WO2011127671A1 - Method for extracting aluminium hydroxide and alumina from byproduct obtained during refining metal magnesium with aluminium or aluminium alloy as reducer - Google Patents

Method for extracting aluminium hydroxide and alumina from byproduct obtained during refining metal magnesium with aluminium or aluminium alloy as reducer Download PDF

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WO2011127671A1
WO2011127671A1 PCT/CN2010/073122 CN2010073122W WO2011127671A1 WO 2011127671 A1 WO2011127671 A1 WO 2011127671A1 CN 2010073122 W CN2010073122 W CN 2010073122W WO 2011127671 A1 WO2011127671 A1 WO 2011127671A1
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aluminum
cao
solution
decomposition
naal
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PCT/CN2010/073122
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French (fr)
Chinese (zh)
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冯乃祥
王耀武
胡文鑫
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东北大学
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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

Definitions

  • the present invention relates to a method for extracting aluminum hydroxide and aluminum oxide, and more particularly to a method for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or an aluminum alloy as a reducing agent.
  • the reducing agent is ferrosilicon
  • the raw material is dolomite
  • the main chemical component of dolomite is CaC0 3 ⁇ MgC0 3 , which generates CaO ⁇ MgO after calcination at high temperature.
  • the ferrosilicon powder is compounded according to the chemical reaction equation (1), and then formed into a mass. Then, it is placed in a vacuum reduction furnace, and vacuum reduction is performed at a temperature of about 125 CTC to obtain magnesium metal.
  • the amount of reducing agent ferrosilicon is generally greater than about 10% of the theoretical compounding amount of the above chemical reaction equation.
  • the ratio of the reaction material to the product metal magnesium is 4.78:1, but the industrial actual material/magnesium is 6:1. That is to say, industrially, silicon-heated magnesium smelting produces about 5 tons of ash per ton of magnesium (the main component is 2CaO ⁇ Si0 2 ). This ash can in principle be used as a raw material for cement production in cement plants, but The added value is very low and the factory has abandoned it.
  • the by-product of the invention for vacuum-thermal reduction of magnesium metal by using aluminum or aluminum silicon alloy powder as a reducing agent is a bulk material mainly composed of a compound composed of CaO and A1 2 3 3 as a main component.
  • Alumina in by-products is a valuable metallurgical and chemical raw material. If the alumina in the slag is extracted and recycled, it can not only add a chemical product to the magnesium smelter, but also heat the aluminum. The production cost of producing magnesium metal by vacuum thermal reduction is greatly reduced. Summary of the invention
  • the present invention provides a method for extracting aluminum hydroxide and aluminum oxide from residual by-product slag after preparing magnesium metal by vacuum heat reduction method using aluminum or aluminum alloy as a reducing agent, which can heat aluminum
  • the by-product slag of magnesium smelting by vacuum thermal reduction is recovered and utilized, thereby greatly improving the economic efficiency of the magnesium plant.
  • the vacuum magnesium reduction method using aluminum or aluminum alloy as a reducing agent is carried out by the following steps:
  • Dolomite, magnesite ore, brucite and limestone are used as raw materials for calcination, in which dolomite is calcined.
  • the temperature is 1000 ⁇ 1200°C, and the CaO ⁇ MgO material is obtained after calcination; the calcination temperature of the magnesite ore is 800 ⁇ 1000°C, and the MgO-containing material is obtained after calcination; the calcining temperature of the brucite is 800 ⁇ 1000°C, After calcination, the MgO-containing material is obtained; the calcination temperature of the limestone is 1000-1200 ° C, and the CaO-containing material is obtained after calcination; two or more of the above four materials are mixed to prepare a MgO/CaO molar ratio of 1.5 ⁇ 18 raw materials.
  • the raw materials prepared above are ground to less than 100 mesh in a ball mill and uniformly mixed to obtain a powder to be reduced.
  • the reducing agent is aluminum powder or aluminum alloy powder with a particle size of less than 1 mm, and is made into a reaction material, and the reducing agent is added in an amount of 1.03 to 1.1 times the amount required for the reaction theory;
  • the aluminum alloy powder described is an aluminum silicon alloy powder or an aluminum magnesium alloy powder.
  • the reaction material is pressed into a dough or a block.
  • the lumps or block reaction materials are placed in a high-temperature vacuum reduction reactor with a magnesium crystallizer for vacuum reduction reaction.
  • the pressure in the reaction furnace is less than 30 Pa, and the reaction temperature is 900-1250 ° C.
  • the reaction produces gaseous magnesium metal.
  • the magnesium crystallizer is condensed and crystallized into metallic magnesium.
  • CaO + 3MgO + 2A1 3Mg + CaO ⁇ A1 2 0 3 ( 5 ) wherein the by-product slags are CaO ⁇ 2A1 2 0 3 , CaO ⁇ 6A1 2 0 3 , 12CaO ⁇ 7A1 2 0 3 and CaO ⁇ A1 2 0 One or a mixture of two or more of 3 .
  • the ratio of CaO and MgO in the batch should take into account the behavior of the component content of silicon in the reducing agent during the reduction process.
  • the method for extracting A1 2 0 3 and Al(OH) 3 by using the by-product of the metal thermal reduction reaction under the above vacuum condition is as follows: 1. First, the agglomerate The by-products are crushed and ground to below 100 mesh, and then the milled slag is placed in a Na 2 CO 3 solution or placed in a mixed solution of Na 2 CO 3 and NaOH at 50-300 ° C.
  • the slag A1 2 0 3 is leached, and the A1 2 0 3 in the leaching solution is present in the leaching solution in the form of NaAl(OH) 4 , and the CaO in the slag is precipitated in the form of CaCO 3 come out.
  • the decomposition is carried out by seed, it is necessary to add ⁇ 1( ⁇ ) 3 seed crystal to the solution containing NaAl(OH) 4 for seed seed decomposition, and to decompose NaAl(OH) 4 into Al(OH) 3 and Na(OH).
  • the ⁇ 1( ⁇ ) 3 formed after the decomposition of the seed in the solution is separated by filtration to obtain the product Al(OH) 3 , and a solution composed of Na(OH) and partially undecomposed NaAl(OH) 4 ; 3 Most of them are used as final products, and some are returned as seed crystals to the seed decomposition vessel to separate and decompose NaAl(OH) 4 .
  • the produced Al(OH) 3 can be calcined at a temperature of 800 ° C or higher to dehydrate Al(OH) 3 .
  • the NaAl(OH) 4 solution leached from the slag is decomposed by carbon to form ⁇ 1( ⁇ ) 3 , it is necessary to introduce C0 2 gas into the solution containing NaAl(OH) 4 in the carbon decomposition reaction vessel for carbon.
  • the decomposition is carried out to decompose NaAl(OH) 4 to form ⁇ 1( ⁇ ) 3 and Na 2 C0 3 products.
  • the CO 2 required for the carbon fraction process is derived from the CO 2 by -product formed by the dolomite or magnesite calcination process.
  • the Al(OH) 3 formed by the decomposition of carbon is separated from the Na 2 CO 3 solution formed by carbonation to form commercial aluminum hydroxide.
  • the produced Al(OH) 3 can be calcined at a temperature of 800 ° C or higher to dehydrate Al(OH) 3 to obtain an alumina product.
  • the desiliconization in the step 2 is a conventional alumina industrial desiliconization method.
  • the concentration of sodium carbonate is 80-150 g/L
  • the liquid-solid ratio of the Na 2 C0 3 solution to the slag is 50-1000 g/L, that is, leaching per liter of the leaching solution 50 ⁇ 1000g slag
