The work concerns the dynamic behaviour of a porous, isothermal catalyst pellet in which a simultaneous chemical reaction, diffusion and adsorption take place. The impact of the reactant adsorption onto the pellet dynamics was evaluated. A linear isotherm and a non-linear Freundlich isotherm were considered. Responses of the pellet to sinusoidal variations of the reactant concentration in a bulk gas were examined. It was demonstrated that the dynamics of the pellet is significantly affected both by accounting for the adsorption and by the frequency of the bulk concentration variations. The sorption phenomenon causes damping of the concentration oscillations inside the pellet and damping of its effectiveness factor oscillations. Depending on the frequency of the concentration oscillations in the bulk, the remarkable oscillations can involve an entire volume of the pellet or its portion in the vicinity of the external surface.
A proper selection of steam reforming catalyst geometry has a direct effect on the efficiency and economy of hydrogen production from natural gas and is a very important technological and engineering issue in terms of process optimisation. This paper determines the influence of widely used seven-hole grain diameter (ranging from 11 to 21 mm), h/d (height/diameter) ratio of catalyst grain and Sh/St (hole surface/total cylinder surface in cross-section) ratio (ranging from 0.13 to 0.37) on the gas load of catalyst bed, gas flow resistance, maximum wall temperature and the risk of catalyst coking. Calculations were based on the one-dimensional pseudo-homogeneous model of a steam reforming tubular reactor, with catalyst parameters derived from our investigations. The process analysis shows that it is advantageous, along the whole reformer tube length, to apply catalyst forms of h/d = 1 ratio, relatively large dimensions, possibly high bed porosity and Sh/St ≈ 0.30-0.37 ratio. It enables a considerable process intensification and the processing of more natural gas at the same flow resistance, despite lower bed activity, without catalyst coking risk. Alternatively, plant pressure drop can be reduced maintaining the same gas load, which translates directly into diminishing the operating costs as a result of lowering power consumption for gas compression.
The main goal of the considered work is to adjust mathematical modeling for mass transfer, to specific conditions resulting from presence of chemical surface reactions in the flow of the mixture consisting of helium and methanol. The thermocatalytic devices used for decomposition of organic compounds incorporate microchannels coupled at the ends and heated to 500 ◦C at the walls regions. The experiment data were compared with computational fluid dynamics results to calibrate the constants of the model’s user defined functions. These extensions allow to transform the calculations mechanisms and algorithms of commercial codes adapting them for the microflows cases and increased chemical reactions rate on the interphase between fluid and solid, specific for catalytic reactions. Results obtained on the way of numerical calculations have been calibrated and compared with the experimental data to receive satisfactory compliance. The model has been verified and the performance of the thermocatalytic reactor with microchannels under hydrogen production regime has been investigated.
The results of activity studies of four catalysts in methanol synthesis have been presented. A standard industrial catalyst TMC-3/1 was compared with two methanol catalysts promoted by the addition of magnesium and one promoted by zirconium. The kinetic analysis of the experimental results shows that the Cu/Zn/Al/Mg/1 catalyst was the least active. Although TMC-3/1 and Cu/Zn/Al/Mg/2 catalysts were characterised by a higher activity, the most active catalyst system was Cu/Zn/Al/Zr. The activity calculated for zirconium doped catalyst under operating conditions was approximately 30% higher that of TMC-3/1catalyst. The experimental data were used to identify the rate equations of two types - one purely empirical power rate equation and the other one - the Vanden Bussche & Froment kinetic model of methanol synthesis. The Cu/ZnO/Al2O3 catalyst modified with zirconium has the highest application potential in methanol synthesis.
Hydrogen (H2) and liquid petroleum gas (LPG) sensing properties of SnO2 thin films obtained by direct oxidation of chemically deposited SnS films has been studied. The SnS film was prepared by a chemical technique called SILAR (Successive Ionic Layer Adsorption and Reaction). The sensor element comprises of a layer of chemically deposited SnO2 film with an overlayer of palladium (Pd) sensitiser. The Pd sensitiser layer was also formed following a chemical technique. The double layer element so formed shows significantly high sensitivity to H2 and LPG. The temperature variation of sensitivity was studied and the maximum sensitivity of 99.7% was observed at around 200°C for 1 vol% H2 in air. The response time to target gas was about 10 seconds and the sensor element was found to recover to its original resistance reasonably fast. The maximum sensitivity of 98% for 1.6 vol% LPG was observed at around 325°C. The sensor response and recovery was reasonably fast (less than one minute) at this temperature.
