CN101845550A - Method for extracting aluminum hydroxide and aluminum oxide from side product obtained by preparing magnesium metal by taking aluminum or aluminum alloy as reducing agent - Google Patents

Method for extracting aluminum hydroxide and aluminum oxide from side product obtained by preparing magnesium metal by taking aluminum or aluminum alloy as reducing agent Download PDF

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CN101845550A
CN101845550A CN201010144062A CN201010144062A CN101845550A CN 101845550 A CN101845550 A CN 101845550A CN 201010144062 A CN201010144062 A CN 201010144062A CN 201010144062 A CN201010144062 A CN 201010144062A CN 101845550 A CN101845550 A CN 101845550A
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aluminum
solution
magnesium metal
naal
aluminium hydroxide
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CN101845550B (en
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冯乃祥
王耀武
胡文鑫
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Northeastern University China
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Northeastern University China
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Priority to PCT/CN2010/073122 priority patent/WO2011127671A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
    • 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
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
    • C01F7/068—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from carbonate-containing minerals, e.g. dawsonite
    • 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
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
    • C01F7/0693—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention relates to a method for extracting aluminum hydroxide and aluminum oxide from a side product obtained by preparing magnesium metal by taking aluminum or an aluminum alloy as a reducing agent, comprising the following steps of: crushing material blocks; wet-milling; leaching alkali liquor; filtering and separating CaCO3 generated in the leaching process to obtain an NaAl (OH)4 solution; then carrying out desiliconization treatment on the NaAl (OH)4 solution; then carrying out seed precipitation or carbonization precipitation so that NaAl (OH)4 contained in the NaAl (OH)4 solution is decomposed; and then filtering and separating the aluminum hydroxide generated by the decomposition from a mother solution. The method can be used for preparing the aluminum hydroxide and the aluminum oxide by sufficiently utilizing obtained ash residues and adopting a resolution method when preparing the magnesium metal, enhances the economic benefits of extracting the magnesium metal and reduces the environmental pollution and the preparation cost of the magnesium metal.

Description

From being that reductive agent is produced and extracted aluminium hydroxide and method of alumina the by product of MAGNESIUM METAL with the aluminum or aluminum alloy
Technical field
The present invention relates to the extracting method of a kind of aluminium hydroxide and aluminum oxide, particularly a kind of from being that reductive agent is produced and extracted aluminium hydroxide and method of alumina the by product of MAGNESIUM METAL with the aluminum or aluminum alloy.
Background technology
Present industrial vacuum metal hot reducing method is produced in the production of MAGNESIUM METAL, and its reductive agent is a ferrosilicon, and raw material is a rhombspar, and the main chemical compositions of rhombspar is CaCO 3MgCO 3, it generates CaOMgO after high-temperature calcination, after levigate and ferrosilicon powder by chemical equation (1) prepare burden, the group of making, place the vacuum reducing stove then, under the temperature about 1250 ℃, carry out vacuum reducing and produce MAGNESIUM METAL.
Figure GSA00000081872000011
But in actual industrial production, the dosage of reductive agent ferrosilicon is general all greater than pressing about 10% of the theoretical dosage of above-mentioned chemical equation.
Can calculate by above-mentioned chemical equation, be the magnesium-smelting silicothermic process of reductive agent with the ferrosilicon at present, its reaction mass is 4.78: 1 with the ratio of product MAGNESIUM METAL, but the material/magnesium of industrial reality is 6: 1, that is to say industrially will produce 5 tons lime-ash with one ton of magnesium of the every production of magnesium-smelting silicothermic process (major ingredient is 2CaOSiO 2), this lime-ash can be used as the raw material that cement is made in the cement mill in principle, but owing to having handled that the very low general factory of its added value all abandons it.
It is reductive agent with the MgO/CaO mol ratio with aluminium scrap or scrap aluminium alloy powder is material vacuum thermal reduction refining magnesium technology greater than 1 material that nearest Feng Naixiang, Wang Yaowu and Hu Wenxin have been invented a kind of, thereby the material/magnesium that makes metallothermics refining magnesium is than reducing widely.Because material/magnesium has not only improved labor productivity widely than reducing widely, and the energy consumption that makes magnesium smelt production reduces widely.This invention be that the by product of reductive agent vacuum-thermal reduction production MAGNESIUM METAL is that a kind of compound of mainly being made up of CaO and Al2O3 is the lumpy material of major ingredient with aluminium or aluminum silicon alloy powder, aluminum oxide in the by product of this lumpy material is a kind of of great value metallurgy and industrial chemicals, if the aluminum oxide in this slag is extracted recovery and utilization, not only can make magnesium-smelting plant increase Chemicals, and the production cost that will make the aluminothermy vacuum-thermal method produce MAGNESIUM METAL reduce widely.