  • the concentration of sodium carbonate in the mixed solution is 20-150 g/L
  • the concentration of sodium hydroxide is 80-300 g/L.
  • the liquid-solid ratio of the mixed solution to the slag is 50 to 1000 g/L.
  • the leaching time in the above method is 20 to 200 minutes.
  • the seed when the leached CaO-containing and A1 2 0 3 slag have a main chemical composition of CaO ⁇ 2A1 2 0 3 or CaO ⁇ 6A1 2 0 3 or a mixture of the two, the seed contains a small amount of NaAl after decomposition.
  • the (OH) 4 NaOH solution is subjected to carbonation treatment of a portion of the NaOH in the causticizing vessel, and then the Al(OH) 3 formed during the partial carbonation is filtered to become NaOH and Na 2 C0.
  • the mixed solution of 3 is returned to the leaching agent as a raw material in the wet mill.
  • the chemical composition of the material in the dissolution raw material is mainly CaO ⁇ A1 2 0 3 or 12CaO ⁇ 7A1 2 0 3 or a mixture of the two
  • the NaOH solution containing a small amount of Na after decomposition is subjected to carbonation treatment, followed by filtration.
  • ⁇ 1( ⁇ ) 3 formed after carbonation the NaOH in the solution completely changed to Na 2 C0 3 , and the Na 2 CO 3 solution was returned to the leaching agent as a raw material in the wet mill.
  • the main chemical component of the leached raw material is CaO ⁇ 2A1 2 0 3 or CaO ⁇ 6A1 2 0 3 or a mixture of the two
  • the Na 2 C0 3 in the mother liquor after carbon separation needs to be partially causticized, so that the Na 2 CO 3 portion of the mother liquor is converted into NaOH, the causticizing agent is calcium oxide, and the partially causticized carbon mother liquor contains NaOH.
  • the Na 2 C0 3 chemical component which is returned to the leaching agent as a raw material in the wet mill; when the main chemical component of the leached raw material is CaO ⁇ A1 2 0 3 or 12CaO ⁇ 7A1 2 0 3 or a mixture of the two
  • the Na 2 C0 3 contained in the mother liquor after the carbon separation is no longer subjected to causticization treatment, but is directly used to circulate the mother liquor into the wet mill as a raw material leaching agent.
  • the method of the invention can make full use of the obtained ash and prepare the aluminum hydroxide and the aluminum oxide by the decomposition method, thereby improving the economic benefit of preparing the metal magnesium, reducing the environmental pollution and reducing the magnesium metal. Preparation costs.
  • Fig. 1 is a flow chart showing the process for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as a reducing agent according to Example 1 of the present invention.
  • Example 2 is a schematic flow chart showing a process for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as a reducing agent according to Example 2 of the present invention.
  • Fig. 3 is a flow chart showing the process for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as a reducing agent according to Example 3 of the present invention.
  • Fig. 4 is a flow chart showing the process for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as a reducing agent according to Example 4 of the present invention.
  • the slag whose main component is CaO ⁇ 2A1 2 0 3 or CaO ⁇ 6A1 2 0 3 or a mixture of the two is ground and placed in a mixed solution composed of NaOH and Na 2 CO 3 , and the mixed solution may also be contained.
  • a small amount of NaAl(OH) 4 component then leaching the alumina in the ash to a NaAl(OH) 4 solution at a temperature of 50-300 ° C, and then filtering to dissolve the NaAl(OH) 4 solution and leaching generated during the slag separation CaC0 3, then (OH) 3 was added a seed crystal ⁇ 1 ( ⁇ ) NaAl 4 in the solution, so NaAl (OH) 4 solution was decomposed at a temperature 50-9CTC the precipitation of Al (OH) 3 Then, ⁇ 1( ⁇ ) 3 is filtered out and washed, and the obtained ⁇ 1( ⁇ ) 3 - part is used as a seed crystal to return the NaAl(OH) 4 solution for the seed decomposition process, and the other part is used as the industrial ⁇ 1 ( ⁇ ) 3 product. Or the obtained Al(OH) 3 is calcined at 800-1200 ° C to obtain an A1 2 0 3 product.
  • the mother liquor After seeding and filtering out the Al(OH) 3 formed by decomposition, the remaining liquid is the mother liquor.
  • the mother liquor mainly contains NaOH formed by the decomposition of Al(OH) 3 by the seed crystal and NaAl(OH) 4 which is not completely decomposed. .
  • the mother liquor is then transferred to a carbonation vessel, The C0 2 gas is introduced, and a part of the NaOH in the mother liquid is carbonated to Na 2 C0 3 , and then Al(OH) 3 formed in a part of the carbonation process is filtered out, and the filtrate contains NaOH and Na 2 C0 3 , and the filtrate is filtrated.
  • the leaching agent as the raw material is recycled. The process is shown in Figure 1.
  • the reduction material composed of MgO and CaO is prepared by preparing magnesium metal mainly from CaO ⁇ A1 2 0 3 or 12CaO ⁇ 7A1 2 0 3 , or by two Aluminum hydroxide and aluminum oxide are extracted from the slag composed of the mixture.
  • the slag whose main component is CaO ⁇ A1 2 3 3 or 12CaO ⁇ 7A1 2 0 3 or a mixture of the two is ground and placed in a solution whose main component is Na 2 CO 3 , and the solution may also contain a small amount of NaAl. (OH) 4 component, then leaching the alumina in the ash to a NaAl(OH) 4 solution at a temperature of 50-30 CTC, and then filtering to form a NaAl(OH) 4 solution and a leaching process.
  • OH OH
  • the mother liquor mainly contains NaOH formed by the decomposition of Al(OH) 3 by the seed crystal and NaAl(OH) 4 which is not completely decomposed. .
  • the mother liquor is transferred to a carbonation vessel, and C0 2 gas is introduced, and a part of the NaOH in the mother liquor is carbonated to Na 2 C0 3 , and then Al(OH) 3 formed in the partial carbonation process is filtered out, and the filtrate contains NaOH and Na 2 CO 3 , the filtrate was returned to the wet mill for recycling as a leaching agent for the raw material.
  • the process is shown in Figure 2.
  • the slag having a main chemical composition of CaO ⁇ 2A1 2 0 3 or CaO ⁇ 6A1 2 0 3 or a mixture of the two is ground and placed in a solution consisting of NaOH and Na 2 C0 3 , and the mixed solution may also be contained.
  • a small amount of NaAl(OH) 4 component, leaching the alumina in the ash to a NaAl(OH) 4 solution at a temperature of 50-300 ° C, and then filtering to make the NaAl(OH) 4 solution and the leaching process The CaC0 3 slag produced in the separation is separated, and then C0 2 is introduced into the NaAl(OH) 4 solution to decompose the NaAl(OH) 4 in the solution to form an Al(OH) 3 precipitate and Na 2 C0 3 , and then Filtration gives ⁇ 1( ⁇ ) 3 , and the obtained ⁇ 1( ⁇ ) 3 is calcined at 800-1200 °C to obtain industrial A1 2 0 3 , and the mother liquor filtered out of Al(OH) 3 is called carbon mother liquor, and the carbon mother liquor is mainly It is a composition of a permanent Na 2 C0 3 solution, and then a portion of Na 2 C0 3 in the mother liquor is reacted with CaO formed by calcination of limestone to
  • the reduction material composed of MgO and CaO is prepared by preparing magnesium metal mainly from CaO ⁇ A1 2 0 3 or 12CaO ⁇ 7A1 2 0 3 , or by two Aluminum hydroxide and aluminum oxide are extracted from the slag composed of the mixture.
  • the slag whose main component is CaO ⁇ ⁇ 1 2 0 3 or 12CaO ⁇ 7A1 2 0 3 or a mixture of the two is ground and placed in a solution whose main component is NaCO 3 , and the solution may also contain a small amount of NaAl (OH).
  • the alumina in the ash is leached to make a NaAl(OH) 4 solution, and then filtered to make the NaAl(OH) 4 solution and the leaching process to form solid Al (OH) 3 and NaC0 3 solution, and then filtered to obtain ⁇ 1 ( ⁇ ) 3 , the obtained ⁇ 1 ( ⁇ ) 3 is calcined at 800-1200 ° C to obtain industrial A1 2 0 3 , and the NaCO 3 solution is returned to the leaching of magnesium ash slag , forming a closed loop.
  • the process is shown in Figure 4.

