AU2007338485B2 - Process and plant for the thermal treatment of particulate solids, in particular for producing metal oxide from metal hydroxide - Google Patents

Process and plant for the thermal treatment of particulate solids, in particular for producing metal oxide from metal hydroxide Download PDF

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AU2007338485B2
AU2007338485B2 AU2007338485A AU2007338485A AU2007338485B2 AU 2007338485 B2 AU2007338485 B2 AU 2007338485B2 AU 2007338485 A AU2007338485 A AU 2007338485A AU 2007338485 A AU2007338485 A AU 2007338485A AU 2007338485 B2 AU2007338485 B2 AU 2007338485B2
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Prior art keywords
fluidized
bed reactor
bed
oxygen
solids
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AU2007338485A1 (en
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Michael Missalla
Guenter Schneider
Werner Stockhausen
Michael Stroeder
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Metso Corp
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Outotec Oyj
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23LSUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
    • F23L7/00Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
    • F23L7/007Supplying oxygen or oxygen-enriched air
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00Feed or outlet devices; Feed or outlet control devices
    • B01J4/001Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002Nozzle-type elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005Separating solid material from the gas/liquid stream
    • B01J8/0055Separating solid material from the gas/liquid stream using cyclones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005Separating solid material from the gas/liquid stream
    • B01J8/006Separating solid material from the gas/liquid stream by filtration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1809Controlling processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818Feeding of the fluidising gas
    • B01J8/1827Feeding of the fluidising gas the fluidising gas being a reactant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872Details of the fluidised bed reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/44Fluidisation grids
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14Methods for preparing oxides or hydroxides in general
    • C01B13/18Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • C01F7/441Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
    • C01F7/445Dehydration 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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • C22B1/10Roasting processes in fluidised form
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C10/00Fluidised bed combustion apparatus
    • F23C10/02Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed
    • F23C10/04Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed the particles being circulated to a section, e.g. a heat-exchange section or a return duct, at least partially shielded from the combustion zone, before being reintroduced into the combustion zone
    • F23C10/08Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed the particles being circulated to a section, e.g. a heat-exchange section or a return duct, at least partially shielded from the combustion zone, before being reintroduced into the combustion zone characterised by the arrangement of separation apparatus, e.g. cyclones, for separating particles from the flue gases
    • F23C10/10Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed the particles being circulated to a section, e.g. a heat-exchange section or a return duct, at least partially shielded from the combustion zone, before being reintroduced into the combustion zone characterised by the arrangement of separation apparatus, e.g. cyclones, for separating particles from the flue gases the separation apparatus being located outside the combustion chamber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00115Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00141Coils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00477Controlling the temperature by thermal insulation means
    • B01J2208/00495Controlling the temperature by thermal insulation means using insulating materials or refractories
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00504Controlling the temperature by means of a burner
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/0053Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00548Flow
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00654Controlling the process by measures relating to the particulate material
    • B01J2208/0069Attrition
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002Chemical plants
    • B01J2219/00004Scale aspects
    • B01J2219/00006Large-scale industrial plants
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/34Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

This invention relates to a process for producing e.g. anhydrous metal oxide from metal hydroxide, wherein the metal hydroxide is at least partly dehydrated and preheated, before the metal hydroxide is introduced into a fluidized-bed reactor (19), in which the metal hydroxide is heated to a temperature of about 650 to about 1250°C by combustion of fuel, and metal oxide is generated, wherein primary air and/or secondary air enriched with oxygen is supplied to the fluidized-bed reactor (19). To achieve a rather low dust emission and a small amount of grain disintegration, the oxygen or the gas enriched with oxygen is introduced into the fluidized-bed reactor (19) with a low gas velocity.

