SUBLIMATION OF PURE SUBSTANCES IN GAS FLUIDIZED BEDS AT ATMOSHPERIC PRESSURE.

This paper deals with the sublimation of large bodies, or “objects”, made up from a pure substance in a bubbling gas fluidized bed of considerably smaller particles, or “fines”. The influence of such parameters as the gas velocity, the bed temperature, the size and the adsorption capacity of the fines has been investigated.

The results obtained clearly show that the rate of sublimation in fluidized beds is far higher than in air alone. It increases with increasing bed temperature, decreasing particle size, increasing powder mass capacity, and roughly varies as a parabolic function of time. It has also been observed that the temperature difference between the bed and the object surface, or “temperature depression”, depends on the fines characteristics as well as on bed temperature, but is independent of gas velocity when good solid mixing conditions are achieved.

Bed-to-object heat and mass transfer coefficients have been deduced from data points and attempts have been made to provide a reasonable theory to account for them. After a complete examination, the idea of interpreting transport phenomena based on a well-adapted “surface renewal model” has been proposed.     

GAS HOLDUP IN UNIFORMLY AERATED BUBBLE COLUMN REACTORS

Conditions of the stable performance of gas distributing plates were studied and the effect of plate geometry on gas holdup of uniformly aerated gas-liquid beds was investigated. The ratio of plate holes opened for gas passage was determined as a function of gas hole velocity and critical values of gas hole velocity corresponding to the onset of stable performance of distributing plates were obtained.

Two regimes of bubbling were observed under conditions of stable uniform gas distribution; the regions of their existence being determined by the values of gas flow velocity and distributing plate parameters. Considerable increase of gas holdup was observed in the region of “foam” bubbling compared to the “turbulent” bubbling regime commonly encountered in bubble column reactors. The character of the bed and hence its gas holdup value were affected by the geometry of distributing plates in the “foam” bubbling region while no such effect was observed under “turbulent” bubbling conditions.     

ESTIMATION OF FUNCTIONS IN DRYING EQUATIONS

In drying problem, particularly for drying foodstuff, modelling is very difficult. Many physical effects have to be taken into account for mass transfer ; then mass transfer coefficient varies

In different models unknown functions must be estimated. It is particularly the case in simple models of drying using average values of water content, where the mass transfer varies versus mean water content in falling rate period. On the other hand in the “diffusion model” we have the same problem concerning the diffusion coefficient which must be also estimated

The method we propose in this paper for these two models : simple and “diffusion model” of drying consists from measurements of temperature and water content of the product to search a numerical approach of the unknown function. This method uses optimization techniques on computer and least squares criterion between model values and experimental data

Results are given for the “diffusion model” applied to shelled corn drying to find the diffusion coefficient and for a simple 11107 del applied to plum drying to find the mass transfer coefficient.     

Book Reviews

“lssledovaniya v oblasti poverkhnostnykh sil” (“Research on surface forces”) B. V. Deryagin, editor. Nauka Publ., Moscow 1967.544 pp. Rubles 3.00.

G. D. Andreevskaya, “Vysokoprochnye Orientirovannye Steklo-plastiki” (“High-strength Oriented Glass-Plastics”). Nauka Publ., Moscow 1966. 370 pp., Rubles 2.12.

A. D. Zimon, “Adgeziya pyli i poroshkov” (“Adhesion of dust and powders”) Khimiya Publ., Moscow 1967.372 pp. Rubles. 1.51.

J. J. Bikerman, “The Science of Adhesive Joints”. Academic Press, New York 1968.349 pages. $16.00.     

COMPARISON OF SUPERHEATED STEAM AND AIR OPERATED SPRAY DRYERS USING COMPUTATIONAL FLUID DYNAMICS.

In this paper a numerical simulation of a spray dryer using the computational fluid dynamics (CFD) code Fluent is described. This simulation is based on a discrete droplet model and solve the partial differential equations of momentum, heat and mass conservation for both gas and dispersed phase.

The model is used to simulate the behaviour of a pilot scale spray dryer operated with two drying media : superheated steam and air Considering that there is no risk of powder ignition in superheated steam, we choosed a rather high inlet temperature (973 K). For the simulation, drop size spectrum is represented by 6 discrete droplets diameters, fitting to an experimental droplets size distribution and all droplets are injected at the same velocity, equal to the calculated velocity of the liquid sheet at the nozzle orifice.

It is showed that the model can evaluate the most important features of a spray dryer : temperature distribution inside the chamber, velocity of gas, droplets trajectories as well as deposits on the walls. The model predicts a fast down flowing core jet surrounded by a large recirculation zone. Using superheated steam or air as a drying medium shows only slight differences in flow patterns. Except for the recirculation which is tighter in steam.

