Global Kinetics of Direct Dimethyl Ether Synthesis Process from Syngas in Slurry Reactor over a Novel Cu-Zn-Al-Zr Slurry Catalyst

The direct synthesis process of dimethyl ether (DME) from syngas in slurry reactors is considered to be promising because of its advantages in caloric transfer. In this paper, the influences of operating conditions (temperature, pressure and weight hourly space velocity) on the conversion of CO, selectivity of DME and methanol were studied in a stirred autoclave over Cu-Zn-Al-Zr slurry catalyst, which is far more suitable to liquid phase dimethyl ether synthesis process than bifunctional catalyst commercially. A Langmuir- Hinshelwood mechanism type global kinetics model for liquid phase DME direct synthesis based on methanol synthesis models and a methanol dehydration model has been investigated by fitting our experimental data. The model parameters were estimated with MATLAB program based on general Genetic Algorithms and Levenberg-Marquardt method, which is suitably fitting experimental data and its reliability was verified by statistical test and residual error analysis.

Thermal Distribution in Axial-Flow Fixed Bed with Flowing Gas

This paper reported an experimental research of steady-state heat transfer behaviour of a gas flowing through a fixed bed under the different operating conditions. Studies had been carried out in a fixed-bed packed methanol synthesis catalyst percolated by air at appropriate flow rate. Both radial and axial direction temperature distribution had been investigated under the different operating conditions. The effects of operating conditions including the reactor inlet air temperature, the heating pipe temperature and the air flow rate on temperature distribution was investigated and the experimental results showed that a higher inlet air temperature was conducive to uniform temperature distribution in the fixed bed. A large temperature drop existed at the radial direction, and the temperature drop increased with the heating pipe temperature increasing under the experimental conditions; the temperature profile of the vicinity of the heating pipe was strongly affected by the heating pipe temperature. A higher air flow rate can improve the heat transfer in the fixed bed. Based on the thermal distribution, heat transfer models of the fixed bed could be established, and the characteristics of the temperature distribution in the fixed bed could be finely described, that had an important practical significance.

Investigation of the Synthesis of Alcohols Byproducts in Fischer-Tropsch Synthesis on Modified Fe-Cu Catalyst: Reactivity and Mechanism

The influence of copper promoters and reaction conditions on the formation of alcohols byproducts of a common Fischer-Tropsch synthesis used iron-based catalysts were investigated. A good compromise of 28%Cu/FeKLaSiO2 can lead to the optimization of an improved Fischer-Tropsch catalyst. The product distribution shifts towards hydrocarbons with increasing the reaction temperature, while pressure promotes the formation of alcohols. It was found that the production of either alcohols or hydrocarbons followed A-S-F distributions, and their α parameters were essentially different which indicated a competition in the growing chain between the two species. TPD after acetaldehyde adsorption gave strong evidence of the insertion of a C1 oxygen-containing species into an alkyl chain.

La promoted Ni/α-Al2O3 Catalysts for Syngas Methanation

The Ni/α-Al2O3 catalysts with different amounts of La as promoter from 0 to 4 wt % were prepared, characterized and their catalytic activity was investigated in syngas methanation reaction. Effects of reaction temperature and lanthanum loading on carbon oxides conversion and methane selectivity were also studied. Adding certain amount of lanthanum to 10Ni /α-Al2O3 catalysts can decrease the average NiO crystallite diameter which leads to higher activity and stability while excessive addition would cause deactivation quickly. Stability on stream towards deactivation was observed up to 800 min at 500 °C, 0.1MPa and 600000 mL·g-1·h-1.

Conversion of Methanol to Propylene over a High Silica B-HZSM-5 Catalyst

Hydrothermally synthesized high silica borosilicates with the MFI structure was subjected to several characterization techniques. The effect of boron on the structure and acidity of HZSM-5 catalyst were studied by XRD, SEM, N2 adsorption, solid state NMR, NH3-TPD. It was confirmed that boron had entered the framework in the boron samples. The results also revealed that strong acidity was weakened and weak acidity was strengthened by the boron added zeolite framework compared with parent catalyst. The catalytic performance was carried out in a fixed bed at 460°C for methanol to propylene (MTP) reaction. The results of MTP reaction showed a great increment of the propylene selectivity and excellent stability for the B-HZSM-5. The catalyst exhibited about 81% selectivity to C2 = - C4 = olefins with 40% selectivity of propylene as major component at near 100% methanol conversion, and the stable performance in the studied period was 100h.

Mathematical Simulation of Bubble Column Slurry Reactor for Direct Dimethyl Ether Synthesis Process from Syngas

Based on a global kinetics of direct dimethyl ether (DME) synthesis process from syngas, a steady-state one-dimensional mathematical model for the bubble column slurry reactor (BCSR) has been established. It was built on the assumption of plug flow of gas phase, sedimentation-dispersion model of catalyst grains and isothermal chamber regardless of reaction heats and rates for the design of an industrial scale bubble column slurry reactor. The simulation results indicate that higher pressure and lower temperature were favorable to the increase of CO conversion, DME selectivity, products yield and the height of slurry bed, which has a coincidence with the characteristic of DME synthesis reaction system, and that the height of slurry bed is lessen with the increasing of operation temperature in the range of 220-260℃. CO conversion, the optimal operation conditions in BCSR were proposed. 

Adsorption of H2 and CO on Iron-based Catalysts for Fischer-Tropsch Synthesis

The adsorption properties of CO and H2 on iron-based catalyst with addition of Zr and Ni were investigated using temperature programmed desorption process. It was found that on the carburized iron-based catalysts, molecular state and dissociative state CO existed together. The addition of Zr was preferential for the molecular state adsorption of CO on iron-based catalyst and the presence of Ni was beneficial to the dissociative adsorption of CO. On H2 reduced catalysts, hydrogen mainly adsorbs on the surface iron sites and surface oxide sites. On CO reduced catalysts, hydrogen probably existed as the most stable CH and OH species. The addition of Zr was not benefit to the dissociative adsorption of hydrogen on iron-based catalyst and the presence of Ni was preferential for the dissociative adsorption of hydrogen.

Hydrogenation of Acetic Acid on Alumina-Supported Pt-Sn Catalysts

Three alumina-supported Pt-Sn catalysts have been prepared by means of co-impregnation and characterized by XRD and N2 adsorption. The influence of catalyst composition and reaction conditions on the conversion and selectivity were investigated in the hydrogenation of acetic acid in an isothermal integral fixed bed reactor. The experiments were performed on the temperature interval 468-548 K, liquid hourly space velocity (LHSV) of 0.3-0.7h-1, pressures between 1.0 and 5.0Mpa. A good compromise of 0.75%Pt-1.5%Sn can act as an optimized acetic acid hydrogenation catalyst, and the conversion and selectivity can be tuned through the variation of reaction conditions.