Dynamics of the fischer-tropsch synthesis over a supported cobalt catalyst

Step-change experiments between H₂, CO, and syngas mixtures with time resolution of ca. 0.3 s were undertaken to critically test mechanisms proposed in the literature for the Fischer-Tropsch synthesis. A silica-supported cobalt catalyst was used. Results suggest C₂₊ olefins and branched paraffins form from a carbon deposit on the catalyst surface. Two pathways appear to exist for methane formation. The first of these is from the carbon deposit through direct hydrogenation and through hydrogenolysis of the long-chain materials formed. The second pathway is hydrogenation of strongly adsorbed CO.     

Studies of the fischer-tropsch synthesis on a colbalt catalyst. III. mechanistic formulation of the kinetics of selectivity for higher hydrocarbon formation

Mechanistic models are derived to quantify selectivity in the Fischer-Tropsch synthesis. The models are fitted to experimental selectivity data obtained on a cobalt catalyst and are found to give a satisfactory fit. Results show that branching reactions can be explained by assuming a rate limiting 1-2 hydrogen shift. For small molecules the 1-2 shift takes place on one site, whereas larger molecules need an adjacent sit for the shift to take place. The “break” arises from the sum of two Anderson-Schulz-Flory distributions arising on two different locations.     

The effects of catalyst surface heterogeneity on the fischer-tropsch synthesis

We find that the surface energetic heterogeneity of Fischer-Tropsch catalysts is either not important kinetically or may be masked by the effect of increasing molecular size, so that the classical Anderson-Schulz-Flory distribution is routinely observed in product distributions. The anomalous yields of C₁ and C₂ observed in many cases may also be due to surface heterogeneity but can in practice be readily, and more conveniently, accounted for by assigning individual rate constants to their formation. The “break” sometimes observed in ASF distributions cannot be explained by surface heterogeneity and is best explained by the presence of two distinct modes of product formation.     

Fischer-Tropsch synthesis by reduced graphene oxide nanosheets supported cobalt catalysts: role of support and metal nanoparticle size on catalyst activity and products selectivity

In this paper,a series of cobalt catalysts supported on reduced graphene oxide(rGO)nanosheets with the loading of 5,15 and 30 wt-%were provided by the impregnation method.The activity of the prepared catalysts is evaluated in the Fischer-Tropsch synthesis(FTS).The prepared catalysts were carefully characterized by nitrogen adsorption-desorption,hydrogen chemisorption,X-ray diffraction,Fourier transform infrared spectroscopy,Raman spectroscopy,temperature programmed reduction,transmission electron microscopy,and field emission scanning electron microscopy techniques to confirm that cobalt particles were greatly dispersed on the rGO nanosheets.The results showed that with increasing the cobalt loading on the rGO support,the carbon defects are increased and as a consequence,the reduction of cobalt is decreased.The FTS activity results showed that the cobalt-time yield and turnover frequency passed from a maximum for catalyst with the Co0 average particle size of 15 nm due to the synergetic effect of cobalt reducibility and particle size.The products selectivity results indicated that the methane selectivity decreases,whereas the C5+selectivity raises with the increasing of the cobalt particle size,which can be explained by chain propagation in the primary chain growth reactions.     

The fischer—tropsch synthesis over a ruthenium catalyst under composition cycling

The influence of feed composition cycling on the activity and selectivity of the Fischer-Tropsch synthesis over an alumina-supported ruthenium catalyst was investigated using a fixed-bed reactor at 211°C and 446 kPa total pressure. Forced composition cycling suppressed the overall synthesis rate but increased the rates of formation of the C₁ to C₄ paraffins and shifted the paraffin/olefin ratio.     

负载型Co基F-T合成催化剂中贵金属助剂促进作用的研究进展

在负载型Co基催化剂中添加少量贵金属助剂能显著影响催化剂活性、选择性与稳定性。贵金属助剂的添加提高了Co活性组分的还原度与分散度,增加了催化剂表面的活性位数目,改变了催化剂的几何结构和电子结构,影响CO、H₂或中间产物的吸附活化行为,抑制催化剂积炭和金属Co小粒子的再氧化。综述贵金属助剂对催化剂活性中心性质、反应物的吸附活化行为和催化剂反应稳定性的影响。     

费托合成钴催化剂的失活与再生研究进展

为降低费托合成钴催化剂成本,提高费托合成钴催化剂的稳定性和寿命,分析了费托合成钴催化剂的失活与再生机理,论述了费托合成钴催化剂的再生方法。结果表明,中毒、烧结长大、积碳、氧化及固相反应是造成费托合成钴催化剂失活的主要原因。通过净化原料气、调节钴与载体相互作用、调整催化剂配方及工艺条件、控制钴颗粒尺寸及体系中水和H2的分压比等措施可以提高催化剂稳定性和寿命。通过脱蜡、氧化、还原可实现催化剂再生,氧化是再生的关键步骤,要注意氧化过程中升温速率、热量移除等问题;多次的氧化和还原过程可增加再生催化剂中金属钴与还原助剂的均匀性,提高再生催化剂的活性。     

Studies of the fischer-tropsch synthesis on a cobalt catalyst i. evaluation of product distribution parameters from experimental data

Two models describing the distribution of linear and monomethyl alkanes in Fischer-Tropsch products from a cobalt catalyst are formulated. Distribution parameters for monomethyl isomers are derived by assuming either a post-branching effect on linear chain growth or a decreasing reactivity toward branching with increasing chain length. Distribution parameters for each of the models have been extracted from an extensive experimental data set. We find that the experimental results are well represented by both the models. A “break” in the distribution of linear paraffins has also been observed and is modelled as a sum of the yields of two Anderson-Schulz-Flory distributions. We postulate that the two chain growth processes which produce the distributions are governed by two kinds of termination.     

