PERFORMANCE OF AN ANNULAR CATALYTIC THREE-PHASE REACTOR FOR A SECOND ORDER REACTION

A novel annular catalytic three-phase reactor is theoretically investigated for a second order hydrogenation reaction. The results indicate that the ratio of the gaseous reactant to the liquid reactant within the reaction zone of the annular reactor can be adjusted by changing the reactor dimensions and the concentration of the gaseous reactant in the feed. As a consequence, the annular reactor may have a significant advantage over the trickle-bed reactor with respect to the selectivities that may be achieved in the reactor.     

A LIMITATION OF REUSING THE CATALYST IN TRI-LIQUID-PHASE CATALYTIC SYSTEMS

This work demonstrates important factor influencing the reusability of the phase transfer catalyst in the third liquid phase in addition to the role of the possible loss of catalyst due to the dissolution of the catalyst into the aqueous and organic phases. When the catalyst might react with the byproducts, in addition to reacting with the organic substrate and aqueous nucleophile, it would lose its catalytic activity. The substitution reaction between the organic substrate and an aqueous nucleophile (sodium phenolate) with tetra-n-butylammonium bromide as a phase-transfer catalyst was employed as a model reaction and was performed in a batch reactor. Three organic substrates, including allyl bromide, n-butyl bromide, and ethyl 2-bromoisobutyrate, were tested. Each of the third liquid phases formed in these tri-liquid-phase catalytic systems was utilized three times to observe the change in the activity of the catalyst. The catalyst in the third liquid phase can be reused without any loss of its catalytic activity when allyl bromide or n-butyl bromide is utilized as the organic substrate; however, the catalytic activity declines when ethyl 2-bromoisobutyrate is the organic reactant. Therefore, the organic reactant plays a crucial role in determining whether the catalyst can be reused or not.     

A LIMITATION OF REUSING THE CATALYST IN TRI-LIQUID-PHASE CATALYTIC SYSTEMS

This work demonstrates important factor influencing the reusability of the phase transfer catalyst in the third liquid phase in addition to the role of the possible loss of catalyst due to the dissolution of the catalyst into the aqueous and organic phases. When the catalyst might react with the byproducts, in addition to reacting with the organic substrate and aqueous nucleophile, it would lose its catalytic activity. The substitution reaction between the organic substrate and an aqueous nucleophile (sodium phenolate) with tetra-n-butylammonium bromide as a phase-transfer catalyst was employed as a model reaction and was performed in a batch reactor. Three organic substrates, including allyl bromide, n-butyl bromide, and ethyl 2-bromoisobutyrate, were tested. Each of the third liquid phases formed in these tri-liquid-phase catalytic systems was utilized three times to observe the change in the activity of the catalyst. The catalyst in the third liquid phase can be reused without any loss of its catalytic activity when allyl bromide or n-butyl bromide is utilized as the organic substrate; however, the catalytic activity declines when ethyl 2-bromoisobutyrate is the organic reactant. Therefore, the organic reactant plays a crucial role in determining whether the catalyst can be reused or not.     

Potential catalyst savings in heterogeneous gaseous spiral coiled reactor utilizing selective wall coating – A computational study

This study numerically evaluates the effect of secondary flow on the reaction performance in heterogeneous gaseous spiral coiled reactor utilizing selective wall coatings. Laminar multispecies gas flow in spiral coiled reactor with circular and square cross-section is investigated using a validated three-dimensional computational fluid dynamics (CFD) model. Various selective wall coating strategies are evaluated within a range of Reynolds number. The reactor performance is measured not only based on the conversion rate but also in terms of figure of merit (FoM) defined as reaction throughput per unit pumping power and catalyst coating active area. The results indicate that secondary flow enhance reaction performance and improve catalyst utilization, especially at the outer wall. By maximizing this effect, the requirement of expensive catalyst materials can be minimized. This study highlight the potential of selective catalyst coating in coiled reactor for process intensification and cost reduction in various applications.     

