Scaling-out selective hydrogenation reactions: From single capillary reactor to monolith

Selectivity and kinetic studies of the Pd-catalysed hydrogenation of 2-butyne-1,4-diol were performed in a single capillary channel, and monoliths consisting of 1256 capillaries and 5026 capillaries in (I) the pressure range 100-300 kPa (II) the temperature range 298-328 K using a 30% v/v 2-propanol/water solvent. All reactors were operated in downflow mode such that the reaction fluid was in Taylor flow. Transport calculations indicated that liquid-solid transport resistances were low (<5%) and energies of activation were found to be in the range 32-34 kJ mol⁻¹. While the reaction was first order in hydrogen concentration, the order with respect to 2-butyne-1,4-diol changed over the concentration range investigated. A model based upon a Langmuir-Hinshelwood mechanism was applied and found to predict reasonably well the experimental reaction rates. High selectivity values towards the 2-butene-1,4-diol were found in both the single- and multiple-capillary reactors, even at 100% conversion of the alkyne.     

Study of the catalyst deactivation in an industrial gasoil HDS reactor using a mini-scale laboratory reactor

The activity of a hydrodesulphurization catalyst loaded in an industrial hydrotreater is studied at start up and end of run. Catalyst initial and final activity was determined by performing HDS experiments at industrial conditions in a laboratory mini-scale hydrotreater. The results show that the deactivation of the catalyst samples collected from three different places of the industrial reactor do not vary significantly, the maximum difference among the catalyst samples, being less than ±4%. The experimentally determined deactivation level of the catalyst samples is compared with the deactivation estimated for the same industrial reactor and the same load using a hybrid neural network model trained with operational data of the industrial and the results are in close agreement. Catalyst deactivation appears to be faster for hydrogen consumption reactions than for hydrodesulphurization reactions indicating a decreasing hydrogen consumption trend with time in operation for specific sulphur content in the product.     

Modeling of acetophenone hydrogenation over a Rh/C catalyst in a slurry airlift reactor

The hydrogenation of acetophenone in a slurry airlift reactor was conducted over a wide range of operating conditions. An important deactivation of the catalyst was experimentally observed and an empirical deactivation law was optimized. The deactivation rate constant increases with the inlet concentration and gas flow rate and decreases with the catalyst loading. The product selectivity measured in the slurry airlift reactor did not fit well with the computed one. The computation was performed using the results of the kinetic and hydrodynamic studies. A sensitivity analysis pointed out that the mass transfer is not limited. To perform a good fit with the experiments it was necessary to change some rate constants. This readjustment was justified by the difference in catalyst pretreatment between the continuous and the semi-batch reactor where significant catalyst pretreatment effects were shown.     

Experimental procedure for kinetic studies on egg-shell catalysts: The case of liquid-phase hydrogenation of 1,3-butadiene and n-butenes on commercial Pd catalysts

A study of the liquid-phase hydrogenation of 1,3-butadiene on commercial Pd/Al₂O₃ catalysts of the “egg-shell” type has been performed. Experimental conditions (40°C, 4 atm and high conversion of the di-olefin) were selected in accordance to industrial operating conditions employed for selective hydrogenation of 1,3-butadiene. Three experimental schemes were tested: a slurry reactor, a rotating-basket reactor, and a recirculation system with an external fixed-bed reactor. Significant drawbacks shown by the two former devices were mainly derived from the very high activity and the egg-shell structure of the catalysts. Instead, the recirculation system was found to be an excellent alternative.

Although Pd is present only within a very thin external layer (around 50–250 μm), strong diffusion effects impairing selectivity were observed. Plausible kinetic expressions corresponding to nine series–parallel overall reactions are derived from a mechanistic model. To deal with this network of fast reactions, a rather complex set of computational and predictive tools were employed. A worked out example from several replicates demonstrates the capability of both, experimental and data analysis procedures, for inferring kinetic parameters of the proposed model.     

