WO2008052249A1 - Method for alumina production - Google Patents
Method for alumina production Download PDFInfo
- Publication number
- WO2008052249A1 WO2008052249A1 PCT/AU2007/001617 AU2007001617W WO2008052249A1 WO 2008052249 A1 WO2008052249 A1 WO 2008052249A1 AU 2007001617 W AU2007001617 W AU 2007001617W WO 2008052249 A1 WO2008052249 A1 WO 2008052249A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- calcination
- steam
- aluminium trihydroxide
- aluminium
- trihydroxide
- Prior art date
Links
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
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/447—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes
- C01F7/448—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes using superatmospheric pressure, e.g. hydrothermal conversion of gibbsite into boehmite
-
- 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
Definitions
- the present invention relates to a method for the calcination of aluminium trihydroxide. More specifically, the present invention relates to a method for the calcination of aluminium trihydroxide using steam.
- the Bayer process is widely used for the production of alumina from aluminium containing ores, such as bauxite.
- the process involves contacting alumina- containing ores with recycled caustic aluminate solutions, at elevated temperatures, in a process commonly referred to as digestion.
- aluminium trihydroxide is added as seed to induce the precipitation of further aluminium trihydroxide therefrom.
- the precipitated aluminium trihydroxide also known as hydrate or gibbsite, is separated from the caustic aluminate solution, with a portion of the aluminium trihydroxide being recycled to be used as seed and the remainder recovered as product.
- the remaining caustic aluminate solution is recycled for further digestion of alumina- containing ore.
- the recovered aluminium trihydroxide may not be completely dry and may contain both unbound and physically bound water.
- unbound water refers to water that maybe on the surface of the aluminium trioxide
- physically bound water refers to water that may be held in, for example, interstitial pores of the aluminium trioxide.
- aluminium trihydroxide is heated to produce alumina, in a process known as calcination.
- water is a byproduct of the calcination reaction, as aluminium trihydroxide produces aluminium trioxide (AI 2 O 3 ), also known as alumina, according to the following reaction: 2AI(OH) 3 ⁇ AI 2 O 3 +3H 2 O
- the calcination reaction can produce a variety of distinct and measurable aluminous structures. These include aluminium trioxide structural forms and aluminium oxyhydroxide structural forms.
- the preferred composition of smelter grade alumina contains mostly the, so-called, gamma form, but also quantities of other alumina phases (e.g. alpha, kappa, chi, etc.).
- alumina shall be understood to encompass all structural forms or phases of aluminium trioxide including gamma alumina.
- aluminium oxyhydroxide shall be understood to encompass all structural forms or phases of aluminium oxyhydroxide including boehmite.
- calcination shall be taken to encompass the complete or partial removal of the physically and chemically bound and unbound water entering with the aluminium hydroxide feed to the calciner.
- Calcination is an energy intensive process.
- the water released as steam from the aluminium trihydroxide during calcination ( ⁇ 0.53 t water/tA) is lost to the atmosphere through the stacks together with its latent heat energy ( ⁇ 1.2 GJ/tA).
- Additional water is also released to the atmosphere as steam from the unbound water entering with the aluminium trihydroxide feed to the calciner and from the products of combustion.
- large quantities of fuel are used to vaporise unbound water and heat the dried aluminium trihydroxide whereby it passes through a series of intermediate crystalline forms prior to reaching the final desired alumina form.
- Direct heat transfer equipment and methods for drying and decomposition of aluminium trihydroxide to form an alumina product and steam include the use of static calciners, kiln calciners, electrical resistance heating, hot oil or salt baths, heating by inductance, lasers, plasmas, microwave radiation and combustion of fuels.
- combustion gases from the furnace section of the calciner mix directly with the hydrated substance being calcined. After calcination, the gases are separated, e.g. through cyclones and electrostatic precipitators for dust capture.
- the stack gases are a mixture of the products of combustion and water vapour.
