Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
  • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
  • C01F7/308—Thermal decomposition of nitrates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/51—Particles with a specific particle size distribution
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S423/00—Chemistry of inorganic compounds
  • Y10S423/09—Reaction techniques
  • Y10S423/16—Fluidization

Definitions

• the present invention relates to a novel process for the decomposition of aluminum nitrate nonahydrate to produce alumina.
• OMPI disclose the complete thermal decomposition of aluminum nitrate by (a) heating the metal nitrate in the form of a thin film to a temperature higher than the tempera ⁇ ture of its decomposition, (b) in the presence of steam to obtain a solid product and substantially complete recovery of all nitric acid.
• heating tubes described in the patent are their U-tube arrange ⁇ ment in the fluidized bed design with indirect heating coils. Such an arrangement would be impractical for using a condensing heat transfer fluid, such as steam, due to difficulty in withdrawing the condensate.
• Patent 3,898,043 the production of a material pre ⁇ senting no handling problems is stated as an objective.
• the patent discusses problems reported in the prior art of handling a sticky, glue-like material formed during the hydrolysis process.
• the A.D. Little patent purports to resolve this problem by an improved decomposition process.
• the A.D. Little patent admits to prior patents using steam for hydrolysis to recover substantially all the nitrate values from decompo ⁇ sition as nitric acid, but states that the problems of the prior art are overcome (col. 3, line 2. U.S. Patent 3,898,043).
• a method for the decomposition of aluminum nitrate crystals to alumina comprising the steps of:
• step (c) decomposing the product of step (b) at a temperature of between about 150 and about 200°C and recovering the heat of condensation of the resul ⁇ tant vapors; (d) further decomposing the product of step (c) in a fluidized bed decomposer at a tempera ⁇ ture of between about 300 and about 400 ⁇ C to reduce the residual nitrate concentration in the product to between about 5 and about 10 weight percent;
• step (e) decomposing the product of step (d) in a fluidized bed decomposer at a temperature of between about 500 and about 800°C to reduce the residual nitrate concentration in the product to below about 3 percent by weight;
• step (f) calcining the product of step (e) at a temperature of at least about 1000 ⁇ C.
• the naturally occurring concentration of water vapor in the first stage decomposer upwards of 70 volume %, is thought to be sufficient to retard the formation of noncon- densable NO x gases from nitric acid.
• OMPI described herein for the decomposition of aluminum nitrate to alumina, nitric acid, and various gases including NO ⁇ , H 2 0, and 0 2 involves feeding to the decomposition process washed aluminum nitrate nonahydrate (Al(N0 3 ) 3 .9H 2 0) crystals and adhering wash liquor obtained in the purification step as described in USP 3,804,598.
• the feed crystals and adhering wash liquor are sent to a melting step where the crystals are melted and the resulting feed solution is preheated before feeding to an evaporative step.
• the objective of the evaporative step is to provide as much evaporation as possible while producing a feed liquor to a low temperature decomposer that is sufficiently fluid to feed through the nozzle means into the fluidized bed.
• the low temperature decomposer may be fed directly with aluminum nitrate nonahydrate melt, or diluted melt, if desired, or other aluminum nitrate containing streams, such as impurity purge streams produced during prepara ⁇ tion of the purified ANN crystals.
• the evaporator is preferably a long-tube, once-through evaporator, primarily because of its economic advantages.
• The. long tube evaporator comprises a cylindrical closed-end shell supplied with steam through which relatively long heat-exchanger tubes extend. Liquor flows once through the tubes entering at one end and discharging at the other as a mixture of liquid and vapor.
• the tubes are sufficiently long to provide adequate pressure drop to insure an even distribution of feed liquor among the tubes.
• a vapor header and/or vapor-liquid separators separate the vapor from concentrated liquid. The concentrated liquid is removed from the evaporator and is not recycled. Vapor is routed to a suitable process heat recovery condenser.
• Various heat transfer media may be used on the shell side of the evaporator to supply heat.
• the heat flows through the tube walls to the liquor.
• Steam is the conventionally used fluid, although in this method a heat transfer medium flowing counter currently from a decomposition stage may also be used. It is within the existing art to design and operate a suitable once- through evaporator and select a suitable heat transfer medium to accomplish the concentration of the aluminum nitrate liquor in the evaporative step.