Summary of the invention
At the problems referred to above, the invention provides and a kind ofly extract aluminium hydroxide and method of alumina after the MAGNESIUM METAL the last by product slag charge from producing for the reductive agent vacuum-thermal method with the aluminum or aluminum alloy, this method can be reclaimed the by product slag charge of aluminothermy vacuum-thermal method refining magnesium and be utilized, thereby can improve the economic benefit of magnesium factory widely.
The vacuum-thermal method magnesium refining method that with the aluminum or aluminum alloy is reductive agent carries out according to the following steps:
1, be raw material with rhombspar, giobertite, brucite and Wingdale, calcine respectively that wherein the calcining temperature of rhombspar is 1000～1200 ℃, the calcining back obtains to contain the CaOMgO material; The calcining temperature of giobertite is 800～1000 ℃, and the calcining back obtains to contain the MgO material; The calcining temperature of brucite is 800～1000 ℃, and the calcining back obtains to contain the MgO material; The calcining temperature of Wingdale is 1000～1200 ℃, and the calcining back obtains to contain the CaO material; In above-mentioned four kinds of materials two or more mixed, be mixed with the MgO/CaO mol ratio and be 1.5～18 raw material.
2, the raw material of above-mentioned preparation is levigate to 100 orders and mix in ball mill, obtain powder to be restored.
3, add reductive agent in powder to be restored, reductive agent is aluminium powder or the Al alloy powder of granularity below 1mm, makes reaction mass, and the add-on of reductive agent is 1.03～1.1 times of reaction theory institute expense; Described Al alloy powder is aluminum silicon alloy powder or aluminium-magnesium alloy powder.
4, reaction mass is pressed into bulk or bulk.
5, bulk or block reaction mass are placed carry out the vacuum reducing reaction in the high-temperature vacuum reduction reaction furnace that has the magnesium crystallizer, the Reaktionsofen internal pressure is less than 30Pa, 900～1250 ℃ of temperature of reaction, reaction generate gaseous metal magnesium condensation-crystallization on the magnesium crystallizer and become MAGNESIUM METAL.
To produce the scheme of MAGNESIUM METAL as follows for metallothermic reduction reaction under the vacuum condition:
Because people such as Feng Naixiang invention is the vacuum-thermal method refining magnesium of reductive agent with the aluminum or aluminum alloy, use with the MgO/CaO mol ratio greater than 1 reduction reaction material, it presses the difference of MgO/CaO molar ratio ingredient size, and the by product slag charge behind its vacuum reducing reaction refining magnesium contains different chemical constitutions by following vacuum-thermal reduction reaction:
CaO+6MgO+4Al＝6Mg+CaO·2Al 2O 3 (2)
CaO+18MgO+12Al＝18Mg+CaO·6Al 2O 3 (3)
12CaO+21MgO+14Al＝21Mg+12CaO·7Al 2O 3 (4)
CaO+3MgO+2Al＝3Mg+CaO·Al 2O 3 (5)
Wherein the accessory substance slag charge is respectively CaO2Al 2O 3, CaO6Al 2O 3, 12CaO7Al 2O 3And CaOAl 2O 3In one or more mixtures.
When reducing agent used alusil alloy, the CaO in the batching and the charge ratio of MgO should be taken into account the behavior of component content in reduction process of silicon in the reducing agent, and the silicon in the alusil alloy can exist following chemical reaction with the reaction of MgO in the batching and CaO:
2CaO+2MgO+Si＝2Mg+2CaO·SiO 2 (6)
The present invention utilizes the accessory substance of metallothermic reduction reaction under the above-mentioned vacuum condition to extract Al 2O 3And Al (OH) 3Method as follows:
1, at first with below broken wet-milling to 100 order of crumby accessory substance, the slag charge that this is levigate is put into Na then 2CO 3In the solution, or put into Na 2CO 3In the mixed solution that forms with NaOH, under 50～300 ℃ temperature, with the Al of slag charge 2O 3Leach the Al in the leachate 2O 3With NaAl (OH) 4Form be present in the leachate, and the CaO in the slag charge is with CaCO 3Form be precipitated out.