Kinetic modeling of FCC process

Catalytic cracking of petroleum fractions a process termed as FCC is usually carried out in a reactor block with somewhat complicated hydrodynamic regime. The reactor block is considered as a combination of two different reactors. The riser is a near ideal plug-flow displacement of the catalyst and reaction mixture, while the main reactor vessel (separator) is considered as an ideal mixing CSTR. Temperature gradient along the plug-flow riser can vary on a linear and non-linear dependence. This is reflected by the thermal effect on the cracking products, along the altitude of the riser. Moreover, it can exert a considerable influence on the selectivity of the process in general, as characterized by the diversity of different hydrocarbon groups both in the gaseous and liquid products. The fluid catalytic cracking (FCC) is a process of conversion of a heavy oil fraction into lighter products in a catalytic fluidized reactor. The chemical composition and the structure of the feed are reflected on the catalyst's selectivity and the amount of coke deposited. It is, therefore, necessary to consider the feed type on modeling the process. Cracking reaction in the model was represented as a five-stage process. Reaction rates for the plug-flow riser and the ideal mixing separator are described mathematically in differential and algebraic forms. The model takes into account, exponential dependence of the specific reaction rate on temperature, as well as reflects the influence of the real and bulk catalyst densities, circulation rate, equilibrium and fresh catalyst's activities, reactor pressure, feed rate and unit construction. The model was developed based on a data taken from an industrial FCC unit, that were used to compute the kinetic constants and other parameters. Concrete computed kinetic parameters were compared with corresponding experimental data for adequacy. FCC process is in constant technological development with modernization of especially the riser reactor. Kinetic modeling of the catalytic FCC reactor will give a further understanding of the process and explain the complicated mechanism involved for an efficient and optimal conversion of the feed stock.     

Hurdles and solutions for reactions between gas and liquid in a monolithic reactor

In this paper, proof of principle experiments and exploratory work that solves the problem of ensuring that a gaseous and a liquid reactant are available at the catalytically active site at the same time by separating the reaction and the transport of the gaseous reactant. The equipment consisted of an autoclave in which a feed was saturated with hydrogen, a reactor with a catalyst coated on a monolith, a pump to circulate the feed/product stream, and devices to control and monitor the process.

A lot of information of how the process can be practised was gathered during the work. Conversion per pass should be below the amount of hydrogen that can be dissolved in the liquid to avoid coke deposition (and hence deactivation) of the catalyst. The effectiveness of the catalyst coated on the monolith was found to be 100%.

Several variations of the process design and catalysts used were explored. Integration of the monolith with a heat exchanger will obviously allow for the use of the process for very exothermic reactions like (nitro)benzene hydrogenation. A monolith to which Rh-cyclooctadiene-1,2-bis-diphenylfosfino-ethane (a homogeneous catalyst) was tethered was equally active in hydrogenation of 1-hexene as Rh-cyclooctadiene-1,2-bis-diphenylfosfino-ethane tethered to a standard alumina. This allows (fine)chemical producers to repeatedly use the expensive homogeneous catalysts without the need for separation of the catalyst from the reaction mixture.     

Analysis of a two-phase catalytic reaction in a millimeter-scale reactor

The synthesis of a catalyst for a two-phase catalytic reaction, a millimeter-scale reactor experiment, and an analysis model for the prediction of reactor performance are presented in this paper. The catalyst nano-particulate perovskite La_0.8Sr_0.2CoO₃ was prepared by a modified sol-gel method, in which PAA (poly acrylic acid) was added to catalyst precursors. A millimeter-scale reactor experiment with the prepared catalyst was carried. Concentrated hydrogen peroxide was decomposed in the reactor and the characteristics of the reactor were measured in terms of temperature distributions and liquid production rates. The results indicated a flow regime transition, which caused the change of reactor performance. An analysis model for two-phase catalytic reaction based on the lumped flow reactor model and the diagnostic data obtained on the temperature distributions and liquid production rates is proposed. Temperature distributions and heat transfer characteristics of the reactor were predicted by a semi-empirical analysis. In this analysis, the model of the Nusselt number (Nu) was proposed as . This expression of the model reflects the effects of temperature and coordinate location on the heat transfer characteristics of the reactor. From the modeled reactor, characteristics such as the increase of heat transfer in the mid and rear parts of the reactor with the increase of reactant flow rate were obtained. With the obtained results, a tool for the design and analysis of a down-scaled catalytic reaction device was obtained.     