• the aluminum nitrate solution feeding the evaporator which is obtained by melting A1(N0 3 ) 3 .
• 9H 2 0 crystals and adhering wash liquor is in a concentration range of about 13 to 13.5% A1 2 0 3 -
• the evaporator vapor concentration is in the range of about 45 to 55% HNO., (by weight).
• the evaporator vapor head operating pressure is in the range of about 10-20 psig or even higher if desired, with a corresponding temperature range of about 125 to 165°C.
• the autogen ⁇ ous vapor pressure of the evaporator is sufficient to push evaporator discharge liquor through the decomposer feed nozzle without the need of a pump.
• a feed pump may be used, however, if required, but sufficient net positive suction head must be provided. Precautions must also be taken to prevent freezing of the concentrated aluminum nitrate solution in the pipe or pump. Insulation normally provides such protection.
• the evaporator vapor consists essentially of condensable nitric acid and water vapor with only minimal non-condensables, such as air dissolved in the feed.
• the heat of condensation of this vapor is recovered in a condenser on the melter, which melts the evaporator feed, and/or in heat sinks required for the preparation of ANN crystals.
• the heat of conden ⁇ sation and any sensible heat due to cooling of super ⁇ heated vapor or subcooling of condensate is transferred through the tubes to the melting crystals and adhering mother liquor or to the melt. It is within the state of the art to properly design and operate appropriate condensing systems to recover this heat for beneficial reuse, as aforesaid or for the generation of steam.
• the objective of the low temperature decom ⁇ poser is to remove HN0 3 and H 2 0 from the concentrated feed solution such that the evolved vapor will be condensable to aqueous nitric acid at elevated temperature with a minimum of noncondensable vapors present in order to maximize heat recovery for benefi ⁇ cial reuse.
• This objective is accomplished by- feeding the evaporator discharge to a first stage decomposer, of fluidized bed design, controlled in a
• OMPI temperature range 150 ⁇ C to 200°C with a preferred temperature range of about 170°C-190°C. At tempera ⁇ tures above about 195 ⁇ C undesirable amounts of NO ⁇ gases begin to form, the presence of which increases the difficulty of condensation in the heat recovery condenser.
• the fluidized bed may be a conventional design with a chamber, usually cylindrical, containing a fluidized bed of particles and a vapor disengaging section at the top.
• a gas distribution plate with tuyeres or pipe with downward facing holes is mounted horizontally, near the bottom of the decomposer as is common practice in design of a fluidizing bed. Fluidizing gas is admitted through this distribution plate. Fluidizing gas is provided by recycled vapor from the first stage decomposer. Liquor from the evaporator is fed to the fluidized bed under pressure through a nozzle or nozzles mounted usually in the side chamber below the level of the fluidized bed.
• Zenz (“Bubble Formation and Grid Design,” I. Chem. E. Symposium Series No. 30, 1968: Instn. Chemical Engineers, London, P. 3-8) discusses the importance of penetration into the fluidized bed for atomizing gas and liquid feed in providing a properly atomized feed that will minimize scaling and presents
• Penetration depth is a function of the velocity and density of the fluid through the nozzle, and the Zenz reference gives quantitative correlations for this relationship.
• Atomizing gas for the nozzle is supplied by vapor from the first stage decomposer. Steam or air may also be used for atomizing fluid, particularly for start-up.
• Heat is supplied to the fluidized bed indirectly through heat transfer tubes, preferably finned, mounted in the bed with one of various possible heat transfer media circulating inside the tubes, such as steam, molten salt, NAK, or aromatic mineral oils such as Dowtherm.
• a furnace fired by an acceptable fuel is used to provide heat to the medium.
• the medium is caused to circulate through heating means wherein it absorbs heat and then through the tubes of the fluid bed and back to the heating means.
• the heat transfer medium circulating through the second stage decomposer may be used to circulate through the first stage heat transfer tubes after it leaves the second stage.
• the particular alternate selected will depend on a heat balance and economics of the total system. It is within the state of the art to design such a heating system to minimize energy consumption, while providing the heat required to achieve the desired decomposition and temperature level.