Influence of concentration waves on the fischer—tropsch reaction

Investigation of the hydrocarbon rate formation behaviour during the Fischer—Tropsch synthesis under periodic concentration forcing reveals the existence of resonance peaks for certain choices of cycle parameters. These peaks appeared under symmetrical cycling with a mean feed composition of 17–5% CO (balance H₂) at both low (less than 0-001 cps) and high (greater than 0-01 cps) frequencies for the alkanes. Although methane was more strongly stimulated under periodic operation than other hydrocarbons, the rate enhancement observed for C₂ to C₆ products signalled the potential for ‘tuning’ selectivity in this mode of operation.     

SiO2负载钴系催化剂的环己烯环氧化性能

采用沉积沉淀法制备不同负载量的SiO₂（硅胶）负载钴氧化物催化剂,采用X射线衍射（XRD）、X射线光电子能谱（XPS）、透射电镜（TEM）、N₂吸脱附等手段对催化剂进行表征,结果表明钴系氧化物为Co₃O₄,并且钴氧化物均匀地负载在SiO₂（硅胶）载体上,其活性组分的粒子大小集中分布在2～10nm。将制备的催化剂应用于环己烯环氧化反应,以环己烯、分子氧为原料,异丁醛为催化助剂,N,N-二甲基甲酰胺（DMF）为反应溶剂,在高压釜中进行。同时将SiO₂负载钴氧化物催化剂与不同载体上制备的钴系催化剂进行比较,发现催化剂用量0.20g、环己烯2.00g、异丁醛3.50g、反应温度50℃、反应时间5h、氧气压力4MPa时,环己烯的转化率和环氧环己烷的选择性分别可达到66.56%和71.03%。     

Studies of the fischer-tropsch synthesis on a cobalt catalyst II. Kinetics of carbon monoxide conversion to methane and to higher hydrocarbons

Six Langmuir-Hinshelwood-Hougen-Watson models have been derived for the kinetics of conversion of carbon monoxide to hydrocarbons in the Fischer-Tropsch synthesis. The models were fitted to experimental data obtained in an internal recycle reactor over a wide range of operating conditions. Two models, one based on the hydrogenation of surface carbon and the other on a hydrogen-assisted dissociation of carbon monoxide as rate limiting steps were both able to provide a satisfactory fit to the experimental rate data. A general model was also developed for the rate of methanation in the presence of higher hydrocarbons. The same two rate limiting assumptions as those used in formulating the rate of total CO conversion are used in these models. The two models were fitted to experimental data for methane formation. It was the model assuming CH formation as rate limiting that showed the best fit for both CO conversion for CH₄ formation.     

费托合成钴催化剂载体改性研究进展

载体和钴物种之间的相互作用对费托钴催化剂分散度和还原度具有重要影响,载体改性可以调节载体与钴物种之间的相互作用。简要介绍了费托合成钴催化剂载体改性技术及其对载体与钴物种相互作用的影响,结果表明:改性载体和钴物种之间相互作用增加时,分散度升高,还原度降低;改性载体和钴物种之间互相作用降低时,则分散度降低,还原度升高;通过多载体掺杂改性、无机助剂改性及载体表面有机改性可有效调节载体和钴物种之间的相互作用,使得催化剂具有适中的还原度和分散度,从而提高催化剂的活性。     

干燥温度对Co/SiO2费托合成催化剂结构和性能的影响

采用浸渍法制备了钴负载质量分数15％的Co/SiO2催化剂,考察干燥温度对催化剂性能的影响.随着干燥温度升高,催化剂活性先增大后减小,但对产物选择性没有明显影响.BET、SEM、XRD和H2 - TPR测定结果表明,改变干燥温度可以影响钴在催化剂中的分布状态,从而使催化剂结构、晶粒度和还原性能发生相应变化,这些效应的叠...     

