WO2024074144A1 - 赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺 - Google Patents

赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺 Download PDF

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WO2024074144A1
WO2024074144A1 PCT/CN2023/123286 CN2023123286W WO2024074144A1 WO 2024074144 A1 WO2024074144 A1 WO 2024074144A1 CN 2023123286 W CN2023123286 W CN 2023123286W WO 2024074144 A1 WO2024074144 A1 WO 2024074144A1
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solid waste
red mud
reaction
fly ash
coal gangue
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PCT/CN2023/123286
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English (en)
French (fr)
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许波
许益铭
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淄博益海环保科技有限公司
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Publication of WO2024074144A1 publication Critical patent/WO2024074144A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D9/00—Nitrates of sodium, potassium or alkali metals in general
    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • 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
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B11/00—Making pig-iron other than in blast furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B11/00—Making pig-iron other than in blast furnaces
    • C21B11/10—Making pig-iron other than in blast furnaces in electric furnaces
    • 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 belongs to the technical field of industrial solid waste recycling and utilization, and specifically relates to a comprehensive resource utilization process for red mud, fly ash, steel slag and coal gangue solid waste.
  • Red mud in the alumina production process fly ash in the power industry, metallurgical steel slag in the metallurgical industry, and coal gangue in the energy and mining industry all face the problem of large production volumes and high difficulty in treatment.
  • the common treatment methods for the above solid wastes are as follows: (1) large-scale impermeable membrane landfill storage and landfill; (2) a very small amount of solid waste is used as small products such as building materials, sand and gravel, permeable bricks, insulation cotton, insulation slag, etc. after treatment.
  • patent CN107083485A discloses a comprehensive utilization method of alumina red mud, which uses vacuum thermal reduction to treat red mud, uses carbon or aluminum as a reducing agent, and reduces the iron oxide in the red mud to metallic iron under vacuum conditions, and then separates the iron in the reduced slag through magnetic separation for the production of reduced iron powder, so that the combined sodium oxide is reduced to metallic sodium and distilled out, thereby achieving the purpose of removing alkali from the red mud and recovering alkali, and at the same time, other valuable substances in the red mud (such as scandium, niobium, cesium, etc.) are reduced to a metallic state and form an alloy with aluminum, thereby separating from the slag whose main components are silicon oxide and aluminum oxide, achieving the effect of harmless treatment of alumina red mud and comprehensive recovery of valuable elements.
  • red mud such as scandium, niobium, cesium, etc.
  • Alumina red mud also contains a certain amount of metal elements with high economic value such as calcium, magnesium, and titanium, which have not been extracted and utilized, and the recovered silicon oxide and aluminum oxide components are of low purity, which limits its scope of application.
  • Patent CN102586613A discloses a method for recovering vanadium from vanadium-containing steel slag, wherein the vanadium-containing steel slag is reacted in a NaOH solution with a mass concentration of 10-50% to obtain a reaction slurry, the reaction slurry is diluted with a diluent to obtain a mixed slurry, and the mixed slurry is subjected to solid-liquid separation to obtain calcium-rich tailings and a dissolving solution, a desiliconizing agent is added to the dissolving solution to remove impurities, and then solid-liquid separation is performed to obtain a de-impurity liquid and silicon-containing slag, and the de-impurity liquid is cooled and crystallized to obtain a sodium vanadate product.
  • This method enables the vanadium leaching rate to reach 99%, but it only extracts and utilizes the vanadium in the vanadium-containing steel slag, and does not systematically recycle other elements contained in the steel slag. New solid waste and waste liquid will be generated during the extraction process, and resource utilization of solid waste has not been achieved, and the economic value is not high.
  • the technical problem to be solved by the present invention is to provide a comprehensive resource utilization process for red mud, fly ash, steel slag and coal gangue solid wastes, which has a short treatment process, low energy consumption, high product added value, can continuously and large-scale treat solid wastes, and no wastewater or waste residue is discharged during the treatment process, which is green and environmentally friendly.
