ON THE BEHAVIOR OF CONSECUTIVE ENZYMATIC REACTIONS IN CYCLICALLY OPERATED REACTORS

The dynamics of a process involving consecutive enzymatic reactions were investigated for a case in which the reactions are carried out in a cyclically operated reactor. Each cycle of the operation protocol involves three phases. During phase I the reactor operates in a semi-batch mode involving input of the reactants. During the second phase, the vessel operates in a batch mode. During phase III the reactor has an output only and a fraction of its contents are emptied before another identical cycle begins.

It was found that there are regimes in the operating parameter space where the system can reach more than one limit cycle (multistability). Using computer software based on the bifurcation theory for forced systems, as well as one- and two-parameter continuation algorithms, the impact of various parameters on the dynamics of the system was investigated. The results are presented in the form of diagrams. Conditions under which formation of the intermediate product in the reaction sequence is maximized were also investigated.

Production of the intermediate product in a limit cycle was compared to that obtained in batch and semi-batch operation. Implications of the proposed operation protocol for process optimization and pollution prevention are discussed.     

THE EFFECT OF SUBSTRATE MASS TRANSFER LIMITATIONS IN AN IMMOBILIZED ENZYME MEMBRANE REACTOR

An unstirred ultrafiltration cell can be quite easily converted into an immobilized enzyme reactor. Indeed, if suitable amounts ofproteic solutions are fed and if the protein molecular weight exceeds the membrane cut off, gel precipitation occurs onto the active surface of the membrane because of concentration polarization phenomena. Two different gel formation procedures have been followed. Indeed, two different proteic solution have been injected, namely

1.a mixture of an inert protein and the enzyme

2.co-polymer obtained by co-cross-linking the enzyme and the inert protein.

Substrate mass transfer limitations which occur in the gel immobilized enzyme reactor have been considered. The relevance of mass transfer resistances upstream from the immobilized gel layer has been discussed together with the intrinsic enzyme kinetics.

A heterogeneous gel model has been proposed which adequately describes the experimental results. Effectiveness factor correlations of fairly general applicability have been also presented.     

EXPERIMENTAL EVALUATION OF SELECTIVITY IN SLOW AROMATIC CHLORINATIONS

A dispersion plug flow reactor model (DPFR) has been derived and experimentally verified to predict product distribution and selectivity for commercial aromatic halogenation reactions. From the model recommendations for process modifications to reduce the amounts of undesirable byproducts arising from similar reactions can be obtained. The selectivity of the monochlorinated product is shown to depend on kinetic and hydrodynamic parameters, mixing in the reactor and chlorine solubility. The pertinent variables are arranged in five dimensionless groups which include the kinetic and hydrodynamic Damkohler Numbers, the Peclet Number, ratio of the rate constants and the ratio of chlorine solubility to the inlet aromatic concentration.

A micro pilot plant which duplicates industrial conditions for benzene and toluene chlorination was constructed to test the DPFR model. Chlorination studies were performed under a range of conditions. Hydrodynamic parameters required for the model were obtained from published correlations. The model prediction of selectivity agreed within 8% for all the experimental results, and actually better than 5% for most runs.

A graphical technique which provides recommendations for reducing the dichlorinated products is presented along with examples for both the design of a reactor, and troubleshooting of an existing reactor system.     

ATMOSPHERIC CONTACT DRYING OF GRANULAR BEDS WETTED WITH A BINARY MIXTURE

When regarding the atmospheric contact drying of granular beds wetted with a liquid mixture, both the drying rate and the selectivity of the process, i.e. the change of moisture composition, are of interest. The batch drying of a free flowing ceramic substance, wetted with a 2-propanol-water mixture, is investigated in a rotary dryer with heated wall and air flow.

The theoretical analysis is based on physical models for heat and mass transfer, moisture migration and particle transport, which are presented in examples.

The experimental and theoretical results show that higher selectivities can be achieved by reducing the particle size because of the lower liquid-phase mass-transfer resistance. An increase of the rotational speed leads to a higher drying rate with slightly decreased selectivity if the particles are sufficiently small, since contact heat transfer is enhanced.     

RECIRCULATING REACTOR FOR THE STUDY OF MULTIPHASE KINETICS

A new laboratory reactor was set up to measure kinetic coefficients in a solid (catalyst)-liquid-gas reacting system.

The reactor consists of two parts: an absorber, where the liquid is partially saturated by the gas reactant and a reacting zone, where the liquid alone, containing the dissolved gas, flows through a fixed bed of catalyst.