• a preferred arrangement of the heat transfer tubes within the fluidized bed is a vertical configuration with steam entering at the top and condensate leaving at the bottom.
• the U.S. Atomic Energy Commission (publications cited above) used horizontal bayonet type heaters with NAK as the heat transfer medium.
• the A.D. Little patents discussed above show vertical U-tube arrangements of the heat transfer tubes, which would be satisfactory for single phase media but not for condensing media, such as steam. Condensate removal would be a problem in the latter case.
• the heat input is controlled to maintain a temperature that will insure a sufficiently low level of noncondensables in the vapor.
• An acceptable non- condensable level can be judged by the heat transfer coefficient in the heat recovery device. The lower the noncondensable level, the higher will be the heat transfer coefficient. Maximizing the heat transfer coefficient will maximize heat recovery, which is a major objective of the first stage decomposer.
• the preferred control temperature is about 170°C-190 ⁇ C.
• the volumetric percent of water vapor in the first stage decomposer off-gas resulting from stoichiometry of the decomposition during proper operation is in the range of about 65 to 75 percent. This concentration of water is considerably above that indicated in the A.D.
• Vapors from the first stage decomposer are condensed, and the heat of condensation is recovered
• O PI to provide heat to various heat sinks in the process, particularly in the aluminum nitrate nonahydrate purification step. Any noncondensables that may be present are sent to an acid reconstitution area.
• Particle size control in fluidized beds is discussed in some detail in the publication by the AEC previously cited.
• the significant variables in particle size control are nozzle gas-to-feed volumetric ratio, bed operating temperature, fluidizing gas velocity and feed solution concentration.
• the rate of elutriation of fines at a given temperature usually increases as nozzle atomizing gas-to-liquid feed ratio increases.
• the recovered portion of these fines is recycled to the bed, and if additional fines are needed to provide sufficient seed particles to maintain particle size control controlled amounts of fines recovered from the off gases of the second and third stage decomposers described herein ⁇ after may be added also.
• the overall heat transfer coefficient from the heating tubes to the fluidized bed primarily depends on the mass median particle diameter and the superficial fluidizing air velocity. At a fixed fluidizing air velocity, the heat transfer rate increases with a decrease in the particle size.
• Spray drying per se is not desired in the fluidized bed calcination process because the resulting small, low-density particles are subject to rapid elutriation. Spray drying is deliberately minimized by maintaining the fluidized bed level high enough to ensure submergence of the spray zone within
• the fluidized bed decomposer is equipped with a dust collection system, preferably a cyclone, and collected dust is returned to the fluidized bed. Any uncollected dust accompanies the off-gas to the heat recovery unit, wherein it dissolves in the condensed acid.
• high temperature refers to a temperature of between about 540°C and 800°C, medium temperature to a temperature of between about 300 ⁇ C and about 400°C and low temperature to a temperature of between about 150 and about 200 ⁇ C.
• the primary objective of the second and third stage decomposers is to remove most of the remaining nitrate from the solid particles discharging the first stage decomposers.
• this further decomposition may be accomplished in a single unit, the preferred method is to divide the operation into medium and high temperature steps to minimize energy consumption and reduce equipment size.
• the preferred embodiment employs fluidized bed decomposers in a single vertical shell with characteristics as described previously for the low temperature stage fluidized bed decomposer.
• fluidiz ⁇ ing gas passes countercurrently from the third (high temperature) stage to the second (medium temperature) stage. Fluidizing gas for the high temperature stage is provided by recycling a portion of the off-gas from the medium temperature stage decomposer.
• Vapor from the medium temperature third stage that is not required for fluidization in the high temperature stage is routed to a sensible heat recovery unit, such as a waste heat boiler, and then to an acid reconstitution process.
• a sensible heat recovery unit such as a waste heat boiler
• off-gas from either the second stage or the third stage may be recycled on itself to
• S URETY _ ' OMPi provide fluidizing and atomizing gas.
• the remaining off-gases from the stages are routed to a sensible heat recovery unit, such as a waste heat boiler, and then to acid reconstitution.
• a sensible heat recovery unit such as a waste heat boiler
• acid reconstitution During the start-up steam or air may be used for fluidizing gas.
