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PROCESS ASPECTS OF REGENERATION IN A MULTIPLE HEARTH FURNACE

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PROCESS ASPECTS OF REGENERATION IN A MULTIPLE HEARTH FURNACE

TABLE OF CONTENTS Section I II III IV Description Page

Introduction ...................................................................................................... 3 Multiple Hearth Furnace Description................................................................ 4 Reactivation Process - Zones and Outline of Sizing Factors........................... 7 Determining the Basic Factors Required for Rational Sizing Calculations .......................................................................... 10 A. Drying Zone.............................................................................................. 10 B. Pyrolysis Zone.......................................................................................... 11 C. Reaction Zone .......................................................................................... 12

Calculation of Hearth Area and Furnace........................................................ 19 A. Reaction Zone Alternatives ...................................................................... 19 B. Pyrolysis Zone.......................................................................................... 25 C. Drying Zone.............................................................................................. 27

VI VII

Some Brief Experiments Regarding Reaction Rates ..................................... 29 Conclusions.................................................................................................... 31 References..................................................................................................... 36 Table of Appended Figures............................................................................ 33 Appended Figures.......................................................................................... 34

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SECTION I INTRODUCTION Discussion of the methods of calculating the size multiple hearth furnace required for a given carbon activation requirement by usual chemical engineering process calculations will serve as a useful framework within which to discuss variations in what diverse adsorption processes require of the reactivator, methods of determining the work to be done in reactivation, and some possible directions for exploration aimed at reduction of carbon losses and/or improvement of quality of reactivated carbon. The effort to show a rational method of size calculation may be useful in itself for those who are required to do such sizing. All figures are appended at the back of the paper.

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SECTION II MULTIPLE HEARTH FURNACE DESCRIPTION Figure 1 shows a cross section of multiple hearth furnace. Since the equipment is well known only a few brief points about mechanical and process aspects peculiar to this type of apparatus will be made. Briefly, the multiple hearth furnace is a device to accomplish heat and mass transfer, between gases and solids, passing the gases and solids counter currently through a series of compartments, or stages, in each of which the gas travels in mixed laminar flow over solids, spread in thin furrowed layers, that are periodically raked, to both mix the solids and advance them through the compartment. Heat transfer is both by direct convection and radiation from the gas to the thin wide spread area of solids, and by indirect transfer to the brick walls and parallel brick compartment roof followed by re-radiation to the solids, plus minor amounts of conduction through the hearth floor from the gases of the compartment next below. Mass transfer is solely by convection as the gases pass over the solids in laminar flow. Burners, supplying oxidizing or reducing products of combustion of fuel burned, nozzles injecting steam, or air injection nozzles apart from fuel burners can be placed at any hearth. Thus temperature and atmosphere can be changed quite sharply from one hearth compartment to the next. If the carbon reaction zone covers two or more hearths, early reaction while the carbon is heavily laden with residue from adsorption may be carried out at one temperature and atmosphere, and final reaction as the carbon nears the regenerated state may be carried out under a different atmosphere or temperature. As to solids flow, it is apparent that the carbon is spread relatively thinly over a large area and stirred periodically. For a given furnace, and at given volumetric feed rate, the faster the center shaft is turned, the shorter the retention time. The conveyance of material through the furnace is by positive displacement. All particles have equal retention time except for some slippage and/or some short circuiting giving about a + 5% range to particle retention time under conditions of normal bed depth. The faster the center shaft is turned the more frequent the stirring and the shorter the interval in which particles lying on top of the bed remain there. Up to a three minute interval this time between stirrings has not been grossly or obviously significant in reactivation results. Neither has the effect of intervals between stirrings been really fully investigated.

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There is, however, a danger in turning the shaft too fast for a given feed rate. The average bed depth becomes too thin to completely cover the distance between one rabble tooth and another. The effect over rapid stirring excessively reducing bed depth is shown in Figures 2 and 3. This can be a source of excessive carbon loss. It should be noted that the rabbled bed of carbon is left in furrows, or corrugations. The interface between carbon and gases, which is the determinant of capacity, is actually 1.2 to 1.4 times the nominal -- or plan view hearth area, as the angle of repose of the carbon goes from 30o to 45o. It is noteworthy that the rabbling action itself is extremely gentle. In recent test runs reactivating powdered carbon, some light agglomerates were fed, along with the main carbon stream. After passing six hearths they were visible still as agglomerates in the product collection drum, but so friable that they could not be picked out between two fingers but had to be spooned out of the main mass for examination. Similarly some years ago a client took the trouble to pass animal bone char through a cold 8-hearth 14'-3" O. D. multiple hearth at several tons/hour rate, and then into a bucket elevator and back through the furnace for 30 cycles. Bone char shows more or less the same results on standard NBS abrasion testing as does some common commercial active carbons. As a result of this test the client reported that furnace attrition loss (disappearance plus creation of 60 mesh particles) was 0.3% per cycle. This makes one wonder how the commonly reported 5% losses in carbon regeneration are created. The amount of carbon in the act of falling from hearth to hearth is at all times constant and, in granular carbon applications, of negligible area for heat and mass transfer. A furnace of 175 sq ft/hearth nominal area, 227 sq ft of actual furrowed surface with 4 ft hearth spacing, would have in suspension between each hearth a lb of material at all times. This would have a total particle surface area for 30 mesh average size material of about 12.5 sq ft, but it falls in a relatively tight stream, not totally dispersed in the gas and probably represents at most 1 or 2 sq ft of actual surface exposure.

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This is considered fortunate as individual particles showered through active gas would receive heat through all sides of the particle. Also they would contact gas of the concentration of reactant's extent that is normal to the main body gases above furnace hearths, which is very strongly reactive. Surface gasification and not depth of pore penetration would be expected. In the hearth bed, even the surface particles receive heat from one side only, half their surface area, and conduct much of that away through the downward facing side. The gas composition around the particles in the bed of the reaction zone are believed to be quite different from that of the main stream of gases over the bed due to the laminar gas flow and stagnant film at the bed surface.

