AU601873B2

AU601873B2 – Steam producing process and products
– Google Patents

AU601873B2 – Steam producing process and products
– Google Patents
Steam producing process and products

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Publication number
AU601873B2

AU601873B2
AU23636/88A
AU2363688A
AU601873B2
AU 601873 B2
AU601873 B2
AU 601873B2
AU 23636/88 A
AU23636/88 A
AU 23636/88A
AU 2363688 A
AU2363688 A
AU 2363688A
AU 601873 B2
AU601873 B2
AU 601873B2
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AU
Australia
Prior art keywords
steam
pressure
decomposer
water
product
Prior art date
1983-11-07
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Application number
AU23636/88A
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AU2363688A
(en

Inventor
Chanakya Misra
Steven William Sucech
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Howmet Aerospace Inc

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Aluminum Company of America
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1983-11-07
Filing date
1988-10-11
Publication date
1990-09-20

1988-10-11
Application filed by Aluminum Company of America
filed
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Aluminum Company of America

1989-01-19
Publication of AU2363688A
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patent/AU2363688A/en

1990-09-20
Application granted
granted
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1990-09-20
Publication of AU601873B2
publication
Critical
patent/AU601873B2/en

2004-07-23
Anticipated expiration
legal-status
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Status
Ceased
legal-status
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Classifications

F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING

F22—STEAM GENERATION

F22B—METHODS OF STEAM GENERATION; STEAM BOILERS

F22B1/00—Methods of steam generation characterised by form of heating method

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C

C01B5/00—Water

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

C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water

C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination

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

C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water

C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination

C01F7/445—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination making use of a fluidised bed