- US5336480 teaches the calcination of aluminium trihydroxide by indirectly heating the aluminium trihydroxide in a pressurised container and collection of the steam released.
- the specification teaches that a bed of the aluminium trihydroxide exhibits self-fluidising behaviour on heating due to steam release from the aluminium trihydroxide upon decomposition.
- steam is generated for supply to the digester and evaporator portions of the Bayer process by heating aluminium trihydroxide in a decomposer to drive off unbound, physically bound and some chemically bound water from the aluminium trihydroxide. More specifically, the aluminium trihydroxide is heated indirectly in tubes by hot exhaust gases. The water evolved in the tubes in the gaseous state flows upwardly and is said to fluidise the particle beds in the tubes. This has been termed self-fluidising, as the fluidising gas comes from the particles themselves. During start-up, steam from an auxiliary steam source may be used to fluidise particles in the tubes, until self-fluidisation is achieved. - A -
- the present invention permits the utilisation of smaller pressure containers that the method of US5336480, which requires a large pressure container; a consequence of the relatively low gas-side heat transfer coefficient. Further consequences of the large size for this unit include the need to accommodate thermal expansion and difficulties associated with uniformly distributing the solids.
- steam will be understood to encompass dry steam (steam which does not contain water held in suspension mechanically), wet steam (steam which contains water held in suspension), saturated steam (steam at the temperature of the boiling point which corresponds to its pressure) or superheated steam (steam heated to a temperature higher than the boiling point corresponding to its pressure).
- alumina and the aluminium oxyhydroxide may be provided in numerous structural forms. Without being limited by theory, it is believed that the present invention may be utilised to control the alumina and aluminium oxyhydroxide structural forms so produced.
- the temperature of the steam is preferably at least about 250 0 C. Without being limited by theory, it is believed that the steam usage to achieve the desired level of decomposition (it would be advantageous at some stage to discuss what the 'desired level' of decomposition is) is reduced by increasing the steam supply temperature. More preferably, the temperature of the steam is about 480 0 C. Without being limited by theory, it is believed that where the temperature of the steam is greater than about 480 0 C, the calciner may require construction from specialised materials such as nickel-chromium alloys. In a highly preferred form of the invention, the temperature of the steam is greater than 480 0 C.
- the pressure of the steam is greater than atmospheric pressure. In a highly preferred form of the invention, the pressure of the steam is greater than about 6 bar.
- the pressure and temperature of the steam exiting the calcination unit are suitable for further use in a bauxite refinery.
- the pressure of the steam exiting the calcination unit is greater than about 6 bar.
- the use of steam at high pressure means that the steam resulting from the calcination process can be produced at a temperature and pressure suitable for further use in the refinery. Further, the use of steam at high pressure reduces the physical size of the equipment required for the calcination.
- the energy required for the thermal decomposition of aluminium trihydroxide to alumina and/or aluminium oxyhydroxide decreases with increasing pressure.
- the steam is superheated steam.
- the method comprises the further step of:
- the step of subjecting the aluminium trihydroxide and the mixture of alumina and aluminium oxyhydroxide to a second calcination stage may be performed by any means known in the art including direct calcination with combustion fuel gases, indirect calcination with combustion fuel gases, direct calcination with steam, indirect calcination with steam, solar, electrical resistance and microwave calcination.
- the step of subjecting the aluminium trihydroxide and the mixture of alumina and aluminium oxyhydroxide to a second calcination stage is performed in a separate calcination unit.
- the second calcination stage comprises direct calcination with combustion fuel gases
- the second calcination stage may be conducted in a gas suspension calciner.
- the temperature of the second calcination stage will be determined by the required alumina product properties. For example, it is known that alumina for ceramics applications requires calcination temperatures about 1250 0 C whilst conventionally alumina calcination for the production of smelter grade alumina is conducted at about 850 to 1100 0 C. It is believed that the second calcination stage may be conducted at a lower temperature.
- the second calcination stage is conducted at temperatures between about 600 and 950 0 C.