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SECTION III REACTIVATION PROCESS - ZONE AND OUTLINE OF SIZING FACTORS It is usually considered that thermal regeneration of carbon occurs at 1500oF to 1850oF by reaction of water vapor and/or carbon dioxide with whatever is left of the adsorbate after the adsorbate, along with the original carbon, has been heated to these temperatures. Clearly reaction cannot begin until the material has been heated to reaction temperature, and heating cannot begin until the carbon has been dried. Thus, there are three steps which may, with best design and operation, occur in three separate furnace zones rather than overlap. They are a reaction zone, a heating zone and a drying zone, considering them from the bottom of the furnace upward, following the path of the gas flow, and also naming them in their probable order of importance rather than their order of occurrence. The reactions expected are: 1. 2. 3. C + H2O CO + H2 C + CO2 2 CO (endothermic 4800* BTU/lb carbon) K equilibrium 1700oF = 47.8 (endothermic 5950* BTU/lb carbon) K equilibrium 1700oF = 52.5

CO2 + H2 CO + H2O (endothermic 37.3 BTU/cu ft any constituent) K equilibrium 1700oF = 0.73

*Assumes carbon is graphite, whereas most of the reactions in regeneration are with a modified form of amorphous carbon. Even at 1500oF equilibrium constants for the first two reactions are high enough (about 10) to expect reaction to go essentially to completion except for kinetic rate limitations. The reaction zone might be expected to be sized by volume of rabbled carbon bed considering that the carbon gasification reactions that occur in it are governed by kinetics and reaction rate limited. Actually it is sized by hearth area. The area exposed to the gases controls mass transfer of reactants from the gas phase to the carbon, and heat transfer to support the endothermic reactions.

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Reactions occur both on and below the surface of the rabble bed, but at diminished rate with each successive layer of depth due to a combination of shielding from heat transfer and shielding from reactants, by layers of carbon nearer the surface. Within the normal range of bed depths previously discussed, no variation of carbon gasification rate is found with varying frequency of stirring, varying retention time or depending on bed depth beyond the minimum required for full hearth area coverage. If one wishes, one could consider the reaction zone to be determined by a volume of carbon bed, but one would have to assume a certain limited bed depth as being effective - probably about 2" and thus volume would be reduced in effect to area times a constant. The hearth area for the reaction zone can be established by determining an amount of carbon to be gasified per hour and dividing by a rate of gasification expressed in pound fixed carbon gasified per hour per square foot. The question of sizing the reaction zone then becomes a matter of deciding how much carbon is to be gasified per pound of product and at what rate: subjects to be discussed in some detail further on in the paper. Once the conditions in the reactivating zone are established, the temperature, volume, mass and composition of the gases entering the pyrolysis zone from the activation zone are fixed. Conditions in the pyrolysis zone, if it does not overlap with the reaction zone, can be altered from those that would result from simply flowing reaction zone gases across the pyrolysis zone hearths. Temperature can be lowered by adding steam or raised by adding air (to react with CO and H2 in the gases from the reaction zone) or by firing fuel. Often, depending upon design and operation and adsorbate character, the pyrolysis zone shades into or overlaps with the reaction zone, the transition being gradual as thermal decomposition of the adsorbate subsides and water vapor plus carbon dioxide reactions increase in rate.

The sizing of the pyrolysis zone and also of the drying zone above it, is simply a matter of heat exchange area required to transfer into the rabbled bed the heat required for heating carbon, adsorbate and water: evaporating water; heating carbon and adsorbate; plus any heat of reaction for pyrolysis of the adsorbate.

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There are all kinds of possibilities for minimizing the area required by raising gas temperatures and thus raising the temperature difference creating heat transfer, or minimizing fuel by burning either CO and H2 from the reaction zone, or organic vapors given off during charring of the adsorbate. The exact method of calculation will be discussed later with an example. At present let it be said that the preparation step of drying the carbon is not at all a factor in carbon losses and quality within the usually applied range of conditions. Before detailed sizing calculations data must be obtained and decisions made on various points that may effect quality, losses and furnace size.

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SECTION IV DETERMINING THE BASIC FACTORS REQUIRED OR RATIONAL SIZING CALCULATIONS A. DRYING ZONE All that is really needed for calculating the size of the drying zone is to know the pounds per hour of water that will enter the furnace with the spent carbon and must therefore be evaporated. Usually the furnace is preceded by a slurry dewatering device that is in common use by others and one accepts the reported experiences of others who use the planned device, as to the percent moisture to be expected in the feed. It was once common to wash the carbon "in situ" in fixed bed adsorption columns, using hot water for the wash, and then allow the carbon to either drain by gravity or be more rapidly purged of water by blowing a small volume of compressed air through the column. For this condition, we expected 37% to 45% moisture. Lately, it is more common to deliver a slurry of carbon to an upwardly inclined screw conveyor, allowing to water the drain to the lower end of the screw conveyor, counter to the flow of carbon. For this condition we have come to expect 45% to 55% moisture in the dewatered carbon. A fairly wide range of expected moisture content is given for both devices because the moisture content will be affected by two or three factors beside the dewatering device used. When carbon is dewatered in a stationary bin, the temperature of the final wash water, the use or non use of compressed air to break the film of water between particles, and the time allowed for dewatering, all affect the result. With the dewatering screw, the primary variable is the particle size of the carbon and whether or not the space between the screw and the shell of the screw conveyor is periodically cleaned of fine particles and possible mold growth, to allow free drainage of water. Also when the adsorbate loading is relatively high, more of the pore volume in the carbon is filled with adsorbate and there is less pore volume available for moisture. Hence moisture contents in the lower end of the ranges stipulated above, can be expected. 0.3 to 0.5 pounds adsorbate per pound of original carbon would qualify as being a relatively high adsorbate load. In the case of either dewatering device it must be remembered that moisture content is usually stated on an "as received" basis, so it is the weight of water divided by the weight of water plus weight of original carbon plus weight of adsorbate. Therefore, one needs to know the weight of adsorbate per weight of original carbon in order to calculate the pounds of water to be evaporated per hour in producing a given rate of regenerated carbon product.

