ hydrocarbons are formed as the result of the conversion of alkyl intermediates into hydroalkene intermediates, which can decompose to give olefins or undergo hydrogenation to give saturated hydrocarbons. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 175–179, May–June, 2008.     

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.     

Mn和Zr助剂对介孔碳负载钴基催化剂费托合成反应性能的影响

采用浸渍法制备了Mn和Zr改性的介孔碳负载钴基催化剂,采用X射线衍射（XRD）、比表面积测定、H₂程序升温还原（H₂-TPR）、H₂/CO程序升温脱附（TPD）及X射线光电子能谱（XPS）等手段对催化剂的物化性质进行了表征,采用固定床反应器对其F-T反应性能进行了研究。结果表明,Mn或Zr助剂的添加均降低了CH₄的选择性。其中,Mn助剂的添加提高了C_2-4的选择性,提高了烯烷比,而Zr的添加提高了钴物种的分散度,增加了反应活性位点,显著提高了钴基催化剂的F-T反应活性和C₅₊选择性。     

焙烧温度对含Mg助剂的铁基催化剂F-T合成反应性能的影响

采用连续共沉淀和喷雾干燥技术相结合的方法制备了Mg助剂的Fe/Cu/K/SiO2催化剂,采用N2物理吸附、XRD、MES 和H2-TPR等表征手段,考察了焙烧温度对催化剂比表面积、体相结构和还原性能的影响。结果表明,随着焙烧温度的升高,催化剂的比表面积降低,平均孔径增大,体相中α-Fe2O3晶粒逐渐增大,催化剂变的越来越难还原,其结构更加稳定。在H2/CO （摩尔比）= 2.2、250 ℃、2.0 MPa和2 000 h－1于固定床反应器考察了焙烧温度对该催化剂F-T合成反应性能的影响,结果表明,随着焙烧温度的升高,催化剂的F-T合成反应活性降低,在运行过程中反应活性逐渐增加直至达到平稳,但达到平稳所需的诱导期越来越长;提高焙烧温度使烃产物分布向重质烃方向转移,有利于降低CH4的选择性,促进重质烃的生成。     

在Co/SiO2作催化剂的Fischer-Tropsch反应中温度对合成气吸附行为及稳定性的影响

考察了反应温度对Co/SiO2催化剂在Fischer-Tropsch(F-T)合成中合成气吸附行为及稳定性的影响. 采用FTIR, TPSR, XRD, BET, HTPD和TPR等手段对催化剂进行了表征. 结果表明, CO在催化剂表面的吸附为活化吸附, 在270 ℃仍稳定存在, 随着反应温度的升高, 催化剂上发生的主反应由CO加氢链增长反应向Boudouard反应转化, 当反应温度≥350 ℃时, 以Boudouard反应为主. 另外, 随反应温度升高, 金属钴的烧结现象变得明显, 并伴随着硅酸钴或水合硅酸钴物种的生成. 在催化剂的失活因素中, 烧结为主要原因.     

Nanosized cobalt-based catalyst prepared by supercritical phase condition for Fischer-Tropsch synthesis

A series of nanosized Co/Zn/Mn/K composite catalysts for Fischer-Tropsch synthesis (FTS) were prepared by supercritical fluid drying (SCFD) method and common drying (CD) method. The nanosized cobalt-based catalysts were characterized by XRD, TEM and BET techniques. Their catalytic performances were tested in a slurry-bed reactor under FTS reaction conditions. The drying and crystallization were carried out simultaneously during SCFD, therefore, the catalysts prepared by SCFD method have ideal structure and show the FTS performance superior to the others prepared by CD method. The FTS activity and selectivity were improved via adding Zn, Mn and K promoters, and less CH₄ and CO₂ as well as higher yield of C₅₊ products were achieved. The optimal performance of a 92% CO conversion and a 65% C₅₊ product yield was obtained over a catalyst with the component of Co/Zn/Mn/K = 100/50/10/7. Furthermore, the catalytic performance was studied under the conditions of liquid-phase and supercritical phase slurry-bed, and C₅₊ product yield were 57.4% and 65.4%, respectively. In summary, better catalytic performance was obtained using the nanosized catalyst prepared by SCFD method under supercritical reaction conditions, resulting in higher conversion of CO, less CO₂ byproduct, and higher yield of C₅₊ products.     