The ricircle of the liquid in the absorber maintains a high concentration of the gas reactant in the liquid also in the zone of reaction, allowing the use of a high mass of catalyst (significative from a statistical point of view) and the achievement of sufficiently high conversion.

The tested reaction is the catalysed hydrogenation of ∝-metylstyrene: in order to consider a drastic situation and to verify the results with the literature data, the experimental conditions examined corresponded to very high chemical reaction rate (instantaneous reaction) at the surface of the pellets.

The tests were carried out with the reactor working both in batchwise and in continuous operative mode (steady state); the results show the reliability of the new reactor above all when the steady state operation is considered. For the use of the reactor in batchwise condition, the accumulation of the product inside the catalyst particles must be considered for an accurate measurement of the kinetic parameters,     

MAXIMIZING SELECTIVITY OF LIQUID-LIQUID REACTION SYSTEMS. CONTROL OF THE DISPERSION PROCESS

Currently available information on droplet coalescence and break-up rates in turbulent flows in mixing vessels can be used to control drop sizes in dispersed phase equipment. The effect of drop size distributions on the selectivity and productivity in multi-reaction systems is examined in this paper.

The reaction system features the primary desired product (C) as resulting from reaction (in the bulk phase) between a reactant (A) in the drop phase and a second reactant (B) in the bulk phase. An adverse reaction is also envisaged which consumes (C) by further reaction with (B) to form a waste product. While small drops promote conversion because of large interfacial area, larger drops promote selectivity because of the facility of the product to re-enter the drop phase avoiding further reaction (to form waste) in the bulk phase. The effect of the bivariate distribution of drop size and reactant (A) concentration in the feed to a continuous stirred tank reactor on the selectivity and productivity of (C) is investigated within the framework of film theory while neglecting drop dynamics such as coalescence and break-up.

The results show the selectivity can be substantially improved by controlling drop size and distribution of the reactants among the differently sized droplets. Contrary to conventional wisdom which emphasizes creation of interfacial area by promoting very small droplets, it emerges that optimal distributions of drop size and reactant concentration which maximize productivity of the desired product exist. The practical implications are discussed.     

EXPERIMENTAL STUDY OF THE SELECTIVE HYDROGENATION OF STEAM CRACKING C2CUT. FRONT END AND TAIL END VARIANTS

Selective hydrogenation is the habitual industrial process to eliminate the most unsaturated hydrocarbons, which are harmful for later applications. In this paper, the kinetics of the selective hydrogenation of a C₂ mixture over two palladium/alumina catalysts with both front end and tail end variants, have been studied. Experiments have been carried out to analyse the influence of temperature, hydrogen/acetylene molar ratio, carbon monoxide content in the feed and hydrocarbon volumetric flow rate on the corresponding conversion and selectivity.

The experiments were performed in an integral plug flow reactor and the integral method was used for the kinetic analysis. The minimization of the objective function was made by the Marquardt algorithm for multiple response and the continuity equation set integrated by fourth order Runge-Kutta technique.

The most adequate models were the power law type for the experimental range. The comparison between experimental and observed values of the acetylene and ethane molar fraction in the hydrocarbon mixture, which are used for minimization, confirm the suitability of the fit.     

ADDITION OF PORE DIFFUSION LIMITATION TO THE “UCKRON-I” KINETIC RATE OF METHANOL SYNTHESIS

Kinetic data with pore diffusion limitation on methanol synthesis were generated by extending the “UCKRON-I” kinetic rate expression. The best fit model and the extended “true” model were compared using their respective rates to simulate temperature profiles in a non-isothermal plug flow tubular reactor.

The objective of this work was to add pore diffusion resistance to the UCKRON-1 kinetic rate for methanol synthesis (Berty, et al. 1983). Kinetic modeling of the data with 5% experimental error added, showed the best model to be that developed from a previous kinetic model (Shalabi, et al. 1983) with apparent activation energy approximately one-half the activation energy at no pore diffusion.

Methods used in this work to determine and evaluate pore diffusion parameters can be utilized for other reaction systems where pore diffusion may play a role in reaction rate.

Temperature profiles estimated from reactor simulation studies showed good argeement between ideal and predicted models for temperature.     

KINETICS OF THE HYDROLYSIS OF ACRYLONITRILE TO ACRYLAMIDE OVER RANEY COPPER

Measurements of the kinetics of the hydrolysis of acrylonitrileover Raney copper catalysts have been made in the temperature range 40 to 100°C in a tubular reactor operated differentially with and without recycle and over concentration ranges of 0-25 weight percent acrylonitrile, 0-35 weight percent acrylamide and 40-99 weight percent water.

