GAS MIXING IN SLUGGING AND TURBULENT FLUIDIZED BEDS

The gas phase mixing in a fluidized bed of glass beads (d_p = 0.362 mm) in the slugging and turbulent flow regimes has been studied in a 0.1 m-ID × 3.0 m high Plexiglas column.

The gas dispersion in the downstream of the bed has been described by a diffusion process with the axial and radial dispersion coefficients. The radial dispersion coefficient of the gas phase is nearly constant with the variation of gas velocity in the slugging flow regime, but it increases with an increase in gas velocity in the turbulent flow regime.

Appreciable backmixing of the gas phase is pronounced in the slugging flow regime whereas the lower gas backmixing is produced in the turbulent flow regime. The gas backmixing coefficient increases with an increase in gas velocity in the slugging flow regime, but it decreases slightly with an increase in gas velocity in the turbulent flow regime.

The radial mixing and backmixing coefficients of the gas in terms of Peclet numbers have been correlated with the relevant dimensionless parameters (U_g/U_mf, p_s/p_g, d_p/D_t).

The gas flow pattern in the bed has been well represented by a simplified model based on the two gas phases in the dilute and dense phases which are percolating through the bed in plug flow. The present model can predict the gas exchange coefficient between the phases, the fractions of the dilute phase, the interstitial gas in the dense phase, and the interstitial gas velocity in the bed.     

EFFECTS OF GEOMETRY ON HYDRODYNAMICS IN EXTERNAL-LOOP AIRLIFT REACTORS

Experimental investigations were carried out in model external-loop airlift reactors. Two reactors of laboratory scale (riser liquid height ranged between 1.16-1.56 m, riser diameter 0.03 m, A_D/A_R ratio between 0.111-1,000, total liquid volume V_T = (1.189-2.446).10^-3m³) and pilot-plant scale (riser liquid height of 4.4 and 4.7 m, respectively, riser diameter 0.200 m, A_D/A_R ratio of 0.1225 and 0.040 m, total liquid volume, V_T = (0.144-0.170) m³) were used.

The influences of reactor geometry characterized by some parameter as: A_D/A_R ratio, liquid height in riser and downcomer and liquid height in gas separator, together with the amount of introduced air, on the basic hydrodynamic design parameters: gas holdup and liquid circulation velocity were analysed.

The influence of gas sparger design on gas holdup and liquid velocity was found to be negligible.

The experimental liquid circulation velocity was correlated using a simplified form of the energy balance in airlift reactors, valid for external-loop airlift reactors with almost complete phase separation at the top.

An original dimensionless correlation for gas holdup prediction involving superficial velocities of gas and liquid, cross sectional areas, dispersion height, riser diameter, as well as Froude number, was obtained.     

MAGNETICALLY STABILIZED FLUIDIZATION PART I GAS AND SOLIDS FLOW

A fluidized bed of magnetic particles, such as iron or magnetite, can be stabilized by applying an external magnetic field, as was shown earlier by Rosensweig and coworkers. The stabilization results in a suppression of bubble formation, little solids mixing and a much narrower residence time distribution of the gas flow; the gas flow rate in the dense phase is increased. In this experimental study the axial and radial mixing coefficients in the gas flow were determined as functions of several variables, such as gas flow rate and magnetic field strength. It appeared that the radial mixing coefficient is comparable to that in a fixed bed, and the axial mixing coefficient was greater than in a fixed bed but smaller than in a fluidized bed without stabilization. The axial mixing is the result of some channelling.

The mixing of the solids is very low, and if there is a continuous solids flow through the bed, deviations from plug flow can be reduced by increasing the magnetic field strength.

Apparently, the magnetically stabilized fluidized bed is well suitable for countercurrent gas-solid operations.     

CHARACTERIZATION OF FLUIDIZED BED REACTORS WITH GAS TRACER MEASUREMENTS

In a steady state bench scale fluidized bed the decomposition reaction of NaHCO₃ was carried out. The residence times distributions, DRT, of carbon dioxide (the gaseous product) and non adsorbing argon (the reference tracer) were mass spectroscopically measured as a function of the bed temperature. By means of single-, two- and three-phase dispersion models as well as by a cell model, the DRT's were evaluated on line by a computer.

