The use of copper-based binary catalysts, Cu/Zr oxides and Cu/Al oxides, has been examined to produce hydrogen from ethanol in the ethanol steam reforming process. The examined catalysts were compared with non-noble bicomponent catalysts consisting of oxides of nickel and cobalt: Ni/Zr Co/Zr, Ni/Al and Co/Al, prepared and tested in the identical way. Catalytic tests were carried out in the fixed-bed reactor in the temperature range 433–873 K for initial molar ratio of ethanol to water equal to 1:3. Ethanol conversion approached near 100%. Catalysts were characterized by XRD, TPR. Cu/Zr oxides. The catalyst showed very good selectivity. It is significant that carbon monoxide appeared only above 600 K and its selectivity has not exceeded 3% in the higher temperature range. No methane has been detected. Hydrogen yield was relatively stable in the temperature range from 513 to 873 K. Similarly, in the presence of Cu/Al oxides neither CO nor CH4 were found in the products. The correlation between activity of examined catalysts and textural properties was not found.
This paper presents the kinetics of methanol synthesis from carbon dioxide and hydrogen over a Cu/Zn/Zr/Ga catalyst. Kinetic studies were carried out in a continuous-flow fixed-bed reactor in a temperature range from 433 to 513 K, pressures from 3 to 8 MPa, and GHSV from 1660 to 10,000 1/h for initial molar fractions of hydrogen from about 0.48 to 0.70, carbon dioxide from 0.05 to about 0.22, and carbon monoxide from 0 to about 0.07. Significant effects of temperature and the composition of the reaction mixture on the conversion degrees α1 and α2 were found. The Cu/Zn/Zr/Ga catalyst showed good stability over 960 h. XRD and CO2TPD characterisation were performed. Thefinally obtained results of kinetic tests were developed in the form of Langmuir–Hinshelwood kinetic equations. The numerical Levenberg–Marquardt method was used to estimate the kinetic equations. The average relative error of fitting the kinetic equations to the experimental data was 18%.
The application of copper-based catalysts in the production of pure hydrogen in the steam reforming of ethanol was performed. The tricomponent Cu/Zr catalysts with about 4 mass% addition of nickel, cobalt, or cerium have been prepared in our laboratory. The properties of obtained catalysts were compared with bimetallic Cu/Zr catalyst prepared and tested according to the same procedure. Catalytic tests were carried out in the continuous flow fixed–bed reactor in the wide temperature range of 433–593 K for initial molar ratio of ethanol to water equal to 1:3. Catalysts were characterized by XRD, TPR, CO2–TPD, and TPO methods. Cu/Zr/Ce catalyst proved to be the best; hydrogen yield reached the value of 400 L/(kgcat.∙h), selectivity towards carbon monoxide was below 0.5% and the one towards methane wasnot detected. Additions of Ni or Co did not bring significant improvement in activity.
27 May 2019 in International Journal of Chemical Kinetics
Biogas, one of the important controllable renewable energy sources, may be split into two streams: bio-CH4 and bio-CO2 using, among others, membrane processes. The proper optimization of such processes requires the knowledge of phenomena accompanying each specific CH4–CO2–membrane system (e.g., competitive sorption or swelling). The phenomena were analyzed for the polysulfone-based membrane used in a developed adsorptive–membrane system for biogas separation. The Dual Mode Sorption and partial immobilization models were used to describe the solubility and diffusion of CO2, CH4 and their mixtures in this material. The parameters of the models were determined based on pure-gas sorption isotherms measured gravimetrically and permeances of CO2/CH4 mixture components from our previous studies. It was found, among other things, that the membrane swelling caused by CO2 was observed for pressures higher than 5 bar. The real selectivity (permselectivity) of CO2 vs. CH4 is significantly lower than the selectivity of pure gases (ideal selectivity), while the solubility selectivity of CO2 vs. CH4 in the mixture is higher than that of pure gases. This is due to the better affinity of CO2 towards the tested polysulfone membrane, making CO2 the dominant component in competitive sorption. The reduction in the permselectivity is mainly due to an approximately two-fold decrease in the CO2 diffusion rate in the presence of CH4. It was also found that the fraction of solubility in the fractional free volume (FFV) is dominant for both gases, pure and mixed, reaching 65–73% of the total solubility. Moreover, in CO2/CH4 mixtures, the mobility of methane in FFV disappears, which additionally confirms the displacement of methane by CO2 from FFV.
12 September 2020 in International Journal of Chemical Kinetics