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

C01P2002/00—Crystal-structural characteristics

C01P2002/02—Amorphous compounds

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

C01P2004/00—Particle morphology

C01P2004/01—Particle morphology depicted by an image

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

C01P2004/00—Particle morphology

C01P2004/01—Particle morphology depicted by an image

C01P2004/03—Particle morphology depicted by an image obtained by SEM

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

C01P2004/00—Particle morphology

C01P2004/60—Particles characterised by their size

C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

C01P2006/00—Physical properties of inorganic compounds

C01P2006/12—Surface area

Description

AUSTRALIAc187 Patents Act COMPLETE SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged: 00 0 000 00 00 0 0 0 0 0 000 00 00 0 0 0 0 0 00 0 0 O0 0 00 0 00 o0 0 0 00 0 00 0 0 0 0 00 0000 0 0 o 0 0 000000 0 0 0 000000 0 0 Complete Specification Lodged: Accepted; Published: Priority amendments made under Sectibn 49 and is cbrrect for printing.
Related Art: APPLICANT’S REF.: DIV. OF 30963/84 Name(s) of Applicant(s): ALUMINUM COMPANY OF AMERICA Address(es) of Applicant(s): Actual Inventor(s): 1501 Alcoa Building Mellon Square Pittsburg, Pennsylvania 15219 UNITED STATES OF AMERICA Chanakya Misra Steven William Sucech
I
Address for Service is: PHILLIPS, ORMONDE AND FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne, Australia, 3000 Complete Specification for the invention entitled: “STEAM PRODUCING PROCESS AND PRODUCTS”
I
The following statement is a full description of this invention, including the best method of performing it known to applicant(s): PI9/3/84 1 B This application is divided from Australian application 30963/84 and the disclosure of application 30963/84 is hereby incorporated by reference into the present application.
It is an object of the invention to provide a method of producing steam for steam-consuming processes.
This, as well as other objects which will become apparent in the discussion that follows, are achieved according to the present invention, by heating a water-containing, solid substance for generating steam.
According to the prife invontc-iorejiE providod-y in a process utilizing steam, the method of producing at S least a portion of said steam, comprising heating a solid substance at a temperatu greater than 250 0 C in a decomposer at a pressure gr ter than one atmosphere gage pressure for decomposing said subst ce to drive off chemically combined water, and (ii) for yielding said wate in the form of S steam at a pressure greater than one at sphere gage pressure, removing said steam fr the decomposer, and capturing said steam for said process, said process being external to said ecomposer.
The invention has part’ ularly advantageous application in conjunction ith water removal from aluminum r| hydroxide to prepare alu ina particularly as feed for the Hall-Heroult electrol ic process for producing aluminum metal. The aluminu hydroxide, in a moist or dry condition, is heated in a de omposer under self-fluidizing conditions, or fluidized b steam, and without contact by exhaust gases from fuel co ustion, so that pure steam is obtained.
Pressures re typically in the 20 to 500 psia range, in order t t the steam will be at pressure suitable for use.
This eam is available for use as process steam in a Bayer ref* ing plant and also for power generation in usual steam e gines or turbines. New alumina products are obtained. An 2 L i According to the present invention there is provided a method of producing and utilising steam in a steam consuming process, said method comprising: producing steam in a first stage of the process: heating a solid substance having chemically combined water of crystallisation at a temperature greater thLn j 250 0 C in a decomposer at a pressure greater than one atmosphere gage pressure such that: said substance is decomposed to drive off at 7east a portion of its chemically combined water of crystallisation, and (ii) said water in the form of steam at a pressure greater than one atmosphere gage pressure is produced in said decomposer; 0 00 o 00 removing said steam from said~ decomposer; and 00V capturing said steam for use in said process; and 0 C a 00(11) using said steam from said first stage in a second stage of said process conducted outside said decomposer.
00 0 0, 0 0 20 application in conjunction with water removal from aluminum hydroxide to prepare alumina particularly as feed for the Hall-Herc’ult electrolytic process for producing aluminum metal. The aluminum hydroxide, in a moist or dry condition, is heated in a decomposer under self-fluidizing 000conditions, or fluidized steam, and without contact by exhaust gases from fuel combustion, so that pure steam is obtained. Pressures are typically in the 20 to 500 psia range, in order that the steam will be at pressure suitable for use. This steam is available for use as cc cc ccc 30 process steam in a Bayer refining plant and also for power generation in usual steam cngines or turbines.
New alumina products obtained from the preferred embodiment of the method of the present invention are the subject of Australian Patent No. 587934, herein incorporated by reference. An important advantage achieved is that there is less breakage of particles during water removal than is the case during the f lash or kiln calcination, prior art techniques of water removal.
~TAB
An additional advantage is that an alumina product can be obtained which is characterized by a reduced amount of the parallel fissuring typifying alumina from atmospheric pressure, flash and kiln calcination of aluminum hydroxide. The alumina product obtained by the preferred 1 embodiment of the method of this invention is stronger than i” c
AB
B-2bthe flash or kiln calcination, prior art techniEu- water removal. An additional advantage is t an alumina product can be obtained which is cha erized by a reduced ampunt of the parallel fj Ing typifying alumina from atmospheric pressur ash and kiln calcination of aluminum hydroxide.