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Perhaps less attention is being paid to the dewatering of carbon than might be justified at present fuel prices, because the "as received" basis of stating moisture content is somewhat deceptive. It seems surprising to note that 40% moisture is b pound of water per pound of dry solids and 50% moisture is one pound of water per pound of dry solids; not 10% more moisture nor 25% more moisture but 50% more water to evaporate. B. PYROLYSIS ZONE For proper calculation of the heat transfer required during pyrolysis, the weight of adsorbate per unit weight of original carbon should be known and the heat of reaction for thermal decomposition of the adsorbate should also be known. Generally an exact knowledge of these two facts is not critical in the sizing of the pyrolysis zone since the assumption of a half pound of adsorbate per pound of original carbon (the maximum we have ever experienced) and of 250 BTU/lb of adsorbate endothermic heat of pyrolysis would not significantly affect the total furnace size. It is difficult to envision a situation where the heat of pyrolysis of the adsorbate or the amount of adsorbate being different from the above assumption would cause any problem. Knowing the weight of adsorbate per unit weight of original carbon has greater importance for estimation of the drying zone, and for consideration of the heating value of organic vapors which can be used in the drying zone as a cost-free source of heat; than this has for sizing the pyrolysis zone. Maximum removal by pyrolysis is desired because the more adsorbate removed by pyrolysis, the less char will be left to be removed by reaction with H2O and CO2. Removal of char by reaction has generally been incomplete in respect to pores of about 30 Angstrom unit diameter and smaller. Removal of char by reaction is generally accompanied by loss from the outside of the particle and enlargement of macro pores.(1)(2) Macro pore enlargement is not only a weight loss but weakens the particle, inviting additional handling loss in subsequent cycles. While maximum removal by pyrolysis is desirable, such removal should probably not be maximized by maximizing char temperature during pyrolysis. Graphitization begins at about 1600oF and it would seem desirable to keep the fresh char as chemically reactive as possible, to encourage gasification reactions to react with such char preferentially to reaction with original active carbon structure. The original carbon structure has presumably been made less chemically reactive by stripping reactive portions and exposure to

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high temperature during the manufacturer's activation. All this leads to a desire for a procedure to maximizing organic removal by pyrolysis. Goos(3) working in wood charcoal has suggested that the most rapid rate of temperature rise results in the lowest char yield. He reports the ability to reduce charcoal yield from wood from 35% to 14% by reducing the time of pyrolysis from days to seconds. If that applies, the multiple hearth is a naturally excellent tool, as once the spent carbon is dry, each piece as it comes to the surface will rise in seconds to within roughly 100oF of the gas temperature. Usually gases over the hearth where pyrolysis is occurring are at 1500oF to 1800oF. If, as will be shown later, design and operating conditions are carefully established for the purpose, the solids as a whole, will heat from 200oF to 1500oF in a small area, which depending on shaft speed, may represent 5 to 20 minutes retention time. A fluid bed would be better yet but would involve other problems especially if pyrolysis were not done as a separate step. All that can be recommended at present is to avoid overheating during pyrolysis and avoid slow baking. To help avoid overheating during pyrolysis, the H2O content of the gases is kept high and CO and H2 minimized, endothermic reaction will begin at 1500 and increase in rate with increasing temperature and prevent the carbon from recycling full gas temperature. The gas temperature should be limited to 1700oF or thereabouts. To avoid slow baking during periods of less than design throughput, the effective furnace area can be shortened by either moving the reaction zone up and letting the last hearths at the furnace bottom be simply steam purged, or by reducing temperatures drastically over the drying zone to leave the carbon wet until just before reaching the reaction zone. In design calculations, it seems desirable to seek means for minimizing the pyrolysis zone area and thus the time the material will take to pyrolyze, by maximizing heat transfer rate in this zone.

C.

REACTION ZONE The object is clearly to remove all the char left by pyrolysis of the adsorbate without any reaction with the original carbon structure.

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1.

Determination of Char formed by Adsorbate Pyrolysis: The first requirement for design data is to know how much char will be left by pyrolysis. The adsorbate weight can be determined by knowing the particle density, as determined by mercury displacement, for the carbon in its virgin state and again after it has been spent. The ratio of spent particle density to virgin particle density minus one, equals the pounds adsorbate per pound original carbon. Spent carbons should also be devolatilized by heating in covered crucibles to 1740oF for 72 minutes. Again the ratio of spent and pyrolyzed particle density to virgin carbon density equals pounds char formed per pound original carbon. The indicated char formation must of course, be corrected for ash gain or loss from the virgin state to the pyrolyzed state. It is of some academic interest to compare the two ratios for an indication of char yield in terms of pounds char per pound adsorbate, as gathering experience in this regard can help the designer to guess what to expect of different classes of compounds and might help in studying various pyrolysis conditions. If mercury density apparatus is not readily available, careful ABD (Average Bulk Density) determinations have proven to give closely similar results. One advantage of using average bulk density instead of particle density is that exactly the same sample can be used for virgin density determination, spent and dried, used for spent density determination and pyrolyzed in one or more crucibles and again used for pyrolyzed density determination. With mercury particle densities the material is made useless for adsorption or pyrolysis so the problem of getting three identical portions of carbon sample arises. The carbon sample for the above purposes must be carefully prepared by properly riffling or quartering a small sample of carbon. Commercial carbon particle densities and average bulk densities vary too much from time to time, lot to lot and top of a bag to bottom of a bag to run the spent and pyrolyzed densities on random samples and compare with published virgin densities or densities from another random portion of the same bag of carbon.

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Often the problem arises of determining expected char gasification requirements when the plant producing the stream to be treated by carbon is not yet built. The above procedure can easily be used on pilot size samples or even with bench work, producing simulated waste streams. With particle density determination by mercury displacement, only about 20 grams of carbon need be spent in adsorption service. If the adsorption system is not yet designed, and it is uncertain whether the carbon will be spent to equilibrium with the stream entering the adsorption process, it is of course safest to do furnace design work from a sample spent to exhaustion. This sample may have released lighter components of a mixed adsorbate and replaced them with heavier components, but the heavier components usually show the highest char yield and will thus result in safe furnace sizing, on both counts - maximum loading and maximum char yield from adsorbate. The above procedure of determining adsorbate load and char to be expected from pyrolysis is much preferred to calculation of adsorbate load from column tests by integration of treated volume and reduction of stream components. The latter method too often overlooks stream components adsorbed but unmonitored because they are not intentionally removed as an object of treatment, or includes material removed from the stream but biologically oxidized on the carbon and so no longer present at reactivation. Also measurements of stream components often given results in terms BOD, COD, TOC or color which cannot be accurately translated into pounds adsorbate per pound original carbon. Most important, stream change measurements leave the furnace designer to guess, from experience, how much of the adsorbate will be easily removed by simple or destructive distillation, and how much will remain as hard to remove residual char from pyrolysis. This not only affects furnace sizing but also anticipated losses. 2. Extra Carbon to be Gasified from Original Structure, Reaction Conditions and Reaction Rate: Having determined the amount of char deposited by adsorbate pyrolysis, two related questions remain before rational calculation of furnace size can be undertaken: What will the carbon reaction rate in lbs/hr/sq ft of hearth area be, and how much carbon is to be gasified in this way? a. Gasification of Overall Carbon Structure It must be expected that the original carbon structure will compete with the char left from the adsorbate for the privilege of reacting with the available H2O and CO2 molecules. Even if all of the original carbon's structure was uniformly covered by fresh char from the adsorbate (a condition which probably never exists, deviation

