A numerical study of pellet model consistency with respect to molar and mass average velocities,pressure gradients and porosity models for methanol synthesis process: Effects of flux models on reactor performance

The objective of this work is to compare mass- and mole based diffusion flux models, convection, fluid velocity and pore structure models for methanol synthesis process. Steady-state models have been derived and solved using least-squares spectral method (LSM) to describe the evolution of species composition, pressure, velocity, total concentration and diffusion fluxes in porous pellets for methanol synthesis. Mass diffusion fluxes are described according to the rigorous Maxwell Stefan model, dusty gas model and the more simple Wilke model. These fluxes are defined with respect to molar- and mass averaged velocities. The different effects of choosing the random- and parallel pore models have been investigated. The effects of Knudsen diffusion have been investigated. The result varies significantly in the dusty gas model. The effectiveness factors have been calculated for the methanol synthesis process for both mass- and mole based pellet models. The values of effectiveness factors for both mass- and mole based pellet models do not vary so much. The effect of Wilke-, Maxwell–Stefan- and dusty gas mass diffusion fluxes on the reactor performance have been studied. Steady-state heterogeneous fixed bed reactor model is derived where the intra-particle mass diffusion fluxes in the voids of the pellet are described by Wilke-, Maxwell–Stefan- and dusty gas models. Furthermore, the total computational efficiency of the heterogeneous fixed bed reactor model is calculated with several closures for the intra-particle mass diffusion fluxes. The model evaluations revealed that:

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The mass- and mole based pellet models are not completely consistent. However, the small deviation (less than 2%) between mass- and mole based pellet models is due to the model equations are not fully consistent. If one pellet model is to be chosen for the methanol synthesis process, the optimal diffusion flux model is the Maxwell–Stefan model.     

A numerical study of multicomponent mass diffusion and convection in porous pellets for the sorption-enhanced steam methane reforming and desorption processes

Mass-based mathematical models have been formulated to describe the evolution of species mass fraction, pressure, velocity, density and mass diffusion flux in porous pellets for steam methane reforming (SMR) and sorption-enhanced steam methane reforming (SE-SMR) with CO₂ capture and desorption. The internal- and overall effectiveness factors have been calculated for the steam methane reforming, the sorption-enhanced steam methane reforming with a CaO-based adsorbent and the desorption processes. The accuracy of choosing the Wilke model to describe multicomponent diffusion instead of using the more costly Maxwell–Stefan- and Dusty gas models have been investigated. The different effects of choosing the random pore-, multi-grain- and the parallel-pore models have been investigated. Using an average size of the micro-particle the results obtained by in the multi-grain model, are slightly different than those for the parallel-pore model.The model evaluations revealed that:

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  The rate determining steps for the SMR process are basically the chemical kinetics, but the internal diffusion flux rate is also important as the main conversion takes place close to the external surface of the pellet. The SE-SMR process is basically chemical kinetics controlled. The approximate values of the efficiency factors for SE-SMR processes are around 1 and for the desorption it is around 0.02.

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  In general, the optimal diffusion flux model is the dusty gas model.

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  The multi-grain model is optimal pore model for the SMR and SE-SMR pellets.

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  There is a uniform temperature within the pellet.

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  The diffusion fluxes dominate over the convective fluxes. The pressure gradients and velocity vanish due to the imposed symmetry conditions.

     

Fuels and Energy for the Future: The Role of Catalysis

There are many reasons to decrease the dependency on oil and to increase the use of other energy sources than fossil fuels. The wish for energy security is balanced by a wish for sustainable growth. Catalysis plays an important role in creating new routes and flexibility in the network of energy sources, energy carriers, and energy conversion. The process technologies resemble those applied in the large scale manufacture of commodities. This is illustrated by examples from refinery fuels, synfuels, and hydrogen and the future role of fossil fuels is discussed.     

Fuels and Energy for the Future: The Role of Catalysis

Abstract

There are many reasons to decrease the dependency on oil and to increase the use of other energy sources than fossil fuels. The wish for energy security is balanced by a wish for sustainable growth. Catalysis plays an important role in creating new routes and flexibility in the network of energy sources, energy carriers, and energy conversion. The process technologies resemble those applied in the large scale manufacture of commodities. This is illustrated by examples from refinery fuels, synfuels, and hydrogen and the future role of fossil fuels is discussed.     