2, will leach the back material and filter, leach throw out CaCO 3, and NaAl (OH) 4Be present in the filtrate; Filtrate enters after desiliconization carries out kind of branch decomposition or the decomposition of carbon branch in kind of branch or the carbon capacitance divider, make NaAl (OH) 4Be decomposed into aluminium hydroxide (Al (OH) 3).
If with kind divide decomposing then need to containing NaAl (OH) 4Solution in add Al (OH) 3Crystal seed carries out the crystal seed kind and decomposes, and makes NaAl (OH) 4Resolve into Al (OH) 3And Na (OH), plant the Al (OH) that generates after decomposing in the solution 3Obtain product A l (OH) after separating after filtration 3, and by Na (OH) and the undecomposed NaAl of part (OH) 4The solution that forms; The Al (OH) that generates 3Most of as final products, part turns back to as crystal seed and removes kind of a branch decomposing N aAl (OH) in the decomposition of crystal seed container 4
If needing final product is Al 2O 3, can be with the Al (OH) that generates 3Calcine in the temperature more than 800 ℃ and to make Al (OH) 3Dehydration gets final product.
If the NaAl that from slag charge, leaches (OH) 4Solution adopts carbon to decompose and generates Al (OH) 3, then need to divide in the decomposition reaction container to containing NaAl (OH) at carbon 4Solution in feed CO 2Gas carries out carbon and decomposes, and makes NaAl (OH) 4Decompose and generate Al (OH) 3And Na 2CO 3Product.Carbon divides process required CO 2Come from the CO that rhombspar or wagnerite calcination process generate 2By product.Carbon decomposes the Al (OH) that generates 3Divide the rear Na that generates through filtering with carbon 2CO 3Solution namely forms commodity aluminium hydroxide after separating.
If needing final product is Al 2O 3, can be with the Al (OH) that generates 3Calcine in the temperature more than 800 ℃ and to make Al (OH) 3Dehydration can obtain alumina product.
In the said method, the desiliconization in the step 2 is to adopt conventional aluminium oxide industry desilication method.
Work as in the aforesaid method and adopt Na 2CO 3When solution leached, the concentration of yellow soda ash was 80～150g/L, Na 2CO 3The liquid-solid ratio of solution and slag charge is 50～1000g/L, and promptly every liter of leach liquor leaches 50～1000g slag charge; When adopting Na 2CO 3When the mixing solutions of forming with NaOH leached, the concentration of yellow soda ash was 20～150g/L in the mixing solutions, and concentration sodium hydroxide is 80～300g/L, and the liquid-solid ratio of mixing solutions and slag charge is 50～1000g/L.
Extraction time is 20～200min in the aforesaid method.
In the said method, contained CaO and Al when what leach 2O 3Its main chemical composition of slag charge be CaO2Al 2O 3Or CaO6Al 2O 3Or during both mixtures, plant and contain a small amount of NaAl (OH) after decomposing 4NaOH solution in the causticization container, make part NaOH in the solution carry out carbonating to process, filter out afterwards the Al (OH) that generates in the part carbonation 3, make it to become and contain NaOH and Na 2CO 3Mixed solution, return in the wet-milling device leaching agent as raw material.The chemical analysis of the material in the stripping raw material is mainly CaOAl 2O 3Or 12CaO7Al 2O 3Or during both mixtures, plant the NaOH solution that contains a small amount of Na after decomposing and will carry out carbonating and process, filter out afterwards the Al (OH) that generates after the carbonating 3, the NaOH in the solution becomes Na fully 2CO 3, with this Na 2CO 3Solution returns in the wet-milling device leaching agent as raw material.
In the said method, when the raw material main chemical that is leached is CaO2Al 2O 3Or CaO6Al 2O 3Or during both mixtures, Na in the mother liquor after carbon divides 2CO 3Need to carry out the part causticization, make the Na in the mother liquor 2CO 3Partial Conversion becomes NaOH, and its caustic is calcium oxide, and the carbon mother liquid after the part causticization contains NaOH and Na 2CO 3Chemical constituent is returned it in the wet-milling device leaching agent as raw material; When the main chemical that is leached raw material is CaOAl 2O 3Or 12CaO7Al 2O 3Or during both mixtures, the contained Na of mother liquor after carbon divides 2CO 3No longer carry out causticization and process, the leaching agent as raw material recycles in the wet-milling device but directly this mother liquor is input to.