Description

WO 2008/077462 PCT/EP2007/010680 Process and Plant for the Thermal Treatment of Particulate Solids, in particular for Producing Metal Oxide from Metal Hydroxide 5 This invention relates to a process and a plant for the thermal treatment of particu late solids, such as the production of burnt gypsum or the dehydration of other salts, combustion of residues with organic pollutants (e.g. sewage sludge), calci nation of refractory ores (e.g. gold ores), calcination of CaCO 3 and other carbon ates, breakdown of CaSO 4 , other sulfates or other salts such as nitrates, but in 10 particular the production of preferably anhydrous metal oxide from metal hydrox ide. In doing so, the metal hydroxide is at least partly dehydrated and preheated, before the metal hydroxide is introduced into a fluidized-bed reactor, in which the metal hydroxide is heated to a temperature of about 650 to about 1250*C by com bustion of fuel and metal oxide is generated, wherein primary air, which is en 15 riched with oxygen to an oxygen content of about 22 to about 99.9 % (in the con text of the present application the cited oxygen content always is considered as % per volume), and/or secondary air, which is enriched with oxygen to an oxygen content of about 30 to about 99.9 %, is supplied to the fluidized-bed reactor. 20 The production of metal oxide from metal hydroxide in a circulating fluidized bed is known for instance from DE 198 05 897 C1. In DE 197 22 382 Al it is proposed to enrich the gas supplied to a fluidized-bed reactor with stationary fluidized bed with oxygen. Via Laval nozzles, the oxygen should be introduced into the reactor with supersonic speed above the distributor plate. In the case of a stationary fluidized 25 bed this is necessary, because with lower gas velocities the oxygen supply noz zles will scale due to the high temperature in the fluidized bed and the high ther mal transfer between fluidized bed and nozzles and therefore will achieve an only short service life. On the other hand, the very high velocity of the oxygen-enriched gas in the fluidized bed leads to a strong load of the granular solids, similar to the 30 load in a jet mill, whereby the solids can disintegrate to a strong to very strong - 2 extent depending on the strength thereof. In most cases, such grain disintegration is undesirable. In the process according to DE 198 05 897 C1, the solids throughput can be in 5 creased, when correspondingly more heat is provided via the fuel. As long as only air not enriched with oxygen is used for combustion, the gas velocities in an existing plant will be increased, which can lead to an increased emission of dust and also to an increased grain disintegration of the fine-grained solids. Similarly, increased gas velocities can occur when an existing plant is switched 10 over from a fuel of high calorific value to a fuel of low calorific value with the same solids throughput, as long as air is supplied for combustion. Both the increased dust emission occurring with higher gas velocities and the increasing grain disintegration and the resulting deterioration of the product 15 quality are regarded as unsatisfactory. The present invention relates to a process for the thermal treatment of particulate solids, wherein the solids are at least partly dehydrated and preheated, before the solids are introduced into a circulating fluidized-bed of a 20 fluidized-bed reactor in which the solids are heated to a temperature of 650 to 1250*C by combustion of fuel and new solids are generated, wherein primary air for fluidizing the fluidized-bed, which is enriched with oxygen to an oxygen content of 22 to 99.9%, and/or secondary air, which is enriched with oxygen to an oxygen content of 30 to 99.9%, is supplied to the fluidized-bed reactor, 25 wherein the primary air and the secondary air is introduced into the fluidized bed reactor with a gas velocity between 5 and 300 m/s, and wherein the fuel is preheated prior to entering the fluidized-bed reactor. At the same time, the gas velocity in the dust filter of the process may be 30 decreased as a result of the oxygen enrichment of the secondary air, whereby dust emission can also be reduced. It was noted that the supply of oxygen enriched secondary air into the fluidized-bed reactor also leads to a distinct 36377381 (GHMatters) P80975.AU 3109/12 -3 increase in performance during calcination. This provides either for an increased production of metal oxide from metal hydroxide under the same basic conditions or for the use of fuels of lower calorific value without a reduction of the plant performance or for a combination of both modifications. In particular 5 when using fuels of lower calorific value, which have a high content of inert constituents, larger volume flow rates would be obtained in the plant for producing metal oxide without oxygen enrichment of the secondary air, which also leads to higher gas velocities. At the same time, the air requirement for combustion is reduced for instance in the case of fuel gas from an air 10 gasification of bituminous