Ni/Al_2O_3 catalysts for syngas methanation: Effect of Mn promoter

Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method. The catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM. Their catalytic activity towards syngas methanation reaction was also investigated using a fixed-bed integral reactor. It was demonstrated that the addition of manganese to Ni/Al2O3 catalysts can increase the catalyst surface area and average pore volume, but decrease NiO crystallite size, leading to higher activity and stability. The effects of reaction temperature, pressure and weight hourly space velocity （WHSV） on carbon oxides conversion and CH4 formation rate were also studied. High carbon oxides conversion, CH4 selectivity and formation rate were achieved at the reaction temperature range of 280 300℃.

Reaction and deactivation kinetics of methanol-to-olefins process based on a special TGA reactor

Thermax 700 thermo gravimetric analysis （TGA） instrument is introduced for the investigation of the reaction and deactivation kinetics of Methanol-to-Olefins （MTO） process with SAPO-34 catalyst.By the use of a special sample basket,the TGA instrument can be viewed as a plug flow fixed-bed reactor,while the weight change of SAPO-34 during reaction can be recorded online.Kinetic data are acquired in the temperature range of 648.2？748.2 K and space velocities of 7.08？35.91 h^-1 （WHSV）.Catalyst activity is expressed with average coke content,and selectivity for different products is related as a function of coke content and temperature.Methane is also introduced into the lumping kinetic model,and power exponent function with first-order reaction is adopted for model deduction.Exponential function is tested to give the best fit for catalyst activity and product selectivity with the highest correlation coefficient.The nicely agreed results between experimental and calculated data suggest that the overall kinetic model would be meaningful in both product distribution prediction and reactor simulation.

Effect of the operation parameters on the Fischer-Tropsch synthesis in fluidized bed reactors

For the Fischer-Tropsch synthesis(FTS), this paper presents a numerical investigation in a 3 D fluidized bed reactor. The effect of the operation parameters such as bed temperature, superficial gas velocities, particle size and bed heights is discussed. A 3 D-CFD model coupled with FTS chemical kinetics was set up. The computational results are compared with experimental data in terms of the components production rates, etc. The analysis shows that the bed heights, the bed temperature, the superficial gas velocities and particle sizes affect the C_(5+) selectivity and the reaction rates. Product yields are dependent on the operating conditions especially the temperature.

Effects of the Different Supports on the Activity and Selectivity of Iron-Cobalt Bimetallic Catalyst for Fischer-Tropsch Synthesis

Silica, alumina, and activated carbon supported iron-cobalt catalysts were prepared by incipient wetness impregnation. These catalysts have been characterized by BET, X-ray diffraction （XRD）, and temperature-programmed reduction （TPR）. Activity and selectivity of iron-cobalt supported on different carriers for CO hydrogenation were studied under the conditions of 1.5 MPa, 493 K, 630 h^-1, and H2/CO ratio of 1.6. The results indicate that the activity, C4 olefin/（C4 olefin＋C4 paraffin） ratio, and C5 olefin/（C5 olefin＋C5 paraffin） decrease in the order of Fe-Co/SiO2, Fe-Co/AC1, Fe-Co/Al2O3 and Fe- Co/AC2. The activity of Fe-Co/SiO2 reached a maximum. The results of TPR show that the Fe-Co/SiO2 catalyst is to some extent different. XRD patterns show that the Fe-Co/SiO2 catalyst differs significantly from the others; it has two diffraction peaks. The active spinel phase is correlated with the supports.

LDV measurements of particle velocity distribution in an annular stripper

Particle descent velocities in an annular stripper were measured by a laser Doppler velocimetry(LDV)system.In the radial direction,particle descent velocity was relatively constant in the mid-region of the stripper and increased towards the walls on both sides,exhibiting an anti-U-shaped distribution.Particle descent velocity in the radial mid-region increased with the increase of superficial gas velocity,and the maximum in the outer wall region increased significantly with the increase of solid mass flux.Superficial stripping gas velocity had stronger effect on particle velocity distributions near the stripper gas distributor,and such effect weakened with the increase of the distance from the distributor.Local particle velocity and its radial profiles could be adjusted by changing the superficial stripping gas velocity.Empirical formulas were established to describe the relationships between the local particle velocity and cross-sectional averaged velocity based on the effects of operating conditions and measuring positions.The result showed that the predicted data was in good agreement with the experimental value.

Effects of promoters on catalytic performance of Fe-Co/SiO_2 catalyst for Fischer-Tropsch synthesis

2%Fe-10%Co/SiO2 catalysts with different potassium or zirconium loadings were prepared by aqueous incipient wetness impregnation and tested for Fischer-Tropsch synthesis in a flow reactor, using H2/CO = 1.6 （molar ratio） in the feed, under the condition of an overall pressure of 1 MPa, GHSV of 600 h^-1 and temperature of 503 K. The zirconium and potassium promoters remarkably influenced hydrocarbon distribution of the products. CO conversion increased on the catalysts with the increase of zirconium loadings, which indicated that zirconium enhanced the activity of iron-cobalt catalysts. Low potassium loadings also enhanced the activity of the catalysts. However, high potassium loading made CO conversion on the catalysts decrease and weakened the secondary hydrogenations. The catalyst was characterized by BET, XRD and TPR. The catalyst characterization revealed that the Co3O4 phase was presented on the fresh catalyst, whereas the spinel phase of Fe-Co alloy and CoO existed on the used catalyst.