- direct steam calcination produces different alumina structure(s) to that produced in the first stage of conventional calcination.
- the method preferably comprises the further step of:
- the steam is used in the step of:
- the method comprises the further step of:
- the method comprises the further step of:
- the step of drying the aluminium trihydroxide can decrease energy consumption.
- the method comprises the further step of
- dewatering the aluminium trihydroxide in a pressure filter which may include the use of steam.
- Figure 1 is a schematic flow sheet showing a Bayer Process circuit
- Figure 2 is a schematic flow sheet showing how a method in accordance with the present invention may be utilised in a Bayer Process circuit.
- FIG. 1 shows a schematic flow sheet of the Bayer process circuit 10 for a refinery using a single digestion circuit comprising the steps of:
- aluminium trihydroxide 24 is fed into a duct and heated by direct contact with steam 34 at approximately 480 to 650 0 C and greater than 6 bar, best seen in Figure 2.
- the steam 34 heats and dries the aluminium trihydroxide 24.
- the mixing of the steam 34 and aluminium trihydroxide 24 results in the release of chemically bound water as water vapour relative to the level of energy available in the mixed streams.
- the resulting steam released mixes with the heating steam 34.
- the decomposition of the aluminium trihydroxide 24 results in an increase in the steam mass flow 38 exiting the mixing phase.
- Sufficient steam is added so that the mixture temperature is about 300 0 C.
- the steam 38 and solids 36 are separated using gas/solids separation technology such as filtration.
- the overall energy reduction resulting from pressure calcination is through using the released water vapour as process steam.
- the separated steam 38 is split into two streams 40 and 42.
- Stream 40 passes through a recirculation blower 44 to a steam re-heater 46 via stream 48, heated to about 480 to 650 0 C and returned as stream 34 and mixed with further aluminium trihydroxide 24.
- Stream 42 which is actually the water released from the aluminium trihydroxide is cooled to the plant steam requirement which is achieved by water addition 50 which creates further steam 52 and the steam discharged to the plant steam circuit.
- the solids 36 from the gas/solids separation step are passed from the pressurised stage to a Gas Suspension Calciner (GSC) 54 operating at approximately atmospheric pressure where they are heated to about 850 0 C to achieve the target product quality.
- GSC Gas Suspension Calciner
- Hot gases 56 from the GSC 54 are used in the steam re-heater 46 to heat the recirculated steam 48 to the recirculation temperature of about 480 to 650 "C. Due to the heat balance, it may be necessary to add fuel 58 to the steam re- heater 46. Water 60 is added for further heat recovery from the hot gases prior to the hot gas being discharged to the stack 61.
- Hot Alumina 62 is cooled with cooling air 64 and water 66 prior to discharging as product 68.
- the cooling air 64 is therefore preheated prior to passing 70 to the GSC 54.
- Fuel 72 e.g. gas or oil
- Fuel 72 is added to the GSC 54 to maintain the required temperature.
- the water streams 66, 60 may be used for a variety of purposes in the plant as required by the heat balance.
- the heated water may be used to cool the process steam (i.e. as stream 50) or these water streams may be used to supplement the recirculated steam flow 34.
- the products of combustion from the calcining stage are used to dry and preheat the aluminium trihydroxide.
- the products of combustion are also used to provide partially counter current heat exchange in the calcining section.
- the present invention utilises a second calcination stage employing products of combustion from a gas suspension calciner, it is not possible for the products of combustion to provide partially counter current heat exchange in the calcining section. Consequently, products of combustion from the second calcination stage are used to reheat the steam required for the pressure calcination section as shown in Figure 2.
- the temperature of the gas suspension calciner is about 850 0 C, there may not be sufficient energy available in the products of combustion to provide all of the steam and it may be necessary to provide further fuel and air to provide the required heat to reheat the recycled steam.
- steam is recycled from the pressure calcination stage through the steam re-heater 46.
- significant quantities of steam are required at 480 to 650 0 C.
