Kinetic behaviour of immobilized enzyme membrane reactors

Enzyme immobilization techniques which are founded on protein gelification onto the active surface of an ultrafiltration membrane are discussed in connection with p-nitro-phenyl-phosphate hydrolysis by acid phosphatase (E.C.3.1.3.2.)Two different immobilized enzyme membrane reactor layouts have been considered. In both the enzyme has been confined within a gel layer onto the active surface of the U.F. membrane. The gel formation has been obtained by means of a concentration polarization technique. In the first reactor the enzyme has been cogelified with albumin, in the second it has been previously co-cross-linked with the same albumin and subsequently ultrafiltered.The reduction in activation energy which is shown by both immobilized enzyme configurations as compared to the corresponding soluble enzyme tests, clearly indicates that a combined substrate mass transfer/reaction step is rate controlling.     

MULTIPHASE HYDRODYNAMICS AND SOLID-LIQUID MASS TRANSPORT IN AN EXTERNAL-LOOP AIRLIFT REACTOR—A COMPARATIVE STUDY

The solid-solid mass transfer performance of an external-loop airlift reactor was measured by dissolution of benzoic acid coated on nylon-6 particles, and the hydrodynamics of the gas-liquid-solid multiphase system in the airlift reactor were investigated. The solid-liquid system was designed to simulate the micro-carrier culture of animal cells, and some typical suspensions of immobilized enzyme particles.

The solid-liquid mass transfer coefficient remained constant below a superficial air velocity of 0.04 ms^-1 for the particles examined, but increased rapidly with further increase in gas velocity. Solids loading (0.3-3.5% w/w) did not affect the mass transfer coefficient in turbulent flow.

The mass transfer coefficient was correlated with energy dissipation rate in the airlift reactor. The mass transfer coefficient in stirred vessels, bubble columns, fluidized beds, and airlift reactors was compared.

Over an energy dissipation Reynolds number of 4-400, the solid-liquid mass transfer coefficient in the airlift device was comparable to that obtainable in fluidized beds. The performance of the airlift was distinctly superior to that of bubble columns and stirred tanks.     

Welding Mechanisms of Plastics: A Review

Strength of welded joints is a function of technological parameters of the production process. The type of function is dependent on the welding mechanism. Different mechanisms were found under various welding conditions. The processes included in the plastic welding mechanism are divided into two groups:

1) Processes which realize the joining of the parts.

2) Processes which create conditions for the first group to proceed. The first series of processes includes:

a) diffusion of macroradicals, molecular segments or molecules of the polymer which can be either in a solid, melted or dissolved state.

b) convective mass transfer.

c) recombination of macroradicals across the contact surface.

d) physical (surface) interaction.

e) any combination of processes described above.

The second group contains:

a) formation of the real contact surface.

b) formation of the macroradicals.

c) destruction and removal of inert layers which prevent real contact of active material.

Each process and the conditions of its proceeding are discussed individually.     

PRODUCTION OF ETHANOL WITH SACCHAROMYCES CEREVISIAE IN A CONTINUOUS REACTOR Note III: an experimental, kinetic study with suspended, recycled biomass

By way of comparison with the kinetic investigation of the continuous production of ethanol in a tubular reactor with immobilized yeasts, a study was carried out of continuous fermentation in a stirred reactor, with final separation and recycling of the microorganisms. Flocculation with potassium ferrocyanide and zinc sulphate was used to separate the biomass. The maintenance of the metabolic activity was assessed. Next, discontinuous fermentation at various substrate and biomass concentrations was performed to determine the kinetics of glucose-ethanol transformation by flocculated and reinoculated Saccharomyces Cerevisiae.

Once again, the kinetic expression was a Michaelis-Menten equation, with un-competitive inhibition of the substrate and linear inhibition of the product.

The values observed for the various parameters were not very different from those for a biomass immobilized on an inert support or for a free biomass. Finally, the productivities of several types of reactor are compared.     

DEVELOPMENT AND VALIDATION OF A PROCESS SIMULATOR FOR DRYING SUBBITUMINOUS COAL

Drying subbituminous coal has never been practiced commercially. The commercial dryers built to date have been designed for drying surface moisture in conjunction with upstream coal preparation facilities. This type of drying is mainly controlled by input energy and the basis of the design is an energy balance. In drying inherent moisture from subbituminous coal, the thermal conductivity of the coal and the diffusion of molecular water within coal particles impose limitations on the process conditions. Energy input and solids residence time in the dryer have to be controlled properly for simultaneously balancing the heat and mass transfer within the coal particles. Improper control of either parameter can cause fires and explosions during the key steps of the drying process—drying and cooling