Analysis of the particle swarm algorithm in the optimization of a three-phase slurry catalytic reactor

The Particle Swarm Optimization (PSO) method was employed to optimize an industrial chemical process characterized by being difficult to be optimized by conventional deterministic methods. The chemical process is a three phase catalytic slurry reactor (tubular geometry) in which the reaction of the hydrogenation of o-cresol producing 2-methyl-cyclohexanol is carried out. The optimization problem was formulated considering as input variables the operating conditions of the reactor and as objective function the maximization of productivity, subject to the environmental constraint of conversion. The process was represented by a multivariable non-linear rigorous mathematical model and in order to solve the optimization problem, the performance of the PSO algorithm was evaluated considering four sets of parameters values suggested by the literature. PSO demonstrated to be efficient and robust to solve the constrained optimization problem, independently of the values of the PSO parameters. The solution of the rigorous mathematical model of the reactor was associated with a high computational burden, and although the PSO algorithm presented high rate of convergence, the attempt to make possible the optimization in a timeframe suitable to real time applications failed because the algorithm lost robustness (fraction of the number of runs the algorithm reached the optimization goal) when run with a reduced number of function evaluations. Therefore, if this type of application is desired, simplified mathematical models with fast and simple numerical methods must be preferred.     

CFD simulation of a chemical-looping fuel reactor utilizing solid fuel

A computational fluid dynamic (CFD) study has been carried out for the fuel reactor for a new type of combustion technology called chemical-looping combustion (CLC). CLC involves combustion of fuels by heterogeneous chemical reactions with an oxygen carrier, usually a granular metal oxide, exchanged between two reactors. There have been extensive experimental studies on CLC, however CFD simulations of this concept are quite limited. In the present paper we have developed a CFD model for the fuel reactor of a chemical-looping combustor described in the literature, which utilized a Fe-based carrier (ilmenite) and coal. An Eulerian multiphase continuum model was used to describe both the gas and solid phases, with detailed sub-models to account for fluid–particle and particle–particle interaction forces. Global reaction models of fuel and carrier chemistry were utilized. The transient results obtained from the simulations were compared with detailed experimental time-varying outlet species concentrations (Leion et al., 2008) and provided a reasonable match with the reported experimental data.     

Model based control of a liquid swelling constrained batch reactor subject to recipe uncertainties

This work presents the application of nonlinear model predictive control (NMPC) to a simulated industrial batch reactor subject to safety constraint due to reactor level swelling, which can occur with relatively fast dynamics. Uncertainties in the implementation of recipes in batch process operation are of significant industrial relevance. The paper describes a novel control-relevant formulation of the excessive liquid rise problem for a two-phase batch reactor subject to recipe uncertainties. The control simulations are carried out using a dedicated NMPC and optimization software toolbox OptCon which implements efficient numerical algorithms. The open-loop optimal control problem is computed using the multiple-shooting technique and the arising nonlinear programming problem is solved using a sequential quadratic programming (SQP) algorithm tailored for large-scale problems, based on the freeware optimization environment HQP. The fast response of the NMPC controller is guaranteed by the initial value embedding and real-time iteration technologies. It is concluded that the OptCon implementation allows small sampling times and the controller is able to maintain safe and optimal operation conditions, with good control performance despite significant uncertainties in the implementation of the batch recipe.     

糠醛在Pd-Cu膜反应器中催化加氢合成糠醇

以糠醛催化加氢合成糠醇作为模型反应,采用共沉淀法制备的Cu/MgO-K₂O作为催化剂,考察了Pd-Cu膜反应器的加氢性能.膜反应器由双套管组成,采用分别进料的方式操作.即糠醛气化后由载气带入中心膜管的催化床层,而氢气则进入管壳层通过Pd-Cu合金膜渗透到反应区.在不同条件下分别进行糠醛催化加氢反应,考察了糠醛转化率、产品糠醇选择性和收率,并与传统的共进料填充床反应器进行比较.研究结果显示,膜反应器比传统的填充床反应器具有产品收率高、选择性好和副产物少的特点.此外,本文结合催化剂的组成、结构和表面形貌的表征对催化剂的催化活性和失活行为进行了讨论.     