The general behaviour of droplets in air or steam are quite the same : smallest droplets are entrained by the central core and largest ones are taken into the recirculation zone. In superheated steam, the droplets penetrate to a greater extent in the recirculation zone. Also, they evaporate faster. The contours of gas temperature reflect these differences as these two aspects are strongly coupled. In both air and steam there is a “cool” zone which is narrower in steam than in air. Finally, the panicle deposit problem seems to be more pronounced in air than in steam.

Adding to the inherent interest in using superheated steam as a drying medium, the model predicts attractive behaviour for spray drying with superheated steam. In particular. under the conditions tested with the model, a higher volumetric drying rate is obtained in superheated steam.     

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.     

ABSORPTION AND DESORPTION TO AND FROM LIQUID FILMS ON INCLINED PLANES

Two published theoretical models are examined and applied to experimental results for absorption and desorption. The system used was CO₂/H₂O and studies were made for liquid film flow down inclined planes. Experimental results give “Reduced” values of mass ransfer rates.

Interferometric studies give interfacial concentration, penetration and film depths, and take-up of carbon dioxide. In the case of desorption the interferograms are distorted by “deflections.”

All the experimental values for absorption and desorption differ from those calculated from theoretical models.

Desorption is not a mirror image of absorption, and it is approximately 75% of the transfer rate of absorption over a wide operating range.

A comparison is made of the behaviour of static pools and flowing liquid films.     

CARBON COMBUSTION RATES AND TEMPERATURES IN SHALLOW FLUIDIZED BEDS

The mechanism of combustion of carbon in shallow fluidized beds at temperatures 750-1000°C is studied by measuring burning rates and temperatures of spherical carbon particles ranging from 2 mm to 12 mm diameter directly in an experimental fluidized bed. Among variables investigated were inert particle size, superficial fluidizing velocity, temperature, the influence of neighbouring active particles and oxygen concentration in the fluidizing gas.

Under the experimental conditions explored, combustion was mainly kinetically controlled, so that with carbon particles larger than about 4 mm, burning rates are significantly higher than those predicted by combustion models which assume combustion to be controlled by the rate at which oxygen diffuses through a stagnant particulate phase surrounding the burning particle. The higher burning rate seems to arise because the greater mobility of particles in the bed causes the restriction to oxygen flow to the carbon surface offered by the particulate phase to be reduced and has important consequences for combustor design.

Measured carbon particle temperatures were influenced considerably by bed operating conditions ranging from 15 to 215°C higher than bed temperature.

Measured burning rates of carbon particles were found to be reduced significantly when other active particles were present in the bed. This sensitivity of burning rate to changes in active particle concentration in the bed was shown to be increasingly important once the concentration of carbon in the bed exceeded about 1%

Increasing the bed inert particle size, superficial fluidizing velocity, oxygen concentration in the fluidizing gas and bed temperature resulted in higher burning rates. The implication of these findings on combustor design are discussed.     

A NONDESTRUCTIVE METHOD TO MEASURE RESIDUAL ADSORPTION CAPACITY OF CHARCOAL FILTERS

High surface area charcoal bed filters have been used for over a half a century to adsorb undesirable vapors from gas streams. One problem encountered when using these niter beds is that there is presently no simple, reliable, nondestructive method to measure their Residual Adsorption Capacity, RAC. This is particularly critical in situations where harmful vapors are being adsorbed.

An investigation has been underway to use pulses of weakly adsorbed gases such as ethane and/or methane to measure RAC. The hypothesis being that these weakly adsorbed gases will “count” unoccupied adsorption sites. In the present study, dimethyl methylphosphonate (DMMP) was used to “irreversibly” occupy available siles to various extents on different niters. The Reduced Retention Time. θ, (the ratio of the adjusted retention time to the space time) and the Resolution (R) between peaks of methane and ethane were found to correlate to RAC under dry and wet (humid) conditions.     

TRANSITION OF FLOW REGIME IN FLUIDIZED BEDS WITH SLANTING BLADE BAFFLES

A flow model is proposed to investigate the transition of flow regime from bubbling to turbulent fluidization postulating that the flow in the emulsion phase follows the Richardson-Zaki equation.

Void fraction of the whole bed ε_f and the mean velocity of bubbles U_b were measured in fluidized beds of 0.3 and 0.5 m ID, in which slanting blade baffles were positioned. Mo-catalyst, silica gel, sand and glass beads with size between 135-443 μm were fluidized by air.

Void fraction of the emulsion phase ε _e was calculated on the basis of the above model. Correlating ε _e with superficial gas velocity U_ƒ, we found that ε _e was very close to ε _mƒ in the bubbling regime and that e, increased with increasing U_ƒ in the turbulent regime.