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from it depending upon the distribution of various adsorbate species in the solution being purified) one would still expect the outside of the structure and the lining of the very large diffusion pores to be cleaned of fresh char before the adsorption macro pores and adsorption micro pores were cleared of fresh char. Such pores are the route by which H2O and CO2 will travel to reach the adsorption pores. Juhola(2) indicates a much faster reaction rate for a carbon of coarse pore structure than for one of the fine pore structure which seems reason-able support for this contention. Since the reaction we desire is not with fixed carbon but with a soft, freshly made char from pyrolysis, which may still contain some hydrogen, nitrogen, sulfur or other atoms, there might be hope of a reaction condition that would be highly selective, giving a faster reaction rate with the new soft char than with the original active carbon structure. A very brief preliminary investigation of this possibility will be reported at the end of the paper, though it is quite inadequate to serve as more than a hint of the desirability of further work in this direction. It is this author's suggestion, based on general experience, that until better information is available the expectation of gasifying 0.25 pound of original carbon structure per pound of char formed by pyrolysis in a covered crucible at 1740oF would be a reasonable basis for design. A sugar refinery that uses granular active carbon to polish away the last traces of color after the heaviest load of color has been removed on bone char, reports (4) less than 1% carbon makeup required per cycle. It can be anticipated from the conditions of service that the amount of adsorbate per pound of carbon would be extremely small. It is well known that cane sugar adsorbate gives an extremely low yield of fixed carbon from pyrolysis. It was practice in this industry to adsorb such color on charred animal bones and pyrolyze in closed retorts at approximately 900oF. Unless the adsorbate loading was extremely heavy, no great problem of build-up of fixed carbon was observed though the adsorbent was used through 200 cycles of regeneration. This plant report can be taken as an example of how little loss may be attributable to mechanical handling and other mechanical losses in a well designed and well run plant. It has been the author's general experience that the greater the adsorbate loading and the greater the fixed carbon deposited from such adsorbate, the higher the

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carbon make-up requirement can be expected to be.(4) With due allowance for plants which regenerate intermittently, regenerate at small carbon through-put rates and where design or operation is known to be less than ideal, this suggestion of 0.25 pound original carbon loss per pound of fixed carbon formed by pyrolysis, would in all instances given a calculated carbon make-up requirement from non-selective gasification that would not be in obvious conflict with the observed results. The work of Juhola(2) indicates an average carbon volume decrease during the reaction step of about 1.8%. The total weight loss in baking and reactivation to original average bulk density was about 20% and when baking was done at 1700oF with nitrogen only about 40% of the adsorbate remained as char. This would indicate that in relation to the 80% of the sample that was original carbon weight, the char formed by pyrolysis was about 10%. The overall 1.8% loss figure then indicates the loss of 0.18 pounds original carbon per pound char formed by pyrolysis. This is as good agreement between laboratory experiments and the author's rough appraisal of commercial practice which is aimed at producing a safe allowance for maximum losses, as might reasonably be expected. b. Selecting Reaction Zone Conditions It has often been the practice to select reaction zone conditions to maximize the gasification rate so as to use the smallest possible size piece of equipment for a given reactivation capacity. It has proven safe to use a figure of 0.6 pounds fixed carbon gasified per hour per square foot when considering carbons of fine pore structure. There is less experience with carbons of coarse pore structure but the figure of 1.2 pounds fixed carbon gasified per hour per square foot has been verified in laboratory and commercial practice as being safely achievable for such coarse pore structured carbons.

The higher rates were achieved with one commercial carbon, and over three cycles of use the rated seemed to be diminishing. It may be a mistake to attribute the high gasification rate to pore structure. Catalytic mineral content and other causes may exist. These figures of 0.6 or 1.2 lbs/hr are both to be used only if one believes the fixed carbon gasification rate should be maximize in order to minimize equipment size. It

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seems reasonable, however, that pressing the reaction rate to a maximum would minimize the effect of any difference in chemical reactivity between the freshly formed char from pyrolysis and the original carbon structure. Gasification rates are increased by increasing temperature and increasing H2O and CO2 concentration at the reacting surface of the carbon. Mizushima (5) indicates that graphitization of carbon begins at temperatures as low as 1650oF and takes some effect in as little as three minutes. He prepared his starting samples, which presumably had no graphitization, by baking at 1300oF. Limitation of reaction zone gas phase conditions to approximately 1700oF (perhaps 1600oF material temperature) might be desirable both to preserve a difference in chemical reactivity between freshly charred adsorbate and original carbon structure, and in case through lack of control, some charred adsorbate is left to be removed on a subsequent reactivation cycle. It has generally been observed that high gasification rates due to high reactant gas concentrations and high temperature tend to result in product reactivated carbon that has an increased ratio of molasses number to iodine number. Seemingly the coarse pores are cleaned out or enlarged but the fine pores are not. The preliminary experimental work reported at the end of this paper indicates that the lower the temperature of reaction, the greater the reaction rate of fresh char from pyrolysis in ratio to the reaction rate with original carbon structure, at least under conditions of 40% water vapor by volume. In the report of West(1) of the University of Colorado on activation of Wyoming coal it is seen that when activating with only CO2 and nitrogen, gasification occurs in the macro pore structure (pores larger than 28 Angstrom units diameter) and not in the macro pore structure. It is interesting to note, however, that in his comparison with the results of others, reaction in the macro pore structure seems to be reported by all those who use H2O and nitrogen on various carbons and not by those who use CO2 without H2O. In the work of Juhola(2) reviewing the several reactivation runs made before the use of HCl leeching, it can be observed that in very few of these runs is there any increase in the iodine number beyond the iodine number achieved during the baking portion of the run. In some cases, the iodine number actually decreases during the

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activating step. The common denominator of those runs without HCl leeching that do produce an increase in the iodine number during the reaction, seems to be a ratio of steam to CO2 exceeding 3 to 1. Even after HCl leeching a high proportion of steam to CO2 seems to give a greater increase in iodine number between the baked condition and the activated condition. All of the above is less than complete and conclusive survey of conditions but is enough to point towards two conclusions. (1) If one feels that the adsorption process for which the reactivated carbon is intended requires the maximization of iodine number, high steam concentration in relation to CO2 is probably desirable. If only molasses number is of interest there may be no reason for stress on this point. (2) Lower temperatures than the 1800oF gas temperature, which gives maximum gasification rate, may well be desirable to maximize the selectivity of the gasification reactions toward the newly formed char from pyrolysis and away from the original carbon structure. The small experimental work to be reported at the end of the paper will, however, indicate a rapid decrease in reaction rate with decreasing temperatures and therefore the need for a compromise in order not to require very excessive hearth area in the reaction zone. Tentatively gasification rates in the range of two-thirds of those suggested above, specifically 0.4 pounds fixed carbon gasified per hour per square foot for small pore structure carbons, may be a reasonable suggestion to minimize carbon make-up requirements due to non-selective burning. If a 1% reduction in carbon losses could be achieved in this manner, adding 50% to the hearth area, in the reaction zone only, would generally show a very attractive financial return.