Method of the present invention is when producing MAGNESIUM METAL, and the lime-ash that can make full use of acquisition adopts decomposition method to produce aluminium hydroxide and aluminum oxide, has improved the economic benefit of producing MAGNESIUM METAL, reduces environmental pollution, has reduced the preparation cost of MAGNESIUM METAL.
Description of drawings
Fig. 1 for the embodiment of the invention 1 from being that reductive agent is produced and extracted aluminium hydroxide and method of alumina schematic flow sheet the by product of MAGNESIUM METAL with the aluminum or aluminum alloy.
Fig. 2 for the embodiment of the invention 2 from being that reductive agent is produced and extracted aluminium hydroxide and method of alumina schematic flow sheet the by product of MAGNESIUM METAL with the aluminum or aluminum alloy.
Fig. 3 for the embodiment of the invention 3 from being that reductive agent is produced and extracted aluminium hydroxide and method of alumina schematic flow sheet the by product of MAGNESIUM METAL with the aluminum or aluminum alloy.
Fig. 4 for the embodiment of the invention 4 from being that reductive agent is produced and extracted aluminium hydroxide and method of alumina schematic flow sheet the by product of MAGNESIUM METAL with the aluminum or aluminum alloy.
Embodiment
Embodiment 1
Its that produce that magnesium metal generated from the reducing material that is made up of MgO and CaO as the reducing agent vacuum-thermal reduction take aluminium powder or alusil alloy powder is mainly by CaO2Al 2O 3Or CaO6Al 2O 3, or by extracting aluminium hydroxide and aluminium oxide in both slag charges of compositions of mixtures.
Be CaO2Al with its main component 2O 3Or CaO6Al 2O 3Or the clinker of both mixtures is placed on by NaOH and Na through levigate 2CO 3In the mixed solution that forms, also can contain a small amount of NaAl (OH) in the mixed solution 4Composition under 50-300 ℃ temperature, with the alumina leaching in the lime-ash, makes it become NaAl (OH) then 4Solution filters then, makes NaAl (OH) 4The CaCO that generates in solution and the leaching process 3Slag separates, afterwards at NaAl (OH) 4Add Al (OH) in the solution 3Crystal seed allows NaAl (OH) 4Solution decomposes under 50-90 ℃ temperature, separates out Al (OH) 3, filter then with Al (OH) 3Leach and wash, the Al of acquisition (OH) 3A part is returned NaAl (OH) as crystal seed 4The kind of solution is divided decomposition process, and another part is as industrial Al (OH) 3Product is maybe with the Al (OH) that obtains 3Obtain Al 800-1200 ℃ of lower calcining 2O 3Product.
Plant to divide rear and filter out and decompose the Al (OH) that generates 3After, last liquid is mother liquor, mainly exists decomposition of crystal seed in the mother liquor and goes out Al (OH) 3The NaOH of Shi Shengcheng and the NaAl (OH) that does not decompose fully 4Afterwards mother liquor is transported in the carbonating container, feeds CO 2Gas is that the part NaOH carbonic acid in the mother liquor changes into Na 2CO 3, then with the Al (OH) that generates in the part carbonation 3Leach, contain NaOH and Na in its filtrate 2CO 3, this filtrate is turned back in the wet-milling, recycle as former leaching agent of expecting.Flow process as shown in Figure 1.
Embodiment 2
Its that produce that magnesium metal generated from the reducing material that is made up of MgO and CaO as the reducing agent vacuum-thermal reduction take aluminium powder or alusil alloy powder is mainly by CaOAl 2O 3Or 12CaO7Al 2O 3, or by extracting aluminium hydroxide and aluminium oxide in both slag charges of compositions of mixtures.