• Solid particles pass from the second stage decomposer to the third stage decomposer and then to the calciner.
• the preferred method is gravity overflow of solids from the first to the second stage, second to third stage and third to calciner.
• An air lock device such as a rotary air lock may be necessary to prevent bypassing of fluidiz ⁇ ing gases through the solids transport line.
• screw conveyors and screw feeders may be used with appropriate air lock devices.
• Drag conveyors or inclined screw conveyors may be required if space limitations prevent gravity feeding. In order to minimize the possibility of alpha alumina formation, it is desirable to minimize the residence time of the solid particles in the fluidized bed.
• Alpha alumina production in the second or third stage decomposer is undesirable, because it is virtually insoluble in nitric acid. Consequently, a solids trap would have to be provided in the reconstitution process to intercept dust particles escaping the dust collection system on the second or third stage decomposers. In addition, alpha alumina tends to erode the equipment.
• Residence times of less than an hour in the decomposers can permit the necessary transfer of heat to the solid particles for the desired decompo ⁇ sition.
• the second stage decomposer residence time will be less than about 4 hours, and the third stage residence time will be 2 hours or
• the second stage fluidized bed decomposer is operated within a temperature range of about 300° to 400°C to reduce the residual nitrate concentration in the solid product to 5 to 10 weight percent N0 3 -
• the third stage decomposer operates in the range of about 540 to 800°C to reduce the residual nitrate in the solid product to less than 2 weight percent.
• the primary components of the second and third stage decomposer vapors are H 2 o upwards of about 50 volume %, and NO, N0 2 and 0 2 in concentrations approaching equilibrium at the operating temperature.
• heat is supplied to the second and third stage decomposers indirectly in a manner similar to the method of the first stage decomposer.
• An appropriate heat transfer medium such as molten salt or NaK, circulates through heat transfer tubes, preferably finned, mounted within the fluidized bed.
• the heat transfer fluid circulates countercurrently, passing first into the third stage decomposer and then into the second stage, before returning to the furnace to be heated. This countercurrent method is used to achieve optimum heat economy. Additional heat transfer fluid is added directly to the second stage circulation system, if required.
• the heat transfer fluid may also be circulated from the second stage to the first stage and then back to the furnace for reheating.
• the heat transfer fluid itself is heated in a furnace or furnaces fired by an appropriate economical fuel such as coal and caused to circulate as described hereinabove.
• NaK is used as the heat transfer medium a portion of it must be cooled and filtered to remove sodium oxides.
• the cooling may be done by circulating NAK through the first stage decomposer, the evaporator, or other appropriate heat sinks. The particular method used will depend on process requirements and economics.
• fluidized beds are preferred for the second and third stage decomposers, other types of calciners may be used. Indirect heat exchange is required however, so that the off-gas will be reconstitutable to nitric acid in an economical manner. Selection of particular decomposition equipment will depend on process economics.
• the final calcination step is designed to remove the residual nitrate and substantially all of the water from the solid product to give a metallurgi ⁇ cal, chemical or refractory grade of alumina.
• the calcination may be performed in a fluidized bed or other type of calciner such as a rotary.
• the preferred embodiment is a fluidized bed calciner.
• the calci ⁇ nation is performed in a temperature range of about 1000 to about 1200 ⁇ C.
• Heat is supplied directly by combustion of a clean fuel, such as natural gas or a suitable fuel oil.
• a clean fuel must be used in the calcination step to prevent contamination of the alumina. It is well within the known art to design and operate an effective, economical calcination
• the waste heat boiler is equipped with appropriate pollution control equipment for removing alumina dust. Additional NO ⁇ control equipment may be added if desired, but the various published refer ⁇ ences on control of NO ⁇ in stationary fired equipment indicates that no further treatment will be necessary if the system is designed and operated properly.
• the decomposition method thus is begun by melting aluminum nitrate nonahydrate crystals prepared in the fractional crystallization of ANN (USP 3,804,598) and comprising an equivalent concentration of alumina, usually of around 13 to 13.5 weight percent.
• the melting is preferably performed with heat supplied from the heat of condensation of nitric acid vapors.
• the melted nitrate is pumped at a controlled rate into an evaporator, which includes vapor-liquid separation means, of a particularly preferred type, commonly referred to as a long tube vertical evaporator.