In parallel to the Anaconda coal drying pilot plant program, a cross-flow, fluid-bed coal drying/cooling process simulator was developed for: (1) understanding the drying phenomena on an individual particle basis; (2) analyzing potential risks and safety limits, and (3) designing the Anaconda pilot plant program

The development of the process simulator was based on both first principles and laboratory data and can be divided into two phases:

1 Development of a semi-mechanistic drying model for Powder River Basin subbituminous coal employing an analytical solution of the diffusion equation

2.Formulation of a fluid-bed cross-bed cross-flow dryer/cooler simulator employing simultaneous heat and mass transfer

This model was validated against process variables data taken on a 4 tph pilot plant. An operable range, or process envelope, has been developed through the pilot plant experience and the process simulation study. Based on the model predictions, an uncertainly range was defined in the design recommendations of a pioneer coal drying plant in scale-up.     

CONTRIBUTION TO THE ANALYSIS OF THE SELECTIVITY OF GAS-LIQUID REACTIONS PART II: COMPARISON OF EXPERIMENTAL RESULTS WITH MODEL PREDICTIONS

The chlorination of paracresol is used in an experimental study of selectivity in gas-liquid contactors.

Experiments in a batch reactor show the influence on selectivity of the dimensionless numbers presented in Part I and involving competition between mass transfer and chemical reaction together with the hydrodynamics.

The extension of open reactor model presented in Part 1 to the batch reactor permits a comparison between theory and experiments and shows a good agreement     

INVESTIGATIONS INTO PUMPING CHARACTERISTICS OF AXIAL FLOW IMPELLERS IN AN INTERNAL LOOP REACTOR FOR ANIMAL CELL CULTURE

This investigation was intended to aid in the selection of impeller design and operating conditions, which would exhibit minimum turbulence in an internal loop reactor for axial flow velocities up to 18 cm/s.

For this purpose we measured power consumption, liquid flow velocity and mixing time with two marine propellers (pitch ratio tan alpha =1 and 0.57, respectively) and with flat-blade fan-type impellers (blade angles 10 to 90°).

The present results showed that at flow velocities between 7 and 14 cm/s a reduction in the pitch ratio (tan alpha) of the marine propeller from 1 to 0.57 increased the mechanical flow efficiency.

In addition, the fan-type impeller with a blade angle of 20° displayed flow characteristics comparable to the marine propellers; therefore, owing to its simple design, the fan-type impeller offers a practical substitute for the marine propellers.

In cell culture, draft-tubes used in impeller-driven reactors (internal loop reactors) offer two important features:

1. They simplify the design and scale-up process over that of open-blade impellers (flow patterns are more uniform);

2. They provide a mechanical support for bubblte-free membrane oxygenators;

Furthermore, on the assumption that loop reactors display lower bulk turbulence than open blade impellers for similar power consumption, this investigation was intended to aid in the selection of impeller design and operating conditions which would exhibit maximum pumping efficiency (with minimum mixing).

For this purpose, using a pH tracer method, we determined mechanical flow efficiency and dimensionless mixing time, which served as parameters for pumping efficiency to establish the following specific design characteristics:

1. Bulk mixing decreases relative to bulk flow with increasing bulk flow (mixing therefore conforms to the flow-in-pipe model) for two marine propellers (pitch tan alpha = 1 and 0.57) and for fan-type impellers (variable pitch) up to a blade angle of 30°;

2. Liquid velocity increases directly proportional to impeller speed up to 17 cm/s for (above) propellers, as well as fan-type impellers with blade angles of less than 30°;

3. The mechanical efficiency of axial flow (liquid velocity/power input) increases by decreasing the impeller pitch of marine impellers from tan alpha = 1 to tan alpha = 0.57, in the range of 7-14 cm/s;

4. A fan-type impeller (variable pitch) with a pitch angle of 20° displayed flow velocity and mechanical efficiency values, which lay between those of the (above) two marine propellers.

Fan-type impellers are considerably simpler in construction and are simpler to modify than marine propellers; for this reason this impeller type serves as a useful investigational tool. In addition we have found that at an impeller of 20° this type of impeller may be used to substitute marine propellers with a pitch ratio between 1 and 0.57.

We also suggest that square pitch marine propellers are not the most suitable for reactors in which mechanical efficiency of axial flow is critical, such as those for “shear sensitive” animal and plant cells.     

A Control-Volume procedure compared with the Finite-Element method for calculating Stress and Strain during Wood Drying

This paper proposes a suitable method for calculating drying stresses. This is an application of the finite element method (FE) and the so-called control volume (CV) method. The latter has been chosen because most of coupled heat and mass transfer codes are based on CV.

A parallel between the resulting formulation and a particular case of FE method (quadrilateral four-nodes element and Galerkin's method) has been established Both analytical expressions and numerical results were compared. Furthermore, it is shown how to choose interpolation coefficients in CV procedure in order to get exactly the results obtained with FE.

