A Kinetic Model Considering Catalyst Deactivation for Methanol-to-Dimethyl Ether on a Biomass-Derived Zr/P-Carbon Catalyst

A Zr-loaded P-containing biomass-derived activated carbon (ACPZr) has been tested for methanol dehydration between 450 and 550 °C. At earlier stages, methanol conversion was complete, and the reaction product was mainly dimethyl ether (DME), although coke, methane, hydrogen and CO were also observed to a lesser extent. The catalyst was slowly deactivated with time-on-stream (TOS), but maintained a high selectivity to DME (>80%), with a higher yield to this product than 20% for more than 24 h at 500 °C. A kinetic model was developed for methanol dehydration reaction, which included the effect of the inhibition of water and the deactivation of the catalyst by coke. The study of stoichiometric rates pointed out that coke could be produced through a formaldehyde intermediate, which might, alternatively, decompose into CO and H2. On the other hand, the presence of 10% water in the feed did not affect the rate of coke formation, but produced a reduction of 50% in the DME yield, suggesting a reversible competitive adsorption of water. A Langmuir–Hinshelwood reaction mechanism was used to develop a kinetic model that considered the deactivation of the catalyst. Activation energy values of 65 and 51 kJ/mol were obtained for DME and methane production in the temperature range from 450 °C to 550 °C. On the other hand, coke formation as a function of time on stream (TOS) was also modelled and used as the input for the deactivation function of the model, which allowed for the successful prediction of the DME, CH4 and CO yields in the whole evaluated TOS interval.

An Efficient Catalyst of CuPt/TiO2 for Photocatalytic Direct Dehydrogenation of Methanol to Methyl Formate at Ambient Temperature

To obtain high methanol conversion at high methyl formate (MF) selectivity by the thermal reaction of direct dehydrogenation of methanol is a challenging issue due to the thermodynamic restriction. Herein,...

Facile and Rapid Synthesis of Durable SSZ-13 Catalyst using Choline Chloride Template for Methanol-to-Olefins Reaction

In the current study, a facile and rapid synthesis approach for a SSZ-13 catalyst using choline chloride (CC) as a template was proposed, and the catalytic performance for the methanol-to-olefins (MTO) reaction was examined. With a proper amount of CC addition (i.e., m(CC)/m(SiO2)=0.14), uniform and homogeneously distributed cubic SSZ-13 crystals were obtained within 4 h with lower aggregation. The synthesized catalyst demonstrated excellent porous features with a total specific surface area and mesopore volume of 641.71 m2·g−1 and 0.04 cm3·g−1, respectively. The optimized strong and weak acid sites on SSZ-13 were obtained by regulating the m(CC)/m(SiO2) ratio. The less strong acid sites and a larger amount of weak acid sites in the synthesized catalyst were conducive to the catalytic performance of the MTO reaction under a lower reaction temperature (450 °C). The appropriate acidity and well-developed pore structure of synthesized SSZ-13 could also slow down the carbon deposition rate and, thus, significantly improve the catalytic lifetime of the catalyst. The methanol conversion rate and initial selectivity of light olefin using the synthesized catalyst could maintain over 95% and 50%, respectively, and a lifetime of 172 min was achieved. Although the low olefin selectivity of the synthesized SSZ-13 catalyst was slightly lower than that of the purchased one, its desirable features were thought to have good potential for industrial application.

Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol

Synthetic homogeneous system known to date performing methane to methanol conversion using O2 as terminal oxidant is unique and based on copper complex with piperazine-based ligand (Cu3L in Fig. 1) in a medium of acetonitrile. Prior work have shown that in order to achieve catalytic turnover, hydrogen peroxide is needed to regenerate the active site. We show in this paper that reaction solvent based on organic nitrile decompose concurrently with methane activation and that in the absence of either acetonitrile, Cu complex or hydrogen peroxide, the catalytic turnover does not happen. We show in this manuscript that the direct methane oxidation to methanol might have been mediated by catalytic Radziszewski oxidation between acetonitrile and H2O2. Additionally we have discovered that in the absence of methane, peroxide mediated acetonitrile decomposition also makes methanol via a background reaction which was hitherto unknown.

Evaporation of Methanol Solution for a Methanol Steam Reforming System

In a methanol-reforming system, because the mixture of methanol and water must be evaporated before reaching the reforming reaction zone, having an appropriate evaporator design is a fundamental requirement for completing the reforming reaction. This study investigates the effect of the evaporator design for the stable reforming of methanol–water mixtures. Four types of evaporator are compared at the same heat duty of the methanol-reforming system. The four evaporators are planar heat exchangers containing a microchannel structure, cylindrical shell-and-tube evaporators, zirconia balls for internal evaporation, and combinations of cylindrical shell-tubes and zirconia balls. The results show that the evaporator configuration is critical in performing stable reform reactions, especially for the flow-field mode of the evaporator. Additionally, the combination of both internal and external evaporation methods generates the highest performance for the methanol-reforming system, with the methanol conversion reaching almost 98%.