Syngas formation by direct oxidation of methane: Reaction mechanisms and new reactor concepts

The reaction mechanism of direct catalytic oxidation of methane to syngas over a platinum catalyst under high temperature, short contact time conditions was studied with a detailed reactor and reaction model. Based on a detailed analysis of this mechanism, new integrated reactor concepts were deduced. Two concepts were studied in detail: a fixed bed reactor with integrated recuperative heat exchange, and a catalytic membrane reactor with distributed reactant feed. The reactor concepts are presented, and advantages and problems of the concepts are discussed.     

Forced oscillations of concentration in transport reactors

The performance of a transport catalytic reactor is analysed for an adsorption/desorption type model with Eley-Rideal surface kinetics with square wave oscillations in the feed concentration. The inlet average concentration of both the reactants over a period is assumed to be constant. Significant improvement in the yield of product is obtained by increasing the feed concentration of both the reactants in the first fraction of a period. The effect of adsorption capacity of the catalyst, reaction rate constants, and inlet feed mean concentration of the reactants are evaluated. The deactivation of active sites, due to product inhibition, introduces resonance in the yield versus cycle split. The yield of product shows a minimum with respect to cycle split for the type of forcing where one of the reactant concentrations increases and the second reactant concentration decreases in the first fraction of a period.     

Catalytic wet air oxidation of phenol in concurrent downflow and upflow packed-bed reactors over pillared clay catalyst

An experimental study is presented for comparing the behavior of a packed bed reactor in the catalytic liquid-phase oxidation of aqueous phenol with two modes of operation, downflow and upflow. The operating parameters investigated included temperature, reactor pressure, gas flowrate, liquid hourly space velocity and feed concentration. Because of the completely wetted catalyst, the upflow reactor generally performs better for high pressures and low feed concentrations when the liquid reactant limitation controls the rate. The interaction between the reactor hydrodynamics, mass transfer, and reaction kinetics is discussed. For both operation modes, complete phenol removal and significant total organic carbon (TOC) reduction can be achieved at rather mild conditions of temperature (150-170 °C) and total pressure (1.5-3.2 MPa). The results show that the phenol and TOC conversion are considerably affected by the temperature, while the air pressure only has minor influence. Total elimination of TOC is difficult since acetic acid, as the main intermediate, is resistant to catalytic wet oxidation. All tests were conducted over extrudates of Fe-Al pillared clay catalyst, which is stable and maintains its activity during the long-term experimental process. No significant catalyst deactivation due to metal ion leaching and polymer deposition was detected.     

MASS TRANSFER WITH CHEMICAL REACTION IN PARTIALLY WETTED FLAT PLATE CATALYST PELLETS: RIVULET FLOW ANALYSIS

Mass transfer with chemical reaction is analyzed in a system formed by a flat plate solid catalyst, partially wetted by a flowing rivulet of a liquid in contact with a stagnant pure gas. The paper solves the fluid dynamic problem of the liquid phase first, and afterwards incorporates the mass transfer and the chemical reaction. The system is assumed to be isothermal and at steady state, with a first order kinetics whose limiting reactant is in the gas phase. This work studies the influence of the gas-liquid surface tension, the liquid reactant flow rate, the liquid viscosity and the angle of inclination of the solid, upon the wetting factor. The model proposed also predicts the effect of these parameters and the Thiele modulus on the overall effectiveness factor and the molar flux of the limiting gaseous reactant at the catalytic solid-liquid interface in a direct way. This approach makes the wetting factor a non-manipulated variable.     

The effect of liquid flow distribution on the behaviour of a trickle bed reactor

A mathematical model has been formulated of the effect of flow distribution of the liquid phase carrying a dissolved reactant on the progress of an nth order, irreversible, catalytic reaction with heat effects in an adiabatic trickle bed reactor. The model has been stated in terms of the density of irrigation, temperature and concentration of the reactant in the liquid, all treated as spatially distributed variables. Provisions have been made to account for the existence of the flow down the surface of the wall, which has no catalytic effect.Local concentration and temperature have been proven to be coupled by the invariant T + Uγc = γU. The same invariant governs also local concentration and temperature of the wall flow. Mathematically, the model is represented by a coupled set of nonlinear parabolic partial differential equations enabling concentration and temperature fields to be obtained for an arbitrary type of liquid distribution and intensity of the wall flow.Numerical solutions have been obtained by the finite-difference method simulating reactors irrigated by liquid distributors as central discs of different radii, or a central annulus, and strongly exothermic reactions with the reaction order ranging between 0.1 and 2. Numerical results have shown the effect of liquid distribution on the overall reaction conversion to be very complex. Optimum initial distribution varies depending on the reaction order as well as the required degree of conversion. In general, however, the entrance region flow pattern may play a significant role in affecting especially reactions exhibiting kinetics close to zero order (hydrogenations). The effect of the wall flow has been found unambigously adverse to reaching high conversions and of increasing importance for low order reactions.     