The influence of distributed reactant injection along the height of a fluidized bed reactor

A two-phase model is used to simulate spreading the introduction of reactant feed along the height of a fluidized bed reactor for oxidative dehydrogenation of ethane to ethylene. The reactor model is used to predict the reactor performance for different ethane-to-oxygen molar feed ratios, with premixed and non-premixed feed. The proposed model is used to simulate the premixed feed (without secondary injection), and for distributed feed with secondary injection at one, three and five injection levels above the primary distributor. Predictions from the model are shown to compare favourably with experimental data from an industrial pilot reactor of diameter 97 mm. A case study is then employed to explore a wider range of conditions than is possible experimentally. Oxidant distribution is shown to be beneficial in expanding the range of reactant compositions beyond those normally allowed by safety constraints. Distributing the feed over a number of levels improves the reactor performance, especially in reducing the selectivities of undesired by-products. Feeding gas at several levels is generally more promising than introducing feed at a single secondary injection level.     

Enzyme kinetics of kinetic resolution of racemic ibuprofen ester using enzymatic membrane reactor

An ultrafiltration hollow fiber enzymatic membrane reactor was employed to study the kinetics of lipase-catalyzed kinetic resolution of racemic ibuprofen ester. Lipase from Candida rugosa was employed in the hydrolysis reaction both in free form in a batch system and in immobilized form in an enzymatic membrane reactor (EMR). The half life (t_1/2) of immobilized lipase on spongy layer was 105 h at reaction temperature of and 62 h at . This value was 94 h for lipase immobilized on the inner lumen and 45 h for free lipase in batch system at . Excessive substrate was found to inhibit the reaction as an uncompetitive inhibitor. The by-product 2-ethoxyethanol was found to be non-competitive inhibitor to the reaction when it was present in an excess. Michaelis constant (K_m) and maximum reaction rate (V_max) for immobilized lipase were and , respectively; and that for free lipase were and h^-1, respectively.     

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.     

Modeling of monolithic and trickle-bed reactors for the hydrogenation of styrene

A kinetic study into the styrene hydrogenation over a palladium on alumina catalyst has been made. Styrene was used as a model component for pyrolysis gasoline. A kinetic rate expression has been derived and the inhibiting effect of sulfur components has been included. Using this kinetics and mass-transfer models compiled from literature, the performance of two types of reactors for the styrene (pyrolysis gasoline) hydrogenation has been evaluated. A structured reactor such as a monolith has large advantages over a conventional trickle-bed reactor. For the monolithic reactor a more than 3 times higher volumetric productivity is obtained with much less catalyst. The modeling results indicate that deactivation by gum formation should be significantly less due to much better hydrogen mass transfer in the reactor.     

The hydrogenation of cinnamaldehyde by supported aqueous phase (SAP) catalyst of RhCl(TPPTS)3: Selectivity, kinetic and mass transfer aspects

The hydrogenation of trans-cinnamaldehyde catalysed by a supported aqueous phase catalyst of RhCl(TPPTS)₃ [TPPTS: trisodium salt of tris(m-sulfophenyl)phosphine] on silica was investigated in terms of the product selectivity, reaction kinetics and mass transfer characteristics. The hydrogenation is selective at the CC bonds in cinnamaldehyde giving hydrocinnamaldehyde as the main product. To achieve high selectivity (99.9%), it is necessary to employ a low initial concentration of cinnamaldehyde (0.076 M). The selectivity also depended on the reaction operating conditions (pressure, temperature, catalyst loading) and the water content property of the SAP catalyst. Optimum water content of the SAP catalyst giving maximum activity was obtained when the pore volume of the supports was completely filled with water. The overall order of reaction was first-order and therefore the conventional three-phase slurry model was applied to the SAP system for the mass transfer analysis. The gas-liquid mass transfer and the reaction resistances were the controlling steps of comparable significance, while liquid-solid mass transfer resistance was negligible in this system. Under similar conditions, the SAP catalyst gave a lower reaction rate than the analogous biphasic catalyst.     