• a liquor comprising about 18 to 22% alumina concentration at a temperature preferably within the range of about 150 to 165 ⁇ C; and a resultant vapor phase with a nitric acid concentration within the range of about 48 to 52% HN0 3 a t a super-atmospheric pressure.
• the pressure may be selected as desired and controlled within the range of about 5 to 30 psig, or higher if desired.
• the vapor is condensable at elevated temperatures to nitric acid solutions as is required for recovery of the heat of condensation for supply to the melter or to other similar type equipment within the plant or if desired for the generation of low pressure steam.
• the concentrated liquor is pushed by the pressure developed in the evaporator through a suitable conductance means and through a suitable nozzle into the bed of a fluidized bed reactor means wherein the temperature of the bed is maintained at about 150 to about 200°C by indirect transfer from a suitable fluid heat supply means, as for instance steam or NaK, and wherein the fluidizing bed particles, comprising partially decomposed aluminum nitrate material, grow by accretion of thin layers of the said liquid which in turn partially decompose to the composition of the said bed particles with formation of a vapor phase comprising nitric acid and water.
• a portion of the vapor is condensed externally of the reactor, at elevated temperature, to recover as useful heat the heat of condensation thereof and a second portion is compressed by a suitable compressor means, with suitable interstage coolers as may be required to prevent the temperature of the vapors from exceeding about 250°C, preferably 225 ⁇ C.
• the compressed vapors are returned to the fluidized bed to supply the required fluidization gas and any atomizing gas that may be required by the spray nozzles. In this manner, no extraneous gases, as for instance air or steam, need be supplied to the unit during normal operation.
• the condition of the gases is judged by monitoring, in manner well known to the art, the heat-transfer coefficient of the heat-of-condensation- recovery means, which in known manner will decrease as the concentration of non-condensable gases increases.
• the temperature of the bed is lowered, in 5 to 10° increments, until the heat transfer coefficient has regained its desired value.
• the bed temperature is maintained at the highest temperature level that yields a proper heat transfer coefficient to provide a sufficient rate of decomposition of the liquid layer on the particles to solid material, whereby the tendency of..the particles to stick to one another is minimized.
• a second indirectly-heated decomposer which may be a rotary kiln but preferably is a fluidized bed, which is preferred because of the high heat transfer coefficients obtained therein, operating at a temperature upwards of about 300 ⁇ C and preferably within a range of about 340 to 400 ⁇ C at which temperature further decomposition of the partially-decomposed aluminum nitrate material proceeds to a nitrate composition of within a range of about 5 to 10 weight percent, at convenient solid residence times in the bed of about .1 to about 4 hours, with the production of nitrous gases consisting essentially of NO, 0 2 , o 2 and H 2 0.
• a portion of the nitrous gases exiting the bed is compressed in suitable compressor means and returned to provide the fluidizing medium of the bed and the remainder is passed to a nitric acid reconstitution system through suitable means which may include means for recovering a portion of the sensible heat contained therein.
• suitable means which may include means for recovering a portion of the sensible heat contained therein.
• Higher decomposer temperatures and longer residence times than the stated preferred ranges may be employed if desired.
• increase of the residence time beyond that dictated by best design of the indirect-heat-transfer means requires the recirculation of larger portions of the off-gases
• the degree of decomposition of the partially-decomposed solid .aluminum nitrate material is relatively unaffected by temperature within the range of about 370 to about 540°C. We prefer there ⁇ fore to operate the bed at the lowest practical temperature that permits attainment of the aforesaid 5 to 10% nitrate concentration of the decomposed material at minimum practical solids residence times, which temperature does not exceed 400°C.
• Excess bed volume accumulating in the second decomposer by virtue of the continuous feed from the first decomposer, is fed in known manner to a third indirectly-heated decomposer, preferably a fluid bed for reasons stated above, in which preferably the fluidized bed is maintained, by virtue of the indirect heat transfer, at bed temperatures above about 540°C and preferably within the range of about 675 to about 725°C.