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SECTION V CALCULATION OF HEARTH AREA AND FURNACE SIZE After review of the above factors, appropriate experimental work and decisions as to whether to stress minimum equipment size or stress flexibility of reaction conditions and minimization of loss, one is ready to calculate required hearth area for each of the zones and sum them up to reach total hearth area. Furnace calculations should be made from the bottom upward following gas flow. Where heat transfer from the gases to the rabbled bed is to be calculated, the following similar equation is used: q = UA (LMDT) Where: q = heat to enter the bed - BTU/hr U = an empirical heat transfer coefficient BTU/hr - sq - oF A = nominal hearth area (LMDT) = log mean temperature difference between gas and solids on a single hearth The gas temperature is considered constant on a given hearth, equal to a thermo-couple reading, and equal to the temperature at which the gas will leave the hearth after giving up the heat required for transfer to the bed and for superheating vapors and for equipment heat losses. U has been found to be about 3 at low temperature such as 200oF - 500oF, and about 20 at 1700oF to 1800oF and to vary more or less linearly with temperatures between these ranges. As an example, an arbitrary instance has been chosen, starting with the following assumptions: Original Carbon (dosage to adsorption) 2000 lbs/hr Adsorbate Loading 0.3 lbs/lb original carbon 600 lbs/hr Char from Adsorbate - 40% of adsorbate 240 lbs/hr Gasification Conditions: Fine pore retention considered moderately important 1700oF H2O equals 3 times CO2 H2O = CO2 to equal or exceed 40% by volume Reaction rate in gas phase for above conditions (see experimental data to follow) - 0.4 lbs/hr - sq ft. Fuel - natural gas, considered as CH4 - 1000 gross BTU/cu ft Adsorbate Heating Value - 10,000 BTU/lb Feed Moisture - 40% as received The calculations will be shown only far enough to illustrate principals and choices, and the final results

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shown in Figure 4 with gas values and temperatures approximated. (H2O + C and CO2 reaction heat averaged with weight toward C +H2O reaction - to simplify illustrative calculations.) A. REACTION ZONE 1. Hearth Area Calculation: Hearth area required for reaction is calculated as 240 lbs/hr x 1.25 - 0.4 lbs/hr sq ft = 750 sq ft. Adsorbate char was multiplied by 1.25 factor to include excess carbon gasified. The expected loss of original carbon is indicated as 25% of 240 lbs/hr char from adsorbate or 60 lbs/hr or 3% of the original carbon. The calculated hearth area requirement indicates a choice of 2 hearths 232 ft inside diameter, 3 hearths 20 ft inside diameter, or 4 hearths 162 ft inside diameter. Final choice should be made later when the size of other zones is known. In this case 4 162 ft inside diameter hearths were chosen. 2. Selection of Fuel, Air and Steam Flows It is apparent that steam and air, and probably fuel, will have to be added to each and every hearth of the four, to allow control of the atmosphere and temperature as gasification proceeds. The bottom hearth of the 162 ft diameter furnace will have 200 sq ft, a larger area than others above it because there is only one drophole plus the area of the center shaft to subtract from the gross area of a 162 ft circle. By gasifying 0.4 lbs/hr sq ft, we can expect 80 lbs of carbon or 6b moles of carbon to react on this bottom hearth. Case A: Air Plus Steam - No Fuel - Maximum Reaction Rate at 1700oF. If only air and steam were to be added to this hearth, 80 lbs of carbon burned will release 1,126,000 BTU/hr, 300,000 BTU/hr* are needed for heat losses and 394,000 BTU/hr needed for the sensible heat in the gases produced from admission of the required 12,000 SCFH of air. This leaves 432,000 BTU available to heat 12, 375 SCFH of steam, or 589 lbs/hr of 7 lbs steam/lb carbon gasified. The gases leaving the hearth would then consist of: 12,376 SCFH 2,520 SCFH 9,480 SCFH 24,381 SCFH H2O CO2 N2 Total

The water vapor is almost 6 times the CO2 content and approximately 50% of the total gas volume.

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PROCESS ASPECTS OF REGENERATION IN A MULTIPLE HEARTH FURNACE

The actual reaction course would be for H2O and CO2 to react with the carbon, producing H2 and CO in the gas phase. Even where gases with surplus O2 are passed over fixed carbon beds in multiple hearth furnaces, one sees a bed blanketed by a blue CO burning flame. There is a stagnant film over the carbon bed and no O2 will be able to penetrate the CO and H2 coming from the bed to actually reach the carbon, unless air jets are focused directly on the carbon. The author has actually operated multiple hearths under the conditions described above with no terrible effect upon the product or the losses. It is a matter of judgment, however, to say that at 1700oF the maximized reaction rates with 60% H2O and no CO or H2 would probably be undesirable. Case B: Reduced Air Plus Steam - No Fuel. An alternative is to add less air and less steam, but still no fuel. At 400 lbs/hr steam, the endothermic reaction of steam and carbon will require, for 80 lbs carbon gasified per hour, 384,000 BTU/hr; and 300,000 BTU/hr must be allowed for furnace heat losses. Therefore 684,000 BTU/hr available at 1700oF will be required. To produce this heat 3,144 cu ft/hr of CO and H2 must be burned and so 7,486 cu ft /hr of air must be injected to cause such burning. Heat to raise the air to 1700oF was included in figuring 215 net BTU/cu ft CO and H2 burned. The exhaust will consist of: 6,824 SCFH 1,376 SCFH 1,994 SCFH 532 SCFH 5,914 SCFH 16,640 SCFH _______________
*This figure is quite variable depending on furnace construction and especially number of rabble arms and whether rabble arms are insulated. The figure used throughout these simplified example calculations is for reasonably typical construction.