  • the comprehensive resource utilization process of red mud, fly ash, steel slag and coal gangue solid wastes described in the present invention comprises the following steps:
  • step (2) Cooling the liquid slag water separated in step (1) to 30-100°C, then feeding it into a reaction tank, adding sodium salt, and reacting at a temperature of 30-300°C to obtain a reaction liquid and a sludge; passing the reaction liquid into a calcium salt precipitation tank, an aluminum salt precipitation tank, and a silicate tank in sequence, and respectively passing CO2 into the tank for acidification reaction, and filtering to obtain calcium salt, aluminum salt, silicate, and alkali solution in sequence;
  • step (3) concentrating and crystallizing the alkali solution obtained by filtering in step (2), and crystallizing the potassium salt and the sodium salt respectively by utilizing the different saturated solubilities;
  • step (2) drying the sludge obtained in step (2), heating it to 600-1300°C, introducing Cl 2 to react, obtaining gaseous TiCl 4 and residue, cooling the gaseous TiCl 4 to below 120°C, condensing and collecting, and obtaining solid TiCl 4 ;
  • step (4) The residue obtained in step (4) is washed with water in a circulating manner, and then separated by sedimentation to obtain a magnesium-removed residue and a magnesium chloride solution.
  • the magnesium chloride solution is passed into a magnesium hydroxide precipitation tank, and sodium hydroxide is added to react to obtain a magnesium hydroxide precipitate.
  • the solid waste is one or more of red mud, fly ash, steel slag, and coal gangue.
  • the red mud is Bayer red mud, which comprises the following main chemical components by mass percentage: Al 2 O 3 10-20%, SiO 2 5-50%, Fe 2 O 3 5-45%, CaO 1-5%, Na 2 O 8-14%, K 2 O 0.2-3%, MgO 0.5-5%, and TiO 2 1-7%.
  • the fly ash comprises the following main chemical components by mass percentage: Al 2 O 3 3-40%, SiO 2 20-40%, Fe 2 O 3 2-20%, CaO 2-8%, Na 2 O 0.2-3%, K 2 O 0.1-1%, MgO 0.2-3%, and TiO 2 0.2-5%.
  • the steel slag comprises the following main chemical components by mass percentage: Al 2 O 3 6-24%, SiO 2 20-45%, Fe 2 O 3 0.05-1%, CaO 20-50%, Na 2 O 0.2-4%, S 0.2-3%, MgO 1-13%, and TiO 2 0.5-15%.
  • the coal gangue comprises the following main chemical components by mass percentage: C20-30%, Al2O3 10-25%, SiO2 33-43 % , Fe2O3 1.5-12%, CaO0.3-2%, Na2O 1-3 %, S0.3-3%, MgO0.3-2%, and TiO2 0.6-2%.
  • step (1) when heating industrial solid waste, it is preferred to use a hydrogen furnace, a coal coke oven or an electric arc furnace for heating.
  • step (1) the amount of Na 2 CO 3 added is 20 to 80% of the mass of the industrial solid waste.
  • step (1) the amount of O2 added is 3 to 20% of the mass of the industrial solid waste.
  • the reducing agent is one or more of C, CO, and H2 , and the amount of the reducing agent added is 5 to 30% of the mass of the industrial solid waste.
  • the sodium salt is preferably sodium nitrate; the amount of sodium salt added is 10 to 40% of the mass of the slag water.
  • step (2) the acidification reaction temperature is 10-50°C.
  • step (2) a detection instrument and a control instrument are installed in the calcium salt precipitation tank to detect the calcium ion value, control the CO 2 injection amount and the acidity value, accurately separate the calcium salt, and ensure the purity of the product without silicon and aluminum inclusions.
  • the amount of CO 2 added and the acidification reaction time are calculated based on the reaction endpoint of the calcium salt.
  • step (2) a detection instrument and a control instrument are installed in the aluminum salt precipitation tank to detect the aluminum ion value, control the CO 2 injection amount and the acidity value, accurately separate the aluminum salt, and ensure the product purity without silicon inclusions.
  • the amount of CO 2 added and the acidification reaction time are calculated based on the reaction endpoint of the aluminum salt.
  • step (2) a detection instrument and a control instrument are installed in the silicate tank to accurately separate silicate by detecting the acidity value.
  • the amount of CO2 added and the acidification reaction time are calculated based on the reaction endpoint of silicate.
  • step (2) the obtained calcium salt, aluminum salt and silicic acid are dried separately, and further processed to obtain calcium powder, aluminum oxide and silicon dioxide.
  • step (4) the amount of Cl2 added is 50 to 200% of the dry mass of the sediment.
  • step (4) solid TiCl4 is further processed to obtain titanium dioxide.
  • step (5) after the magnesium hydroxide is completely precipitated in the precipitation tank, the upper layer of liquid is passed through an evaporation concentration device to produce sodium chloride.
  • magnesium oxide can be obtained after magnesium hydroxide is precipitated and dried.
  • the demagnesium residue is a rare earth raw material rich in heavy metals.
