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.

Investigation of Ni catalyst activation during plasma-assisted methane oxidation

Atmospheric pressure plasma has shown promise in improving thermally activated catalytic reactions through a process termed plasma-catalysis synergy. In this work, we investigated atmospheric pressure plasma jet (APPJ)-assisted CH4 oxidation over a Ni/SiO2.Al2O3 catalyst. Downstream gas-phase products from CH4 conversion were quantified by Fourier transform infrared spectroscopy (FTIR). The catalyst near-surface region was characterized by in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The catalyst was observed to be activated at elevated temperature (500 °C) if it was exposed to the APPJ operated at large plasma power. “Catalyst activation” signifies that the purely thermal conversion of CH4 using catalysts which had been pre-exposed to plasma became more intense and produced consistently CO product, even if the plasma was extinguished. Without the application of the APPJ to the Ni catalyst surface this was not observed at 500 °C. The study of different exposure conditions of the activated catalyst indicates that the reduction of the catalyst by the APPJ is likely the cause of the catalyst activation. We also observed a systematic shift of the vibrational frequency of adsorbed CO on Ni catalyst when plasma operating conditions and catalyst temperatures were varied and discussed possible explanations for the observed changes. This work provides insights into the plasma-catalyst interaction, especially catalyst modification in the plasma catalysis process, and potentially demonstrates the possibility of utilizing the surface CO as a local probe to understand the plasma-catalyst interaction and shed light on the complexity of plasma catalysis.

THE KINETICS AND MECHANISM OF THE SELECTIVE OXIDATIVE DEHYDROGENATION REACTİON OF METHYLCYCLOPENTANE

The oxidative dehydrogenation of alicyclic diene hydrocarbons refers to scarcely studied heterogeneous catalytic reactions which proceed with the participation of oxygen. The dehydrogenation of methylcyclopentane is an endothermic reaction. To improve the reaction kinetics, this research was to develop a structured catalyst by conductive metals (Cu, Zn, Co, Cr) support which could hold an adherent catalytic layer. The active phase was impregnated onto these support metals and the developed catalyst was tested for the dehydrogenation of methylcyclopentane. The catalyst preparation involved three main key steps which were support oxidative reaction, loading of active particles on the catalyst surface, preparation of an active catalyst layer on the surface finally bringing the catalyst into the active phase. Different types of catalyst activation and deactivation mechanisms stability have been studied in this investigation. The advantage of this works, the oxidative dehydrogenation of methylcyclopentane is that it occurs at the expense of oxygen in the air. The zeolite structure study helped identify the effect of the combination of catalysts, and adsorption of metals on clinoptilolite and dispersion on the selectivity of the catalyst particles. Numerical values of the kinetic parameters were calculated

Effects of iron ions, doping methods and nanotubular morphology on TiO2 solar photocatalytic performance

The effects of Fe2+ and Fe3+ as TiO2 cocatalysts were studied, and the experimental results showed that Fe3+ was more efficient than Fe2+, which needed an intermediate reaction to produce hydroxyl radicals. TiO2 was modified with the aim of improving its structural, optical, and adsorption properties, thus improving its photocatalytic performance. The light range of the catalyst activation process was expanded, which increased the catalyst's ability to absorb visible light. Consequently, this study exploits solar energy in photocatalysis by Fe ion doping using different methods, including impregnation, photodeposition, solvothermal doping, and hydrothermal doping, and evaluates the influence of each doping method on TiO2 optical properties and photocatalytic activity. Enhancing the catalyst adsorption capacity by morphologically modifying TiO2 nanoparticles into nanotubes using the hydrothermal method increases the catalyst surface area from 55 to 294 m2/g, as shown in the MEB and BET results. The effect of combining morphological changes and Fe3+ doping on TiO2 activity was evaluated. We observed a reduction in the TiO2 band gap from 3.29 to 3.01 eV, absorption edge widening, and an increase in the specific surface area up to 279 m2/g; thus, the synthesized catalyst eliminated Cefixime in 120 min.

APPLICATION OF TEMPERATURE CONTROL SYSTEMS AT THE CATALYST ACTIVATION STEP IN THE METHANOL TESTPLANT

Catalyst activation is an important step in methanol synthesis process, achieved by the reduction of CuO precursor producing Cu0 active sites. Testplant’s temperature operation shall be maintainted at 220°C in order to maximize the CuO reduction process in the catalyst activation step. A temperature control system shall be applied in methanol testplant to maintain the temperature during reduction process, due to sensitivity of reduction process to temperature variation and possibility of disturbance such as change in gas flow rate which could affects the operating temperature. Temperature control systems are tested by using step response at the desired setpoint, which is 220°C at pre-heater and reactor and 60°C at sampling line. The tests are conducted by changing the setpoint value at temperature controller and previously stable flow gas in the system (disturbance rejection). The temperature control system proved to be able to response well during the test. In the end, methanol is produced from syngas, indicating catalyst activation success. Keywords: Catalyst Activation; Methanol Testplant; Temperature Controller

Steam reforming of ethanol for hydrogen production: influence of catalyst composition (Ni/Al2O3, Ni/Al2O3–CeO2, Ni/Al2O3–ZnO) and process conditions

Ethanol steam reforming was studied over Ni supported catalysts. The effects of support (Al2O3, Al2O3–ZnO, and Al2O3–CeO2), metal loading, catalyst activation method, and steam-to-ethanol molar feed ratio were investigated. The properties of catalysts were studied by N2 physisorption, TPD-CO2, X-ray diffraction, and temperature programmed reduction. After activity tests, the catalysts were analyzed by TOC analysis. The catalytic activity measurements showed that the addition either of ZnO SSor CeO2 to alumina enhances both ethanol conversion and promotes selectivity towards hydrogen formation. The same effects were observed for catalysts with higher metal loadings. High process temperature and high water-to-ethanol ratio were found to be beneficial for hydrogen production. An extended catalyst stability tests showed no loss of activity over 50 h on reaction stream. The TOC analysis of spent catalysts revealed only insignificant amounts of carbon deposit.

Towards High Efficacy of Pd-Au/C Catalyst for Tetrachloromethane Hydrodechlorination

We present an efficient strategy for synthesising the PdAu catalysts with a homogeneous PdAu alloy phase for environmentally important hydrodechlorination of tetrachloromethane in the gas phase. The synthesis of carbon-supported catalysts involved two major steps: (i) incorporation of palladium and gold nanoparticles into carbon support and (ii) activation of the catalysts. The critical part of this work was to find the optimal conditions for both steps. Thus, the incorporation of the nanoparticles was carried out in two ways, by impregnation and direct redox reaction method using acetone solutions of metal precursor salts. The activation was performed either by a conventional thermal reduction in hydrogen or flash irradiation in a microwave oven. The homogeneity and structure of the PdAu alloy were found to depend on the catalyst activation method critically. In all cases, we observed better homogeneity for catalysts that were subject to microwave irradiation. Moreover, the flash microwave irradiation of prepared catalysts provided catalysts of better stability and selectivity towards the desired products (hydrocarbons) in the hydrodechlorination of tetrachloromethane as compared to the catalyst obtained by conventional thermal activation in hydrogen.