Co/HMS和Co/SiO2催化剂的表征及在费-托合成反应中的催化性能

 HMS介孔分子筛经水热处理得到无定形SiO2,分别以无定形SiO2和HMS为载体,用浸渍法制得了15%Co/SiO2和15%Co/HMS催化剂. 研究表明: 氧化态Co/SiO2和Co/HMS催化剂中的钴物种以Co3O4形式存在,且Co3O4晶粒粒径均较相应催化剂的孔径大,故有部分钴物种存在于催化剂外表面; 氧化态Co/HMS催化剂中的钴物种堵塞孔道较为严重; Co/HMS催化剂中存在较强的金属-载体相互作用,因此Co/HMS催化剂较Co/SiO2催化剂难还原; Co/HMS催化剂还原后具有较高的钴分散度,使其具有优异的费-托合成反应性能.     

多级孔ZSM-5负载的钴催化剂的费-托合成催化性能

采用水蒸气辅助转晶(SAC)法合成了粒径均一(180 nm)的纳米ZSM-5颗粒,颗粒间堆积形成大量的开放介孔,与ZSM-5的微孔共同形成多级孔结构。以该材料为载体采用满孔浸渍法制备了负载量为15%(质量分数)的钴催化剂。采用XRD、SEM、TEM、N_2物理吸附-脱附等表征技术对多级孔ZSM-5载体及其负载催化剂的形貌和结构进行了表征,并对催化剂的费-托合成催化性能进行了测试。结果表明,相比于大颗粒的ZSM-5和商业ZSM-5,多级孔ZSM-5负载的钴催化剂的费-托合成活性最高,CH_4选择性最低,C_(5-20)产物的选择性高达68.9%,这归因于多级孔ZSM-5的介孔孔道有效地促进反应过程中产物的传质扩散以及ZSM-5微孔骨架上的酸中心促进了长链烃产物的二次加氢裂解。     

Synthesis and characterization of multiwall carbon nanotubes/alumina nanohybrid-supported cobalt catalyst in Fischer-Tropsch synthesis

Multiwall carbon nanotubes (MWNTs) and alumina are combined to give a new type of nanohybrid for Fisher-Tropsch synthesis (FTS) catalyst support. Alumina nano-particles (10 wt%) were introduced directly on functionalized MWNTs by a modified sol-gel method. Microstructure observations show that alumina particles were homogeneously dispersed on the inside and outside of modified MWNTs surfaces. 15 wt% cobalt loading catalysts were prepared with this nanohybrid and γ-alumina as a reference, using a sol-gel technique and wet impregnation method respectively. These catalysts were characterized by TEM, XRD, N₂-adsorption, H₂ chemisorption and TPR. The deposition of cobalt nanoparticles synthesized by sol-gel technique on the MWNTs nanohybrid shift the reduction peaks to a low temperature, indicating higher reducibility for uniform cobalt particles. Nanohybrid also aided in high dispersion of metal clusters and high stability and performance of catalyst. The proposed MWNTs nanohybrid-supported cobalt catalysts showed the improved FTS rate (g_HC/(g_cat·min)), CO conversion (%), and water gas shift rate (WGS)(g_CO2/(g_cat·h)) of 0.012, 52, and 30E-3, respectively, as compared to those of 0.007, 25, and 18E-3, respectively, on the γ-alumina-supported cobalt catalysts with the same Co loading.     

Deactivation studies of bifunctional Fe-HZSM5 catalyst in Fischer-Tropsch process

A physical mixture of alkali-promoted iron catalyst with binder based on Fischer-Tropsch synthesis and an acidic co-catalyst （HZSM5） for syngas conversion to hydrocarbons was studied in a fixed bed micro reactor. Deactivation data were obtained during the synthesis over a 1400 h period. The deactivation studies on iron catalyst showed that this trend followed the phase transformation Fe2.2C （ ε′） → Fe5C2 （χ） → Fe3C （θ）, and the final predominant phase of the catalyst was Fe3C （θ）. Deactivation of zeolite component in bifunctional catalyst may be caused by coking over the zeolitic component, dealumination of zeolite crystals, and migration of alkali promoters from iron catalyst under synthesis conditions. The deactivation rate of iron catalyst was also obtained.