Calculated values of the volume fraction of bubble phase δ were correlated with U_ƒ, from which apparent transition point from bubbling to turbulent regime was estimated. Combining information obtained, transition of flow regime in the above type of fluidized beds is discussed     

ELECTROOSMOTIC DEWATERING (EOD) OF CLAYS AND SUSPENSIONS: COMPONENTS OF VOLTAGE IN AN ELECTROOSMOTIC CELL

In the electroosmotic dewatering (EOD) of clays, suspensions and fines, a continuous or interrupted DC voltage, V, is applied between the anode and the cathode. In the previous literature on this subject the components of V have not been completely clarified.

Following a brief outline of the EOD that emphasizes the central role of the electrochemical double layer, we provide an analysis of the components of V, Three case are distinguished

(1)Threshold voltage V-n, for initiating the EOD and its connection to the so-called open-circuit voltage;

(2)EOD at very low voltages viz. around IV;

(3)EOD at very high rates for prolonged times where electrodes such as Al can form barrier oxides and some “caking” is also observed near the a node, This attempt to define the components of V under different conditions of EOD is aimed to identify parameters and processes that arc involved in the effect of V on EOD; RT for example, it is generally not recognized that —pH can form a significant part of V F under some conditions of EOD     

ISOTHERMAL AND NON-ISOTHERMAL MULTICOMPONENT ADSORPTION KINETICS

The model equations in the relaxation form for the multicomponent kinetics of isothermal and non-isothermal adsorption, taking into account all major distinctive features of the interphase heat and mass exchange inside porous grains and at their surface (see points 1 to 4 below) for P (“pore”) and S (“solid”) models of mass transfer within porous grains of the adsorbent, have been obtained.

First for isothermal and non-isothermal kinetics in the mixed kinetics region of mass and heat exchange in the absence natural mutual diffusion and natural thermal-diffusion the essential influence effective mutual diffusion and effective thermal-diffusion is shown.

Recommendations on the use of model equations of adsorption kinetics for describing isothermal and non-isothermal adsorption dynamics of multicomponent mixtures in the inner-diffusion and mixed (outer- and inner-diffusion) kinetic region of heat and mass exchange are made.     

DRYING OF GRANULAR PARTICLES IN A MULTISTAGE INCLINED FLUIDIZED BED WITH MECHANICAL VIBRATION

A mathematical model for the drying rate of granular particles in a multistage inclined fluidized bed(IFB) is presented from the standpoint of simultaneous heat and mass transfer, with taking the effect of mechanical vibration added vertically into consideration.

Steady-state distributions for the temperatures and concentrations of the particles and the heating gas, and for the moisture content of the particles are numerically calculated based on the present model. The calculated results show fairly good agreement with the experimental data, which were obtained from the drying experiments of brick particles in a three-stage IFB using comparatively low temperature air(40-60°C) as the heating gas.

It has been found within the range of the experimental conditions employed that, the mechanical vibration added vertically enhances the over-all drying rate of the particles and its effect can be considered equivalent to an increase in the air velocity.     

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.     

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.     

RADIAL DISPERSION AND BUBBLE CHARACTERISTICS IN THREE-PHASE FLUIDIZED BEDS

The effects of gas and liquid velocities, liquid viscosity and particle size on the radial dispersion coefficient of liquid phase (D_r) and the bubble properties in three-phase fluidized beds have been determined. A new flow regime map based on the drift flux theory in three-phase fluidized beds has been proposed.

In three-phase fluidized beds, D, increases with increasing gas velocity in the bubble coalescing and in the slug flow regimes, but it decreases in the bubble disintegrating regime. The coefficient exhibits a maximum value in the bed of small particles with increasing liquid velocity at lower gas velocities. However, it increases with increasing liquid velocity at higher gas velocities. In two and three-phase fluidized beds of larger particles (6,8 mm), D_r exhibits a maximum value with an increase in liquid viscosity at lower gas velocities, but it increases at higher gas velocities. The mean bubble chord length and its rising velocity increase with increasing gas velocity and liquid viscosity. However, the bubble chord length decreases with an increase in liquid velocity and it exhibits a maximum value with increasing particle size in the bed. The radial dispersion coefficients in the bubble coalescing and disintegrating regimes of three-phase fluidized beds in terms of the Peclet number in the present and previous studies have been well represented by the correlations based on the concept of isotropic turbulence theory.     