• a test subjecting the second decomposer product to rapid heat-up rates approaching those attainable by injecting solids into a fluid bed yielded residual nitrate contents of about 3-1/2 to 5% and LOI values of 5 to 8% at temperatures within the range of about 540 to 620°C, residual nitrate values of less than 1% and LOI values of 3 to 5% at about 700 ⁇ C, and nitrate values near zero at about 800 ⁇ C. It was also observed that at the cited nominal retention times little or none of the alumina value is converted to the alpha crystal modification. Although an amount of alpha
• OMPI alumina may be desired in the final metallurgical grade alumina, it is not desired in the decomposers because the alpha modification is highly abrasive, and is also subject to autogenous grinding in the beds with attendant production of excessive fine materials which must be removed from the gaseous effluent.
• the substantial importance of residence time is indicated by the experience with the fluid bed aluminum nitrate decomposer of the AEC wherein, at a bed temperature of about 400°C but with solids hold up times of the order of 50 hours, nitrate concentrations as low as 3% have been obtained with the simultaneous production of substantial amounts of the alpha alumina modification. Dust formation was so severe that boron compounds had to be added to the feed to the bed to suppress the alpha alumina formation.
• the decomposed product of the third fluidized bed preferably containing less than 1% nitrate, is moved by known means to a final direct-fired calcination means and exposed to temperatures upwards of about 1000 ⁇ C, depending upon the permissable final water content, to complete the conversion to metallur ⁇ gical grade alumina.
• a final direct-fired calcination means preferably containing less than 1% nitrate
• temperatures upwards of about 1000 ⁇ C depending upon the permissable final water content
• the calciner is operated at slightly less than stoichiometric air-to-fuel ratio to reduce the N0 ⁇ to N 2 , and any unburned fuel is subsequently oxidized with excess air at lower temperatures in a waste-heat boiler, a method of operation that is well known in the art of operating stationary fired furnaces and boilers.
• Each of the two shell sections had steam supply means (100 psig plant process steam) at its top and condensate removal means at its lower end.
• the titanium tube was connected through a pressure-smoothing chamber to a metering pump at the lowest end; the two sections of the tube were joined together at the center and the top end of the tube extended about 18 inches into a 3-inch I.D. x 4 ft. long Pyrex glass pipe, which served as the vapor head.
• the said Pyrex glass pipe was fitted at the top with a pressure gauge and a vapor exhaust pipe connected through a ball valve to a water-cooled condenser.
• the bottom of the glass vapor head was fitted with a discharge pipe to the fluidized bed decomposer.
• the fluidized bed decomposer was fabricated of 304 stainless steel pipe consisting of an 8-inch diameter by 36-inch tall fluidized bed section and a 12-inch diameter by 18-inch tall vapor head. Flui ⁇ dizing air was supplied at the bottom of the column through a plenum chamber and gas distribution plate with fourteen tuyeres. The air supply is heated with shell and tube steam heaters using plant 100 psig steam. At the top of the vapor head a 4-inch pipe outlet was connected to a cyclone dust collector. The 4-inch cyclone overflow line was connected to a water cooled condenser, and the outlet of the con ⁇ denser was connected to a wet scrubber.
• Concentrated liquid feed from the once through, long tube evaporator was introduced to the fluidized bed through a modified, concentric, air atomizing nozzle.
• the nozzle was a Spraying Systems Co., Wheaton, Illinois standard J Nozzle body with spray set up number 1-A in which the air cap hole size was increased to 1/8-inch to allow greater flow of atomizing air.
• Atomizing air and fluidizing air were metered by rotameters.
• Manometer taps were provided at the top of the vapor head, at two points 10 inches apart near the bottom of the fluidized bed and in the plenum chamber. With these measurements, the fluid ⁇ ized bed height could be determined.
• Thermo-couples connected to a multipoint strip chart recorder were provided at the bottom of the fluidized bed, at the top of the bed on four quadrants, at the top of the vapor head, in the feed line, and in the air supply line.
• the cyclone dust collector downleg was equipped with a valve, which was periodically opened for discharge of dust.
• a product discharge pipe at the bottom of the fluidized bed, equipped with a valve.
• the top of the vapor head was equipped with a valved pipe through which dust or product could be returned to the bed.