Such a stress calculation has been added to the code TRANSPORE in order to obtain a complete drying code which, in addition to heat and mass transfers, solves stress and strain due to shrinkage, Interesting and promising simulations of non-symmetric convective drying are presented. Indeed, for this drying configuration, the stresses induce a global curvature of the section.     

A STUDY OF CLOSED CYCLE DRYING FOR THE COATED FILM WITH ORGANIC SOLVENT ON THE CONTINUOUS SHEET MATERIALS

The conventional drying of the coated film with organic solvent on continuous sheet materials is usually performed in open or one pass drying system using air as the drying medium. The concentration of evaporated organic solvent in the drying system must be low enough to prevent explosion and large volume of off gas from dryer to solvent recovery system is required, resulting in poor heat economy for all the plant

To improve the heat economy of the plant it had been proposed to use a closed cycle drying system, where an inert gas, e.g. nitrogen, is used as the drying medium. High concentration of the organic solvent in the recycle gas mixture may then be used, which results in smaller volume of recycle gas and possibility of applying an inexpensive solvent recovery system of dehumidification. This investigation includes two important problems to realize the closed cycle drying

(1)Measurement of solvent (toluene) evaporation rate from coated film in the gas mixture of toluene andnitrogen over a wide range of toluene/nitrogen ratios (0-1.0) and drying temperature using bench scaleapparatus

(2)Development of a contactless sealing method, using an inert gas, for closed cycle drying of continuoussheet materials. The results of preliminary tests demonstrate its feasibility.     

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.     

PRODUCTION OF ETHANOL WITH SACCHAROMYCES CEREVISIAE IN A CONTINUOUS REACTOR Note II: tests and modelling for a packed tubular reactor with immobilized yeasts

The biochemical production of ethanol has been studied in a packed tubular reactor with Saccharomyces Cerevisiae immobilized on wooden cubes.

The kinetics of the reaction was described in a previous paper. The experimental axial profiles for the substrate and product concentrations are compared with those calculated from a reactor model obtained by introducing the biochemical kinetic expression in the design equations. A good fit between the experimental and the calculated values could only be obtained by including a biological efficiency coefficient.

The reactor was kept in operation for 28 days to assess its technological reliability. It was found to be biologically stable. Its productivity was constant and comparable to that reported in the literature for similar reactors.     

MEASURING OZONATION RATE CONSTANTS IN GAS-LIQUID REACTORS UNDER THE KINETIC-DIFFUSIONAL TRANSITION REGIME

A lumped parameter mathematical model has been developed, which simulates the operation of a gas-liquid stirred reactor in the transition domain between kinetic and diffusional regimes of absorption with reaction.

In order to determine the rate constants and the coefficient of mass transfer, the model has been compared with experimental data for the ozonation of organic substrates in aqueous solution (maleic acid, fumaric acid and phenol), The upper working limit of the method has been determined at about Ha = 25.     

DIRECT OXIDATION OF ETHYLENE TO ACETALDEHYDE IN A HOLLOW FIBER MEMBRANE REACTOR†

A hollow fiber membrane reactor, which resembles a tube-and-shell heat exchanger, was developed for homogeneous catalytic reactions with gas reactants and products. The gas stream flows through the tube side while the reaction takes place in the catalyst solution which fills the shell side. The separation load of product from the catalyst solution can be reduced by using a hollow fiber membrane reactor instead of a conventional bubble column reactor. The reactor operates in a plug-flow pattern with a large mass transfer area per unit volume of catalyst solution

This concept was investigated experimentally using the direct oxidation of ethylene to acetaldehyde reaction in an aqueous solution of palladium (H) chloride-cupric chloride with a silicone rubber membrane reactor and a polypropylene membrane reactor. It was experimentally demonstrated that membrane reactors could achieve higher production rates per unit volume of catalyst than the conventional sparged reactor. The experimental data were in good agreement with the predictions by the mathematical model. The conditions under which the membrane reactor will be more advantageous than the conventional sparged reactors can be readily ascertained with the analytical solution of the simplified membrane reactor model.     

PHENOL RECOVERY WITH SLM USING “CYANEX 923”

The study of the phenol separation-concentration process with the hollow fiber supported liquid membrane technology has been performed. Mixtures of kerosene and CYANEX 923 were used as liquid membrane. The extractant CYANEX 923 is characterized by a high phenol selectivity and an extremely low solubility in the aqueous phase. The introduction of CYANEX 923 in the membrane composition decreases the extractant losses from the pores of the support.