For the concentration range 0 to 7 wt. % acrylonitrile and 0 to 7 wt. % acrylamide, data were fitted by an adsorption model of the type

A + K,CA + KCCC and at higher concentrations by the powers law expression

The activation energy for the reaction was found to be 49.2kJmol^-1. Both models showed that the product acrylamide strongly inhibits the reaction.     

OPTIMIZATION OF THE OPERATION IN A REACTOR WITH CONTINUOUS CATALYST CIRCULATION IN THE GASEOUS BENZYL ALCOHOL POLYMERIZATION

Polymerization of gaseous benzyl alcohol was studied on a commercial zeolite (MZ-7P supplied by Akzo-Chemie) in a jet spouted bed reactor which is an original gas-solid contact technique whose use in this type of processes has not yet been described in relevant literature.

Properties of the catalyst-particles-bed and polymer production are calculated by a simulation routine as a function of the following operating variables: the partial pressure of the benzyl alcohol fed into the reactor and the average residence time of the catalyst particles in the reactor. The simulation method and the kinetic equations used have been checked by experimental data.

An analysis of the effect or the operating conditions is carried out, thus determining the values which enable maximum production.     

SELECTIVITY STUDIES IN THE PHOTOCHLORINATION OF METHANE I: REACTOR MODEL AND KINETIC STUDIES IN A NON-ISOTHERMAL, POLYCHROMATIC ENVIRONMENT

The photochlorination of methane employing nitrogen as an inert diluent is studied in a continuous flow, tubular, non-isothermal, bench-scale, polychromatically irradiated photoreactor with particular emphasis on selectivities.

Using a mechanistic sequence of 22 steps, predictions from the mathematical model are compared with experimental results obtained for three different nominal temperatures (297.9 K, 312.8 K and 322.2 K) and three different radiation sources (40, 360 and 1200 W ) that also differ in their output emission characteristics.

An extremely high sensitivity to some of the values of the employed specific rate constants is found, particularly when an accurate prediction of selectivities is being sought. However, within the reported or attributable errors in the published values of the kinetic constants( ± 5%), the experiments show very good agreement with the computed predictions obtained from the mathematical model of the photoreactor.

Using these experimental results that show excellent reproducibility a complete and reliable set of process independent reaction kinetic constants, and a verified reactor model are obtained which can be used for photoreactor design purposes, including selectivity optimization.     

A KINETIC MODEL FOR THE PRODUCTION OF LIQUIDS FROM THE FLASH PYROLYSIS OF BIOMASS

A kinetically based prediction model for the production of organic liquids from the flash pyrolysis of biomass is proposed. Wood or other biomass is assumed to be decomposed according to two parallel reactions yielding liquid tar and ( gas + char) The tar is then assumed to further react by secondary homogeneous reactions to form mainly gas as a product

The model provides a very good agreement with the experimental results obtained using a pilot plant fluidized bed pyrolysis reactor

The proposed model is shown to be able to predict the organic liquid yield as a function of the operating parameters of the process, within the optimal conditions for maximizing the tar yields, and the reaction rate constants compare reasonably well with those reported in the literature     

THE ROLE OF GAS DISTRIBUTION IN FLUIDIZED BED CHEMICAL REACTOR DESIGN†

The design of fluid bed gas distributors may have a marked influence on the performance of a fluid bed reactor. The primary physical reason for this influence is that the distributor design influences the hydrodynamics and thus the gas/solid contacting pattern in the fluidized bed.

In the paper presented here the influence of distributor design on mass transfer and chemical reaction has been investigated systematically in fluid bed reactors with diameters of 0.2 and 1.0 meter. Coefficients of mass transfer between the bubble phase and the suspension phase were determined from chemical conversion and tracer gas residence time distribution measurements. In the experimental program the height of the fluidized bed was varied between 0.3 m and 0.9 m with superficial gas velocities in the range of 0.06 m/s to 0.30 m/s.

The comparison of the experimental results with a suitably modified and extended two-phase model yields quantitative relationships which allow to account for the influence of the gas distributor in the design of fluid bed chemical reactors.     

SENSITIVITY ANALYSIS OF OPTIMAL CONTROL POLICIES FOR BATCH PROCESSES

The computation of optimal control policies for batch processes, critically depends on the process model employed. The real process may deviate from the assumed model due to external signal or model parameter variations. In this paper we examine the effects of these variations on

(a) the value of the objective function, when the nominal optimal policy is applied

(b) the optimum value of the objective function.

We present quantitative relations between the perturbed and the nominal problems and demonstrate their use through a number of examples.     