Production of gasoline range hydrocarbons from catalytic reaction of methane in the presence of ethylene over W/HZSM-5

The catalytic conversion of a methane and ethylene mixture to gasoline range hydrocarbons has been studied over W/HZSM-5 catalyst. The effect of process variables, such as temperature, percentage of volume of ethylene in the methane stream and catalyst loading on the distribution of hydrocarbons was studied. The reaction was conducted in a fixed-bed quartz-micro reactor in the temperature range of 300–500 °C using percentage of volume of ethylene in methane stream between 25 and 75% and catalyst loading of 0.2–0.4 g. The catalyst showed good catalytic performance yielding hydrocarbons consisting of gaseous products along with gasoline range liquid products. The mixed feed stream can be converted to higher hydrocarbons containing a high-liquid gasoline product selectivity (>42%). Non-aromatics C₅–C₁₀ hydrocarbons selectivity in the range of 12–53% was observed at the operating conditions studied. Design of experiment was employed to determine the optimum conditions for maximum liquid hydrocarbon products. The distribution of the gasoline range hydrocarbons (C₅–C₁₀ non-aromatics and aromatics hydrocarbons) was also determined for the optimum conditions.     

THE ROLE OF LATTICE OXYGEN IN THE DYNAMIC BEHAVIOR OF OXIDE CATALYSTS

The lattice of an oxide catalyst used for oxidation reactions can act as a reservoir for oxygen, storing and releasing it for reactions at the catalyst surface under appropriate conditions. The implication of this oxygen storage property of an oxide catalyst on its dynamic response characteristics has been investigated through an experimental study of 2-butene oxidation over vanadium oxide as a model reaction. Isothermal reaction rate measurements in a differential reactor and nonisothermal studies in a single pellet reactor have been carried out. Following a step increase in the feed butene concentration, isothermal reaction rate overshoot and pellet temperature overshoot were observed. These observations could be modelled in a qualitatively correct way by a very simple model accounting for the participation of lattice oxygen in the catalytic reactions under dynamic conditions. It is demonstrated through model simulations that the ignition characteristics of a catalyst pellet are significantly affected by the participation of the lattice oxygen, when steady state multiplicity is present.     

Membrane Reactor/Separator: A Design for Bimolecular Reactant Addition

Abstract

A membrane reactor (MBR) is used to investigate the effect of selective reactant addition on series-parallel reaction networks, such as the oxidative dehydrogenation of ethane to ethylene. Ethylene is favored in an oxygen-lean environment, while excess oxygen favors the formation of combustion products. Control of the reactant ratio (ethane to oxygen) is crucial to both the overall selectivity and the hydrocarbon conversion. Traditional reactor designs co-feed the bimolecular reactants at the top of the reactor at some preset feed ratio. The MBR uses a tube (porous alumina membrane) and shell configuration. One reactant is fed at the top of a catalyst bed packed within the membrane core. The other reactant permeates into the tube along the length of the reactor via an imposed pressure drop. The reactant ratio is large at the top of the MBR, which leads to high selectivities; as the oxygen is consumed, it is replenished via downstream permeation to improve the ethane conversion. The MBR and a plug flow reactor (PFR) are evaluated at 600 [ddot]C, with identical space velocities, and using a magnesium oxide catalyst doped with samarium oxide. At low to moderate reactant feed ratios, the ethylene yield in the MBR exceeds the PFR by a factor of three, under some conditions. At higher feed ratios, the performance of the PFR nears or exceeds the performance of the MBR.     

Diffusion model of an airlift three-phase catalytic reactor and scale-up

A model of an airlift three-phase catalytic reactor is developed for cases of interphase mass transfer between the gas and the liquid in an airlift pipe and a catalytic reaction at the interface between the liquid and catalyst particles. The model equations give the vertical distribution of the average concentration of the active gaseous component (oxygen) in the gas and liquid phases and the average concentration of the active liquid component (alcohol) using the average velocities in the airlift and drain pipes. The model proposed solves the problem of the scale effect. A hierarchical approach is proposed to determine the model parameters from experimental data.     