The phenol separation and simultaneous concentration process has been checked. The influences of the initial concentration of phenol in the feed solution and sodium hydroxide in the stripping phase and the membrane composition on the separation rate have been investigated in a single-pass mode. The analysis of the membrane composition influence has been performed according to the steady-state mass transfer conservation equation and the associated boundary conditions, leading to the mass transfer parameters of the process     

Control of Drying Process in Mechanically Spouted Bed Dryer

The continuously operated Mechanically Spouted Bed (MSB) dryer of high evaporative capacity can be advantageously used to produce fine powder from paste-like materials, slurries, suspensions and sludges. Due to the thin layer formed on the surface of the spherical inert particles intensive heat and mass transfer occur and the drying process takes place in the constant rate period. Steady state drying conditions can be achieved when the total operational time of partial processes of inert bed drying does not exceed the cycle time of the inert particles.

A laboratory scale MSB dryer has been equipped with a computerised measuring, data acquisition and control system. In the knowledge of the hydrodynamic characteristics of the MSB and giving the enthalpy and mass balances over the dryer a calculation method has been developed for control of drying process.     

MASS-PRODUCTION OF BIOCATALYST-ENTRAPPING ALGINATE GEL PARTICLES BY A FORCED OSCILLATION METHOD

A forced oscillation method applying reverse-piezo electric effect has been proposed for mass-production of biocatalyst-entrapping polymer gel particles. A jet of aqueous alginate solution flowing out through an orifice was disintegrated into droplets by an oscillating pressure which was exerted by a ceramic plate vibrated by the reverse-piezo electric effect. The droplets formed were immediately solidified into gel particles in calcium chloride solution.

The particle production rate by the method was up to 270 particles s^-1 or 1 × 10^-6m³.s^-1 The size of the particles produced were down to I mm depending on the applied frequency. The smallest matrix size of the gel's polymer network was estimated to be around 5 nm.

The method was applied for immobilization of yeast cells. The diameter of immobilized particles was 2.5 mm. The immobilized yeast grew well in the particle. The damage of yeast cells caused by the immobilization was not remarkable     

FIBONACCI SEARCH FOR OPTIMAL FEED LOCATION

A Fibonacci search technique is used in conjunction with a rigorous mullicomponenl distillaiion computer module to find the optimal feed location within a section of a distillation column. The function lo be minimized can be one of the following:

*key component ratio difference

*reflux ratio or reboiler ratio

*condenser duty or reboiler duty

This technique has been used successfully in the relocation of feed stages of many existing distillation columns and thus saved energy consumption. We shall describe this technique with a sample problem.     

GAS-LIQUID DISPERSION WITH PITCHED BLADE TURBINES

The performance of pitched blade turbines in a gas-liquid dispersion has been studied. The two-phase hydrodynamics, gassed power consumption and mass transfer properties have been examined using six blade open turbines with blade angles from 30 to 60 degrees to the horizontal, mounted for down flow.

There are two distinct regimes by which gas leaving the sparger reaches the impeller: at low gas rates this is indirect via the recirculation loops, while at higher gas flow rates the flow is direct.

The transition between these regimes is reflected in power consumption and mass transfer characteristics and is related to the formation of large cavities behind the blades. It was also concluded that, with respect to mass transfer efficiency, a pitched blade turbine is at least as good as a Rushton turbine.     

IMPINGING JET DRYER

In coating and gravure printing, an impinging jet nozzle with high thermal efficiency for drying of coated film was developed.

Trial production 0f 40 kinds of nozzle enables to develop a high-performance impinging jet nozzle with heat transfer coefficient 1.5 times larger than that of current slit nozzle, through measurement of heat transfer coefficient, visualizations of air flow and heat transfer, and measuremenu of jet velocity and turbulence distribution. The purpose of the trial production was to expand a range of high heat transfer and promote turbulence compared with the current nozzle.

Paying attention to mass transfer within gravure ink coated film, drying characteristic of the film was analyzed by numerical solution of a set of equations governing the drying process in which concentration dependencies 0f the diffusion coefficient and the equilibrium vapor pressure were considered.

Applying these analyses. an industrial scale dryer with excellent drying efficiency has finally been developed.     

BOILING TWO-PHASE FLOW HEAT TRANSFER IN A HORIZONTAL BEND

A paucity of heat transfer rate data for boiling two-phase flow through bends was noted after an extensive literature survey, The present work was undertaken to redress this shortcoming.

A boiling water loop, capable of being operated at pressures up to 1300 kpa, was used. The lest section was in the form of a U-tube with two straight horizontal sections connected by a 180^° return bend. Using this loop, pressure drop and heat transfer data were gathered over a wide range of mass and heat fluxes. steam qualities and system pressures.

The data obtained were used to investigate the variation in heal transfer coefficients around the radial positions of the bend. Correlations for heat transfer coefficients for four different radial positions (top. bollom, inside and outside of the bend) have been presented for the first time. A possible explanation for the observed variations in heat transfer coefficients has also been suggested.