- steam should be recycled and in doing so, the steam inlet temperature into the steam re-heater as low as practical.
- a further issue is that, depending on the level of decomposition achieved in the first pressure stage, there may be less energy consumed in the gas suspension chamber.
- the level of decomposition in the pressure stage is high there will be less energy required in the second stage and therefore there is less air required and therefore there is insufficient air to cool the alumina to a low enough temperature to discharge it to conveyor belts etc. Consequently, it is necessary to recover heat from the partially cooled product and this can also be in the form of process steam or heating boiler feed water.
- the embodiments of the invention were formulated, evaluated and refined using a combination of inhouse models built on chemical engineering first principles and tuned to existing Bayer unit operations, an extensive database of Bayer properties and thermodynamic data, Bayer operating experience and flowsheet models built within ASPEN PlusTM, ASPEN Technology Inc. software process simulation software with state-of -the-art physical properties packages, including added Bayer process properties and unit operations built inhouse.
- alumina is produced at benchmark of approximately 3.0 GJ/t (for gas fired plant) and steam at approximately 2.57 GJ/t. Therefore, utilising current equipment to produce the same levels of alumina and steam, the energy consumed would be;
- the present invention offers a significant potential to reduce plant energy costs.
- Table 1 shows the results from data and process models. In each case the targeted steam condition exiting the system to the plant is 8 bar pressure and 220 0 C.
- the saving needs to be evaluated as a comparison of the energy to produce alumina in a conventional calciner plus the energy to produce the same quantity of steam in a conventional boiler operation.
- a 100 tph calciner would require the recirculation of approx 248 tph of steam at approx 650 0 C.
- the main heat exchange duct would be approximately 1.3 m in diameter with a target velocity of 10 ms "1 .
- the diameter would normally be about 2.7 m.
- the second stage equipment would also be smaller. It will be appreciated that the present invention will utilise smaller equipment than conventional gas suspension calciner technology.
- the recycling of large volumes of high temperature steam is believed to be best achieved through the use of turbo machinery. It will be appreciated that as turbo machinery should have clean steam, it may be necessary to filter the steam.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0718257-0A BRPI0718257B1 (en) | 2006-10-30 | 2007-10-24 | method for calcining aluminum hydroxide |
AU2007314134A AU2007314134B2 (en) | 2006-10-30 | 2007-10-24 | Method for alumina production |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2006906025A AU2006906025A0 (en) | 2006-10-30 | Method for Alumina Production | |
AU2006906025 | 2006-10-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2008052249A1 true WO2008052249A1 (en) | 2008-05-08 |
WO2008052249A9 WO2008052249A9 (en) | 2008-07-17 |
Family
ID=39343678
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU2007/001617 WO2008052249A1 (en) | 2006-10-30 | 2007-10-24 | Method for alumina production |
Country Status (4)
Country | Link |
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CN (2) | CN101595057A (en) |
AU (1) | AU2007314134B2 (en) |
BR (1) | BRPI0718257B1 (en) |
WO (1) | WO2008052249A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103771476A (en) * | 2014-01-26 | 2014-05-07 | 郑州金阳光陶瓷有限公司 | Method for producing alpha-aluminum oxide by utilizing gas-suspension roasting furnace |
CN109612298A (en) * | 2018-12-27 | 2019-04-12 | 广西华银铝业有限公司 | A kind of pre-heating system convenient for recovered steam steam exhaust heat |
WO2021144694A1 (en) * | 2020-01-13 | 2021-07-22 | Rio Tinto Alcan International Limited | Calcination apparatus and process using hydrogen |