The steady state transverse and longitudinal concentration profiles of these tracers upstream from the plane source were also measured and evaluated by a dispersion model as well as by a counter current back mixing model. Comparison of the steady state and nonsteady state dispersion coefficient measurements indicate that the longitudinal gas mixing is only partially due to backmixing. The experimentally determined wake fractions agree well with those published in the literature. Since the adsorption rate of CO₂ on the pore surface area of the particles in the dense phase is high no interphase transfer from the interstitial gas of the dense phase into the bubble phase takes place.

The desorption of CO₂ and its return into the interstitial gas and than into the gas phase occurs only slowly and with an initial time lag. The on-line DRT can be used as a diagnostical technique for investigation of the reactor during its operation, if operation disturbances or breakdowns occur.     

EVALUATION OF CONDUCTIVE HEAT TRANSFER MECHANISMS BETWEEN AN IMMERSED SURFACE AND THE ADJACENT LAYER OF PARTICLES IN BUBBLING FLUIDIZED BEDS

The evaluation of the heat transfer coefficient h_wp between a heat exchanging surface immersed in a gas fluidized bed and the adjacent layer of dense phase particles is analyzed in this contribution. Gas convective and radiant effects are not included in the present analysis.

The inclusion of h_wp, or an equivalent formation, in mechanistic models describing heat transfer has been necessary because the sudden voidage variation close to the immersed wall restrains significantly the heat transfer rate. However, there is not at present a widely accepted expression to evaluate h_wp.

A precise formulation for h_wp accounting for transient conduction inside spherical particles, the Smoluchowski effect, the concentration of particles in the adjacent layer (N_p) and an effective separation gap (l₀) is developed here.

Although N_p can be estimated, in principle, from experimental evidence in packed beds, and it is reasonably expected that l₀ = 0, the analysis of experimental heat transfer rates in moving beds, packed beds, and bubbling fluidized beds indicate that values of h_wp are, in general, smaller than expected from these assumptions. Appropriate values of l₀ and N_p are then stimated by fitting the experimental data.

The probable effect of surface asperities is also discussed by analyzing a simplified geometrical model. It is concluded that the parameter l₀ can be also effective to account for particle roughness, independently of thermal properties.     

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.     

HYDRODYNAMIC CHROMATOGRAPHY: THREE DIMENSIONAL LAMINAR DISPERSION IN RECTANGULAR CONDUITS WITH TRANSVERSE FLOW

Experimental observations^1,9 indicate much poorer separations than are predicted by two dimensional theory. The purpose of this work is to explain these differences and suggest ways in which system performance can be improved.

The large effect of span-wise variation in axial velocity caused by side walls on hydrodynamic separations carried out in rectangular conduits with transverse flow is studied theoretically. As the aspect ratio increases, the steady stale retentivity (convection coefficient) approaches an asymptotic value obtained by neglecting side wall effects. However, the dispersion coefficient does not reduce to that for a flow with no side walls. Indeed, the asymptotic steady state dispersion coefficient is at least six times larger than that obtained by two dimensional theory which neglects side wall effects. As the transverse Peclet number increases, the effect of side walls on the dispersion coefficient becomes much larger.

The present three dimensional theoretical predictions, in contrast to two dimensional ones, are in good agreement with the experimental data of Caldwell, et al.⁹ and Kesner, et al.¹ on electrical field flow fractionation. The results indicate that side wall effects may be of major importance in hydrodynamic chromatography even when the aspect ratio is 70 or more.

The adverse effect of side walls may be avoided by having the membranes enclose thin annular regions rather than rectangular conduits. This should improve performance significantly.     