Methane (CH4) sensitivity of zinc oxide (ZnO) thin film has been studied in the present work. The sensor element comprises
of a chemically fabricated ZnO semiconducting layer and a layer of palladium (Pd) as catalyst. The catalyst layer was formed on the surface of semiconducting ZnO following a wet chemical process from palladium chloride (PdCl2) solution. Fundamental features of a sensor element e.g. sensitivity, response time and recovery process has been studied. The effect of operating temperature on performance of the sensor material has been investigated and a choice of optimum temperature was made at around 200oC. The sensor element exhibited reasonable sensitivity of about 86% at this temperature in presence of 1 vol% methane (CH4) in air.
Mordenite-zeolite supported Ca-Cu and Ba-Cu catalysts (Ca-Cu/MOR and Ba-Cu MOR) were successfully fabricated for direct decomposition of both NF3 and N2O gases contained in waste gas stream of (semiconductor) electronics industry. N2O conversion rates of Ca-Cu and Ba-Cu catalysts were 79 and 86%, respectively, at 700°C and 1 atm under space velocity of 5000 h–1. The Ca-Cu catalyst was especially noteworthy in that its capability of converting N2O could be maintained even after its exposure to co-feeding NF3 gas constituent in the waste gas stream. Compositional and surface morphological analyses of the Ca-Cu and Ba-Cu catalysts were made before and after exposure to the waste gas stream to examine any noticeable degradation or change of the catalysts. Unlike Ba-Cu catalyst, SiO2 constituent of the Ca-Cu catalyst was found to remain immune to the NF3-cofeeding waste gas stream, casting a positive prospect for superior and steady N2O decomposition performance via maintenance of its structural integrity.
Semiconductive - resistive sensors of toxic and explosive gases were fabricated from nanograins of SnO2 using thick-.lm technology. Sensitivity, selectivityand stabilityof sensors working in di.erent temperature depend on the way the tin dioxide and additives were prepared. A construction also plays an important role. The paper presents an attitude towards the evaluation of transport of electrical charges in semiconductive grain layer of SnO2, when dangerous gases appear in the surrounding atmosphere.
A detailed comparison of catalytic properties of two different ruthenium-based catalysts in the reaction of homogeneous hydrogenation of acetophenone was performed. Additionally, methods of synthesis of both catalysts were tested and optimized in order to achieve the best possible quality and purity of the final catalysts.
NMR analysis was used to analyze and identify the composition of ruthenium compounds and gas chromatography was used to analyze the conversion rate of hydrogenation reactions.
It was determined that RuCl2(PPh3)3 obtained with a modified method described by Shaw’s group (Shawet al., 2007) had the best catalytic properties in the reaction performed under conditions described in Liang Wang’s publication (Wang et al., 2014). It was also determined that for concentration ratio of substrate to RuCl2(PPh3)3 amounting to 250:1 the conversion rate was much higher than that of the reaction performed with a double dose of the catalyst. Results of experiments also show that samples of the post-reaction solution should be analyzed right after the reaction, because even if they are stored in low temperature the amount of product can change up to 3–5% compared to the base sample and this change is not predictable.
These findings have significant implications for further research of the reaction of homogeneous transfer hydrogenation of ketones. With the right catalysts and methods of their synthesis other parameters of this reaction can be optimized. The most important one is a change of solvent from isopropyl alcohol to a less toxic substance like water. This may increase the value of the reaction in green chemistry and chemical industry.
The study evaluated the curing properties of natural silica sand moulded with 1% by weight Furotec 132 resin binder catalysed by Furocure CH Fast acid and Furocure CH Slow acid. Physical properties of this sand included an AFS number of 47.35, 4.40 % clay, 0 % magnetic components, 0.13 % moisture, and 64.5 % of the size distribution spread over three consecutive sieves (150 – 600 μm). The sand was washed repeatedly to remove all the clay and oven dried. 2 kg washed sand samples were mulled with pre-determined weights of either catalyst to give 30 %, 50 % and 70 % by weight of 20 g Furotec 132 resin which was added last. Furotec 132 resin + Furocure CH Slow acid catalyst system gives longer bench lives and strip times but the maximum compressive strength in excess of 5000 N/cm2 is attained after more than 8.5 hours curing time irrespective of the weight % of catalyst added relative to the resin. On that basis, exceeding 30 weight % Furocure CH Slow acid catalyst when sand moulding with Furotec 132 resin has neither technical nor economic justification. In comparison, the Furotec 132 resin + Furocure CH Fast acid catalyst system was only capable of producing mould specimens with maximum compressive strength above 5000 N/cm2 at 30 weight % catalyst addition rate. At 50 and 70 weight % catalyst addition rates, the mulled sand rapidly turned dark green then bluish with a significant spike in temperature to about 40 oC, far exceeding the optimum curing temperature of Furotec 132. This high temperature accelerates the curing rate but with a very low degree of resin curing which explains the low compressive strength. In fact the sand grains fail to bond and have a dry, crumbly texture implying dehydration. Thus, not more than 30 weight % Furocure CH Fast acid catalyst should be used in sand moulding.