APPLICATIONS OF A NON-PERMSELECTIVE, CATALYTICALLY ACTIVE MEMBRANE, A MODEL STUDY

A theoretical investigation has been presented for applications and features of a non-permselective, catalytic membrane reactor with separated feed of reactors [12-14, 17, 18]. Transmembrane fluxes were calculated from the dusty gas model as a function of a great number of parameters and operation conditions. This study shows that the non-permselective, catalytic membrane reactor with separated feed of reactants (CMRSR) has attractive features to use this reactor in fast and highly exothermic reactions and selectivity improvement in multiple reactions.

When the CMRSR is operated in the transport controlled regime, the process is easy to control and even possesses some self-controllability. Due to the transport conversion, thermal runaway cannot occur which allows operation with concentrated feed of reactants. Furthermore, a transmembrane pressure difference increases both the fluxes and the selectivity, because the reaction products are preferentially directed towards one side of the membrane. The simultaneous increase of both selectivity and fluxes is a remarkable feature of a CMRSR which is in contrast with conventional reactors.     

A STUDY ON THE PERFORMANCE OF THE CATALYTIC POROUS-WALL THREE-PHASE REACTOR

A theoretical investigation of a catalytic porous-wall reactor in which gaseous and liquid reactants approach each other from opposite sides of the catalyst is undertaken. Equations for the annular liquid-channel are coupled with those for the catalytic wall and solved numerically and analytically using a simplified model. For the model reaction under study, the main design and operation parameters which affect reactor performance are the Thiele modulus, Peclet number, width of the liquid channel and the inlet concentration of the reactant in the liquid phase.

The effect of reactor configuration is peculiar to the cylindrical geometry because the thickness and relative location of the catalytic wall as well as the selection of the liquid and gas channels can influence the reactor performance. Thin-walled catalyst tubes have larger effectiveness factors and as the tube radius approaches that of the reactor, conversion in the reactor increases especially when the liquid is saturated with the gaseous reactant. Concentration of the liquid reactant in the feed has a significant effect if the reactant is depleted at some point inside the catalyst wall. Since the reaction zone width can be adjusted by changing the feed composition, this might have important implications with respect to selectivity.     

ON THE SOLUTION OF A MODEL CASE F DEACTIVATION BY SITE POISONING ND PORE BLOCKAGE

The problem of deactivation by active site poisoning and pore blockage is analyzed. A solution technique is presented which considerably simplifies the numerical effort involved in the analysis of the problem. For problems with slab geometry, in particular, closed form solutions are developed which can be conveniently utilized in reactor design problems.

Numerical examples are presented which show that the effect of pore blockage can be quite detrimental to the life of the catalyst, sometimes even more so than the effect of site coverage by a poison.     

OPTIMAL CATALYST DISTRIBUTION AND DILUTION IN NONISOTHERMAL PACKED BED REACTORS

The problem of the optimal distribution of two different catalysts in a nonisothermal packed bed reactor is analyzed. State variable constraints, such as maximum allowable temperature, may be incorporated through a penalty function approach into the steepest ascent solution of this problem.

Loading a wall-cooled reactor with two chemically different catalysts is compared to dilution of a single catalyst with inerts for temperature moderation. A criterion is presented for estimating whether catalyst dilution may be necessary in order to keep reactor temperature below some maximum allowable value.

Conditions for optimal loading with a two-dimensional reactor model are presented and applied to catalyst dilution in a butane oxidation reactor. Suboptimal catalyst loadings are compared with the optimal loading.     

A MONTE-CARLO APPROACH TO THE INTERPRETATION OF BUBBLE PROBE SIGNALS IN FREELY BUBBLING FLUID BEDS†

The interpretation of the signals generated by a double probe may be done by the three characteristic times method:

t₁ the time duration of the pulses;

t₂ the time shift between the signals of the two probes;

t₃ the time interval between two pulses on one channel.

Each of these times is largely dispersed and the corresponding histograms may be constructed.

The present work is a trial to go over from the time histograms to physical properties of the bubbles combining a Monte-Carlo simulation and a flexible simplex optimisation procedure.

As a result, the percentage of oblique bubbles cutting just one level, the bubble size distribution, the average velocity-size relation, and the individual dispersion around it may be defined.

The procedure is finally applied to experimental results obtained with a light probe in a fluid bed of glass beads.     

ATTRITION IN THE BUBBLING ZONE OF A STEADY-STATE FLUIDIZED BED

This paper describes the kinetics of attrition in the bubbling zone of a fluidized bed and focuses on the development of an equation for attrition in continuous fluidized beds operating at steady state.

Laboratory data describing batch attrition of a limestone sorbent are applied to the integrated equations to describe overall attrition rate in a full-scale continuous system.