H2O H2 CO2 CO N2 Total

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Note that: CO2 x H2 = 0.755 H2O CO So K equilibrium at 1700oF (K = 0.73) has been satisfied by application of the reaction CO2 + H2 H2O + CO to any arbitrary initial assumption of how much of the air admitted reacted with CO and how much with H2. Now the H2O is 40.4% of the gas volume and 3.4 times the CO2 content. Total CO2 and H2O is 53% of the gas volume which is still somewhat high for our desired reaction rate, but still less air and steam would result in less than 3 parts H2O per part CO2. Still other choices are open. It could be decided to burn natural gas at stoichiometric fuel air ratio. Case C: 1320 SCFH Methane Burned with Stoichiometric Air - No Steam. Without any steam, the fuel firing rate would be set by heat balance. Needing 300,000 BTU/hr for equipment heat losses, and 416,000 BTU/hr for carbon endothermic reactions, we must burn 1320 cu ft/hr of methane. The gas entering and leaving the bottom hearth would then be: H2O H2 CO2 CO N2 Entering 2,640 SCFH 1,320 SCFH 9,910 SCFH Leaving 1,000 SCFH 1,640 SCFH , 510 SCFH , 810 SCFH 9,910 SCFH 13,870 SCFH TOTAL

With the calculated result about 10% total H2O and CO2 and CO and CO2 ratio exceeding 0.5 - the desired reaction rate of 0.4 lbs/hr sq ft will be certain not to occur. An estimate of 0.1 to 0.2 lbs carbon gasified/hr/sq ft would be the more likely outcome. One should remember that these calculated compositions are gas phase compositions. Some differential of concentration must exist to achieve transfer of H2O and CO2 into the bed and transfer of CO and H2 out of the bed. The H2O and CO2 concentration at the surface of the pores of the carbon would under this circumstance be very small so the reaction rate would slow to leave more oxidant gases and produce less CO and H2.

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Case D - Fuel as Case C Plus 480 lbs/hr Steam and Excess Air. The option then remains of adding steam while still firing stoichio-metrically as in Case C or of adding air and steam. Adding air alone to the above would increase CO2 and H2O, reduce CO and H2 but raise the temperature. To maintain the desired 1700oF, steam would have to be added with the air. Adding 480 lbs/hr of steam (6 times fixed carbon gasified - a rule of thumb found convenient) would require that an extra 370,000 BTU/hr be developed. Adding only air would require burning 1720 cu ft of H2 and CO. Gas composition leaving the hearth would then be, after adjustment to make: [CO2] [H2] [CO] [H2O] = 0.73 = K equilibrium at 1700oF H2O H2 CO2 CO N2 12,180 SCFH ,640 SCFH 1,230 SCFH 90 SCFH 13,190 SCFH 27,330 SCFH Total

Now the H2O + CO2 = 50% of the total gas volume and H2O equals almost ten times CO2 which comes near enough to satisfying our criteria. Case E: 2000 SCFH Methane Burned with Stoichiometric Air Plus 480 lbs/hr Steam. If instead, we added the same 480 lbs/hr of steam and burned fuel stoichiometrically to provide the required extra 370,000 BTU/hr, the gas composition on the bottom hearths would after burning 680 additional cu ft of gas additional to Case C become: 11,990 SCFH 2,090 SCFH 1,640 SCFH 360 SCFH 15,045 SCFH 31,125 SCFH Total This choice, burning fuel instead of just adding air has increased the total gas volume, H2O H2 CO2 CO N2

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PROCESS ASPECTS OF REGENERATION IN A MULTIPLE HEARTH FURNACE

lowered the concentration of oxidizing gases from 50% to 44% and lowered the H2O to CO2 ratio to 8:1 instead of 10:1. There is no information available to guide a clean choice between the last two conditions. The cost of fuel burned instead of air may not be an important consideration since if the fuel is not required here, it may be required* in the drying zone to offset the smaller hot gas volume resulting when air only is added. Some would suggest the higher H2O to CO2 ratio and the higher oxidant concentration of example D to be preferable. Some would feel that difference to be slight and prefer not to lower the CO and H2 concentrations so far because of the risk of adding too much air or having local areas where CO and H2 might not be available to react with air as it is admitted. Lacking a good reason to choose, the designer would plan for burning of fuel and let the operator experiment with increased air to fuel ratio at the burners. We will carry on our example based on Case E. The above examples are intended to clarify the following points. 1. Steam is obviously necessary. Fuel alone fired stoichiometrically will not give the concentrations of CO2 and H2O required for a reasonable reaction rate. Air alone will produce a reactant gas that is all CO2 and no H2O which the literature indicates would produce only external attack and macro pore structure attack but not micro pore reactions. 2. The steam requirement is best related to the gas composition desired. That is percent total oxidants and H2O to CO2 ratio are good criteria for calculating steam requirement. This in turn is related to the fixed carbon being gasified. No inherent connection with lbs/hr of carbon passing through the reaction zone or pounds product/hr, is seen. In the example to be followed just a bit further, Case E, the steam usage after another 550 sq ft of hearth area on 3 more hearths, would be 1800 lbs/hr of 0.90 lbs steam/lb original carbon, But one can readily see that if the fixed carbon that were produced by pyrolysis were half or double the amount shown in the example, so also would the total steam usage recommended be halved or doubled.

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3. Burners and steam admission should be available on each hearth of the reaction zone to provide operational flexibility and the choice of maintaining the specified temperature and composition of each reaction hearth. If the gas composition shown above as leaving the lower reaction hearth simply passed over the next hearth above, practically no reaction could occur as the reactions are endothermic and the gas was already cooled nearly to reaction temperature. Cooling the gases 300oF would not supply enough heat for equipment heat loses, and that would leave the gases too cold for reaction. In the example to be carried forward, a good case could be made for redistributing the steam and fuel and air so that the gasification rates, or even temperature would be different between the last hearth of the four reaction zone hearths and the first hearth. One might wish to slow the reaction of the last hearth, where the carbon is nearly free of char from pyrolysis and increase the reaction rate on the first of the reaction zone hearths, expecting the original carbon structure to be shielded by char. A contrary case for maximizing steam and temperature on the last hearth and allowing a lower steam to CO2 ratio on the first of the reaction hearths can also be made, if only as a steam and fuel saving device. The one approach we would oppose is higher gas temperatures on the upper reaction hearth or accumulation of CO and H2 which would slow the reaction rate and bring the carbon closer to gas temperature. Experimentation in this area of distribution of gas composition and temperature would be useful. Unfortunately, most experimental reactions are made with constant temperature and composition, perhaps overlooking the fact that the nature of the reaction carbon is changing as the reactivation progresses. B. PYROLYSIS ZONE Carrying forward Case E above, the gases leaving the reaction zone and entering the fifth hearth from the bottom are 1700oF and total 130,000 SCFH. The next hearth will have 175 sq ft of nominal area. Since the reaction rate on the hearth below was requiring 0.4 lbs/hr - sq ft x 5200 BTU/lb or 2080 BTU/sq ft and U was 20, the carbon must be heated to 100oF below gas temperature or in other words to 1600oF. The temperature of material entering the last pyrolysis hearth will be assumed and then checked by trial and error calculation.