alumina produced in atmospheric-pressure calcination processes, as indicated by lower attrition indices. As an added benefit, differential calorimetry tests show the process using about 10% less energy as compared to flash or kiln calciners, this saving being in addition to the energy I savings achieved by utilizing the steam coming from the i aluminum hydroxide.
The production of essentially pure steam from aluminum S hydroxide (alumina trihydrate, or “hydrate” for short) can Sbe carried out using a variety of energy sources. Both direct and indirect heating methods are possible. The heating method most applicable for retrofit to an existing calciner is the use of hot combustion gases from the furnace I section of the calciner to indirectly heat the hydrate.
Other heating methods for indirect heat transfer include electrical resistance heating, hot oil or salt baths, heating by inductance, lasers, plasmas, combustion of coal, microwave radiation, nuclear and chemical reactors. The heat source may originate from another process, such as the use of hot gases from a coal gasification unit to decompose i hydrate, or the hydrate may be indirectly decomposed while acting as a coolant to control a highly exothermic reactor.
Direct heat transfer methods for drying and decomposition of hydrate to form an alumina product and pure steam include the use of in-bed, electrical resistance heating, microwave generators, lasers and/or superheated steam.
Figures 1A to 1C compose a process flow schematic of an embodiment of the invention.
3 T 3– F- U
!I
iB Figure 2 is a schematic of an alternative apparatus for use in the process of Figure i.
Figures 3 and 4 are scanning electron micrographs, at 12,000 times magnification; Figure 3 being of a product of the invention and Figure 4 being of a product of the prior art.
A. Continuous Process The invention finds a preferred setting in conjunction with the Bayer process for producing alumina from bauxite.
The Bayer process utilizes steam, for instance, in its digester, where bauxite ore previously crushed in a grinder is treated with sodium hydroxide solution to dissolve aluminum values. Steam provides the heat needed to maintain the temperature and pressure conditions of the slurry in the digester. These are typically in the 1000 to 3000C an3 100 to 500 pounds per square inch absolute pressure (psia) ranges.
Steam is also used, in the evaporator of a Bayer 2Q. plant.
Taking the digester as an example, the steam may heat the slurry directly by being injected right into the slurry for instance, through a pipe opening below the slurry surface. Alternatively, the steam may heat the slurry I indirectly by supplying heat to a heat exchanger in contact with the slurry.
In general, it is of advantage that the steam be completely H 2 0, thus contaning no diluting gases such as air. For instance, the steam should be at least 50 volume-% i 30 water, preferably at least 75 volume-% water, and more preferably at least 94, or even 100, volume-% water. One particular advantage of steam which is pure H20 is its characteristic of condensing at a constant temperature, such constant temperature being a function of pressure. This is of use for temperature control in the process consuming the steam. For instance, 110 psia pure-H 2 0 steam condenses at about 175°C and can be used to maintain a digester temperature of about 150 0 C, the 25 C difference being provided for heat transfer driving force.
JC 4 _i L i 1- I j -~Ei ii i i iii;. ~;-rL~4Lri; ;i~i If the steam is diluted with other gases, such as air, which is uncondensable at temperatures of interest for steam-consuming processes, the H20 in the steam condenses over a range of temperatures (as will be evident from the known variation of dew point with water vapor partial pressure). Additionally, the uncondensable gases represent a dilution of the great heat release obtained as I2 condenses, the heat released by the uncondensable gases as Sthey drop in temperature being relatively insignificant.
A diluting gas such as C0 2 for instance resulting from combustion of a fuel containing carbon, is extremely disadvantageous in the case of direct steam heating in P I Bayer process digester, because the CO reacts with the 2 NaOH needed to dissolve the aluminum values in the bauxite.
The NaOH loss occurs by reaction of the type 2NaOH C0 2 Na2CO3 In the present invention it is proposed to carry out at least the initial part of the calcination of aluminum hydroxide, “hydrate”, by indirectly or directly heating the hydrate in a suitable, pressurized container vessel. This enables collection of steam released under pressure by the evaporation of the free moisture and removal of the i chemically bound water. The separated steam can then be I used in other areas of the alumina refining plant, resulting in considerable energy savings. The partly calcined alumina A product obtained from the pressure decomposition vessel may then be calcined in conventional calcination equipment such as a rotary kiln or a stationary calciner.
Thus, according to one embodiment of the present invention, steam for the Bayer process is obtained by heating aluminum hydroxide, Al(OH) 3 to at least partially calcine it, with the evolved steam being captured for transmission, to the digester. This is unlike previous methods of calcining Al(OH) 3 where, rather than being steam, the gases coming from the calcining are fuel exhaust containing water from the burning of the fuel and from the Al(OH) 3 an example of an analysis being, in 5 L i volume-%, 8% CO 2 55.3% N 2 2.5% 02, and 34.2% H 2 0, as taken from the table on page 34 of Schuhmann’s Metallurgical Engineering, Volume 1, Engineering Principles, Addision Wesley Press Inc., Cambridge, Massachusetts (1952). In such processes, the burning, or burned, fuel-air mixture directly contacts the Al(OH) as it is being dehydrated.
A particular advantage of Al(OH) as a solid used as I a source of steam is that the steam is essentially 100%, S 10 i.e. pure, H 0. This is to be contrasted with, saw dust, where the steam might be contaminated with organic compounds also volatilizing during the liberation of the steam.