Pretreatment of Alumina and Its Influence on the Properties of Co/Alumina Catalysts for Fischer-Tropsch Synthesis

16.6%Co/γ-Al2O3 catalysts prepared by incipient wetness impregnation method were used for Fischer-Tropsch synthesis. The support was pre-treated with different concentration of NH4NO3 aqueous solution. The effect of support pre-treatment on the properties of support and performance of supportedcobalt-based catalysts was investigated. To treat the support with NH4NO3 aqueous solution enlarged the pore of γ-Al2O3, decreased the impurity Na2O content, and weakened the surface acidity of γ-Al2O3. The change in the properties of the support decreased the interaction between cobalt species and support, enhanced the CO hydrogenation rate and the C5＋ selectivity. For all catalysts, increasing the reaction temperature increased the CO hydrogenation rate or the CO conversion, slightly decreased the total hydrocarbon selectivity, and favored the formation of methane and light hydrocarbons, while the chain growth probability decreased. For 16.6%Co/γ-Al2O3 catalysts, prepared with the support treated with 100 g/L NH4NO3 aqueous solution, the CO conversion, the CH4 selectivity, and the C5＋ selectivity were 83.13%, 6.86% and 82.75% respectively, and the chain growth probability was 0.83 under the condition of 493 K, 1.5 MPa, 500 h-1 and the molar ratio of H2 to CO being 2.0 in feed.

Effects of the ratio of Fe to Co over Fe-Co/SiO_2 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.

Online measurement of solids motion in fluidized bed reactor with different distributor for Fischer–Tropsch synthesis

In this paper, the distributions of particle velocity in a gas–solid fluidized bed with branched pipe distributor or circle distributor were measured by using a laser Doppler velocimetry. Our results show that, within a certain range of superficial gas velocity, when using circle distributor, the particle velocity is large and the distribution of the particle velocity is even more compared with the branched pipe distributor. On the basis of the amplitude of tangential movement statistics, the amplitude of tangential movement statistics(AVATMS) decreases with increasing the axial height under the appropriate superficial gas velocity.

Numerical simulation of effect of gas distributor on Fischer-Tropsch synthesis in fluidized-bed reactor

Circular and branched pipe distributors were designed for Fischer-Tropsch synthesis in a fluidized-bed reactor. A numerical investigation of the effects of these distributors on product selectivity and production rate was performed. Under the same conditions, the circular distributor gave higher production rates for small diameter particles. For superficial gas velocities ranging from 5 to 15 times the minimum fluidization velocity, the production rates of methane and C5+(the sum of C10H22 and C22H46)were 18%, which was 2% higher than those using the branched pipe distributor, while the C5+ selectivity was 1% lower. For deeper beds, the circular distributor led to higher production rates and the selectivity for C5+ was 5% lower than that using the branched pipe distributor.

Experimental study on bubble behavior and CFD simulation of large-scale slurry bubble column reactor

Slurry bubble column reactors(SBCR)is a three-phase fluidized reactor with outstanding advantages compared with other reactors and is difficult to scale-up due to lack of information on hydrodynamics and mass transfer over a wide range of operating conditions of commercial interest.In this paper,an experiment was conducted to investigate the bubble behavior in SBCR with a height of 5600 mm and an interior diameter of 480 mm.Bubble rise velocity,bubble diameter,and gas holdup in different radial and axial positions are measured in SBCR using four-channel conductivity probe.Tap water,air,and glass beads(mean diameter 75-150μm)are used as liquid,gas,and solid phases,respectively.It shows that hydrodynamic parameters have good regularity in SBCR.Moreover,a commercial computational fluid dynamics(CFD)package,Fluent,was used to simulate the process in SBCR.The simulations were carried out using axi-symmetric 2-D grids.Data obtained from experiment and CFD simulation are compared,and results show that the tendency of simulation is almost uniform with the experiment,which can help to obtain further understanding about multiphase flow process and establish a model about the synthesis of alcohol ether fuel in SBCR.

Study on direct alcohol/ether fuel synthesis process in bubble column slurry reactor

The recent studies of direct alcohol/ether synthesis process in slurry reactors were reviewed,and the research work in our laboratory was carried out in this paper.a global kinetics model for direct dimethyl ether(DME)synthesis from syngas over a novel Cu-Zn-Al-Zr slurry catalyst was established according to the total of 25 experimental data,and a steady-state one-dimensional mathematical model was further developed in bubble column slurry reactor(BCSR),which was assumed that the bubble phase was plug flow,and the liquid phase was fully mixed flow.The numerical simulations of reactor design of 100000 t/a dimethyl ether pilot plant indicate that higher pressure and lower temperature were favorable to the increase of CO conversion,selectivity of dimethyl ether,product yield and height of slurry bed.The optimal operating conditions for DME synthesis process were obtained:reaction temperature at 240℃,reactor pressure at 5 MPa and reactor diameter of 2.5 m.