A new discretization of space for the solution of multi-dimensional population balance equations: Simultaneous breakup and aggregation of particles

In this work, we show that straight forward extensions of the existing techniques to solve 2-d population balance equations (PBEs) for particle breakup result in very high numerical dispersion, particularly in directions perpendicular to the direction of evolution of population. These extensions also fail to predict formation of particles of uniform composition at steady state for simultaneous breakup and aggregation of particles, starting with particles of both uniform and non-uniform compositions. The straight forward extensions of 1-d techniques preserve 2ⁿ properties of non-pivot particles, which are taken to be number, two masses, and product of masses for the solution of 2-d PBEs. Chakraborty and Kumar [2007. A new framework for solution of multidimensional population balance equations. Chemical Engineering Science 62, 4112-4125] have recently proposed a new framework of minimal internal consistency of discretization which requires preservation of only (n+1) properties. In this work, we combine a new radial grid [proposed in 2008. part I, Chemical Engineering Science 63, 2198] with the above framework to solve 2-d PBEs consisting of terms representing breakup of particles. Numerical dispersion with the use of straight forward extensions arises on account of formation of daughter particles of compositions different from that of the parent particles. The proposed technique eliminates numerical dispersion completely with a radial distribution of grid points and preservation of only three properties: number and two masses. The same features also enable it to correctly capture mixing brought about by aggregation of particles. The proposed technique thus emerges as a powerful and flexible technique, naturally suited to simulate PBE based models incorporating simultaneous breakup and aggregation of particles.     

The synthesis of rutile-type V/Sb mixed oxides, catalysts for the ammoxidation of propane to acrylonitrile: A comparison of high-energy milling and co-precipitation methods

This paper describes the preparation of rutile-type V/Sb mixed oxide (vanadium antimonate) with the ball-milling (mechano-chemical) method starting from single metal oxides, as well as the comparison with a similar system prepared by the co-precipitation method. Samples were tested as catalysts for the gas-phase ammoxidation of propane to acrylonitrile. The mechano-chemical method allowed the preparation of the rutile-type mixed oxide characterized by smaller crystallite size than the catalyst prepared by co-precipitation and calcined at 450 °C. The calcination at 700 °C of the sample prepared by the mechano-chemical method led to a crystalline vanadium antimonate characterized by a higher concentration of cationic defects than the corresponding calcined sample prepared by co-precipitation. This led to a considerably higher activity in propane ammoxidation, but to a lower selectivity to acrylonitrile.     

Accuracy, temporal performance and stability comparisons of discretization methods for the numerical solution of Partial Differential Equations (PDEs) in the presence of steep moving fronts

In this paper, several competitive spatial discretization methods recently developed for the convection term are reviewed and analyzed in terms of accuracy, temporal performance, and stability. This analysis was performed using a prediction–correction DAE integrator within the framework of the MOL (Method Of Lines). The discretization methods are classified by Fixed Stencil (FS), Adaptive Stencil (AS) and Weighted Stencil (WS) approaches and their main characteristics are demonstrated via a number of bench marking tests. Of the 14 discretization methods tested, four have been shown to be the most reliable, when we consider the accuracy of the calculation and the computational time required. Application of commonly-used FS methods to convection-dominated problems containing a moving shock results in a relatively short calculation time. However, almost of the FS methods, except for the first-order upwind FS method, are unstable, providing spurious oscillatory profiles (termed the Gibbs phenomena) near the shock. Employing AS methods such as ENO (Essentially Non-Oscillatory) schemes, this Gibbs phenomena disappears. Therefore, AS methods enhance stability and accuracy but are somewhat prohibitive. WS methods (i.e. Weighted ENO schemes), which use a convex combination of candidate stencils weighted by the ENO idea, can reduce the calculation time, and are inheriting of the non-oscillation nature inherent in the AS methods. The ENO and WENO methods are efficient to track a shock and steep moving front and these methods are essential for numerical schemes which use relatively small number of mesh points.     