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PROCESS ASPECTS OF REGENERATION IN A MULTIPLE HEARTH FURNACE

Assume 2000 lbs/hr original carbon plus 600 lbs adsorbate enter this hearth at 200oF, dry, and that the adsorbate decomposes at an average temperature of 1000oF, requiring 250 BTU/lbs endothermic heat of reaction, and having 0.33 specific heat, which is the same as the carbon. The heat required to be transferred into the carbon is: 600 lbs adsorbate x 250 BTU/lb 600 lbs adsorbate x 1/3 x [1400oF - 200] 2,000 lbs carbon x 1/3 x [1600oF - 200] Total = 250,000 BTU/hr = 280,000 BTU/hr = 935,000 BTU/hr 1,465,000 BTU/hr

If the hearth is fired with fuel and air to maintain 1700oF, the gas temperature will be 1700oF all across the hearth and (LMDT) will be 445oF. A heat transfer coefficient of 18 can be expected. From the previously given q = UA (LMDT), we can calculate a heat transfer of 1,4000,000 BTU/hr which quite nicely checks the assumption of 200oF temperature of carbon entering the hearth. The fuel fired in this case will be about 2,700 CFH of natural gas at 1000 gross BTU/cu ft. However, if we assume no firing on this hearth, the heat supply is the entering gas volume of 130,000 SCFH which gives up only 286,000 BTU/100oF reduction in temperature. If we assume a temperature of 1450oF for the material entering, the heat required to heat this to 1600oF is 2240 lbs char plus carbon 1/3 x 150 = 112,000 BTU/hr. The gas will supply this heat plus an estimated 150,000 BTU/hr equipment loss by cooling 100oF. The gas temperature across the hearth will be 1600oF and (LMDT) as the carbon approaches 1600oF and will be 0. Actually, the carbon just won't quite heat to 1600oF - about 1575oF might be a reasonable guess. Instead of the above, assume the carbon is heated from 1400oF to 1600oF on the first furrow or two of the reaction zone. Then we need only heat the carbon to 1400oF on the last hearth of the pyrolyzed zone. Now an assumed temperature for carbon and adsorbate entering the last pyrolysis hearth of about 900oF and no other temperature assumption will satisfy the heat transfer equation or heat balance equations. The point here is that the pyrolysis zone can be spread over two or three hearths or all done on one hearth depending very critically on whether the last hearth of the pyrolysis zone is fired or not.

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Assuming the last hearth of the pyrolysis zone is fired as in the above instance to maintain 1700oF, by adding air to react with the products of pyrolysis, then this hearth alone is the entire pyrolysis zone and only drying remains. The air will have plenty of fuel from the pyrolysis to react with. The adsorbate was stated to be 600 lbs/hr at 10,000 BTU/lb of 6,000,000 BTU/hr. 240 lbs of char was formed at about 14,000 BTU/lb or 3,300,000 BTU. So the organic vapors released must have had a heating value of 2,700,000 BTU or just enough to serve in place of the natural gas mentioned above. C. DRYING ZONE The gas entering the drying zone now consists of 157,000 SCFH of gas with a mean specific heat of 0.023 BTU/st cu ft and actually at 1700oF. Cooling these to 850oF, exhaust gas temperature will release 3,000,000 BTU/hr. The feed entered as 2600 lbs carbon and adsorbate with 40% moisture or 2/3 lbs water/lb dry feed or 1740 lbs water. The heat for evaporation, superheating of water vapor to 850oF, heating feed solids from 60oF to 200oF plus equipment heat loss will also be about 3,000,000 BTU/hr. No use has been made of the 2,200,000 BTU/hr from residual CO and H2 from the reaction zone. This can be used as fuel value in any required afterburner, or a higher exhaust gas temperature can be allowed to shorten the drying zone. The hearth area for drying can be calculated as previously suggested and is found to be about 300 sq ft assuming 850oF exhaust. Two hearths of 175 sq ft each will provide some safety factor in the drying zone. If the furnace in practice behaved exactly according to theory, the extra drying zone area would result in the material being heated to 300oF to 500oF before entering the pyrolysis hearth, which would be no great change. The points all of these calculations are intended to bring out are: 1. 2. If the adsorbate will give no organic vapors at all, not even by steam distillation, until the carbon is bone dry, no afterburner should be needed. Such adsorbates are seldom encountered. Adding air to the top hearth of this furnace to consume residual CO and H2 could have

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raised the gas temperature to about 1300oF to 1400oF. Pyrolysis would be partly on Hearth #2 and partly on Hearth #3 and reaction would begin on Hearth #3. The reaction rate wanted would then be slightly reduced from 0.4 lbs carbon gasified/hr/sq ft. This might avoid a separate afterburner. 3. If the feed moisture content had been 40%, 2600 lbs/hr water instead of 1740 lbs/hr, there would have been an increased requirement for heat transfer of 963,000 BTU/hr, and one more hearth would be needed. Virtually all of the CO and H2 left from the reaction zone would have to be burned to satisfy heat requirements. Beyond 50% H2O in the feed, for this example, additional fuel would be required. Had Case A, B, or D for the reaction zone been followed, much less fuel would be used in the reaction zone, no surplus fuel would be available at 40% moisture feed (in fact some fuel saved in the reaction zone in some cases would be needed for the drying zone) and then any additional moisture over 40% moisture adds to the fuel bill. If the adsorbate load were less than shown in this example, its heating value less, or unavailable, then increasing or decreasing moisture content of the feed would surely translate directly into increasing or decreasing fuel cost. The same is true in cases where all the exhaust gas including moisture content must be reheated in an afterburner. In short, whether or not decreasing feed moisture content can save fuel depends on a number of other circumstances than the actual level of feed moisture content. 4. The relative hearth areas for drying pyrolysis and reaction change drastically with adsorbate loading and also with burner locations, steam and air entries. One can easily envision that if the example chosen called for 20% adsorbate loading and 20% of that to become fixed carbon, there would be one reaction hearth, one pyrolysis hearth and still a choice of two or three drying hearths at this furnace diameter. In fact, a smaller furnace diameter with half as much area per hearth would have been chosen to give two reaction hearths, still one pyrolysis hearth and perhaps five drying hearths.