A critical comparison of frictional stress models applied to the simulation of bubbling fluidized beds

The behaviour of a gas-solid flow in a bubbling fluidized bed operated near the minimum fluidization condition is strongly influenced by the frictional stresses between the particles, these being highly concentrated and their motion dominated by enduring contact among them and with the walls.The effect of the introduction of frictional stresses in a Eulerian-Eulerian two fluid model based on the kinetic theory of the granular flow is evaluated. The models of Johnson and Jackson [1987. Frictional-collisional constitutive relations for granular materials, with application to plane shearing. Journal of Fluid Mechanics 176, 67-93], Syamlal et al. [1993. Mfix documentation: volume I, theory guide. Technical Report DOE/METC-9411004, NTIS/DE9400087, National Technical Information Service, Springfield, VA], and Srivastava and Sundaresan [2003. Analysis of a frictional-kinetic model for gas-particle flow. Powder Technology 129, 72-85] are compared with the kinetic theory of the granular flow and with experimental data both in a bubbling fluidized bed with a central jet and in a bubbling fluidized bed with a porous distributor. The predicted evolution of the bubble diameter along the height of the fluidized beds is examined, the shapes of the bubbles predicted by the models are compared and the evolution in time of the bubbles is shown. In the case of the bed with a central jet, the bubble detachment time is also calculated. The results show that the introduction of a frictional stress model improves the prediction of the bubbles diameter in a bubbling fluidized bed with a central jet and positively affects the bubbles diameter distribution in a uniformly fed bubbling fluidized bed. The high sensitivity of the model to the value of the particulate phase fraction at which frictional stresses start to be accounted for is pointed out through a sensitivity analysis performed on the Srivastava and Sundaresan [2003. Analysis of a frictional-kinetic model for gas-particle flow. Powder Technology 129, 72-85] model.     

Monitoring stability of reaction and dispersion states in a suspension polymerization reactor using electrical resistance tomography measurements

A system was constructed for visualizing the dispersion states of liquid monomer and polymer droplets in a suspension polymerization reaction in a non-intrusive and continuous manner using electrical resistance tomography measurements.Using this system, a method was established for keeping reaction states stable and the quality of the particles produced good by varying the mixing conditions, such as the rotational speed of the impeller and the injection amount of dispersion reagents, under the principles that the lower the rotational speed of the impeller, the better; and the smaller the injection amount of dispersing agents, the better.It was found that the amount of additional injection significantly affected both the sharpness and the average value of the particle diameter distribution, based on the data of the tomograms.     

Mass transfer and kinetics of the three-phase hydrogenation of a dinitrile over a Raney-type nickel catalyst

The hydrogenation kinetics of a dinitrile over a Raney-type nickel catalyst was evaluated from experiments performed in a fed-batch operating autoclave at 320- and 2- hydrogen pressure. This complex catalytic reaction consists of two main parts: almost 100% selective hydrogenation of the dinitrile to the corresponding aminonitrile and consecutive hydrogenation to either the desired primary diamine or to pyrrolidine via ring formation. An extensive study has been made on the effects of mass transfer in the applied slurry-type reactor for this reaction. The gas-liquid mass transfer is enhanced by the presence of catalyst particles, and at typical hydrogenation conditions, k_La values up to can be reached. A Sherwood correlation for the three-phase reactor showed that important parameters in the gas-liquid mass transfer are stirrer speed and the density and viscosity of the solvent. The kinetic experiments were performed in absence of mass and heat transfer limitations. The kinetic data were modeled using two rate models based on Langmuir-Hinshelwood kinetics, assuming the reaction of dissociatively adsorbed hydrogen and nitrile compound as rate-limiting step. The first model involved competitive adsorption between hydrogen and organic compound and the second model was based on non-competitive adsorption. Both models successfully described both reaction parts. The reaction of dinitrile to aminonitrile is nearly 100% selective due to the relatively strong adsorption of the dinitriles as compared to the aminonitriles. By increasing the hydrogen partial pressure, higher yields of primary amine can be obtained. The models predict that operating in the mass-transfer regime at relatively high temperatures reduces the formation of the primary diamine.     