It is estimated that about one-third of the steam requirement for a Bayer process can be supplied from the water in the Al(OH) 3 product.
A principal equipment of the process is a decomposer vessel. Though the decomposition process may be carried out by any combination of a pressure vessel and indirect heating, an efficient method for carrying out this process is by the use of a fluidized bed. Our investigations have shown that a bed of the hydrate exhibits self-fluidizing behavior on heating due to steam release on decomposition.
High rates of heat transfer to the decomposing hydrate can thus be attained by utilizing this self-fluidizing characteristic.
I With reference now to Figure 1, it illustrates an embodiment where the process of the invention is used in conjunction with a Bayer process. The segments of Figure 1 show as follows: Figure 1A A Bayer process utilizing steam from the process of the invention; Figure 1B Generating steam according to the invention; Figure 1C A flash calciner for bringing partially calcined alumina from Figure 1B to a final, desired water-content suitable for use as metallurgical alumina.
JC 6- 26- A_ I 1 jFirst with respect to Figure 1A, bauxite from bauxite stockpile 10 is ground in grinder 12 and then sent to digeste 14, where it contributes to the solids portion of the slurry in the digester. The liquid portion of the slurry is a suitably concentrated, for example by evaporator 16, NaOH-containing, aqueous solution.
Following digestion, the slurry is fed to residue separation equipment 18, which removes solids remaining from Sthe digestion. Then, solution, free of solids, is fed to precipitator 20, where aluminum hydroxide, Al(OH) 3 crystalline form gibbsite, is precipitated. The resulting slurry is run through filter 22, to yield a solids portion j| through line 24 and a liquids portion through line 26 going to evaporator for concentration for recycle back to digester 14. The Al(OH) 3 filter cake solids in line 24 will have both free moisture, to the extent of 8-16 weight-%, and chemically bound water at 34.5 weight-% on dry Al(OH) 3 Other steps may, of course, be in the Bayer process, for instance a causticization using lime. Thus, Figure 1A S 2 is for the purpose of illustrating how the steam generating process of the invention may be combined with a Bayer process in general, as an example of a steam consuming process, rather than to go into the many fine points of a Bayer process.
According to the invention, steam is generated for Ssupply to the digeste’ and evaporator portions of the Bayer process through lines 28 and 30 by heating Al(OH) 3 in decomposer 32 (Figure 1B) to drive off free moisture and chemically combined water from the Al(OH) 3 The equilibrium state of the removed water is the gaseous 14 state. The decomposer is operated under pressure of suitable magnitude above one atmosphere (14.7 psi) gage pressure to give the temperature desired during condensation of the steam in the Bayer process. The pressure may, for instance, be in the range 20 to 250 psig (pounds per square inch gage pressure).
Feeder 34 is provided to transfer the Al(OH) 3 from essentially atmospheric pressure in line 24 to the elevated, -C 7 0 I I e.g. 20 to 250 psig, pressure of the decomposer 32. Feeding equipment of the type described in pages 99 to 120 of the publication “Workshop on Critical Coal Conversion Equipment” for continuous feeding of coal from a low pressure state to a high pressure state may be used for feeder 34. For example, a suitable feeder would be the Lockheed Kinetic Extruder shown in Slide 6.22 on page 113 of that publication. Alternatively, the feeder could be a pair of lock hoppers, with one feeding under elevated pressure while the other is filling under atmospheric pressure, and vice versa, as illustrated by the Ducon Coal Feed System in Slide 6.26 on page 115. Further identifying information on this “publication is as follows: Huntington, W.V. October 1-3, l 1980, Harry W. Parker, Editor, The Engineering Societies ,j Commission on Energy, Inc., 444 North Capitol Street, N.W., S, Suite 405, Washington, D.C. 20001, Date Published January, 1981, Prepared for the United States Department of Energy, Under Contract No. EF-77-C-01-2468; FE-2468-88, Dist.
Category These feeders permit decomposer 32 to be a continuously, or semicontinuously in the case of e.g. lock t hopper-type systems, operating pressure vessel, where Al(OH) 3 entering chamber 36 falls into a number of tubes 38, of which only three have been shown for schematic purposes. Tubes 38 are at a high temperature, for instance 250 to 650 C, so that free moisture and chemically combined water are driven off as steam. This evolution of l t water in the gaseous state fluidizes the Al(OH) 3 particles in tubes 38. Residence time in the tubes is e.g. 10 to 120 minutes.
The high temperature in the tubes is achieved by hot gases entering chamber 39 through line 40 and leaving through line 42. Chamber 39 is enclosed by side walls 39a, top wall 39b and bottom wall 39c.
As the particles of Al(OH) 3 fall into tubes 38, they pile on top of one another to form a bed. The water evolved from them in the gaseous state flows upwardly toward the vent to line 44 and is sufficient to fluidize the particle JC 8 Lw.8 beds in the tubes. This is termed self-fluidizing, in that the fluidizing gas comes from the partir7les themselves.
During start-up, steam from an auxiliary steam source may be injected into chamber 52 through line 53 to fluidize particles in the tubes 38, until self-fludization is achieved, after which line 53 may be closed. To the extent that the evolved water may not be enough to achieve desired fluidization, such may be supplemented by steam injection through line 53 during water removal from the Al(OH) 3 Steam feedback from line 44 to line 53 is another possibility. Feedback can be used, for example, to maintain fluidization, or prevent bed particles from interbonding, when the process might be placed in idle, as when the need for steam in the Bayer plant is temporarily diminished.