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SECTION VI SOME BRIEF EXPERIMENTS REGARDING REACTION RATES Commercial active carbon made from bituminous coal and of fine pore size, screened to 12 x 16 mesh size was pyrolyzed in covered crucibles at 1740oF for ten minutes, split and a portion spent in a concentrated solution of Di-Nitro Toluene. The spent portion was pyrolyzed at 1200oF in a covered crucible and found to have gained weight from the virgin to the pyrolyzed condition so that 14% of the weight of a the spent pyrolyzed sample was char and 86% original carbon. The samples, virgin and char laden, were exposed to H2O, N2 gas mixtures in the apparatus shown in Figure 5 at various temperatures. Sometimes the reaction boat was entirely filled with carbon, but generally it was filled with sand as shown and covered with a carbon layer averaging one particle deep. Figure 6 shows the reaction rate of virgin carbon of fine pore structure made from bituminous coal, when exposed at 1600oF, with 20% H2O in the gas, using a single layer of carbon, as compared to a 3/8" deep layer with the boat containing all carbon and no sand. Note that the reaction rate more or less doubles when the full bed depth is used. Figure 7 shows the same comparison with 40% H2O and 1800oF, with carbon that was first devolatized at 1740oF. Unfortunately no deeper boats were available in time for experimental proof that still deeper layers would not further increase reaction rate, but other work did indicate very little reaction in the bottom layer, at this depth. Figure 8 shows the results of treating the same carbon with gases containing 40% moisture at various temperatures, and also the gasification rates for the same carbon after being laden with char from Di-Nitro Toluene as described above. The units for the gasification rate scale have been multiplied by two as stated in the label for the ordinate. The plot is exactly correct as shown, but this method of stating gasification rate units makes the actual numbers on the ordinate correspond to what we would extrapolate for full depth of carbon from the previous Figures 6 and 7 and correspond at least reasonably with what we observe in commercial multiple hearth furnaces. In Figure 9 the ratio for the two gasification rate curves of Figure 8 has been plotted again temperature. There is considerable indication that at least for Di-Nitro Toluene as an adsorbate and with only H2O

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present as a reactant, lower temperatures favor reaction with the char in preference to the original active carbon structure. In furnace design, however, this must be balanced against the desire to keep the required hearth area of the reaction zone from becoming excessively large and costly. The unfortunate part of this work is that there is no way of determining how much of the high gasification rate shown for char-laden active carbon is reaction with the char itself and how much is reaction with the original carbon structure. This lack of knowledge must be corrected in future experiments. At the present stage Figures 6 through 9 are shown only as preliminary information that may usefully indicate general trends. It would particularly be wrong to depend heavily upon the exact scale values.

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SECTION VII CONCLUSIONS There is no simple answer to reactivation of various carbons with various adsorbates, especially since different adsorption processes are differently affected by a change in the carbon structure and adsorption properties. Complete and conclusive laboratory studies of reactivation are generally impractical because several cycles of carbon expenditure and regeneration would be required, probably considering several grades or brands of carbon in parallel. The multiple hearth furnace has considerable flexibility in operation, but to make full use of this the furnace, as initially constructed, must be of more than the minimum size and must be equipped with burners and steam injection connections at more than the minimum number of locations. Reactivation furnace sizing and process results to be expected during reactivation, are a function of the adsorbate, the char left by pyrolysis of the adsorbate, initial or added mineral constituents which may catalyze or suppress reactions, the active carbon used, and the feed moisture content. Additionally, plant circumstances such as need or lack of need for retention of iodine number, scale of operation, cost of losses, and value of capital, should be taken into account during design. Small scale reactivators can be designed from precedence without serious hazard of inability to reactivate carbon at all, especially if the carbon and the adsorption job are similar to previous well known cases. It is unlikely that such precedence sizing and precedence operation will give optimum results in relation to carbon losses or quality. Large scale installations deserve some laboratory investigation of the regeneration effects of the particular carbon and particular adsorbate involved, and custom designed to suit the user's need for carbon quality, his economic situation, and to allow flexibility for optimal development during multiple cycles of in-plant carbon reactivation. There are several avenues of approach to more economical and/or more effective reactivation in multiple hearth furnaces, particularly control of pyrolysis and maximized adsorbate removal in that step while avoiding graphitization, investigation of the possible importance of high steam to CO2 ratios, investigation of reaction rate in relation to losses and per structure effects, and continued investigation of variations in the conditions under which fixed carbon gasification occurs while the carbon changes from "heavily char laden" to "nearly regenerated."

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REFERENCES 1. 2. 3. 5. West, Ronald E., "Effect of Porous Structure on Carbon Activation," USEPA, Water Pollution Control Research Series, Project No. 17020 DDC, June, 1971. Juhola, A. J., "Optimization of the Regeneration Procedure for Granular Activated Carbon," USEPA, Water Pollution Control Research Series, Project No. 17020 DAO, July, 1970. Goos, A. W. et al, "Some Experiments in Sawdust Carbonization," Forest Products Research Society, March, 1948. Mitzushima, Sanchi, "Rate of Graphitization of Carbon," Proc. 5th Carbon Conference, Volume 3, Page 439.

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TABLE OF APPENDED FIGURES Figure 1 - Furnace 2 - Bed Too Thin 3 - Rabbling with Proper Bed Depth 4 - Results of Example Process Calculation 5 - Apparatus (4) Tube Furnace Reaction Studies 6 - Gasification Rate of Carbon (Single Layer and Multi-Layer) vs Time 1600oF - 20% H2O 7 - Gasification Rate of Carbon (Single Layer and Multi-Layer) vs Time 1800oF - 40% H2O 8 - Gasification Rate of Char Laden and Virgin Devolatilized Carbon vs Temperature 9 - Ratio of Gasification Rate, Char Laden to Virgin Carbon vs Temperature 41 42 Page 34 35 36 37 38 39 40

(From here tl the end, nine 9 figures must be done on AutoCAD and inserted)

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Figure 1 Furnace

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Figure 2 Bed Too Thin

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Figure 3 Rabbling with Proper Bed Depth

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Figure 4 Results of Example Process Calculation

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Figure 5 Apparatus (4) Tube Furnace Reaction Studies

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Figure 6 Gasification Rate of Carbon (Single Layer and Multiple Layer) Vs. Time 1600oF 20% H2O

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Figure 7 Gasification Rate of Carbon (Single Layer and Multi-Layer) Vs. Time 1800oF 40% H2O

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Figure 8 Gasification Rate of Char Laden and Virgin Devolatized Carbon Vs. Temperature

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Figure 9 Ratio of Gasification Rate, Char Laden to Virgin Carbon Vs. Temperature

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