coal, whereby the cooling of the metal oxide produced becomes less efficient and the solids temperature is increased. As a result, the specific heat requirement is also increased. This disadvantage can be addressed by the gas supplied to the fluidized-bed reactor as primary air and/or secondary air with a low gas velocity is enriched with oxygen, as in this 15 way not only the effective volume flow rate, but also the gas velocities can be decreased. When for instance the ports of the secondary air supply into the reactor are lined with refractory bricks, refractory concrete or a similar material, there will 20 be no scaling even with an increased oxygen concentration and low gas velocities. In known processes, a refractory lining is not possible with the nozzles of the distributor plate. It is within the scope of the present invention that the fuel may be a gaseous 25 fuel, a non-gaseous fuel, or a mixture of gaseous and non-gaseous fuels. In accordance with a particularly preferred embodiment, the gas enriched with oxygen is introduced into the circulating fluidized bed of the fluidized-bed reactor with a gas velocity of less than 100 m/s, in particular between about 10 30 and about 100 m/s. 36377381 (GHMatters) P80975.AU 3109/12 For producing metal oxide, for instance for the production of alumina, it turned out to be particularly advantageous when the calcination in the fluidized-bed reactor is effected at a temperature of about 850 to about 1050*C. 5 In accordance with an embodiment, the reduction of grain disintegration, which can for instance be more than 15%, is greater than the smallest reduction of the gas velocity in one of the units of the plant. The reduction of the gas velocity can vary in the different units of the plant and lie for instance between about 15% and about 30%. 10 A particularly distinct reduction of grain disintegration and dust emission can be achieved in that the primary air supplied to the fluidized-bed reactor with a low flow rate is enriched with oxygen to an oxygen content of 22% to 49% and/or the secondary air is enriched with oxygen to an oxygen content of about 90 to is about 99.5%. Preferably, the gases supplied to the fluidized-bed reactor are indirectly and/or directly preheated with process heat to a temperature between about 100 and about 800*C, in particular between about 150 and about 7500C. By preheating 20 the primary gas, secondary gas and/or e.g. gaseous fuel supplied to the fluidized-bed reactor with process heat, the total energy demand of the process of the invention can further be decreased. As an alternative, it is also possible to preheat the gases supplied to the fluidized-bed reactor with foreign heat. 25 The product temperature of the metal oxide produced with the process of the invention usually should be not more than about 80*C. For this purpose, the metal oxide withdrawn from the fluidized-bed reactor can be cooled indirectly in at least one first cooling stage by direct contact with air and/or oxygen or a mixture of the two and in at least one further cooling stage provided 30 downstream of the at least one direct cooling stage, which constitutes a fluidized-bed cooler. It is particularly preferred when the secondary gas supplied to the fluidized-bed reactor is preheated in at least one of the first 36377381 (GHMatters) P80975.AU 3109112 - 5 and/or second cooling stages. Thus, the oxygen for enrichment of the secondary air can already be added before the cooling stages for the metal oxide, so that the oxygen also contributes to cooling the metal oxide and is preheated at the same time, before it reaches the fluidized-bed reactor. 5 In accordance with a preferred embodiment, at least one of the direct cooling stages includes a delivery conduit, which pneumatically conveys the metal oxide in upward direction, and a separating cyclone. Thus, the solids are at the same time cooled and conveyed to a higher position, which possibly provides io for further transport by the action of gravity. When a fuel of comparatively low calorific value of below 7500 kJ/kg is used for producing alumina from aluminum hydroxide in accordance with the process of the invention, about 1.5 to 3 Nm 3 /h, preferably between about 2 and 3 Nm 3 /h is and particularly preferably between about 2.3 and about 2.5 Nm 3 /h of oxygen (95%) can be admixed to the fluidized-bed reactor per 1 t/d of alumina produced together 25 with the secondary air. By means of the process of the invention, a plant operated for instance with fuel oil as fuel thus can be switched over to a heating gas with a lower calorific value of e.g. about 4000 to about 20 5500 kJ/kg, without reducing the production or deteriorating the product quality. In accordance with a further embodiment, about 23 to about 25 Nm 3 /h of additional air is supplied to the fluidized-bed reactor per 1 t/d of alumina produced, to which additional air about 2 to 4 Nm 3 /h, preferably between about 25 2.5 and 3.5, particularly preferably between 2.9 and about 3.1 N/m 3 of oxygen (95%) is admixed. The amount of additional air supplied to the fluidized-bed reactor thereby is reduced significantly as compared to conventional processes, so that the effective volume flow rate and thus to the same extent also the velocity is reduced. This leads to an unexpectedly high reduction of the grain 30 disintegration and thus to an improvement of the product quality. 