Phenomenological approach to interpret the effect of liquid flow modulation in trickle bed reactors at the particle scale

This work analyzes the influence of liquid flow modulation on the behavior of a reaction occurring in a spherical porous particle within a trickle bed reactor. A single first-order reaction between a gaseous reactant and a non-volatile liquid reactant is considered. Non-steady-state mass balances for gas and liquid reactants are formulated and solved under isothermal conditions in order to focus the analysis on the mass transport effects. Dynamic reactant profiles inside the catalytic particle are obtained for different cycling and system conditions. The enhancement factor (ε) due to periodic operation is defined to evaluate the impact of induced liquid flow modulation on reaction rate. Influence of cycling and system parameters on the enhancement factor is also reported for a wide range of conditions. Experimental trends observed by several authors can be explained with this approach.     

MASS TRANSFER WITH A FIRST ORDER CATALYTIC REACTION IN A THREE-PHASE SYSTEM. TRICKLE FLOW ANALYSIS IN A PERIODICALLY CURVED CATALYTIC SOLID

The present work analyzes the process of mass transfer with chemical reaction in a system formed by a periodically curved catalytic wall, which is wetted by a descending film. Through the film a limiting gaseous reactant is transferred from the stagnant gas phase to the catalyst where the chemical reaction takes place.

The film hydrodynamics is first solved with the unknown free surface through a regular perturbation technique, by expanding the resulting equations in terms of a small parameter: the ratio between the film average thickness and the wave length of the curved solid wall. Assuming that the system is isothermal and at steady state, the mass transfer of the gas is afterwards incorporated. A first order kinetics whose limiting reactant is in the gas phase occurs in the solid phase.

Once the model is established and solved, the influence of the dimensionless parameters upon the effectiveness factor and the solid-liquid Biot number is then studied; important effects are found by changing the solid surface curvature at constant flow rate and catalyst volume. Besides, changes in the flow rate, the Peclet number and the ratio between the solid average width and the film average thickness, show significant effects on the net mass transfer process.     

Comparison of the performance of a direct-contact bubble reactor and an indirectly heated tubular reactor for solar-aided methane dry reforming employing molten salt

A theoretical approach is presented for the comparison of two different atmospheric pressure reactors—a direct-contact bubble reactor (DCBR) and an indirectly heated tubular reactor (IHTR)—to evaluate the reactor performance in terms of heat transfer and available catalytic active surface area. The model considers the catalytic endothermic reactions of methane dry reforming that proceeds in both reactors by employing molten salts at elevated temperatures (700–900 °C) in the absence of catalyst deactivation effects. The methane conversion process is simulated for a single reactor using both a reaction kinetics model and a heat transfer model. A well-tested reaction kinetics model, which showed an acceptable agreement with the empirical observations, was implemented to describe the methane dry reforming. In DCBR, the heat is internally transferred by direct contact with the three phases of the system: the reactant gas bubbles, the heat carrier molten salts and the solid catalyst (Ni-Al₂O₃). In contrast, the supplied heat in the conventional shell-and-tube heat exchanger of the IHTR is transferred across an intervening wall. The results suggest a combination system of DCBR and IHTR would be a suitable configuration for process intensification associated with higher thermal efficiency and cost reduction.     

Rich-Catalytic Lean-burn combustion for fuel-flexible operation with ultra low emissions

A Rich-Catalytic Lean-burn (RCL^®) combustion system was developed for operation on natural gas, but also provides significant advantages for fuel-flexible operation on non-methane fuels. Most notably, fuel-rich operation limits the extent of catalyst-stage reaction based on available oxygen, regardless of the fuel's intrinsic reactivity on the catalyst. Thus, similar catalyst and reactor performance can be obtained for widely varying fuel types.

In addition, catalytic pre-reaction extends the combustor's lean flammability limit for all fuels, allowing low-temperature combustion of both conventional and low-heating-value fuels, with concomitant low NO_x emissions.

This paper presents test results for RCL^® combustion with various fuel types, including gaseous, pre-vaporized liquid, and simulated low-Btu fuels. Although these fuels have widely varying properties, a single type of catalytic reactor was successfully tested for all of these fuels by modifying only the fuel delivery system upstream of the reactor. Test results show similar reactor performance for all fuels tested.