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,     

A STRUCTURAL PORE DEVELOPMENT MODEL FOR CALCINATION

A structural pore development model has been developed to describe microscopic pore evolution from the thermal decomposition reaction of a single calcium carbonate sphere, this model depicts a uniform distribution of equal sized pores growing from the surface of the sphere toward its center while CO₂ is evolved from the pore bottom. The chemical reaction at the interface, as well as heat transfer from the surroundings to the decomposing sphere and transport of CO₂ from the pore bottom to the bulk gas, are included in the model. The model shows good agreement with experimental data for CaCO₃, and limestone particles of size ranging from 10 μm to 1.1 cm in diameter at various background CO₂, pressures and temperatures

The simulation of the calcination reaction confirms the experimental observations indicating slower calcination rates at higher background CO₂ pressures, mainly due to internal unsteady-state buildup of CO₂ in the pore. The effect of the background₂ pressure is significantly more prominent in the smaller particles. The activation energy derived from the model is equal to 38.0 kcal/g-mol which is in the range of those reported by other investigators and is noticeably close to the heat of the calcination reaction.     

HEAT TRANSFER IN TRICKLE-BED REACTORS

The mechanism of radial heat transfer in two-phase flow through packed beds is examined. A model with 2 parameters: an effective radial thermal conductivity in the bed, k_e, and a heat transfer coefficient, h_w, at the wall, give a satisfactory interpretation of the radial temperature profile.

k_e was expressed in terms of a stagnant contribution, due to the heat conduction through the solid and the fluid in the void space, and a radial mixing contribution of the gas and liquid phases, due to the radial component of the velocity of both fluids. The radial mixing contribution of the liquid ( k_e)_L was compared with radial mass dispersion data, and a satisfactory agreement was obtained.

Moreover, ( k_e)was much higher than the gas mixing and the stagnant contributions.

Correlations for hw and k_e)_L have been proposed in accordance with the hydrodynamic regimes of the two-phase flow.     

CO2 SOLUBILITY IN WATER AND BRINE UNDER RESERVOIR CONDITIONS

The reference Henry's constant was determined from 110 solubility data found in the literature for the CO₂/H₂O system over a temperature range of 298 to 523 K and a pressure range of 3.40 to 72.41 MPa. Since the Krichevsfcy-llinskaya equation was used to model the system, a correlation for the A parameter was also developed.

In addition to the Krichevsky-Ilinskaya equation, another two-parameter correlation for the solubility of carbon dioxide in water was obtained by using the Krichevsky-Kasarnovsky equation. The reference Henry's constant and partial molar volume of carbon dioxide at infinite dilution were treated as adjustable parameters. The calculated values of the partial molar volume at infinite dilution did not correspond to experimentally determined values found in the literature. Therefore, a third correlation for the reference Henry's constant was obtained by using the Krichevsky-Kasarnovsky equation in conjunction with the correct values of the partial molar volume. This one parameter (Henry's constant) model did not fit the experimental data as well as the two-parameter models.

The decreased solubility of CO₂ in brine was accounted for empirically by a single factor correlated to the weight percent of dissolved solids. A literature data set of 167 solubilities, with a temperature range of 298 to 523 K and a pressure range of 3.0 to 85.0 MPa, was used to develop this correlation. A wide scatter of data characterizes this correlation, which relates the CO₂ solubility in brine to the CO₂ solubility in water at the same temperature and pressure. The correlation is designed for applications in which the determination of concentrations of individual ions is impractical and the implementation of only one additional parameter is desirable, such as the use of compositional simulators to model miscible displacement in the petroleum industry.

These correlations can be easily implemented into reservoir simulation calculations to account for the effects of CO₂ solubility in brine. These effects are often ignored even though they can have dramatic effects on the performance of the CO₂ enhanced oil recovery process. The correlations presented in this paper for the Henry's constant and the effect of dissolved solids can adequately account for these CO₂ solubility effects.     

EVALUATION OF OVERALL HEAT TRANSFER RATES BETWEEN BUBBLING FLUIDIZED BEDS AND IMMERSED SURFACES

A mechanistic model to evaluate heat transfer rates between the dense phase of gas fluidized beds and immersed surfaces has been recently presented by the authors. This model, denoted Generalized Heterogeneous Model (GHM), is formulated in terms of effective thermal properties for particles and interstitial gas. It has been conceived with the purpose of achieving a generalized formulation accounting simultaneously for conductive, gas convective and radiant effects.

The model was previously tested as regards its capability to predict radiative heat transfer rates in beds at high temperature and gas convective contribution in beds of large particles and high operating pressures.

It is the principal object of this contribution to evaluate the performance of the GHM for a wide range of particle sizes, covering from The purely conductive regime to the gas convection dominant regime.