36377381 (GHMatters) P80975.AU 3109/12 - 6 The present invention also relates to a plant for thermal treatment of particulate solids, in particular for performing a process according to any one of the preceding claims, comprising at least one preheating stage for preheating the solids, at least one fluidized-bed reactor, a means for supplying fuel into the s fluidized-bed reactor with a circulating fluidized-bed, and at least one cooling stage, wherein the cooling stage consists of at least three coolers, wherein at least one of these coolers is arranged and connected with the means for supplying fuel such that for preheating the fuel before entrance into the fluidized-bed reactor the fuel is passed through the at least one cooler, and 10 wherein means are provided for preheating primary air for fluidizing the solids in the fluidized-bed. Preferably, two of the (partial) coolers constitute fluidized-bed coolers. The same can each consist of a plurality of chambers. In accordance with a is preferred embodiment, the further (partial) cooler provided for heating the fuel gas can be a cooling cyclone. A pneumatic conveyor for supplying solids into the fluidized bed reactor can be provided upstream of the fluidized-bed reactor, which pneumatic conveyor 20 preferably is connected with a delivery conduit for hot solids from the fluidized bed reactor via a conduit. For instance, a cyclone provided upstream of the reactor thereby is connected with a cyclone provided downstream of the reactor such that the gas from the cyclone provided upstream of the 36377361 (GHMatters) P80975.AU 3/09/12 WO 2008/077462 PCT/EP2007/010680 -7 reactor can mix with the solids from the cyclone provided downstream of the reac tor. The invention will subsequently be explained in detail by means of embodiments 5 and with reference to the drawing, in which: Fig. 1 schematically shows a flow diagram in accordance with a first em bodiment of the invention, 10 Fig. 2 schematically shows a flow diagram in accordance with a second embodiment of the invention, and Fig. 3 schematically shows a flow diagram in accordance with a third em bodiment of the invention. 15 In the process shown in Fig. 1 to 3, the metal hydroxide to be dehydrated is sup plied through a conveyor screw 1 or the like and introduced into a preheating stage, which can be formed by an entrained-bed preheater 2. A hot gas mixture with temperatures between about 200 and about 5000C is supplied to the en 20 trained-bed preheater 2 through a conduit 3. Via a conduit 4, the solids-gas mix ture is supplied to a filter means 5, which can constitute for instance a bag filter, a cyclone or an electrostatic precipitator. The waste gas of the filter means 5 es capes via a conduit 6. Alternatively, a means for the further waste gas treatment (waste gas scrubber, method for water condensation, etc.) can be provided down 25 stream of the filter means 5. The metal hydroxide dried in this way is delivered through a conduit 7 to the base of a pneumatic conveyor 8, in which solids are supplied to a separating cyclone 10 by supplying air from a conduit 9. The waste gas of the separating cyclone 10 flows through a conduit 11 to a further cyclone 12. 30 WO 2008/077462 PCT/EP2007/010680 -8 The solids obtained in the separating cyclone 10 are delivered through a conduit 13 to a further entrained-bed preheater 14, in which the at least partly dehydrated solids get in direct contact with hot waste gas from a conduit 15 and subsequently are supplied through a conduit 16 into a separating cyclone 17, whose waste gas 5 is supplied to the first entrained-bed preheater 2 via conduit 3. The solids sepa rated in the further separating cyclone 17 are supplied via a conduit 18 to a fluid ized-bed reactor 19 in which temperatures of about 850 to 1050*C exist. In its lower portion, the fluidized-bed reactor 19 includes a relatively dense fluid 10 ized bed 20 of metal oxide particles. The fluidization of this fluidized bed is ef fected by primary air from a conduit 21, which is delivered through a distributor 22 into the lower portion of the fluidized bed 20. In doing so, the primary air is pre heated in an air preheater 23 explained in detail below. 