The steam product of the invention moves through line 44 to a solids separator such as cyclone 46, with solids being returned to the decomposer through line 48 and steam going to the Bayer process through line 50 to lines 28 and It is estimated that steam from the decomposer will make up one-third of the total steam needed by a Ba7er process. The remaining two-thirds will enter line through line 49 and will come from one or more water boilers (not shown). In general, the steam coming froT the decomposer will be in a superheated condition, and this may be cared for by heat loss in the lines or by a heat recovery desuperheater (not shown) to bring the steam to its I saturation temperature at its location of use. For example, condensate returning to water boilers feeding line 49 may be preheated by running through such a desuperheater. Such condensate may also be used to get more heat from the gases in line 42. i The aluminum-bearing product resulting from removal 6Z water from the Al(OH) 3 in tubes 38 collects in the chamber I 52. It now comprises particles of boehmite and/or gamma alumina and X-ray indifferent (no well-defined diffraction pattern) alumina pseudomorphous with aluminum hydroxide.
Gamma alumina is somewhat on the borderline of being X-ray indifferent in that its diffraction pattern is not very JC 9 well-defined. The product loss on ignition (LOI) (3000 to 1200 C) is in the range from 1 to 12%, its surface area in 2 the range 10 to 100 m /g.
Interestingly, in the pressurized decomposer, there is less breakage of particles during water removal than is the case during the flash or kiln calciner, prior art techniques of water removal. In laboratory scale tests, there was no particle breakage as determined by “before” and “after” weight of the -325 mesh particle size fraction; in similar laboratory scale tests for atmcspheric pressure, flash or kiln calciner tests, it is typical to find tiat the -325 mesh size fraction increases in weight by 2 to 5% due to particle breakage.
2 The aluminous product in chamber 52 is next condutedf through pressure-reducing feeder 54 (of the same construction as feeder 34) and line 56 to the flash calcining operation of Figure 1C for further water removal to produce an alumina suitable for electrolysis in the Hall-Heroult process for producing aluminum metal,, J 0 Alternatively, in the case where the higher 0 temperature portion of the 250 to 650 C range in the decomposer has been used, the product in line 56 may be collected as feed for a Hall-Heroult electrolysis. Thus, Example I below shows that sufficiently low LOI values can be achieved for this purpose.
The flash calciner may be built on the principles; described in “Alumina Calcination in the Fluid-Flash Calciner” by William M. Fish, Light Metals 1974, Volume 3 The Metallurgical Society of the American Institute of Mining, Metallurgical and Petroleum Engineers, Inc., New York, New York, pages 673-682, and in “Experience with Operation of the Alcoa Fluid Flash Calciner” by Edward W, Lussky, Light Metals 1980, The Metallurgical Society of AIME, Warrendale, PA, pages 69-79. Alternative equipment are the F. L. Smidth calciner as described in a paper presented at the AIME annual meeting in Dallas in February, 1982, by B. E. Raahauge et al and the Lurgi/VAW calciner as described in the Proceedings of the Second International JC :1 _1 X- Ir-
R
i Symposium of ICSOBA, Volume 3, pages 201-214 (1971).
The flash calciner schematically illustrated in Figure IC receives, e.g. boehmite particles through line 56 and brings them to temperatures in the range 9500 to 1220°C by the action of the fuel through line 58 and the hot gas (line 60) which supports the combustion of the fuel.
Alumina product is collected through line 62. Hot exhaust gases leave through line 64 and are cleaned of entrained alumina in separator 66, with solids being directed through line 68 to line 62 and hot exhaust travelling through line to heat the decomposer.
B. Batch Process The process of Figures 1A to 1C operates continuously. The portion in Figure IB may be operated in a batch mode as illustrated in Figure 2. Figure 1 numerals have been retained where the equipment is the same. This modification is achieved by substitution of a batch decomposer 70 and suitable storage hoppers 72 and 74 to accommodate the still continuous feeds through line 24 from the Bayer process and through line 56 to the flash calciner.
Batch decomposer 70 includes a lid 76, which may be moved between a pressure-sealing position (shown) and an open position (not shown) by releasing clamp 78 and rotating counterclockwise, say 950, about hinge 80. On the lower end of the decomposer is a floor 82. Lid 76 and floor 82 form, together with side walls 84, a chamber 86. With floor 82 in the closed position, as shown, pressure-sealing of chamber 86 is complete. Floor 82 can be rotated counterclockwise about hinge 85, upon release of clamp 86, to open chamber 86 for emptying a batch of product.
Chamber 86 is heated by heat exchanger 88, which is located within chamber 86 and provided with a flow of hot gas through lines 40 and 42. Electric heating is another option.
Back pressure regulator or valve 90, firstly, acts to prevent steam in line 50 from flowing back into decomposer when the pressure in the decomposer is still too low and, L41 11 a, secondly, opens line 50 to steam only after the desired pressure, e.g. 110 psia, has been achieved in the decomposer.
In operation of the batch process, lid 76 is opened, and Al(OH) 3 from hopper 72 is loaded into chamber 86 through line 25. The resulting bed self-fluidizes from the action of heat exchanger 88 in driving free moisture and i chemically combined water from the Al(OH) 3 particles.
As more and more water is driven off as steam, the S pressure within chamber 86 rises. Steam moves through line 44 to cyclone 46 as explained above for continuous operation. When the pressure on valve 90 builds up to a sufficient value, valve 90 opens and steam is supplied i through line 50 to the Bayer proceus.
When sufficient water has been removed, floor 82 is opened and e.g. boehmite product released from chamber 86 in direction 73 into hopper 74.
Before valve 90 opens, the Bayer process can be supplied from any auxiliary steam source supplying steam of desired pressure. The auxiliary source can e.g. include a second decomposer 70 run in alternation with that illustrated in Figure 2.