Abstract

Provided is a method for extracting aluminium hydroxide and alumina from the byproduct obtained during refining metal magnesium with aluminium or aluminium alloy as reducer, which comprises: pulverizing and wet milling the lump material, subjecting the material to extracting in alkali liquor, filtering and separating the CaCO3 produced during extraction to obtain NaAl(OH)4 solution, then subjecting the solution to desiliconization and seed-decomposition or carbonization-decomposition to decompose NaAl(OH)4 in the solution, separating the aluminium hydroxide produced during decomposition from mother liquor by filtration. By this method, at the same time when metal magnesium is refined, aluminium hydroxide and alumina can be prepared by full utilization of the clinker obtained through decomposition method, the economic benefit of refining metal magnesium is improved, environmental pollution is reduced, and the production cost of magnesium is reduced.

Description

从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝和氧化铝 的方法  Method for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as reducing agent
技术领域 Technical field
本发明涉及一种氢氧化铝和氧化铝的提取方法，特别涉及一种从以铝或铝合金为还原剂 制取金属镁的副产物中提取氢氧化铝和氧化铝的方法。  The present invention relates to a method for extracting aluminum hydroxide and aluminum oxide, and more particularly to a method for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or an aluminum alloy as a reducing agent.
背景技术 Background technique
目前工业上真空金属热还原法制取金属镁的生产中， 其还原剂为硅铁， 原料为白云石， 白云石的主要化学成分为 CaC03 · MgC03, 其在高温煅烧后生成 CaO · MgO, 后经磨细与硅 铁粉按化学反应方程式 （1 ) 进行配料、 制成团， 然后置于真空还原炉中， 在 125CTC左右的 温度下进行真空还原制取金属镁。 At present, in the production of magnesium metal by vacuum metal thermal reduction method in the industry, the reducing agent is ferrosilicon, the raw material is dolomite, and the main chemical component of dolomite is CaC0 3 · MgC0 3 , which generates CaO · MgO after calcination at high temperature. After grinding, the ferrosilicon powder is compounded according to the chemical reaction equation (1), and then formed into a mass. Then, it is placed in a vacuum reduction furnace, and vacuum reduction is performed at a temperature of about 125 CTC to obtain magnesium metal.
2 CaO^lgO + Si(Fe) > 2Mg + 2Ca0^i02 ( 1 ) 但在实际工业生产中， 还原剂硅铁的配料量一般都大于按上述化学反应方程式理论配料 量的 10%左右。 2 CaO^lgO + Si(Fe) > 2Mg + 2Ca0^i0 2 ( 1 ) However, in actual industrial production, the amount of reducing agent ferrosilicon is generally greater than about 10% of the theoretical compounding amount of the above chemical reaction equation.
按上述化学反应方程式可以计算出， 目前以硅铁为还原剂的硅热法炼镁， 其反应物料与 产物金属镁的比为 4.78:1，但工业上实际的料 /镁为 6:1，也就是说工业上用硅热法炼镁每生产 一吨镁就会产生 5吨的灰渣 （主要成份为 2CaO · Si02)， 此灰渣原则上可作为水泥厂制造水 泥的原料， 但由于其附加值很低一般工厂都将其弃之处理了。 According to the above chemical reaction equation, it can be calculated that the ratio of the reaction material to the product metal magnesium is 4.78:1, but the industrial actual material/magnesium is 6:1. That is to say, industrially, silicon-heated magnesium smelting produces about 5 tons of ash per ton of magnesium (the main component is 2CaO · Si0 2 ). This ash can in principle be used as a raw material for cement production in cement plants, but The added value is very low and the factory has abandoned it.
最近冯乃祥， 王耀武和胡文鑫发明了一种以废铝或废铝合金粉为还原剂以 MgO/CaO摩尔 比大于 1的物料为原料真空热还原炼镁技术，从而使金属热还原法炼镁的料 /镁比大大地降低。 由于料 /镁比大大地降低， 不仅大大地提高了劳动生产率， 而且也使镁冶炼生产的能耗大大地 降低。 该发明的以铝或铝硅合金粉为还原剂真空热还原生产金属镁的副产物是一种主要由 CaO和 A1203组成的化合物为主要成份的块状物料， 这种块状物料的副产物中的氧化铝是一种 很有价值的冶金和化工原料， 如果将这种渣中的氧化铝加以提取回收和利用， 不仅可以使镁 冶炼厂增加一个化工产品，而且也将使铝热真空热还原法制取金属镁的生产成本大大地降低。 发明内容 Recently, Feng Naixiang, Wang Yaowu and Hu Wenxin invented a vacuum heat reduction magnesium smelting technology using waste aluminum or waste aluminum alloy powder as a reducing agent with a molar ratio of MgO/CaO of more than one, thereby making the metal of the metal thermal reduction method. The /magnesium ratio is greatly reduced. Since the material/magnesium ratio is greatly reduced, not only labor productivity is greatly improved, but also the energy consumption of magnesium smelting production is greatly reduced. The by-product of the invention for vacuum-thermal reduction of magnesium metal by using aluminum or aluminum silicon alloy powder as a reducing agent is a bulk material mainly composed of a compound composed of CaO and A1 2 3 3 as a main component. Alumina in by-products is a valuable metallurgical and chemical raw material. If the alumina in the slag is extracted and recycled, it can not only add a chemical product to the magnesium smelter, but also heat the aluminum. The production cost of producing magnesium metal by vacuum thermal reduction is greatly reduced. Summary of the invention
针对上述问题， 本发明提供了一种从以铝或铝合金为还原剂真空热还原法制取金属镁后 所剩副产物渣料中提取氢氧化铝和氧化铝的方法， 该方法可将铝热真空热还原法炼镁的副产 物渣料加以回收和利用， 从而可以大大地提高镁厂的经济效益。  In view of the above problems, the present invention provides a method for extracting aluminum hydroxide and aluminum oxide from residual by-product slag after preparing magnesium metal by vacuum heat reduction method using aluminum or aluminum alloy as a reducing agent, which can heat aluminum The by-product slag of magnesium smelting by vacuum thermal reduction is recovered and utilized, thereby greatly improving the economic efficiency of the magnesium plant.
以铝或铝合金为还原剂的真空热还原法炼镁方法按以下步骤进行：  The vacuum magnesium reduction method using aluminum or aluminum alloy as a reducing agent is carried out by the following steps:
1、 以白云石、 菱镁矿石、 水镁石和石灰石为原料， 分别进行煅烧， 其中白云石的煅烧 温度为 1000~1200°C， 煅烧后获得含 CaO · MgO物料； 菱镁矿石的煅烧温度为 800~1000°C， 煅烧后获得含 MgO物料； 水镁石的煅烧温度为 800~1000°C， 煅烧后获得含 MgO物料； 石灰 石的煅烧温度为 1000~1200°C， 煅烧后获得含 CaO物料； 将上述四种物料中的两种或两种以 上混合， 配制成 MgO/CaO摩尔比为 1.5~18的原料。 1. Dolomite, magnesite ore, brucite and limestone are used as raw materials for calcination, in which dolomite is calcined. The temperature is 1000~1200°C, and the CaO·MgO material is obtained after calcination; the calcination temperature of the magnesite ore is 800~1000°C, and the MgO-containing material is obtained after calcination; the calcining temperature of the brucite is 800~1000°C, After calcination, the MgO-containing material is obtained; the calcination temperature of the limestone is 1000-1200 ° C, and the CaO-containing material is obtained after calcination; two or more of the above four materials are mixed to prepare a MgO/CaO molar ratio of 1.5~ 18 raw materials.
2、 将上述配制的原料在球磨机中磨细至 100目以下并混合均匀， 获得待还原粉料。  2. The raw materials prepared above are ground to less than 100 mesh in a ball mill and uniformly mixed to obtain a powder to be reduced.
3、 在待还原粉料中加入还原剂， 还原剂为粒度在 1mm以下的铝粉或铝合金粉， 制成反 应物料， 还原剂的加入量为反应理论所需用量的 1.03~1.1倍； 所述的铝合金粉为铝硅合金粉 或铝镁合金粉。  3. Adding a reducing agent to the powder to be reduced, the reducing agent is aluminum powder or aluminum alloy powder with a particle size of less than 1 mm, and is made into a reaction material, and the reducing agent is added in an amount of 1.03 to 1.1 times the amount required for the reaction theory; The aluminum alloy powder described is an aluminum silicon alloy powder or an aluminum magnesium alloy powder.
4、 将反应物料压制成团状或块状。  4. The reaction material is pressed into a dough or a block.
5、 将团状或块状反应物料置于带有镁结晶器的高温真空还原反应炉内进行真空还原反 应， 反应炉内压力小于 30Pa， 反应温度 900~1250°C， 反应生成气态金属镁在镁结晶器上冷凝 结晶成金属镁。  5. The lumps or block reaction materials are placed in a high-temperature vacuum reduction reactor with a magnesium crystallizer for vacuum reduction reaction. The pressure in the reaction furnace is less than 30 Pa, and the reaction temperature is 900-1250 ° C. The reaction produces gaseous magnesium metal. The magnesium crystallizer is condensed and crystallized into metallic magnesium.
真空条件下金属热还原反应制取金属镁的方案如下：  The scheme for preparing magnesium metal by metal thermal reduction under vacuum conditions is as follows:
由于冯乃祥等人发明的以铝或铝合金为还原剂的真空热还原法炼镁， 使用以 MgO/CaO 摩尔比大于 1 的还原反应物料， 其按 MgO/CaO摩尔比配料大小的不同， 其真空还原反应炼 镁后的副产物渣料按下列的真空热还原反应而含有不同的化学组成：  Due to the vacuum thermal reduction method of magnesium invented by Feng Naixiang et al., using aluminum or aluminum alloy as a reducing agent, a reduction reaction material having a molar ratio of MgO/CaO of more than 1 is used, and the vacuum is different according to the molar ratio of MgO/CaO. The by-product slag after the reduction reaction of magnesium smelting contains different chemical compositions according to the following vacuum thermal reduction reaction:
CaO + 6MgO + 4A1 = 6Mg + CaO · 2A1203 ( 2 )CaO + 6MgO + 4A1 = 6Mg + CaO · 2A1 2 0 3 ( 2 )
CaO + 18MgO + 12A1 = 18Mg + CaO · 6A1203 ( 3 )CaO + 18MgO + 12A1 = 18Mg + CaO · 6A1 2 0 3 ( 3 )
12CaO + 21MgO + 14A1 = 21Mg + 12CaO · 7A1203 (4) 12CaO + 21MgO + 14A1 = 21Mg + 12CaO · 7A1 2 0 3 (4)
CaO + 3MgO + 2A1 = 3Mg + CaO · A1203 ( 5 ) 其中副产物渣料分别为 CaO · 2A1203、 CaO · 6A1203、 12CaO · 7A1203和 CaO · A1203中的 一种或两种以上混合物。 CaO + 3MgO + 2A1 = 3Mg + CaO · A1 2 0 3 ( 5 ) wherein the by-product slags are CaO · 2A1 2 0 3 , CaO · 6A1 2 0 3 , 12CaO · 7A1 2 0 3 and CaO · A1 2 0 One or a mixture of two or more of 3 .
当还原剂使用铝硅合金时， 配料中的 CaO和 MgO的配料比应考虑到还原剂中硅的组份 含量在还原过程中的行为， 铝硅合金中的硅会与配料中 MgO和 CaO的反应存在着下列化学 反应：  When the reducing agent is made of aluminum-silicon alloy, the ratio of CaO and MgO in the batch should take into account the behavior of the component content of silicon in the reducing agent during the reduction process. The silicon in the aluminum-silicon alloy and the MgO and CaO in the compound. The reaction has the following chemical reactions:
2CaO + 2MgO + Si = 2Mg + 2CaO · Si02 ( 6 ) 本发明利用上述真空条件下金属热还原反应的副产物提取 A1203和 Al(OH)3的方法如下： 1、 首先将团块状的副产物破碎湿磨至 100 目以下， 然后将此磨细的渣料放入 Na2C03溶 液中，或放入 Na2C03与 NaOH组成的混合溶液中，在 50~300°C的温度下，将渣料的 A1203浸出， 浸出液中的 A1203以 NaAl(OH)4的形式存在于浸出液中， 而渣料中的 CaO以 CaC03的形式沉淀 出来。 2CaO + 2MgO + Si = 2Mg + 2CaO · Si0 2 (6) The method for extracting A1 2 0 3 and Al(OH) 3 by using the by-product of the metal thermal reduction reaction under the above vacuum condition is as follows: 1. First, the agglomerate The by-products are crushed and ground to below 100 mesh, and then the milled slag is placed in a Na 2 CO 3 solution or placed in a mixed solution of Na 2 CO 3 and NaOH at 50-300 ° C. At a temperature, the slag A1 2 0 3 is leached, and the A1 2 0 3 in the leaching solution is present in the leaching solution in the form of NaAl(OH) 4 , and the CaO in the slag is precipitated in the form of CaCO 3 come out.
2、 将浸出后物料进行过滤， 滤出沉淀物 CaC03， 而 NaAl(OH)4存在于滤液中； 滤液经脱 硅后进入种分或碳分容器中进行种分分解或碳分分解， 使 NaAl(OH)4分解成为氢氧化铝 (Al(OH)3)。 2. The material after leaching is filtered, and the precipitate CaC0 3 is filtered out, and NaAl(OH) 4 is present in the filtrate; the filtrate is desiliconized and then enters the seed or carbon container for seed decomposition or carbon decomposition, so that NaAl(OH) 4 decomposes into aluminum hydroxide (Al(OH) 3 ).