15 In addition, gaseous and/or liquid fuel is introduced into the fluidized bed 20 from outside through one or more lances 24, the fuel being heated and ignited by the hot metal oxide particles of the fluidized bed 20. The complete combustion is effected in the reactor 19 together with the preheated secondary air supplied through a conduit 25. The desired calcination temperature is achieved by means 20 of this combustion. The fluidized-bed reactor 19 can also constitute an annular fluidized-bed reactor in accordance with DE 102 60 739. In this case, the supply of secondary air can be effected through the central tube of the annular fluidized-bed reactor. However, it 25 is also possible to divide the supply of secondary air and introduce the same both through a conduit above the distributor plate and through the central tube. The hot waste gas of the fluidized-bed reactor 19, which includes metal oxide, is delivered through a passage 26 into a recirculation cyclone 27. The waste gas of 30 the recirculation cyclone 27 is supplied to the second entrained-bed preheater 14 WO 2008/077462 PCT/EP2007/010680 -9 via conduit 15. Part of the hot solids separated in the recirculation cyclone 27 are returned via a conduit 28 into the fluidized-bed reactor 19, whereas the remaining part of the hot solids is supplied to a first cooling stage through a conduit 29. This first cooling stage is configured such that via a conduit 30 additional air, via a 5 further conduit 31 preheated fluidizing air, and via a third conduit 33 technical oxygen are mixed with each other and supplied to a pneumatic delivery conduit 34 via a further conduit 33. The hot solids from conduit 29 are introduced into this delivery conduit 34, so that the hot solids mix with the mixture of air and oxygen from conduit 33, whereby the solids are cooled, whereas the mixture of air and 10 oxygen is heated. The waste gas of the separating cyclone 10 is admixed to this solids-gas mixture via conduit 11 and then introduced into the cooling cyclone 12 via a conduit 35. In said cooling cyclone, gas and solids are separated from each other, the gas flow being supplied as preheated, oxygen-enriched secondary air to the fluidized-bed reactor 19 via conduit 25. Via conduit 36, the solids are supplied 15 to the fluidized-bed cooler 23, which at the same time constitutes the air preheater for the primary air. The solids are cooled further in the fluidized-bed cooler 23, whereas the primary air is heated in the tube bundles. The primary air heated in this way then is delivered via conduit 21 into the fluidized-bed reactor 19. 20 Fluidizing air is supplied into the fluidized-bed cooler 23 via conduit 37, which is also connected with a further fluidized-bed cooler 38. In the second fluidized-bed cooler 38, the solids are cooled to the desired final temperature by means of one or more liquid cooling media 39. The fluidizing air introduced into the two fluidized bed coolers via conduits 37 is supplied by a blower 41 via a conduit 40. The pri 25 mary air, which is heated in the tube bundles of the first fluidized-bed cooler, is supplied via a further blower 42. Alternatively or in addition to the supply of oxygen via the delivery conduit 34, the technical oxygen can also be admixed to the pri mary air via the blower 42 or to the fluidizing air for the two fluidized-bed coolers 23 and 38 via a conduit 43. 30 WO 2008/077462 PCT/EP2007/010680 - 10 In the embodiment as shown in Fig. 2, a heating gas is used as fuel. As described above, the same is introduced into the fluidized-bed reactor 19 via the lances 24. The heating gas can be preheated before it is supplied to the fluidized-bed reactor 19. For this purpose, the heating gas is supplied via a conduit 44 to the tube bun 5 dle of a further fluidized-bed cooler 45, in which the solids from the cooling cyclone 12 are cooled. The fluidized-bed cooler 45 thus is provided upstream of the fluid ized-bed cooler 23, so that the solids from the cooling cyclone 12 first pass the fluidized-bed cooler 45, then the fluidized-bed cooler 23 and finally the fluidized bed cooler 38. The fluidized-bed coolers can have a different number of chambers. 10 Another embodiment is shown in Fig. 3. Heating gas is likewise used as fuel in the fluidized-bed reactor 19. For this purpose, the heating gas is introduced via a conduit 46 into a further cooling cyclone 47, whose waste gases are introduced into the fluidized-bed reactor 19 via the lances 24. The solids separated in the first 15 fluidized-bed cyclone 12 are introduced into a conduit 48 which for instance serves as pneumatic delivery conduit, into which also opens the conduit 46 for supplying the heating gas. The solids-gas mixture introduced into the second cooling cyclone 47 is separated in the cooling cyclone 47, the solids being supplied to the first fluidized-bed cooler 23 via a conduit 36'. 