I, Proct The steam producing process of the invention as applied to Al(OH) 3 gives new products.
Operating conditions of the pressure decompo r are: temperature: 250-650°C; pressure (steam): 20- psig and residence time: 10-120 minutes. The hyd e decomposes i under these conditions releasing wat as steam under pressure and producing a partiay calcined alumina. Our investigations have shown t the dehydration of alumina hydrate under steam pr sure progresses by initial conversion of the ihydrate (gibbsite) to the oxide-hydroxi boehmite. The boehmite formed then decompos to gamma and/or X-ray indifferent, or amorphous, alum a partially or fully depending on the temperature and C- 12 “STEAM PRODUCING PROCESS AND PRODUCTS” The following statement is a full description of this invention, including the best method of performing it known to applicant(s): P19/3/84 1 1 C. Products The steam producing process of the invention as applied to Al(OH) 3 gives new products which are the i subject of related Australian Patent No. 587934.
Operating conditions of the pressure decomposer are: temperature: 250-650oC; pressure (steam): 20-250 psig and residence time: 10-120 minutes. The hydrate I decomposes under these conditions releasing water as steam 10 under pressure and producing a partially calcined alumina. Our investigations have shown that the dehydration of alumina hydrate under steam pressure progresses by initial conversion of the trihydrate (gibbsite) to the oxide-hydroxide boehmite. The boehmite formed then decomposes to gamma and/or X-ray indifferent, or amorphous, alumina partially or fully depending on the temperature and residence time of the material in the decomposer.
2i iAB 3 9J1 -12a- $)1 t
L
1 1*-*1U n I- YI”LL'”-LI :41 1: Thus, the material coming from the decomposer is boehmite and gamma and/or X-ray indifferent alumina pseudomorphous with aluminum hydroxide. The boehmite content is usually relatively high, in the 10 to 50% range.
Each particle is composed of a plurality of crystals. Loss on ignition (LOI) (300-1200°C) is in the range 1 to 12%, the lower water content material being obtained using the high portion of the e.g. 250 to 650°C temperature range in the decomposer. Surface area will be in the range 10-100 m 2 /g (square meters per gram). Surface area data herein is BET, N 2 adsorption.
In the case where a high temperature, atmospheric cc’ pressure, i.e. at most 10 psig (resulting from blowers to S move the gases), calcination follows the decomposer, the resulting alumina attains an LOI (300-12000C) of less than 2 a surface area in the range of 10-100 m and a modified Forsythe-Hertwig attrition index of 1 to C C c Attrition index data herein is determined according to the method of Forsythe and Hertwig, “Attrition Characteristics of Fluid Cracking Catalysts”, Ind. and Engr.
Chem. 41, 1200-1206, modified in that samples are attrited for only 15 minutes, this time having been found to be better for showing differences in aluminas.
Attrition Index I 100(X Y)/X where X percent plus 325 mesh before attrition, Y percent plus 325 mesh after attrition.
The lower the attrition index, the higher is the resistance S to attrition.
In gene ra4l, A 0e-a1jumna-p-o G-q-o in much stronger, e.g. has a lower attrition index, than alumina made by calcining Al(OH)3 at atmospher- ressure.
There are benefits in combining a-initial pressure decomposition with a terminal tmf~ pheric-pressure calcination. For insta ,the terminal atmospheric-pre e calcination can be run at 850 C, or less, t i-ng LOI (300-1200°C) to 1% or below. This is Sompared to the oer 950°C required prvio”sil’
I
It 13 L ILL–YIL-LII~ In general, the alumina product produced by the preferred embodiment of the present invention is much stronger, e.g. has a lower attrition index, than alumina made by calcining Al(OH) 3 at atmospheric pressure.
There are benefits in combining an initial pressure decomposition with a terminal atmospheric-pressure calcination. For instance, the terminal atmospheric-pressure calcination can be run at 850 0 C, or less, to bring LOI (300-1200 C) to 1% or below. This is to be compared to the over 950°C required previously.
Soo 00 0 o o 0o oo o oo 0 0 0 000 0 0 0 01 o0 0 0 00 030 0 0:o oL a i2~
III
I
I
r An additional benefit is the ability to arrive at an alumina product of 1% LOI, or less, and of surface area in 2 the range 10-100 m without producing any alpha-alumina, a crystalline form of poor solubility in the molten salt bath of a Hall-Heroult cell. In general, the atmospheric-pressure calcination converts the boehmite of the intermediate product to gamma alumina. Thus, boehmite content in the product of the pressure decomposer will mean about 50% gamma alumina content in the product obtained by submitting the product of the pressure decomposer to an atmospheric-pressure calcination.
In both cases, decomposer only or decomposer plus calciner, the product is characterized by at least a reduced amount, and even an absence, of the parallel fissures so characteristic of the alumina that results from aluminum hydroxide calcined at the zero, to perhaps at most the 7, or psig pressures previously used in dewatering the feed for Hall-Heroult cells.
Figure 3, eompared-wi-4th-F-iu-re–4,-eilusrates this important characteristic of products according to the inventionA namely the reduced amount, or even absence, parallel fissuring.
The prior art product (Reference No. AP T182B) of Figure 4 was prepared by calcining Al(OH) 3 in y4lash calciner as described in the above-cited art-icles of Fish and Lussky. It measures 1 to 5% boehmite’ rest amorphous.
As is evident from Figure 4, the pripr art product is characterized by parallel fissuriin. This prior art alumina product had an LOI (300-1200°0 of a surface area of 2 84 m and an attrition dex of The product (Reference No. AP 4052-H2) of Figure 3, which is a product ccording to the invention, was prepared by heating Al(O at 500°C, 120 psig pressure, for one 3 0 hour under s ef-fluidizing conditions and then at 850 C, atmospherc pressure (0 psig), for one hour (the 850 0