如果用种分分解则需向含有 NaAl(OH)4的溶液中加入 Α1(ΟΗ)3晶种进行晶种种分分解， 使 NaAl(OH)4分解成 Al(OH)3和 Na(OH)， 溶液中种分分解后生成的 Α1(ΟΗ)3经过滤分离后得到产 品 Al(OH)3， 以及由 Na(OH)以及部分未分解的 NaAl(OH)4组成的溶液； 生成的 Α1(ΟΗ)3大部分 作为最终产品， 部分作为晶种返回到晶种分解容器中去种分分解 NaAl(OH)4。 If the decomposition is carried out by seed, it is necessary to add Α1(ΟΗ) 3 seed crystal to the solution containing NaAl(OH) 4 for seed seed decomposition, and to decompose NaAl(OH) 4 into Al(OH) 3 and Na(OH). The Α1(ΟΗ) 3 formed after the decomposition of the seed in the solution is separated by filtration to obtain the product Al(OH) 3 , and a solution composed of Na(OH) and partially undecomposed NaAl(OH) 4 ; 3 Most of them are used as final products, and some are returned as seed crystals to the seed decomposition vessel to separate and decompose NaAl(OH) 4 .
如果需要最终的产品为 A1203， 可将生成的 Al(OH)3在 800 °C以上的温度进行煅烧使 Al(OH)3脱水即可。 If the final product is required to be A1 2 0 3 , the produced Al(OH) 3 can be calcined at a temperature of 800 ° C or higher to dehydrate Al(OH) 3 .
如果从渣料中浸出的 NaAl(OH)4溶液采用碳分分解生成 Α1(ΟΗ)3， 则需在碳分分解反应容 器中向含有 NaAl(OH)4的溶液中通入 C02气体进行碳分分解，使 NaAl(OH)4分解生成 Α1(ΟΗ)3和 Na2C03产物。 碳分过程所需的 C02来自于白云石或菱镁石煅烧过程生成的 C02副产物。 碳分 分解生成的 Al(OH)3经过过滤与碳分后生成的 Na2C03溶液分离后即形成商品氢氧化铝。 If the NaAl(OH) 4 solution leached from the slag is decomposed by carbon to form Α1(ΟΗ) 3 , it is necessary to introduce C0 2 gas into the solution containing NaAl(OH) 4 in the carbon decomposition reaction vessel for carbon. The decomposition is carried out to decompose NaAl(OH) 4 to form Α1(ΟΗ) 3 and Na 2 C0 3 products. The CO 2 required for the carbon fraction process is derived from the CO 2 by -product formed by the dolomite or magnesite calcination process. The Al(OH) 3 formed by the decomposition of carbon is separated from the Na 2 CO 3 solution formed by carbonation to form commercial aluminum hydroxide.
如果需要最终的产品为 A1203， 可将生成的 Al(OH)3在 800 °C以上的温度进行煅烧使 Al(OH)3脱水即可得到氧化铝产品。 If the final product is required to be A1 2 0 3 , the produced Al(OH) 3 can be calcined at a temperature of 800 ° C or higher to dehydrate Al(OH) 3 to obtain an alumina product.
上述方法中， 步骤 2中的脱硅是采用传统氧化铝工业脱硅方法。  In the above method, the desiliconization in the step 2 is a conventional alumina industrial desiliconization method.
上述方法中当采用 Na2C03溶液进行浸出时，碳酸钠的浓度为 80~150g/L， Na2C03溶液与 渣料的液固比为 50~1000 g/L, 即每升浸出液浸出 50~1000g渣料； 当采用 Na2C03与 NaOH组 成的混合溶液进行浸出时， 混合溶液中碳酸钠的浓度为 20~150 g/L, 氢氧化钠的浓度为 80-300 g/L, 混合溶液与渣料的液固比为 50~1000 g/L。 In the above method, when leaching with a Na 2 CO 3 solution, the concentration of sodium carbonate is 80-150 g/L, and the liquid-solid ratio of the Na 2 C0 3 solution to the slag is 50-1000 g/L, that is, leaching per liter of the leaching solution 50~1000g slag; When leaching with a mixed solution of Na 2 C0 3 and NaOH, the concentration of sodium carbonate in the mixed solution is 20-150 g/L, and the concentration of sodium hydroxide is 80-300 g/L. The liquid-solid ratio of the mixed solution to the slag is 50 to 1000 g/L.
上述方法中浸出时间为 20~200min。  The leaching time in the above method is 20 to 200 minutes.
上述方法中， 当被浸出的含 CaO和 A1203的渣料其主要化学组成为 CaO · 2A1203或 CaO · 6A1203或两者混合物时， 种分分解后的含少量 NaAl(OH)4的 NaOH溶液要在苛化容器中 使溶液中的部分 NaOH进行碳酸化处理， 之后过滤出部分碳酸化过程中生成的 Al(OH)3， 使之 变成含有 NaOH和 Na2C03的混合溶液， 返回湿磨器中作为原料的浸出剂。 当溶出原料中的物 料的化学成份主要为 CaO · A1203或 12CaO · 7A1203或两者的混合物时， 种分分解后的含少量 Na的 NaOH溶液要进行碳酸化处理， 之后过滤出碳酸化后生成的 Α1(ΟΗ)3， 溶液中的 NaOH完 全变为 Na2C03， 将此 Na2C03溶液返回湿磨器中作为原料的浸出剂。 In the above method, when the leached CaO-containing and A1 2 0 3 slag have a main chemical composition of CaO · 2A1 2 0 3 or CaO · 6A1 2 0 3 or a mixture of the two, the seed contains a small amount of NaAl after decomposition. The (OH) 4 NaOH solution is subjected to carbonation treatment of a portion of the NaOH in the causticizing vessel, and then the Al(OH) 3 formed during the partial carbonation is filtered to become NaOH and Na 2 C0. The mixed solution of 3 is returned to the leaching agent as a raw material in the wet mill. When the chemical composition of the material in the dissolution raw material is mainly CaO · A1 2 0 3 or 12CaO · 7A1 2 0 3 or a mixture of the two, the NaOH solution containing a small amount of Na after decomposition is subjected to carbonation treatment, followed by filtration. Α1(ΟΗ) 3 formed after carbonation, the NaOH in the solution completely changed to Na 2 C0 3 , and the Na 2 CO 3 solution was returned to the leaching agent as a raw material in the wet mill.
上述方法中， 当被浸出的原料主要化学成份为 CaO · 2A1203或 CaO · 6A1203或两者混合 物时， 碳分后的母液中 Na2C03需要进行部分苛化， 使母液中的 Na2C03部分转化成 NaOH， 其 苛化剂为氧化钙， 部分苛化后的碳分母液含有 NaOH和 Na2C03化学组分， 将其返回湿磨器中 作为原料的浸出剂； 当被浸出原料的主要化学成份为 CaO · A1203或 12CaO · 7A1203或两者的 混合物时， 碳分后母液所含的 Na2C03不再进行苛化处理， 而是直接地将此母液输入到湿磨器 中作为原料的浸出剂循环使用。 In the above method, when the main chemical component of the leached raw material is CaO · 2A1 2 0 3 or CaO · 6A1 2 0 3 or a mixture of the two In the case of the carbon, the Na 2 C0 3 in the mother liquor after carbon separation needs to be partially causticized, so that the Na 2 CO 3 portion of the mother liquor is converted into NaOH, the causticizing agent is calcium oxide, and the partially causticized carbon mother liquor contains NaOH. And the Na 2 C0 3 chemical component, which is returned to the leaching agent as a raw material in the wet mill; when the main chemical component of the leached raw material is CaO · A1 2 0 3 or 12CaO · 7A1 2 0 3 or a mixture of the two The Na 2 C0 3 contained in the mother liquor after the carbon separation is no longer subjected to causticization treatment, but is directly used to circulate the mother liquor into the wet mill as a raw material leaching agent.
