Enhancement of catalytic and anti-carbon deposition performance of SAPO-34/ZSM-5/quartz films in MTA reaction by Si/Al ratio regulation

In order to further improve the catalytic performance of zeolite catalyst for methanol to aromatics(MTA)technology, the double-tier SAPO-34/ZSM-5/quartz composite zeolite films were successfully synthesized via hydrothermal crystallization. The Si/Al ratio of SAPO-34 film was used as the only variable to study this material. The composite zeolite material with 0.6Si/Al ratio of SAPO-34 has the largest mesoporous specific surface area and the most suitable acid distribution. The catalytic performance for the MTA process showed that 0.6-SAPO-34/ZSM-5/quartz film has as high as 50.3% benzene-toluenexylene selectivity and 670 min lifetime. The MTA reaction is carried out through the path we designed to effectively avoid the hydrocarbon pool circulation of ZSM-5 zeolite, so as to improve the aromatics selectivity and inhibit the occurrence of deep side reactions to a great extent. The coke deposition behavior was monitored by thermogravimetric analysis and gas chromatograph/mass spectrometer, it is found that with the increase of Si/Al ratio, the active intermediates changed from low-substituted methylbenzene to high-substituted methylbenzene, which led to the rapid deactivation of the catalyst. This work provides a possibility to employ the synergy effect of composite zeolite film synthesizing anti-carbon deposition catalyst in MTA reaction.

Construction of a macromolecular structural model of Chinese lignite and analysis of its low-temperature oxidation behavior

The aim of this paper is to analyze the change in the active structure of lignite during the process of lowtemperature oxidation by constructing a molecular structure model for lignite. Using quantum computation combined with experimental results of proximate analysis, ultimate analysis, Fourier transform infrared spectroscopy(FTIR) and X-ray photoelectron spectroscopy(XPS), a structural model for the large molecular structure was constructed. By analyzing the bond lengths in the model molecule, the evolution law for the active structure of lignite was predicted for the process of low-temperature oxidation. In low-temperature oxidation,alkanes and hydroxyls are the primary active structures observed in lignite, though ether may also react. These active functional groups react with oxygen to release heat, thereby speeding up the reaction between coal and oxygen. Finally, the content of various functional groups in the process of lignite low-temperature oxidation was analyzed by infrared analysis, and the accuracy of the model was verified.

Multiple linear equation of pore structure and coal–oxygen diffusion on low temperature oxidation process of lignite

This work aimed at studying the feasibility of calculating the coal-oxygen diffusion properties during the low temperature oxidation process of lignite so as to predict its spontaneous combustion process. Coal samples were oxidized in air ambient under different temperatures. Scanning Electron Microscope was used to indicate the surface morphology changes of oxidization. Then, based on fractal theory and flow characteristics, the ffactal dimension of gas diffusion in the pore ways was calculated under different temperature. Considering pore size distribution, connectivity distribution and Fick diffusion mechanisms, the relationship between the gas diffusivity change with pore area ffactal dimension and porosity was investigated, and multiple linear equation of the coal- oxygen diffusion coefficients and pore parameters was obtained. Comparison between the experimental data and model prediction verifies the validiW of the model. The research provides a theoretical basis for the prediction model of coal-oxygen diffusion law.

Catalytic kinetics of dimethyl ether one-step synthesis over CeO_2–CaO–Pd/HZSM-5 catalyst in sulfur-containing syngas process

CeO_2–CaO–Pd/HZSM-5 catalyst was prepared for the dimethyl ether(DME) one-step synthesis in a continuous fixed-bed micro-reactor from the sulfur-containing syngas. The catalytic stability over hybrid catalyst of CeO_2–CaO–Pd/HZSM-5 was investigated to ensure that the kinetics experimental results were not significantly influenced by induction period and catalytic deactivation. A large number of kinetic data points(40 sets) were obtained over a range of temperature(240–300 °C), pressure(3–4 MPa), gas hourly space velocity(GHSV)(2000–3000 L·kg^(-1)·h^(-1)) and H_2/CO mole ratio(2–3). Kinetic model for the methanol synthesis reaction and the dehydration of methanol were obtained separately according to reaction mechanism and Langmuir–Hinshelwood mechanism. Regression parameters were investigated by the method combining the simplex method and Runge–Kutta method. The model calculations were in appropriate accordance with the experimental data.

A study on the catalytic performance of Pd/γ-Al_(2)O_(3),prepared by microwave calcination,in the direct synthesis of dimethylether

A series of Pd/γ-Al_(2)O_(3) hybrid catalysts were prepared by impregnation and subsequent calcination under microwave irradiation.The catalysts were used for direct synthesis of dimethylether(DME)from syngas.The results show that calcination under microwave irradiation improved both the activity and selectivity of the catalysts for DME synthesis.The optimum power of the microwave was determined to be 420 W.Under such optimum conditions,CO conversion,DME selectivity and time space yield of DME were 60.1%,67.0%,and 21.5 mmol$mL-1$h^(-1),respectively.Based on various characterizations such as nitrogen physisorption,X-ray diffraction,COtemperature-programmed desorption,and Fourier transform infrared spectral analysis,the promotional effect of the microwave irradiation on the catalytic property was mainly attributed to both the higher dispersion of Pd and the significant increase in the adsorption on the CO-bridge of Pd.Microwave irradiation with very high power led to the increase in CO-bridge adsorption and thereby decreased the catalytic activity,whereas the coverage by metallic Pd of the active sites on acidicγ-Al_(2)O_(3) significantly occurred under microwave irradiation with very low power,resulting in a decrease in the selectivity to DME.