Also, the main assumptions incorporated in the model are revised and some modifications are introduced, mainly on the basis of the results obtained by Mazza et al. (1997b).     

ON THE PERMEATION OF SOME GASES THROUGH THE LAMELLAE OF STATIC FOAMS. A PRELIMINARY APPROACH

Basing on the capillary method for the determination of foam bubble size, a method was proposed for establishing values of permeability coefficients of several gases. The permeability coefficients of He, Ar, H₂, N₂, CH₄ through the lamellae of static foam bubbles were preliminarily determined using this method.

A rough dependence of the N₂ permeability coefficient through the lamellae of static foam bubbles on the foam wetness and surfactant concentration was also found.

The results obtained lead to the conclusion that the Princen-Mason diffusion model of gas permeation through an isolated soap film was inadequate in the case of permeation through lamellae of bubbles forming a static foam.

A hypothesis that the gas permeation through the lamellae of a static foam is primarily caused by liquid convection in the lamellae core was put forward.     

ALTERNATIVE GENERATION OF H2, CO AND H2, CO2 MIXTURES FROM STEAM-CARBON DIOXIDE REFORMING OF METHANE AND THE WATER GAS SHIFT WITH PERMEABLE (MEMBRANE) REACTORS

A new process is proposed which converts CO₂ and CH₄ containing gas streams to synthesis gas, a mixture of CO and H₂ via the catalytic reaction scheme of steam-carbon dioxide reforming of methane or the respective one of only carbon dioxide reforming of methane, in permeable (membrane) reactors. The membrane reformer (permreactor) can be made by reactive or inert materials such as metal alloys, microporous ceramics, glasses and composites which all are hydrogen permselective. The rejected CO reacts with steam and converted catalytically to CO₂ and H₂ via the water gas shift in a consecutive permreactor made by similar to the reformer materials and alternatively by high glass transition temperature polymers. Both permreactors can recover H₂ in permeate by using metal membranes, and H₂ rich mixtures by using ceramic, glass and composite type permselective membranes. H₂ and CO₂ can be recovered simultaneously in water gas shift step after steam condensation by using organic polymer membranes. Product yields are increased through permreactor equilibrium shift and reaction separation process integration.

CO and H₂ can be combined in first step to be used for chemical synthesis or as fuel in power generation cycles. Mixtures of CO₂ and H₂ in second step can be used for synthesis as well (e.g., alternative methanol synthesis) and as direct feed in molten carbonate fuel cells. Pure H₂ from the above processes can be used also for synthesis or as fuel in power systems and fuel cells. The overall process can be considered environmentally benign because it offers an in-situ abatement of the greenhouse CO₂ and CH₄ gases and related hydrocarbon-CO₂ feedstocks (e.g., coal, landfill, natural, flue gases), through chemical reactions, to the upgraded calorific value synthesis gas and H₂, H₂ mixture products.     

HIGH TEMPERATURE CAPTURE OF CARBON DIOXIDE: CHARACTERISTICS OF THE REVERSIBLE REACTION BETWEEN CaO(s) and CO2(g)

The reversible reaction between CaO(s) and CO₂(g) may ultimately find application in a high temperature process to control CO₂ emissions from advanced power generation processes. At appropriate temperature and pressure combinations, CO₂(g) is removed from the gas phase and captured as CaC₃(s). At higher temperature and/or lower pressure, the reaction is reversed to produce a gas stream having high CO₂(g) concentration suitable for use or ultimate disposal. Both the calcination and carbonation reactions have been studied in an electrobalance reactor as a function of temperature, pressure, and gas composition. Multicycle tests have provided preliminary information on sorbent durability. Solid structural property characteristics have been measured as a supplement to the reaction studies.

Rapid and complete calcination of CaCO₃ can be achieved at temperatures as low as 750°C under one atmosphere of N2. Higher pressure reduces the calcination rate while the presence of CO₂ in the calcination atmosphere requires the use of higher temperature. Mild calcination conditions produce a CaO product which is most reactive during the carbonation phase. Carbonation is characterized by a rapid initial reaction rate followed by an abrupt transition to a quite slow rate. Significant reduction in CO₂ capacity between the first and second carbonation cycles, ranging from 15% under favorable reaction conditions to more than 30% at severe conditions, was found. However, the capacity loss tended to moderate as the number of cycles increased.     