• Heat was supplied to the bed by 225 psig steam, generated in a portable generator, through nine stainless steel 3/4-inch by 12-inch long heat exchanger tubes equipped with sixteen 5/8-inch by 1/16-inch spot welded, longitudinal fins for a total heat transfer area of approximately 17.7 square feet.
• the tubes were mounted vertically in the fluidized bed with eight tubes on the circumference and one in the center. Steam was admitted through a distribution block at the top of the assembly, and condensate was collected in a manifold at the bottom of the assembly and discharged through a steam trap.
• the feed tank, metering pump, evaporator, decomposer and transfer lines were insulated and steam traced to prevent heat loss.
• Concentrated liquor was discharged from the long tube, once through evaporator under the pressure existing in the evaporator vapor head through a 1/4-inch feed line into the decomposer feed nozzle. Atomizing air was metered into the feed nozzle to provide a calculated penetration depth of 3/4-inch. This penetration depth was found to be important in avoiding nozzle scale formation.
• the initial pressure (after start-up) of the evaporator vapor was set to 7 psig.
• the feed rate drifted down to about 4.8 lb/hr. during the 90 minutes of steady operation, and the pressure was increased to 11 psig.
• the steam pressure on the second section of the evaporator also was lowered to 65 psig to reduce the evaporator discharge concentration.
• the increased viscosity of the higher concentration feed made flow of evaporator discharge to the decomposer nozzle difficult.
• the normal operating temperature in the fluidized bed was 370°F; the normal steam- ressure in the decomposer heat exchange tubes was 225-230 psig (397-401 °F). This corresponded to a delta T of 25 to 30 ⁇ F between the steam and the fluidized bed.
• the superficial fluidizing velocity in the fluidized bed was 0.30 feet per second.
• the fluidizing and atomizing air had been heated to 250°F.
• the starting material for the fluidized bed was calcined alumina.
• a sample of the decomposer product was withdrawn, dissolved in hot water, and the soluble portion analyzed.
• the original alumina was insoluble in water, so the percent soluble was a measure of the extent of the decomposition.
• the soluble portion of the sample analyzed as 47.8% 1 2 0 3 and 38.7% HNO., by weight. Examination of the feed nozzle revealed that no scaling had occurred during the run.
• a screen analysis was also performed on a sample of decomposer product. A screen analysis of the original metallurgical alumina is given for comparisons.
• a comparison of the two screen analyses demonstrates the marked growth of the original alumina particles.
• the feed solution introduced below the level of the fluidized bed, coated the bed particles, and as the water and nitric acid evolved, layers of basic aluminum nitrate were deposited on the existing bed particles.
• This example demonstrates the successful evaporation of aluminum nitrate solution of very approximately melted aluminum nitrate nonahydrate composition to a concentration exceeding 18% 1 2 0 without precipitation of basic aluminum nitrate with a condensable vapor of approximately 45% HNO.,.
• the run also demonstrated the successful feeding of -aluminum nitrate solution through an atomizing nozzle using only pressure generated by evaporation in the long tube evaporator into a fluidized bed without scale formation.
• Vapors produced in the decomposer were passed through a water-cooled, low temperature (27-43°C) condensor wherein substantially all of the condensable HN0 3 and water vapors were condensed; and the residual tail gas was sampled and analyzed for N0 ⁇ values.
• the cool condensate obtained during this test assayed 47.3% HN0 3 and 1.7% dissolved alumina by weight. It would be satisfactory for recycling to a process comprising the extraction of alumina values from, for instance, clay to prepare fresh aluminum nitrate feed liquor for the evaporator.

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• 1979
  • 1979-07-27 US US06/061,297 patent/US4223000A/en not_active Expired - Lifetime
• 1980
  • 1980-05-09 JP JP50165680A patent/JPS56500930A/ja active Pending
  • 1980-05-09 WO PCT/US1980/000552 patent/WO1981000401A1/en not_active Ceased
  • 1980-07-08 ZA ZA00804110A patent/ZA804110B/xx unknown
  • 1980-07-09 CA CA355,768A patent/CA1122781A/en not_active Expired
  • 1980-07-25 AR AR281919A patent/AR222886A1/es active
• 1981
  • 1981-02-24 EP EP19800901344 patent/EP0032493A4/en not_active Withdrawn

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