Performance of catalytic reactors for the hydrogenation of CO2 to hydrocarbons

Fluidized bed and slurry reactors were employed to increase the CO₂ conversion and desirable product selectivity in the direct hydrogenation of CO₂ to hydrocarbons over K-promoted iron catalysts, as it is beneficial for the removal of heat generated due to highly exothermic nature of the reaction. The iron catalysts (Fe-K/Al₂O₃ and Fe-Cu-Al-K) were characterized by BET surface area, CO₂ and H₂ chemisorption, temperature-programmed reduction (TPR), X-ray diffraction (XRD) and temperature-programmed hydrogenation (TPH). The results of TPR and TPH study clearly indicated that co-precipitated Fe-Cu-Al-K catalyst has much higher reducibility and catalytic activity of CO₂ hydrogenation at low temperature than Fe-K/Al₂O₃. The performance of fluidized bed or slurry reactors was superior to that of fixed bed reactor for the CO₂ hydrogenation over Fe-Cu-Al-K catalyst in terms of CO₂ conversion and hydrocarbon productivity. Moreover, light olefins and heavy hydrocarbons were selectively synthesized in fluidized bed and slurry reactors, respectively. The optimum operation conditions and the effects of operating variables on the CO₂ conversion and its product distribution in these catalytic reactors were also discussed.     

Study of gas-liquid stirred reactor stability taking into account the temperature influence on gas solubility

The paper is devoted to the dynamic behavior and stability of gas-liquid stirred reactor taking into account the temperature influence on gas solubility. Since the rate of gas-liquid processes is very sensitive to concentration of gas reactant dissolved in liquid, even weak fluctuations of temperature can significantly influence on process pass. There are two cases of temperature influence on gas solubility are possible: (1) the solubility decreases with increasing temperature; (2) the solubility grows with increasing temperature. The first case is typical for majority of gases. The second case occurs more rarely but has a great practical importance. It takes place, for example, for the hydrogenation of many compounds in organic solvents (such as benzene, toluene, isopropyl alcohol and others). A model of gas-liquid process has been developed to demonstrate the stability of gas-liquid reactor. It has been shown that the gas solubility behavior has an influence on the form of heat production curve and therefore on the multiplicity of the steady states. The areas of multiplicity and limit cycles were found and the phenomenon of hysteresis in the reactor was shown. A criterion to determine whether the multiplicity is possible under the given conditions was found. By means of an analysis of a mathematical model the stability of steady states of the reactor was studied.     

CFD simulation of the hydrodynamics and reactions in an activated sludge channel reactor of wastewater treatment

This paper presents a complete CFD modelling of a wastewater gas-liquid cross-flow reactor, taking into account hydrodynamics, mass transfer and biological reactions. Transfer processes, kinetics model and assumptions made are described in detail. The simulations have been successfully compared to experimental results obtained in a bench scale reactor. Chemical oxygen demand (COD), nitrate, ammonium and oxygen concentrations have been measured along the length of the reactor and compared to the simulated profiles. A very good agreement has been obtained for the COD and nitrate concentration profiles. Agreement for the oxygen concentration profile is reasonably good with respect to the experimental uncertainty. These results have been obtained without any adjustment of the kinetics parameters. The basics of a three-phase CFD model taking into account the transfer between flocs and wastewater, as well as the inhomogeneous concentration of biomass due to the hydrodynamics of the reactor, are proposed as perspectives.     

Ethanol oxidation in a trickle-bed reactor using a hydrophobic catalyst: Effect of dilution with hydrophilic particles

Ethanol oxidation at moderate temperature and atmospheric pressure is carried out in a trickle-bed reactor using a hydrophobic catalyst and pure oxygen as the oxidizing agent. The influence of diluting the hydrophobic catalyst with different proportions of the hydrophilic inert support is particularly studied by performing comparative experiments at different operating conditions. Reactor performance is not significantly modified when the hydrophobic catalyst is diluted with the hydrophilic support in a 50% mass proportion. For a larger dilution, 75% (w/w), significant differences in ethanol conversions are found for certain conditions, presumably due to the influence of the liquid holdup, gas–liquid interfacial areas and wetting efficiency characterizing a bed with a major proportion of hydrophilic particles.