US11391181B2 (en) | 2020-11-30 | 2022-07-19 | Rondo Energy, Inc. | Thermal energy storage system with system for deep discharge of thermal storage blocks |
WO2022261726A1 (en) * | 2021-06-17 | 2022-12-22 | The University Of Adelaide | Method and apparatus for alumina calcination |
US11913362B2 (en) | 2020-11-30 | 2024-02-27 | Rondo Energy, Inc. | Thermal energy storage system coupled with steam cracking system |
US11913361B2 (en) | 2020-11-30 | 2024-02-27 | Rondo Energy, Inc. | Energy storage system and alumina calcination applications |
US12018596B2 (en) | 2020-11-30 | 2024-06-25 | Rondo Energy, Inc. | Thermal energy storage system coupled with thermal power cycle systems |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109065810A (en) * | 2018-08-15 | 2018-12-21 | 寿光众新晶体材料有限公司 | A kind of preparation method of aluminum oxyhydroxide slurry |
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JPH1160237A (en) * | 1997-08-21 | 1999-03-02 | Nakamichi Yamazaki | Continuos hydrothermal synthesis of alumina particle |
-
2007
- 2007-10-24 AU AU2007314134A patent/AU2007314134B2/en active Active
- 2007-10-24 BR BRPI0718257-0A patent/BRPI0718257B1/en active IP Right Grant
- 2007-10-24 WO PCT/AU2007/001617 patent/WO2008052249A1/en active Application Filing
- 2007-10-24 CN CNA2007800405966A patent/CN101595057A/en active Pending
- 2007-10-24 CN CN201510537457.0A patent/CN105236458A/en active Pending
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JPH1160237A (en) * | 1997-08-21 | 1999-03-02 | Nakamichi Yamazaki | Continuos hydrothermal synthesis of alumina particle |
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DATABASE WPI Week 199213, Derwent World Patents Index; AN 1992-103891 * |
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CN103771476A (en) * | 2014-01-26 | 2014-05-07 | 郑州金阳光陶瓷有限公司 | Method for producing alpha-aluminum oxide by utilizing gas-suspension roasting furnace |
CN109612298A (en) * | 2018-12-27 | 2019-04-12 | 广西华银铝业有限公司 | A kind of pre-heating system convenient for recovered steam steam exhaust heat |
WO2021144694A1 (en) * | 2020-01-13 | 2021-07-22 | Rio Tinto Alcan International Limited | Calcination apparatus and process using hydrogen |
US11603776B2 (en) | 2020-11-30 | 2023-03-14 | Rondo Energy, Inc. | Energy storage system and applications |
US11702963B2 (en) | 2020-11-30 | 2023-07-18 | Rondo Energy, Inc. | Thermal energy storage system with steam generation system including flow control and energy cogeneration |
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US11391181B2 (en) | 2020-11-30 | 2022-07-19 | Rondo Energy, Inc. | Thermal energy storage system with system for deep discharge of thermal storage blocks |
US11619144B2 (en) | 2020-11-30 | 2023-04-04 | Rondo Energy, Inc. | Thermal energy storage system with steam generator having feedback control |
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US11867096B2 (en) | 2020-11-30 | 2024-01-09 | Rondo Energy, Inc. | Calcination system with thermal energy storage system |
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US11913362B2 (en) | 2020-11-30 | 2024-02-27 | Rondo Energy, Inc. | Thermal energy storage system coupled with steam cracking system |
US11913361B2 (en) | 2020-11-30 | 2024-02-27 | Rondo Energy, Inc. | Energy storage system and alumina calcination applications |
US11920501B2 (en) | 2020-11-30 | 2024-03-05 | Rondo Energy, Inc. | Thermal energy storage system with steam generation system including flow control and energy cogeneration |
WO2022261726A1 (en) * | 2021-06-17 | 2022-12-22 | The University Of Adelaide | Method and apparatus for alumina calcination |
Also Published As
Publication number | Publication date |
---|---|
CN101595057A (en) | 2009-12-02 |
CN105236458A (en) | 2016-01-13 |
WO2008052249A9 (en) | 2008-07-17 |
AU2007314134B2 (en) | 2013-11-07 |
AU2007314134A1 (en) | 2008-05-08 |
BRPI0718257A2 (en) | 2014-01-21 |
BRPI0718257B1 (en) | 2021-02-17 |
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