Be CaOAl with its main component 2O 3Or 12CaO7Al 2O 3Or the clinker of both mixtures is Na through the levigate main component that is placed on 2CO 3Solution in, also can contain a small amount of NaAl (OH) in the solution 4Composition under 50-300 ℃ temperature, with the alumina leaching in the lime-ash, makes it become NaAl (OH) then 4Solution filters then, makes NaAl (OH) 4The CaCO that generates in solution and the leaching process 3Slag separates, afterwards at NaAl (OH) 4Add Al (OH) in the solution 3Crystal seed allows NaAl (OH) 4Solution decomposes under 60-90 ℃ temperature, separates out Al (OH) 3, filter then, with Al (OH) 3Leach and wash, the Al of acquisition (OH) 3A part can be used as crystal seed and returns NaAl (OH) 4The kind of solution is divided decomposition process, and another part can be used as industrial Al (OH) 3Product is maybe with the Al (OH) that obtains 3Can obtain Al 800-1200 ℃ of lower calcining 2O 3Product.
Plant to divide rear and filter out and decompose the Al (OH) that generates 3After, last liquid is mother liquor, mainly exists decomposition of crystal seed in the mother liquor and goes out Al (OH) 3The NaOH of Shi Shengcheng and the NaAl (OH) that does not decompose fully 4Afterwards mother liquor is transported in the carbonating container, feeds CO 2Gas is that the part NaOH carbonic acid in the mother liquor changes into Na 2CO 3, then with the Al (OH) that generates in the part carbonation 3Leach, contain NaOH and Na in its filtrate 2CO 3, this filtrate is turned back in the wet-milling, recycle as former leaching agent of expecting.Flow process as shown in Figure 2.
Embodiment 3
Its that produce that magnesium metal generated from the reducing material that is made up of MgO and CaO as the reducing agent vacuum-thermal reduction take aluminium powder or alusil alloy powder is mainly by CaO2Al 2O 3Or CaO6Al 2O 3, or by extracting aluminium hydroxide and aluminium oxide in both slag charges of compositions of mixtures.
Be CaO2Al with its main chemical composition 2O 3Or CaO6Al 2O 3Or the clinker of both mixtures is through levigate NaOH and the Na of being placed on 2CO 3In the solution that forms, also can contain a small amount of NaAl (OH) in the mixed solution 4Composition under 50-300 ℃ temperature, with the alumina leaching in the lime-ash, makes it become NaAl (OH) 4Solution filters then, makes NaAl (OH) 4The CaCO that produces in solution and the leaching process 3Slag separates, afterwards to NaAl (OH) 4Pass into CO in the solution 2, make the NaAl (OH) in the solution 4Carry out carbon and decompose generation Al (OH) 3Sediment and Na 2CO 3, filter then and obtain Al (OH) 3, the Al of acquisition (OH) 3 can obtain industrial Al 800-1200 ℃ of lower calcining 2O 3, filter out Al (OH) 3Mother liquor be called carbon mother liquid, carbon mother liquid mainly is Na forever 2CO 3Solution composition makes the part Na in the mother liquor afterwards 2CO 3The CaO that generates with limestone calcination carries out causticizing reaction generation NaOH and CaCO 3, the CaCO that the part causticizing reaction generates 3Through after the isolated by filtration, last solution is NaOH and Na 2CO 3Mixed solution, this solution refines again the leaching of the lime-ash of magnesium accessory substance clinker after levigate as leachate, form a closed cycle.Flow process as shown in Figure 3.
Embodiment 4
Its that produce that magnesium metal generated from the reducing material that is made up of MgO and CaO as the reducing agent vacuum-thermal reduction take aluminium powder or alusil alloy powder is mainly by CaOAl 2O 3Or 12CaO7Al 2O 3, or by extracting aluminium hydroxide and aluminium oxide in both clinkers of compositions of mixtures.
Be CaOAl with its Main Ingredients and Appearance 2O 3Or 12CaO7Al 2O 3Or the clinker of both mixtures is NaCO through levigate its Main Ingredients and Appearance that is placed on 3Solution in, also can contain a small amount of NaAl (OH) in the solution 4Composition under 50-300 ℃ temperature, with the alumina leaching in the lime-ash, makes it become NaAl (OH) 4Solution filters then, makes NaAl (OH) 4The CaCO that solution and leaching process generate 3Slag separates, afterwards to NaAl (OH) 4Pass into CO in the solution 2, make the NaAl (OH) in the solution 4Carry out carbon and decompose, obtain solid Al (OH) 3And NaCO 3Solution filters then and obtains Al (OH) 3, the Al of acquisition (OH) 3Can obtain industrial Al 800-1200 ℃ of lower calcining 2O 3, and NaCO 3Solution returns the leaching of refining magnesium lime-ash, forms a closed cycle.Flow process as shown in Figure 4.