DEVELOPMENT OF RADIAL MODELS FOR FORMATION DAMAGE IN POROUS MEDIA

The continuously changing velocities in radial geometry have a significant effect on process characteristics, making it an intellectually challenging problem. In practical operations, fluid is generally pumped down injection wells from where it flows radially outward. Simulating this radial system with linear models is definitely restrictive. Consequently, the need for developing radial models for flow and particle entrapment in porous media is both fundamental and applied.

A radial network model, covering a 120° angle, has been developed to simulate formation damage due to deep bed filtration (DBF) of injected suspensions. The models draws upon our previously developed concepts of “wave-front movement” and “flow-biased probability” for linear systems. Systematic studies have been performed on formation damage using monodispersed and polydispersed suspensions. Case studies have been presented for constant flow rate and constant pressure injections, and comparisons are made between linear and radial systems.

Results show that the results obtained from linear models are conservative in comparison to those obtained from radial models. Furthermore, the use of monodispersed particles in mathematical models would show smaller differences between linear and radial predictions than would actually occur for polydispersed particles.     

ON CHARACTERIZATION AND MITIGATION O F COMBUSTION HAZARDS INVOLVED IN THE HANDLING OF PARTICULATE MATERIALS: A REVIEW OF THREE BOOKS

The three publications reviewed herein deal with the complex of hazards which may derive from the agricultural and commercial handling of combustible particulate and gaseous materials. The principal thrusts of each book differ substantially from those of the other two. This review first attempts to consider the essential combustion processes which underlie the hazards of common concern in all three works. Each of the three books is then considered on an individual basis. The three publications are designated Books (1)- (3) respectively and are listed below:

(1) “User Guide to Fire and Explosion Hazards in the Drying of Particulate Materials.” 1977. Institution of Chemical Engineers. Warwick Printing Company Limited, England.

(2) “Prevention of Grain Elevator and Mill Explosions.” 1982. NAS-NRC Publication NUB 367-2. National Academy Press, Washington, D. C.

(3) “Guidelines for the Investigation of Grain Dust Explosions.” 1983. NAS-NRC Publication NMAB 367-4, National Academy Press, Washington, D. C.     

Aging Process of Metal/Epoxy Laminates Investigated with X-ray Photoelectron Microscopy and Spectroscopy

In this article we describe the application of X-ray photoelectron spectroscopy to epoxy/dicyandiamide laminates on zinc galvanized steel which were aged under different environmental conditions involving high humidity and temperatures.

X-ray photoelectron microscopy allows us to identify the distribution of chemical elements with a lateral resolution of 10μm. Areas selected in the microscopy mode were then analyzed in the spectroscopy mode in order to get information on the local chemical composition.

We compared the spectroscopic features of the aged but freshly delaminated surfaces of samples stored under ambient conditions at room temperature with samples exposed to the “Kataplasmann” and the “KWT” test, respectively. Furthermore, a comparison was made with a model sample which was prepared in vacuum and on which the curing process was investigated.

Though there is no substantial loss in the lap-shear strength of the samples, we find drastic spectroscopic changes in the Kataplasma and KWT treated samples compared with the sample kept at room temperature. We conclude that the chemical changes induced by these tests cause an internal interphase boundary between the epoxy/metal interface and the bulk adhesive along which delamination occurs. Comparison with the behavior of the water-vapor-treated model sample gives evidence that hydrolysis is the main reaction in these tests.

The results described here complement our former study.¹     

Improvement of the Durability of Zinc-Coated Steel/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and hot-dipped galvanized (G2F) or electroplated-phosphated (EZ2) steel have been investigated. The degradation mechanisms have been studied after three accelerated ageing tests: the “cataplasme humide” (“C.H.T.”), immersion (“I.T.”), and salt spray (“S.S.T.”) tests. X-ray photoelectron spectroscopy (XPS) analysis of fracture surfaces after ageing have shown that anodic dissolution of the zinc-coating is responsible for debonding in all cases and that intergranular corrosion phenomena account for poorer performances of the hot-dipped galvanized substrate during “C.H.T.” and “I.T.” Silane coupling agents were successfully used as primers on both substrates to increase the hydrolytic stability of the metal/adhesive interface. XPS results indicate that both the interfacial dissolution of the phosphate coating of EZ2 and intergranular corrosion of G2F are delayed for silane-primed specimens. The observed improvements do not appear to depend on the nature of the silane coupling agents. Alkylsilanes have been found to perform as well as silanes having a group capable of reacting with the epoxy/dicyandiamide system.

Additional tests were carried out in view of the possible application of organosilane reagents as additives in corrosion-protective oils. Good durability properties have been obtained by priming the metal coupons with a standard oil/silane mixture prior to bonding.

When corrosion was the controlling degradation mechanism as is the case during the salt spray test, silane treated specimens did not generally perform better than control specimens.