本发明的方法在制取金属镁的同时， 能够充分利用获得的灰渣采用分解方法制取氢氧化 铝和氧化铝， 提高了制取金属镁的经济效益， 减少环境污染， 降低了金属镁的制备成本。 附图说明  The method of the invention can make full use of the obtained ash and prepare the aluminum hydroxide and the aluminum oxide by the decomposition method, thereby improving the economic benefit of preparing the metal magnesium, reducing the environmental pollution and reducing the magnesium metal. Preparation costs. DRAWINGS
图 1为本发明实施例 1的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝 和氧化铝的方法流程示意图。  BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the process for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as a reducing agent according to Example 1 of the present invention.
图 2为本发明实施例 2的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝 和氧化铝的方法流程示意图。  2 is a schematic flow chart showing a process for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as a reducing agent according to Example 2 of the present invention.
图 3为本发明实施例 3的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝 和氧化铝的方法流程示意图。  Fig. 3 is a flow chart showing the process for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as a reducing agent according to Example 3 of the present invention.
图 4为本发明实施例 4的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝 和氧化铝的方法流程示意图。  Fig. 4 is a flow chart showing the process for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or aluminum alloy as a reducing agent according to Example 4 of the present invention.
具体实施方式 Detailed ways
实施例 1 Example 1
从以铝粉或铝硅合金粉为还原剂真空热还原由 MgO和 CaO组成的还原物料制取金属镁所 生成的其主要由 CaO · 2A1203或 CaO · 6A1203， 或由两者的混合物组成的渣料中提取氢氧化铝 和氧化铝。 From the vacuum reduction of aluminum powder or aluminum-silicon alloy powder as a reducing agent to produce magnesium metal from the reduction material composed of MgO and CaO, which is mainly formed by CaO · 2A1 2 0 3 or CaO · 6A1 2 0 3 , or by two Aluminum hydroxide and aluminum oxide are extracted from the slag composed of the mixture.
将其主要成分为 CaO · 2A1203或 CaO · 6A1203或两者混合物的渣块经磨细后置于由 NaOH 和 Na2C03组成的混合溶液中， 混合溶液中也可以含有少量 NaAl(OH)4成份， 然后在 50-300 °C 的温度下， 将灰渣中的氧化铝浸出， 使其成为 NaAl(OH)4溶液， 然后过滤， 使 NaAl(OH)4溶液 与浸出过程中生成的 CaC03渣分离， 之后在 NaAl(OH)4溶液中加入 Α1(ΟΗ)3晶种，让 NaAl(OH)4 溶液在 50-9CTC的温度下进行分解， 析出 Al(OH)3， 然后过滤将 Α1(ΟΗ)3滤出并洗涤， 获得的 Α1(ΟΗ)3—部分作为晶种返回 NaAl(OH)4溶液的种分分解工序， 另一部分作为工业 Α1(ΟΗ)3产 品， 或将获得的 Al(OH)3在 800- 1200 °C下煅烧获得 A1203产品。 The slag whose main component is CaO · 2A1 2 0 3 or CaO · 6A1 2 0 3 or a mixture of the two is ground and placed in a mixed solution composed of NaOH and Na 2 CO 3 , and the mixed solution may also be contained. A small amount of NaAl(OH) 4 component, then leaching the alumina in the ash to a NaAl(OH) 4 solution at a temperature of 50-300 ° C, and then filtering to dissolve the NaAl(OH) 4 solution and leaching generated during the slag separation CaC0 3, then (OH) 3 was added a seed crystal Α1 (ΟΗ) NaAl 4 in the solution, so NaAl (OH) 4 solution was decomposed at a temperature 50-9CTC the precipitation of Al (OH) 3 Then, Α1(ΟΗ) 3 is filtered out and washed, and the obtained Α1(ΟΗ) 3 - part is used as a seed crystal to return the NaAl(OH) 4 solution for the seed decomposition process, and the other part is used as the industrial Α 1 (ΟΗ) 3 product. Or the obtained Al(OH) 3 is calcined at 800-1200 ° C to obtain an A1 2 0 3 product.
种分后并过滤出分解生成的 Al(OH)3后， 所剩液体为母液， 母液中主要存在着晶种分解 出 Al(OH)3时生成的 NaOH以及未完全分解的 NaAl(OH)4。 之后将母液输送到碳酸化容器中， 通入 C02气体， 是母液中的部分 NaOH碳酸化成 Na2C03， 然后将部分碳酸化过程中生成的 Al(OH)3滤出， 其滤液中含有 NaOH和 Na2C03， 将此滤液返回到湿磨中， 作为原始料的浸出剂 循环使用。 流程如图 1所示。 After seeding and filtering out the Al(OH) 3 formed by decomposition, the remaining liquid is the mother liquor. The mother liquor mainly contains NaOH formed by the decomposition of Al(OH) 3 by the seed crystal and NaAl(OH) 4 which is not completely decomposed. . The mother liquor is then transferred to a carbonation vessel, The C0 2 gas is introduced, and a part of the NaOH in the mother liquid is carbonated to Na 2 C0 3 , and then Al(OH) 3 formed in a part of the carbonation process is filtered out, and the filtrate contains NaOH and Na 2 C0 3 , and the filtrate is filtrated. Returning to the wet mill, the leaching agent as the raw material is recycled. The process is shown in Figure 1.
实施例 2 Example 2
从以铝粉或铝硅合金粉为还原剂真空热还原由 MgO和 CaO组成的还原物料制取金属镁所 生成的其主要由 CaO · A1203或 12CaO · 7A1203， 或由两者的混合物组成的渣料中提取氢氧化 铝和氧化铝。 From the vacuum reduction of aluminum or aluminum-silicon alloy powder as a reducing agent, the reduction material composed of MgO and CaO is prepared by preparing magnesium metal mainly from CaO · A1 2 0 3 or 12CaO · 7A1 2 0 3 , or by two Aluminum hydroxide and aluminum oxide are extracted from the slag composed of the mixture.