C
treatment corresponding to a flash calcining operation).
T e product resulting from this treatment was about Gamma alimina. raR amorph and har an TLT nF 0% a 14 i:i
I
L 1 Figure 3, compared with Figure 4, illustrates this important characteristic of products produced by the preferred embodiment of the method according to the invention, namely the reduced amount, or even absence, parallel fissuring.
The prior art product (Reference No. AP T182B) of Figure 4 was prepared by calcining Al(OH) 3 in a flash calciner as described in the above-cited articles of Fish and Lussky. It measures 1 to 5% boehmite, rest amorphous. As is evident from Figure 4, the prior art product is characterized by parallel fissuring. This prior art alumina product has an LOI (300-1200 C) of 2 a surface area of 84 m and an attrition index of The product (Reference No. AP 4052-H2) of Figure 3, a which is a product produced by the preferred embodiment of the method according to the invention, was prepared by heating AI(OH) 3 at 500°C, 120 psig pressure, for one hour under self-fluidizing conditions and then at 850°C, atmospheric pressure (0 psig), for one hour (the 8500C treatment corresponding to a flash calcining operation).
The product resulting from this treatment was about gamma alumina, rest amorphous, and had an LOI of a 2 surface area of 51 m /g and an attrition index of 6.
Clear from a comparison of Figure 3 with Figure 4 is, in this example, a complete absence of parallel fissuring in the product produced by the preferred embodiment of the method of the invention.
It is thought that a beneficial result of the lack 30 of parallel fissuring is an ability of the product produced by the preferred embodiment of the method of the present invention to be handled and transported with a lesser production of fines as compared with material having the parallel fissuring. In any event, this product is stronger, as evidenced by characteristically lower values of the modified Forsythe-Hertwig attrition index.
Thus, for a given Al(OH) 3 feed, it is possible to achieve consistently lower attrition indices for the A-14ar~L, u rur~~ i-rr-nuul~FY I ii 11
IF
it Lj4 alumina feed for Hall-Heroult cells. For example, for a given Al(OH) 3 feed, the attrition index will be at least 2 units lower for the product produced by the preferred embodiment of the present invention than it would be for a product of the same LOI achieved in an atmospheric pressure calcination. Furthermore, attrition indices lower than those of previous commercial alumina products are obtainable using the preferred embodiment of the present invention. Thus, it is known that different Al(OH)3 feeds give different attrition indices in atmospheric pressure calcination. Lower attrition indices are said to result from well crystallized Al(OH) 3 while higher indices come from weakly crystallized Al(OH) 3 Using well crystallized Al(OH) 3 in atmospheric pressure calciners, the lower attrition indices previously obtained were 4 or 5. Using the preferred embodiment of the present invention, well crystallized Al(OH) 3 yields attrition indices of 2 or less.
Further illustrative of the invention are the following examples: Example 1 A product (Reference No. AP 4302-6) was decomposed according to the present invention by transferring heat through the walls of a container and into a bed of Al(OH)3 in the container. The temperature in the bed was 600 C. Heating was for a period of one hour.
Pressure was 120 psig. The bed self-fluidized under the action of the ct C rcC gaseous water, steam, coming off the particles. There was no particle breakage during this process, i.e. no increase in the weight of the -325 mesh size fraction. The product obtained by this procedure had an LOI (300-12000C) of a surface area of 94 m /g and an attrition index of 4. X-ray diffraction analysis gives the following results: about 2% boehmite (X-ray diffraction pattern matching those of cards 5-0190 and 21-1307 of the Joint Committee on Powder Diffraction Standards, Swarthmore, PA), rest gamma and amorphous.
Example II A product (Reference No. AP 4064) was prepared according to the present invention by transferring heat through container walls and into a bed of A1(OH) 3 in the decomposer container. Bed conditions were 500 0 C, 120 psig pressure, one hour residence time. The material in the bed self-fluidized under the action of the gaseous water being evolved during decomposition. A product containing 28% boehmite resulted. Subsequently, the product of this high pressure treatment was heated at 850 C, atmospheric pressure (0 psig), for one hour (this 850°C treatment corresponding to a flash calcining operation). The final product had an LOI (300-12000C) of a surface area of m /g and an attrition index of 2. X-ray diffraction analysis gave the following results: 0% boehmite, rest gamma and amorphous.
Example III Products Me t i-nvont A iii were prepared as in Example II, except for the following differences. Decomposer bed temperature was 400°C. Analysis of the product from the decomposer: surface area 40 m 2 LOI 13.4%, attrition index 5, %-boehmite 44%. Analysis of the product from the 850 C, atmospheric-pressure calcining: LOI %-boehmite surface area 41 m2/g.
1 ~l 16 Example
IV
Products f th in-n-in were prepared as in Example II, except for the following differences. Decomposer bed temperature was 4000C, pressure 200 psig, time at pressure 3/4 hour. Analysis of the product from the decomposer: surface area 19 m2 LOI 16%, attrition index 9, %–boehmite 44%. Analysis of the product from the 850 0
C,
atmospheric-pressure calcining: LOI %-boehmite 0%, 2 surface area 30 m attrition index 9.
Example V Products af tho inventean were prepared as in Example II, except for the following differences. Decomposer bed temperature was 400 0 C, pressure 60 psig, time at pressure 2 hours. Analysis of the product from the decomposer: surface area 63 m LOI 11.3%, %-boehmite 30%. The atmospheric-pressure calcining was at 750 0 C, again for 1 hour. Analysis of the product from this calcining was: LOI 0 surface area 65 m2/g and attrition index 6.
20 surface area 65 m /g and attrition index 6.
1\i 17 L -Irri I bit