F-T合成非均匀型Co／ZrO2／SiO2催化剂的研究

采用无定形SiO2为载体,制备出蛋壳型F—T合成催化剂。利用SEM、EDS等技术考察了钴基催化剂的结构和还原性能。结果表明,催化剂的反应活性在很大程度上取决于可利用的氧化钴的量。助剂ZrO2的添加有利于提高催化剂的分散程度、催化活性及C5^＋选择性。     

The effect of cobalt on the activation of fused iron catalyst for ammonia synthesis

BET, scanning electron microscopy, X-ray diffraction, Mössbauer spectroscopy, X-ray fluorescence spectroscopy and McBain thermobalance were used to investigate the effect of cobalt on the reduction behavior and activity of used iron catalyst for ammonia synthesis. Activity tests were carried out under 10 MPa in the 350–450°C temperature rang. Studies were performed on the traditional multipromoted iron catalyst and on the series of catalysts prepared with addition of cobalt. Addition of cobalt promoted the iron catalyst for ammonia synthesis. The most active sample was that containing approx. 5.5% wt Co. Cobalt changed the reduction behavior of the catalyst. The rate of the surface change during reduction was higher for the case of the ‘cobalt catalyst’; however the rate of mass change was higher for a typical iron catalyst. The process of reduction was probably followed by the formation of an Fe₃Co compound and by the surface faceting, with the exposure of an Fe(111) plane.     

Kinetics modelling of Fischer-Tropsch synthesis over an industrial Fe-Cu-K catalyst

The kinetic experiments of Fischer-Tropsch synthesis (FTS) over an industrial Fe-Cu-K catalyst are carried out in a micro-fixed-bed reactor under the conditions as follows: temperature of 493-542 K, pressure of 10.9-30.9 bar, H₂/CO feed ratio of 0.98-2.99, and space velocity of 4000-10?000 h⁻¹. The effects of secondary reactions of olefins are investigated by co-feeding C₂H₄ and C₃H₆. A detailed kinetics model taking into account the increasingly proven evidence of the olefin re-adsorption mechanism is then proposed. In this model, different sites are assumed for FTS reactions and water gas shift (WGS) reaction, respectively. Rate expressions for FTS reactions are based on the carbide polymerisation mechanism, in which olefin re-adsorption is considered to be a reverse step of olefin desorption reaction. Rate expression for WGS reaction is based on the formate mechanism. An integral reactor model considering both FTS and WGS kinetics is used to describe the reaction system, and the simultaneous estimation of kinetic parameters is conducted with non-linear regression procedure. The optimal model shows that the rate determining steps in FTS reactions proceed via the desorption of hydrocarbon products and the adsorption of CO and the slowest step in WGS reaction is the desorption of gaseous carbon dioxide via formate intermediate species. The activation energies of FTS reactions and WGS reaction are in good agreement with literature values.     

助剂对活性炭负载钴催化剂氨合成活性的影响

采用四槽高压连续流动反应器研究了添加助剂Ba、K和Sm对活性炭负载钴催化剂氨合成活性的影响,结果发现,添加助剂Ba、K和Sm可以提高催化剂的氨合成活性,其中,Ba的促进效果最好,Ba与Co物质的量比为0.3时,催化活性最高。在Ba-Co/AC催化剂中,助剂Sm的加入降低了催化剂的氨合成活性,而少量K助剂(K与Co物质的量比为0.25～0.5)可以提高其催化性能,在10 MPa、10 000 h^-1和450 ℃条件下,双助剂催化剂的氨合成活性可达120 mmol·(g·h）^-1,进一步增加K的量,其氨合成活性下降。     

Self-Tuning control of fischer-tropsch synthesis in a tube-wall reactor

This paper describes the implementation of a self-tuning controller (STC) on a bench-scale tube-wall reactor for the Fischer-Tropsch synthesis using a plasma-sprayed iron catalyst. The concentration of the hydrocarbons in the C₁₀ range in the reactor effluent was controlled by manipulating the H₂/CO ratio of the inlet synthesis gas. The output of the self-tuner was cascaded to two PI-controllers which maintained a constant total inlet gas flow rate as well as ensuring the desired H₂/CO ratio. The concentration measurement was performed by an on-line gas chromatograph with an analysis time of approximately 30 s. The performance of the STC in set-point tracking, rejection of randomly occurring deterministic disturbances, and estimation and adaptation to the unknown process dead time was investigated. The STC was able to reduce the variance of the process output and of the manipulated variable when compared to the variances obtained with a PI-controller.     

Fischer-Tropsch synthesis on supported cobalt catalysts promoted by platinum and rhenium

An investigation of the CO hydrogenation of Pt- or Re-promoted 8.7 wt% Co/Al₂O₃ (1.0 wt% Pt or 1.0 wt% Re) has been carried out at two different conditions: 473 K, 5 bar, H₂/CO = 2 and 493 K, 1 bar, H₂/CO = 7.3. The addition of Pt or Re significantly increases the CO hydrogenation rate (based on weight of Co), but the selectivity was not changed by the presence of Pt or Re. The results show that the observed increases in the reaction rates are caused by increased reducibility and increased number of surface exposed Co-atoms. Steadystate isotopic transient kinetic analysis (SSITKA) with carbon tracing was used to decouple the effects of the concentration of active surface intermediates and the average site reactivity of intermediates during steady-state CO hydrogenation. The SSITKA results show that the concentration of active surface intermediates leading to CH₄ increased as a result of the addition of a noble metal promoter. However, the average site activity was not significantly affected upon Re or Pt addition.