将其主要成分为 CaO · A1203或 12CaO · 7A1203或两者的混合物的渣块经磨细后置于主要 成分为 Na2C03的溶液中， 溶液中也可以含有少量 NaAl(OH)4成份， 然后在 50-30CTC的温度下， 将灰渣中的氧化铝浸出， 使其成为 NaAl(OH)4溶液， 然后过滤， 使 NaAl(OH)4溶液与浸出过程 中生成的 CaC03渣分离，之后在 NaAl(OH)4溶液中加入 Al(OH)3晶禾中，让 NaAl(OH)4溶液在 60_90 °C的温度下进行分解， 析出 Al(OH)3， 然后过滤， 将 Al(OH)3滤出并洗涤， 获得的 Al(OH)3—部 分可作为晶种返回 NaAl(OH)4溶液的种分分解工序， 另一部分可作为工业 Al(OH)3产品， 或将 获得的 Al(OH)3在 800-1200 下煅烧可获得八1203产品。 The slag whose main component is CaO · A1 2 3 3 or 12CaO · 7A1 2 0 3 or a mixture of the two is ground and placed in a solution whose main component is Na 2 CO 3 , and the solution may also contain a small amount of NaAl. (OH) 4 component, then leaching the alumina in the ash to a NaAl(OH) 4 solution at a temperature of 50-30 CTC, and then filtering to form a NaAl(OH) 4 solution and a leaching process. CaC0 3 slag separation, then (OH) was added Al (OH) 3 crystal grain in NaAl 4 solution, so NaAl (OH) 4 was decomposed at a temperature of 60_90 ° C, the precipitated Al (OH) 3, and then filtered Al(OH) 3 is filtered out and washed, and the obtained Al(OH) 3 - part can be used as a seed to return the NaAl (OH) 4 solution for the decomposition of the seed, and the other part can be used as the industrial Al (OH) 3 product. Al (OH) 3 obtained or obtainable eight 1203 product calcined at 800-1200.
种分后并过滤出分解生成的 Al(OH)3后， 所剩液体为母液， 母液中主要存在着晶种分解 出 Al(OH)3时生成的 NaOH以及未完全分解的 NaAl(OH)4。 之后将母液输送到碳酸化容器中， 通入 C02气体， 是母液中的部分 NaOH碳酸化成 Na2C03， 然后将部分碳酸化过程中生成的 Al(OH)3滤出， 其滤液中含有 NaOH和 Na2C03， 将此滤液返回到湿磨中， 作为原始料的浸出剂 循环使用。 流程如图 2所示。 After seeding and filtering out the Al(OH) 3 formed by decomposition, the remaining liquid is the mother liquor. The mother liquor mainly contains NaOH formed by the decomposition of Al(OH) 3 by the seed crystal and NaAl(OH) 4 which is not completely decomposed. . After that, the mother liquor is transferred to a carbonation vessel, and C0 2 gas is introduced, and a part of the NaOH in the mother liquor is carbonated to Na 2 C0 3 , and then Al(OH) 3 formed in the partial carbonation process is filtered out, and the filtrate contains NaOH and Na 2 CO 3 , the filtrate was returned to the wet mill for recycling as a leaching agent for the raw material. The process is shown in Figure 2.
实施例 3 Example 3
从以铝粉或铝硅合金粉为还原剂真空热还原由 MgO和 CaO组成的还原物料制取金属镁所 生成的其主要由 CaO · 2A1203或 CaO · 6A1203， 或由两者的混合物组成的渣料中提取氢氧化铝 和氧化铝。 From the vacuum reduction of aluminum powder or aluminum-silicon alloy powder as a reducing agent to produce magnesium metal from the reduction material composed of MgO and CaO, which is mainly formed by CaO · 2A1 2 0 3 or CaO · 6A1 2 0 3 , or by two Aluminum hydroxide and aluminum oxide are extracted from the slag composed of the mixture.
将其主要化学组成为 CaO · 2A1203或 CaO · 6A1203或两者的混合物的渣块经磨细后置于 NaOH和 Na2C03组成的溶液中， 混合溶液中也可以含有少量 NaAl(OH)4成份， 在 50-300 °C的温 度下， 将灰渣中的氧化铝浸出， 使其成为 NaAl(OH)4溶液， 然后过滤， 使 NaAl(OH)4溶液与浸 出过程中产生的 CaC03渣分离， 之后向 NaAl(OH)4溶液中通入 C02， 使溶液中的 NaAl(OH)4进 行碳分分解生成 Al(OH)3沉淀物和 Na2C03，然后过滤得到 Α1(ΟΗ)3，获得的 Α1(ΟΗ)3在 800-1200 °C下煅烧可获得工业 A1203，过滤出 Al(OH)3的母液称为碳分母液，碳分母液主要是永 Na2C03溶 液组成， 之后使母液中的部分 Na2C03与石灰石煅烧生成的 CaO进行苛化反应生成 NaOH和 CaC03，部分苛化反应生成的 CaC03经过过滤分离后，所剩溶液为 NaOH和 Na2C03的混合溶液， 此溶液又作为浸出液进行炼镁副产物渣块磨细后的灰渣的浸出， 形成一个闭路循环。 流程如 图 3所示。 The slag having a main chemical composition of CaO · 2A1 2 0 3 or CaO · 6A1 2 0 3 or a mixture of the two is ground and placed in a solution consisting of NaOH and Na 2 C0 3 , and the mixed solution may also be contained. A small amount of NaAl(OH) 4 component, leaching the alumina in the ash to a NaAl(OH) 4 solution at a temperature of 50-300 ° C, and then filtering to make the NaAl(OH) 4 solution and the leaching process The CaC0 3 slag produced in the separation is separated, and then C0 2 is introduced into the NaAl(OH) 4 solution to decompose the NaAl(OH) 4 in the solution to form an Al(OH) 3 precipitate and Na 2 C0 3 , and then Filtration gives Α1(ΟΗ) 3 , and the obtained Α1(ΟΗ) 3 is calcined at 800-1200 °C to obtain industrial A1 2 0 3 , and the mother liquor filtered out of Al(OH) 3 is called carbon mother liquor, and the carbon mother liquor is mainly It is a composition of a permanent Na 2 C0 3 solution, and then a portion of Na 2 C0 3 in the mother liquor is reacted with CaO formed by calcination of limestone to form NaOH and CaC0 3 , after CaC0 3 generated by partial causticization is separated by filtration, the remaining solution is a mixed solution of NaOH and Na 2 C0 3 , and this solution is used as a leaching solution to leaching the ash residue after grinding the magnesium slag by-product slag , forming a closed loop. The process is shown in Figure 3.
实施例 4 Example 4
从以铝粉或铝硅合金粉为还原剂真空热还原由 MgO和 CaO组成的还原物料制取金属镁所 生成的其主要由 CaO · A1203或 12CaO · 7A1203， 或由两者的混合物组成的渣块中提取氢氧化 铝和氧化铝。 From the vacuum reduction of aluminum or aluminum-silicon alloy powder as a reducing agent, the reduction material composed of MgO and CaO is prepared by preparing magnesium metal mainly from CaO · A1 2 0 3 or 12CaO · 7A1 2 0 3 , or by two Aluminum hydroxide and aluminum oxide are extracted from the slag composed of the mixture.
将其主要成份为 CaO · Α1203或 12CaO · 7A1203或两者混合物的渣块经磨细后置于其主要 成份为 NaC03的溶液中， 溶液中也可以含有少量 NaAl(OH)4成份， 在 50-30CTC的温度下， 将灰 渣中的氧化铝浸出， 使其成为 NaAl(OH)4溶液， 然后过滤， 使 NaAl(OH)4溶液与浸出过程生成 得到固体 Al(OH)3和 NaC03溶液， 然后过滤得到 Α1(ΟΗ)3， 获得的 Α1(ΟΗ)3在 800-1200 °C下煅烧 可获得工业 A1203， 而 NaC03溶液返回炼镁灰渣的浸出， 形成一个闭路循环。流程如图 4所示。 The slag whose main component is CaO · Α1 2 0 3 or 12CaO · 7A1 2 0 3 or a mixture of the two is ground and placed in a solution whose main component is NaCO 3 , and the solution may also contain a small amount of NaAl (OH). 4 component, at 50-30CTC, the alumina in the ash is leached to make a NaAl(OH) 4 solution, and then filtered to make the NaAl(OH) 4 solution and the leaching process to form solid Al (OH) 3 and NaC0 3 solution, and then filtered to obtain Α1 (ΟΗ) 3 , the obtained Α 1 (ΟΗ) 3 is calcined at 800-1200 ° C to obtain industrial A1 2 0 3 , and the NaCO 3 solution is returned to the leaching of magnesium ash slag , forming a closed loop. The process is shown in Figure 4.