Claims (6)

1. a method of extracting aluminium hydroxide and aluminium oxide from the accessory substance of producing magnesium metal take aluminum or aluminum alloy as reducing agent it is characterized in that by fragmentation, wet-milling, the alkaline leaching of expecting piece, filters to isolate the CaCO that generates in the leaching process 3, obtain NaAl (OH) 4Solution, then solution is carried out desiliconization and processes, carry out again kind of branch or carbon branch, make the NaAl (OH) in the solution 4Decompose, will decompose afterwards the aluminium hydroxide and the mother liquor that produce and carry out isolated by filtration; If obtain aluminium oxide, again aluminium hydroxide is made Al (OH) being higher than to calcine under 800 ℃ the temperature 3Dehydration becomes Al 2O 3Form etc. step and technical process.
2. the method for extracting aluminium hydroxide and aluminium oxide from the accessory substance of producing magnesium metal take aluminum or aluminum alloy as reducing agent according to claim 1 is characterized in that raw materials usedly containing CaO and Al for producing take aluminium or alusil alloy as reducing agent vacuum-thermal reduction MgO/CaO material behind the magnesium metal 2O 3Accessory substance clinker material.
3. the method for extracting aluminium hydroxide and aluminium oxide from the accessory substance of producing magnesium metal take aluminum or aluminum alloy as reducing agent according to claim 1 is characterized in that as the NaAl (OH) with alkaline leaching 4Leachate when kind divide to decompose producing aluminium hydroxide, its used crystal seed is Al (OH) 3, plant and divide the Al (OH) that generates after the decomposition reaction 3With obtain aluminium hydroxide after the mother liquor isolated by filtration.
4. according to claim 1 or the 3 described methods of from the accessory substance of producing magnesium metal take aluminum or aluminum alloy as reducing agent, extracting aluminium hydroxide and aluminium oxide, it is characterized in that being contained CaO and Al when what leach 2O 3Its main chemical composition of slag charge be CaO2Al 2O 3Or CaO6Al 2O 3Or during both mixtures, plant and contain a small amount of NaAl (OH) after decomposing 4NaOH solution in the causticization container, make part NaOH in the solution carry out carbonating to process, filter out afterwards the Al (OH) that generates in the part carbonation 3, make it to become and contain NaOH and Na 2CO 3Mixed solution, return in the wet-milling device leaching agent as raw material; The chemical analysis of the material in the stripping raw material is mainly CaOAl 2O 3Or 12CaO7Al 2O 3Or during both mixtures, plant the NaOH solution that contains a small amount of Na after decomposing and will carry out carbonating and process, filter out afterwards the Al (OH) that generates after the carbonating 3, the NaOH in the solution becomes Na fully 2CO 3, with this Na 2CO 3Solution returns in the wet-milling device leaching agent as raw material.
5. according to claim 1 from being that reductive agent is produced and extracted aluminium hydroxide and method of alumina the by product of MAGNESIUM METAL with the aluminum or aluminum alloy, it is characterized in that when containing NaAl (OH) 4Leach liquor adopt the carbon branch to decomposite Al (OH) 3The time, it is the CO that rhombspar or giobertite calcining produce that its used carbon divides decomposition agent 2Gas, carbon decomposes the Al (OH) that the back is produced 3Be commodity Al (OH) with the solid product after the mother liquor filtering separation 3, Al (OH) 3Can get the commodity aluminum oxide at temperature lower calcination greater than 800 ℃.
6. the method for extracting aluminium hydroxide and aluminium oxide from the accessory substance of producing magnesium metal take aluminum or aluminum alloy as reducing agent according to claim 1 is characterized in that the raw material main chemical that is leached when quilt is CaO2Al 2O 3Or CaO6Al 2O 3Or during both mixtures, Na in the mother liquor after carbon divides 2CO 3Need to carry out the part causticization, make the Na in the mother liquor 2CO 3Partial Conversion becomes NaOH, and its caustic is calcium oxide, and the carbon mother liquid after the part causticization contains NaOH and Na 2CO 3Chemical constituent is returned it in the wet-milling device leaching agent as raw material; When the main chemical that is leached raw material is CaOAl 2O 3Or 12CaO7Al 2O 3Or during both mixtures, the contained Na of mother liquor after carbon divides 2CO 3No longer carry out causticization and process, the leaching agent as raw material recycles in the wet-milling device but directly this mother liquor is input to.
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