20 Example 1: Improvement of a plant for use of a gas of low calorific value An existing plant for producing 3300 t of alumina per day is operated with fuel oil which has a calorific value of 39876 kJ/kg. This plant should be switched over to a 25 heating gas which merely has a calorific value of 4642 kJ/kg. There should still be achieved an alumina production of 3300 t/d. About 8000 Nm 3 /h of oxygen (95%) are admixed to the additional air, and the heating gas is preheated. This preheating of the heating gas is effected either in 30 the fluidized-bed cooler 45 as shown in Fig. 2 to 180 0 C or, if the gas quality per- WO 2008/077462 PCT/EP2007/010680 - 11 mits, directly to 450 0 C by the cooling cyclone 47 in accordance with the embodi ment as shown in Fig. 3. Via the lances 24, the oxygen is introduced into the fluidized-bed reactor 19 together with the heating gas with a gas velocity between about 20 and about 50 m/s. The alumina leaves the fluidized-bed cooler 38 with a 5 product temperature of not more than 80 0 C. Due to the above-described supply of oxygen into the fluidized-bed cooler 19, the aluminum production of 3300 t/d can also be maintained with the fuel of lower calorific value. At the same time, an improvement of the product quality is 10 achieved by a reduction of the grain disintegration. The effective volume flow rates in the plant are smaller or maximally equal to the effective volume flow rates of the heating oil case. Dust emission thereby can be minimized. The oxygen content in the gas outlet of the fluidized-bed reactor 19 is equal to the oxygen content in the heating oil case. 15 Example 2: Quality improvement of the product in terms of grain disintegra tion In a plant in accordance with the embodiment as shown in Fig. 1, in which there 20 are produced 3300 t of alumina per day with an air quantity of 120000 Nm 3 /h, about 10000 Nm 3 /h of oxygen (95%) are admixed via conduit 32 to the additional air supplied via conduit 30, the supply of additional air via conduit 30 being re duced by about 40000 Nm 3 /h. Thus, an oxygen content of about 34.3% is obtained in conduit 33. The effective volume flow rate and hence the gas velocity are re 25 duced thereby in the entrained-bed preheater 14 and the separating cyclone 17 by about 18%, in the cooling cyclone 12 by about 28%, and in the fluidized-bed reac tor 19 and the recirculation cyclone 27 by about 16%. As a result, the grain disin tegration of the alumina can be reduced by more than 16%.
- 11a In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the 5 stated features but not to preclude the presence or addition of further features in various embodiments of the invention. It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of 10 the common general knowledge in the art, in Australia or any other country. 2430981_1 (GHMatters) 6/10/10

Claims (20)

1. A process for the thermal treatment of particulate solids, wherein the solids are at least partly dehydrated and preheated, before the solids are 5 introduced into a circulating fluidized-bed of a fluidized-bed reactor in which the solids are heated to a temperature of 650 to 1250 0 C by combustion of fuel and new solids are generated, wherein primary air for fluidizing the fluidized-bed, which is enriched with oxygen to an oxygen content of 22 to 99.9%, and/or secondary air, which is enriched with oxygen to an oxygen content of 30 to 10 99.9%, is/are supplied to the fluidized-bed reactor, wherein the primary air and the secondary air is introduced into the fluidized-bed reactor with a gas velocity between 5 and 300 m/s, and wherein the fuel is preheated prior to entering the fluidized-bed reactor. is
2. The process according to claim 1, wherein the primary air and/or secondary air is introduced into the fluidized-bed reactor with a gas velocity of less than 200 m/s.
3. The process according to claim 1, wherein the primary air and/or the 20 secondary air is introduced into the fluidized-bed reactor with a gas velocity between 10 and 100 m/s.
4. The process according to any one of claims 1 to 3, wherein the particulate solids are metal hydroxide which is converted to metal oxide. 25
5. The process according to any one of the preceding claims, wherein the primary air supplied to the fluidized-bed reactor is enriched with oxygen to an oxygen content of 22 to 49% and/or secondary air enriched with oxygen to an oxygen content of 90 to 99.5%. 30
6. The process according to any one of the preceding claims, wherein the oxygen-enriched air flows supplied to the fluidized-bed reactor are indirectly 36377381 (GHMatters) P80975.AU 3/09/12 - 13 and/or directly preheated with process heat to a temperature between 100 and 800*C, in particular between 150 and 750*C.
7. The process according to any one of the preceding claims, wherein the 5 heating gas supplied to the fluidized-bed reactor is indirectly and/or directly preheated with process heat to a temperature between 100 and 300*C, in particular between 150 and 250 0 C.
8. The process according to any one of the preceding claims, wherein the 10 metal oxide withdrawn from the fluidized-bed reactor is indirectly cooled in at least one first cooling stage by direct contact with air and/or oxygen or a mixture thereof and in at least one further cooling stage, which constitutes a fluidized bed cooler, downstream of the first cooling stage. 15
9. The process according to any one of claims 6 to 8, wherein the gases supplied to the fluidized-bed reactor are preheated in at least one of the first and/or second cooling stages.
10. The process according to any one of claims 8 or 9, wherein at least one 20 of the first cooling stages includes a delivery conduit, which pneumatically delivers the metal oxide in upward direction, and a separating cyclone.