Claims

杈 利 要 求 书 Profit request
1、 一种从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝和氧化铝的方法， 其特征在于是由料块的破碎、 湿磨、 碱液浸出、 过滤分离出浸出过程中生成的 CaC03， 得到 NaAl(OH)4的溶液， 然后将溶液进行脱硅处理， 再进行种分或碳分， 使溶液中的 NaAl(OH)4进 行分解， 之后将分解产生的氢氧化铝与母液进行过滤分离； 如果要得到氧化铝， 再将氢氧化 铝在高于 80CTC的温度下进行煅烧使 Al(OH)3脱水变成 A1203等步骤和工艺过程组成的。 A method for extracting aluminum hydroxide and aluminum oxide from a by-product of preparing magnesium metal by using aluminum or an aluminum alloy as a reducing agent, which is characterized in that the material is broken, wet-milled, lye leached, and filtered. CaC0 3 formed during the leaching process, a solution of NaAl(OH) 4 is obtained, and then the solution is subjected to desiliconization treatment, and then seed or carbon is fractionated to decompose NaAl(OH) 4 in the solution, followed by decomposition. The aluminum hydroxide is separated from the mother liquor by filtration; if alumina is to be obtained, the aluminum hydroxide is calcined at a temperature higher than 80 CTC to dehydrate Al(OH) 3 into A1 2 0 3 and the like. .
2、根据权利要求 1所述的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝 和氧化铝的方法， 其特征在于所用原料为以铝或铝硅合金为还原剂真空热还原 MgO/CaO物料 制取金属镁后的含 CaO和 A1203的副产物渣块物料。 2. A method for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or an aluminum alloy as a reducing agent according to claim 1, wherein the raw material used is reduced by aluminum or aluminum silicon alloy. The agent is vacuum-heat-reduced MgO/CaO material to prepare a by-product slag material containing CaO and A1 2 3 after obtaining magnesium metal.
3、根据权利要求 1所述的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝 和氧化铝的方法， 其特征在于当用碱液浸出的 NaAl(OH)4的浸出液用种分分解生产氢氧化铝 时， 其所用晶种为 Α1(ΟΗ)3， 种分分解反应后生成的 Α1(ΟΗ)3与母液过滤分离后获得氢氧化铝。 A method for extracting aluminum hydroxide and aluminum oxide from a by-product of preparing magnesium metal from aluminum or an aluminum alloy as a reducing agent according to claim 1, characterized in that NaAl(OH) 4 is leached with an alkali solution. When the leachate is decomposed to produce aluminum hydroxide by seeding, the seed crystal used is Α1(ΟΗ) 3 , and the Α1(ΟΗ) 3 formed after the decomposition reaction of the seed is separated from the mother liquid by filtration to obtain aluminum hydroxide.
4、根据权利要求 1或 3所述的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧 化铝和氧化铝的方法， 其特征在于当被浸出的含 CaO和 A1203的渣料其主要化学组成为 CaO · 2A1203或 CaO · 6A1203或两者混合物时， 种分分解后的含少量 NaAl(OH)4的 NaOH溶液 要在苛化容器中使溶液中的部分 NaOH进行碳酸化处理，之后过滤出部分碳酸化过程中生成的 Al(OH)3， 使之变成含有 NaOH和 Na2C03的混合溶液， 返回湿磨器中作为原料的浸出剂； 当溶 出原料中的物料的化学成份主要为 CaO · A1203或 12CaO · 7A1203或两者的混合物时， 种分分 解后的含少量 Na的 NaOH溶液要进行碳酸化处理， 之后过滤出碳酸化后生成的 Α1(ΟΗ)3， 溶液 中的 NaOH完全变为 Na2C03， 将此 Na2C03溶液返回湿磨器中作为原料的浸出剂。 A method for extracting aluminum hydroxide and aluminum oxide from a by-product of preparing magnesium metal from aluminum or an aluminum alloy as a reducing agent according to claim 1 or 3, wherein when leached CaO and A1 2 are contained When the main chemical composition of 0 3 slag is CaO · 2A1 2 0 3 or CaO · 6A1 2 0 3 or a mixture of the two, the NaOH solution containing a small amount of NaAl(OH) 4 after decomposition of the seed is to be in the causticized container. Part of the NaOH in the solution is carbonized, and then the Al(OH) 3 formed during the partial carbonation is filtered to become a mixed solution containing NaOH and Na 2 CO 3 , and returned to the wet mill as a raw material. Leaching agent; when the chemical composition of the material in the eluting raw material is mainly CaO · A1 2 0 3 or 12CaO · 7A1 2 0 3 or a mixture of the two, the NaOH solution containing a small amount of Na after decomposition is subjected to carbonation treatment. Then, Α1(ΟΗ) 3 formed after carbonation is filtered out, and NaOH in the solution is completely changed to Na 2 C0 3 , and the Na 2 CO 3 solution is returned to the leaching agent as a raw material in the wet mill.
5、根据权利要求 1所述的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝 和氧化铝的方法， 其特征在于当含 NaAl(OH)4的浸出液采用碳分分解出 Al(OH)3时， 其所用碳 分分解剂为白云石或菱镁矿石煅烧产生的 C02气体， 碳分分解后所产生的 Al(OH)3与母液过滤 分离后的固体产物即为商品 Al(OH)3， Al(OH)3在大于 800°C的温度下煅烧可得商品氧化铝。 A method for extracting aluminum hydroxide and aluminum oxide from a by-product of preparing magnesium metal from aluminum or an aluminum alloy as a reducing agent according to claim 1, wherein the leaching solution containing NaAl(OH) 4 is carbon. When Al(OH) 3 is decomposed, the carbon decomposition agent used is C0 2 gas produced by calcination of dolomite or magnesite ore, and the solid product after separation of Al(OH) 3 and mother liquor by carbon decomposition That is, the commercial Al(OH) 3 , Al(OH) 3 is calcined at a temperature greater than 800 ° C to obtain commercial alumina.
6、根据权利要求 1所述的从以铝或铝合金为还原剂制取金属镁的副产物中提取氢氧化铝 和氧化铝的方法， 其特征在于当被浸出的原料主要化学成份为 CaO · 2A1203或 CaO · 6A1203或 两者混合物时， 碳分后的母液中 Na2C03需要进行部分苛化， 使母液中的 Na2C03部分转化成 NaOH, 其苛化剂为氧化钙， 部分苛化后的碳分母液含有 NaOH和 Na2C03化学组分， 将其返回 湿磨器中作为原料的浸出剂； 当被浸出原料的主要化学成份为 CaO · A1203或 12CaO · 7A1203 或两者的混合物时， 碳分后母液所含的 Na2C03不再进行苛化处理， 而是直接地将此母液输入 到湿磨器中作为原料的浸出剂循环使用。 6. A method for extracting aluminum hydroxide and aluminum oxide from by-products of preparing magnesium metal from aluminum or an aluminum alloy as a reducing agent according to claim 1, wherein when the main chemical component of the leached raw material is CaO. When 2A1 2 0 3 or CaO · 6A1 2 0 3 or a mixture of the two, the Na 2 C0 3 in the mother liquor after carbon separation needs to be partially causticized, so that the Na 2 CO 3 portion in the mother liquor is converted into NaOH, the causticizing agent For calcium oxide, the partially caustic carbon mother liquor contains NaOH and Na 2 CO 3 chemical components, which are returned to the wet mill as a raw material leaching agent; when the main chemical component of the leached raw material is CaO · A1 2 0 When 3 or 12CaO · 7A1 2 0 3 or a mixture of the two, the Na 2 C0 3 contained in the mother liquor after the carbon separation is no longer causticized, but the mother liquor is directly fed into the wet mill as a raw material for leaching. The agent is recycled.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106185975A (en) * 2016-07-22 2016-12-07 山东钢铁股份有限公司 A kind of method utilizing blast furnace slag to prepare molecular sieve crystal
US10151017B2 (en) * 2016-04-24 2018-12-11 Yadian Xie Method for extracting ultra high purity alumina from wasterwater
CN115159552A (en) * 2022-07-04 2022-10-11 重庆大学 Method for recovering aluminum oxide from aluminum-containing resources
CN115321589A (en) * 2022-09-16 2022-11-11 东北大学 Comprehensive utilization method of by-product in process of preparing titanium or titanium alloy by aluminothermic reduction of fluotitanate

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102464345B (en) * 2010-11-17 2013-11-06 东北大学 Method for producing sandy alumina by using nepheline
CN108658115B (en) * 2018-08-02 2020-03-17 重庆元和精细化工股份有限公司 Method for producing spherical strontium carbonate and sodium aluminate by using strontium-producing waste residues
CN110042240A (en) * 2019-04-29 2019-07-23 安徽工业大学 A kind of technique that vacuum thermit reduction produces lithium metal and magnesium metal simultaneously
CN110055409A (en) * 2019-04-29 2019-07-26 安徽工业大学 A kind of Smelting magnesium technique of exhaust gas waste residue recoverable

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1424256A (en) * 2002-12-23 2003-06-18 广西壮族自治区河池地区矿业有限责任公司 Production of aluminum oxide from iron containing bauxite
CN1562756A (en) * 2004-03-19 2005-01-12 邝中 Technique for extracting alumina from materiel containing calcium aluminate
CN101028935A (en) * 2007-01-26 2007-09-05 长安大学 Method for extracting aluminum hydrate or alumina from coal gangue and method for producing cement from fag end
CN101028936A (en) * 2007-01-26 2007-09-05 长安大学 Method for extracting alumin from aluminous fly-ash and method for producing cement from fag end

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101264910B (en) * 2008-04-25 2010-10-13 河南未来铝业（集团）有限公司 Mother liquor evaporation seed addition method for aluminum hydroxide or aluminum oxide production technique by Bayer process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1424256A (en) * 2002-12-23 2003-06-18 广西壮族自治区河池地区矿业有限责任公司 Production of aluminum oxide from iron containing bauxite
CN1562756A (en) * 2004-03-19 2005-01-12 邝中 Technique for extracting alumina from materiel containing calcium aluminate
CN101028935A (en) * 2007-01-26 2007-09-05 长安大学 Method for extracting aluminum hydrate or alumina from coal gangue and method for producing cement from fag end
CN101028936A (en) * 2007-01-26 2007-09-05 长安大学 Method for extracting alumin from aluminous fly-ash and method for producing cement from fag end

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BI SHIWEN ET AL.: "Research on Extracting Alumina from Blast Furnace Calcium Aluminate slag", LIGHT METALS, 1992, pages 10 - 15, 26 *
HU WENXIN ET AL.: "Vacuum Thermal Reduction Kinetics of Calcined Dolomite with Al-Si-Fe Alloy", THE CHINESE JOURNAL OF PROCESS ENGINEERING, vol. 10, no. 1, February 2010 (2010-02-01), pages 127 - 132 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10151017B2 (en) * 2016-04-24 2018-12-11 Yadian Xie Method for extracting ultra high purity alumina from wasterwater
CN106185975A (en) * 2016-07-22 2016-12-07 山东钢铁股份有限公司 A kind of method utilizing blast furnace slag to prepare molecular sieve crystal
CN115159552A (en) * 2022-07-04 2022-10-11 重庆大学 Method for recovering aluminum oxide from aluminum-containing resources
CN115159552B (en) * 2022-07-04 2024-01-26 重庆大学 Method for recycling aluminum oxide from aluminum-containing resource
CN115321589A (en) * 2022-09-16 2022-11-11 东北大学 Comprehensive utilization method of by-product in process of preparing titanium or titanium alloy by aluminothermic reduction of fluotitanate
CN115321589B (en) * 2022-09-16 2023-09-12 东北大学 Comprehensive utilization method of byproducts in process of preparing titanium or titanium alloy by aluminothermic reduction of fluorotitanate

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