THERMODYNAMIC PROPERTIES OF BINARY LIQUID MIXTURES OF ETHANE AND ETHYLENE WITH METHANE AND THE RARE GASES

Two series of binary liquid mixtures containing either ethylene or ethane have been investigated, at one or more temperatures (usually at the triple-point temperature of the component with the higher melting-point). In the ethylene series liquid-vapour equilibrium and liquid density studies were carried out for mixtures with methane, krypton and xenon; the heats of mixing were also measured for the ethylene + krypton mixtures. In the ethane series, which comprised mixtures with methane, argon, krypton and xenon, all three properties were measured except for the ethane + methane and ethane + argon systems where the enthalpies of mixing were already known. The ethylene + ethane system was also investigated at 161.39 K.

The results have been used to estimate the thermodynamic excess functions G^E, V^E and H^E. The G^E values decrease, within each series, as one moves from the lighter to the heavier rare gas, the values being lower in the ethane series. For the ethane + xenon mixtures both G^E and H^E are negative, showing a weak attraction between the two molecules. The V^E values for the mixtures of hydrocarbons suggest the probable formation of interlocking structures between the two components.

The values of the thermodynamic excess functions have been interpreted in the light of the model of Frisch-Longuet Higgins-Widom for the liquid state.     

ACETIC ACID AS AN OXYGEN CARRIER BETWEEN TWO PHASES FOR EPOXIDATION OF OLEIC ACID

Acetic acid was found to be an effective oxygen carrier for epoxidation of oleic acid. The reaction model of oleic acid epoxidation in the two-phase reaction system was systematically analyzed and the rate determining step was experimentally identified.

The results indicated that the rate of oxidation of the unsaturated acid was independent of the concentration of oleic acid and depended on the mixing rate and the rate of formation peracetic acid which in turn depended on the concentration of acetic acid, strength of acid catalyst and the oxygen source, hydrogen peroxide. In the region of reaction control, the rate equation of epoxidation was found to be

$

where k = 2.98 × 10^-2 M^-2 min^-1 at temperature of 35^°C.     

KINETIC AND STRUCTURAL STUDIES OF REGENERATION OF SULFIDED DOLOMITE IN CARBON DIOXIDE I THE FIRST CYCLE REGENERATION

(Communicated by H. L. Toor)

Half-calcined dolomite (CaCO₃ · MgO) is one of the most promising sorbents for desulfurizing fuel gas at high temperatures. For environmental reasons, the spent dolomite must be capable of regeneration for cyclic use. Regeneration by a mixed gas of H₂O/CO₂ has not met with success due mainly to the deterioration of sorbent reactivity with cycling. This research investigates an alternative method of regeneration using CO₂ alone and its application to cyclic use.

Kinetic data for first cycle regeneration are collected in a TGA system at 500 to 950°C and 1 to 21.4 atm. The effects of gas-composition, preconditioning and solid structure are also studied. The results show that regeneration by CO, is equally effective as by H₂O/CO₂ in terms of sorbenl reactivity. More significantly, the sorbent has shown a much slower deterioration upon cycling. Examination of solid structure by SEM and compositional profile of sulfur by XES reveals that the reaction proceeds topochemically above 700°C and homogeneously below 650°C. A transport-reaction model is developed and shown to agree closely with experimental results.     

TRANSIENT CONVECTIVE MASS TRANSFER IN RECTANGULAR FIELD-FLOW FRACTIONATION CHANNELS

The work of Takahashi and Gill (1980) on the transient convective mass transfer in three dimensional rectangular channels in the presence of a transverse field is extended to include the time dependence of the convection and dispersion coefficients. The methodology of generalized dispersion theory is used to predict the breakthrough curves. The functions, f₀ and f₁, are determined by introducing a two-dimensional Sturm—Liouville operator.

The results suggest that the side wall effects on the axial dispersion cannot be neglected and a dispersion equation with time dependent coefficients is appropriately describable of the practical field-flow fractionation system.     

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