11. The process according to any one of the preceding claims, wherein the fuel has a calorific value of below 7500 kJ/kg, in particular between 4000 and 25 5500 kJ/kg, wherein additional air, to which between 1.5 and 3.5 Nm 3 /h of oxygen (95%) are admixed per 1 t/d-of alumina produced, is supplied to the fluidized-bed reactor.
12. The process according to any one of the preceding claims, wherein 23 to 30 25 Nm 3 /h of additional air, to which between 2 and 4 Nm 3 /h of oxygen (95%) are admixed, are supplied to the fluidized-bed reactor per 1 t/d of alumina produced. 36377381 (GHMatters) P80975 AU 3109112 - 14
13. The process according to claim 1, wherein the metal hydroxide in the fluidized-bed reactor is heated to a temperature of 850 to 1050 0 C by combustion of fuel, and metal oxide is generated. 5
14. The process according to any one of the preceding claims, wherein the reduction of the grain disintegration is greater than the smallest reduction of the gas velocity in one of the units of the plant.
15. A plant for thermal treatment of particulate solids, in particular for 1o performing a process according to any one of the preceding claims, comprising at least one preheating stage for preheating the solids, at least one fluidized bed reactor, a means for supplying fuel into the fluidized-bed reactor with a circulating fluidized-bed, and at least one cooling stage, wherein the cooling stage consists of at least three coolers, wherein at least one of these coolers is is arranged and connected with the means for supplying fuel such that for preheating the fuel before entrance into the fluidized-bed reactor the fuel is passed through the at least one cooler, and wherein means are provided for preheating primary air for fluidizing the solids in the fluidized-bed, and whereby when in use, a secondary air enriched with oxygen is introduced into the 20 fluidized bed with a gas velocity between 5 and 300 m/s.
16. The plant according to claim 15, wherein a pneumatic conveyor for supplying solids into the fluidized-bed reactor is provided upstream of the fluidized-bed reactor, the pneumatic conveyor being connected via a cyclone 25 with a delivery conduit for hot solids from the fluidized-bed reactor via a conduit.
17. The plant according to any one of claims 15 and 16, wherein two of the coolers constitute fluidized-bed coolers. 30
18. The plant according to claim 17, wherein the fluidized-bed coolers each consist of a plurality of chambers. 43939721 (OHMatters) P8O97SAU - 15
19. The plant according to any one of claims 15 to 18, wherein the cooler for heating the fuel gas is a cooling cyclone.
20. A process for the thermal treatment of particulate solids or a plant for s thermal treatment of particulate solids, substantially as herein described with reference to the accompanying drawings and as described in the Examples. 36377381 (GHMatters) P80975.AU 3/09/12
AU2007338485A 2006-12-22 2007-12-07 Process and plant for the thermal treatment of particulate solids, in particular for producing metal oxide from metal hydroxide Ceased AU2007338485B2 (en)

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WO1990012253A1 (en) * 1989-04-13 1990-10-18 A. Ahlstrom Corporation Method and apparatus for recovering heat from solid material separated from gasification or combustion processes
WO2004056701A1 (en) * 2002-12-23 2004-07-08 Outokumpu Technology Oy Process and plant for producing metal oxide from metal compounds
WO2005119126A1 (en) * 2004-05-28 2005-12-15 Alstom Technology Ltd Fluid bed device with oxygen-enriched combustion agent

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DE19542309A1 (en) * 1995-11-14 1997-05-15 Metallgesellschaft Ag Process for the production of aluminum oxide from aluminum hydroxide
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GB1101199A (en) * 1966-11-01 1968-01-31 Texaco Development Corp Ore reduction
US3928021A (en) * 1970-12-28 1975-12-23 Nippon Kokan Kk Process of reducing iron ores
WO1990012253A1 (en) * 1989-04-13 1990-10-18 A. Ahlstrom Corporation Method and apparatus for recovering heat from solid material separated from gasification or combustion processes
WO2004056701A1 (en) * 2002-12-23 2004-07-08 Outokumpu Technology Oy Process and plant for producing metal oxide from metal compounds
WO2005119126A1 (en) * 2004-05-28 2005-12-15 Alstom Technology Ltd Fluid bed device with oxygen-enriched combustion agent

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WO2008077462A3 (en) 2008-09-18
UA100498C2 (en) 2013-01-10
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WO2008077462A2 (en) 2008-07-03

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