Effects of small MoO3 additions on the properties of nickel catalysts for the steam reforming of hydrocarbons: II. Ni---Mo/Al2O3 catalysts in reforming, hydrogenolysis and cracking of n-butane

Addition of molybdenum to nickel catalysts has a favourable effect on their properties in the steam reforming of hydrocarbons. Some attempts were made to explain the mechanism of promoter action by determining the properties of such catalysts in hydrogenolysis and cracking reactions. With small amounts of promoter (≤0.5 wt.%) advantageneous changes in selectivity of steam reforming and disadvantageneous changes in n-butane hydrogenolysis were observed. The promoter does not affect practically the catalyst properties in n-butane cracking. The effect of molybdenum was compared with that of potassium promoter applied in the industry.     

The electro-oxidation of carbon monoxide, hydrogen/carbon monoxide and methanol in acid medium on Pt-Sn catalysts for low-temperature fuel cells: A comparative review of the effect of Pt-Sn structural characteristics

The electrocatalytic activity for CO, H₂/CO and CH₃OH oxidation of Pt-Sn catalysts has been extensively investigated for a possible use as anode materials for low-temperature fuel cells. This paper presents an overview of the relationship between the structural characteristics of the catalysts (catalyst composition, degree of alloying, presence of oxides) and their electrocatalytic activity for the oxidation of the different fuels.     

The mechanism of the poisoning of ammonia synthesis catalysts by oxygenates O2, CO and H2O: an in situ method for active surface determination

The effect of adding an oxygenated poison (O₂, CO or H₂O) to a hydrogen/nitrogen stream producing ammonia over a triply promoted (K₂O, CaO, Al₂O₃) commercial catalyst is not unsurprisingly rapidly to poison the catalyst. However, immediately the oxygenated poison reacts with the catalyst and before total poisoning has occurred, which in these experiments took 10 min, there was an explosive release of ammonia producing concentrations in the gas phase in excess of the equilibrium value. This is thought to be due to a convulsive reorganisation of the surface of the catalyst in forming regions of an oxide overlayer, resulting in the expulsion of the standing surface nitrogen atom coverage as ammonia. However, in contradistinction to the observation of complete poisoning of the triply promoted catalyst shortly after switching the water (2.9%) into the hydrogen/nitrogen stream, when polycrystalline iron was used as the catalyst, after the initial pulse of ammonia was observed, the small quantity of water (2.9%) in the hydrogen/nitrogen stream resulted in an increased rate ( ×3) of ammonia synthesis which declined only slightly over the twenty minute duration of the experiment. The difference in behaviour between the triply promoted catalyst and the polycrystalline iron is thought to be due to the relative ease of reduction of the latter, so that submonolayer quantities of oxide can be stabilised on the surface of the polycrystalline iron. The promoting effect of this oxide overlayer is either structural or electronic; no distinction can be made from these experiments. The technique of injecting either O₂ or CO into a hydrogen/nitrogen stream which is producing ammonia over promoted catalysts in quantities insufficient to cause complete poisoning and measuring the oxygen coverage of the catalyst to a measured decrease in the ammonia synthesis rate, appears to be a ready, in situ method for the determination of the active catalyst area.     

Pretreatment of polypropylene films for the creation of thin polymer layers,part 1: The use of chemical,electrochemical, and UV methods

The surface of a polypropylene (PP) film was activated with chemical, electrochemical, and physical methods, and the effectiveness of these methods was compared. The effects of PP activation were assessed with attenuated total reflection IR spectroscopy (ATR‐IR), SEM microscopy, and an analysis, based on the liquid contact angle, of the free energy components of the surface. The activation of the PP surface, which was dependent on the oxidizing medium, increased the energy of the PP surface layer and formed new chemical (carbonyl) groups, which were identified by IR (ATR) absorption spectroscopy and confirmed by selective surface dyeing. The treatments were ranked in the following order of increasing effectiveness: UV irradiation < 3M nitric acid < 30% hydrogen peroxide < silver nitrate (electrochemical method) < chromic mixture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011