Claims (9)

1. A method of producing and utilising steam in a steam consuming process, said method comprising: producing steam in a first stage of the process: heating a solid substance having chemically combined water of crystallisation at a temperature greater than 250 C in a decomposer at a pressure greater than one atmosphere gage pressure such that: said substance is deccmposed to drive off at least a portion of its chemically combined water of 1 crystallisation, and (ii) said water in the form of steam at a pressure greater than one atmosphere gage pressure is produced in o0 said decomposer; 0′ removing said steam from said decomposer; and capturing said steam for use in said process; and (II) using said steam from said first stage in a second stage of said process conducted outside said decomposer. do

2. A method as claimed in claim 1, wherein the steam produced is used in a process comprising treating a slurry of bauxite ore with sodium hydroxide solution to dissolve 0o,48 aluminum values while maintaining temperature and pressure conditions of the slurry with steam. 30 LLLAA 1639Z 639 -18- I AB

3. A method as claimed in claim 1 or claim 2 wherein the solid substance yields a steam which is essentially 100% H 2 0.

4. A method as claimed in claim 3 wherein the solid substance is Al(OH) 3 A method as claimed in claim 4 wherein the aluminum hydroxide comprises a bed in the step of removing water, said bed being fluidized.

6. A method as claimed in claim 5 wherein the removed water self-fluidizes the bed.

7. A method as claimed in claim 4, the temperature in the step of removing being in the range of 250-650 C.

8. A method as claimed in claim 7, further comprising subjecting the aluminum-bearing product of the step of removing to an atmospheric pressure calcining step at a temperature greater than about

9. A method as claimed in any one of claims 1 to 8 wherein the steam produced is utilized external to said decomposer. A method as claimed in claim 1 substantially as herein described with reference to Figures 1A to 1C or Figures 1A to 1C as modified in accordance with Figure 2, of the accompanying drawings.

11. A method as claimed in claim 1, substantially as herein described with reference to any one of the accompanying Examples. DATED: 6 JANUARY, 1990 PHILLIPS ORMONDE FITZPATRICK Attorneys For: t ALUMINUM COMPANY OF AMERICA 1Z i c 1 -18a- L_ ~L -r PI-‘ ii ~–il

AU23636/88A
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1990-04-18
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1990-05-17
Degussa

AMORPHOUS ALUMINUM OXIDE, METHOD FOR THE PRODUCTION AND USE THEREOF

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The B. F. Goodrich Company
Attrition resistant catalyst support

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