  • the method for comprehensive resource utilization of industrial solid waste of the present invention adopts a combination of chemical, physical and high-temperature incineration methods to separate eight main chemical components accounting for about 99.85% of the content of red mud, fly ash, steel slag and coal gangue solid waste in turn, and obtains products such as iron, aluminum, potassium, sodium, silicon, calcium, titanium and magnesium; the treatment process is short, the energy consumption is low, the product added value is high, and the solid waste can be treated continuously and on a large scale, and no wastewater and waste residue are discharged during the treatment process, which is green and environmentally friendly.
  • the raw materials used in the embodiments are all commercially available conventional products; the process methods adopted in the embodiments are all conventional methods in the art unless otherwise specified.
  • the red mud used in the embodiment is Bayer red mud, which includes the following main chemical components by mass percentage: Al 2 O 3 18.4%, SiO 2 38.2%, Fe 2 O 3 21.8%, CaO 2.4%, Na 2 O 9.5%, K 2 O 0.8%, MgO 3.1%, TiO 2 5.5%, and other components 0.3%.
  • the fly ash used in the embodiment includes the following main chemical components by mass percentage: Al 2 O 3 33.6%, SiO 2 35.8%, Fe 2 O 3 15.7%, CaO 5.3%, Na 2 O 2.2%, K 2 O 0.3%, MgO 2.8%, TiO 2 3.5%, and other components 0.5%.
  • the steel slag used in the embodiment includes the following main chemical components by mass percentage: Al 2 O 3 18.3%, SiO 2 23.1%, Fe 2 O 3 0.5%, CaO 32.4%, Na 2 O 2.5%, S 0.3%, MgO 12.4%, TiO 2 10.1%, and other components 0.4%.
  • the coal gangue used in the embodiment includes the following main chemical components by mass percentage: C 23.6%, Al 2 O 3 20.3%, SiO 2 40.8%, Fe 2 O 3 8.9%, CaO 1.2%, Na 2 O 1.8%, S 0.4%, MgO 1.0%, TiO 2 1.2%, and other components 0.8%.
  • the resource comprehensive utilization method of the present invention is used to treat industrial solid waste red mud.
  • the treatment steps are as follows:
  • step (2) The liquid slag water separated in step (1) is cooled to 80°C, then sent to a reaction tank, sodium nitrate accounting for 24.6% of the mass of the slag water is added, and the reaction is carried out at a temperature of 200°C for 24 hours to obtain a reaction liquid and a sludge; the reaction liquid is sequentially passed into a calcium salt precipitation tank, an aluminum salt precipitation tank, and a silicate tank, and CO2 is respectively passed into the tank for acidification reaction.
  • the acidification reaction temperature is set to 30°C, and the CO2 injection amount and reaction time are adjusted according to the reaction progress in the tank.
  • a detection instrument and a control instrument are installed in the calcium salt precipitation tank.
  • the CO2 injection amount and the acidity value are controlled by detecting the calcium ion value.
  • the calcium ion detection content is 0, the CO2 injection is stopped, the calcium salt is accurately separated, and the product purity is ensured to be free of silicon and aluminum inclusions; a detection instrument and a control instrument are installed in the aluminum salt precipitation tank.
  • the CO2 injection amount and the acidity value are controlled by detecting the aluminum ion value.
  • the CO2 injection is stopped. , accurately separate aluminum salts to ensure product purity without silicon inclusions; install detection instruments and control instruments in the silicate tank to detect the acidity value.
  • step (3) The alkaline solution obtained by filtering in step (2) is concentrated and crystallized, and potassium salt and sodium salt are crystallized separately by utilizing different saturated solubilities.
  • step (2) The sludge obtained in step (2) is dried, heated to 800°C, and Cl2 accounting for 100% of the mass of the sludge is introduced for reaction to obtain gaseous TiCl4 and residue, and the gaseous TiCl4 is cooled to below 120°C, condensed and collected, and purified by distillation to obtain high-purity TiCl4 liquid, which is directly used as a product or further treated by known methods to obtain titanium dioxide.
  • step (4) The residue obtained in step (4) is washed with water in a circulating manner, and then separated by sedimentation to obtain a de-magnesiumized residue and a magnesium chloride solution.
  • the magnesium chloride solution is filtered and passed into a magnesium hydroxide precipitation tank, and sodium hydroxide is added to react to obtain a magnesium hydroxide precipitate.
  • the upper liquid is concentrated by evaporation to produce sodium chloride.
  • the magnesium hydroxide precipitate is dried to obtain magnesium oxide.
  • the de-magnesiumized residue is a rare earth raw material rich in heavy metals.
  • the resource comprehensive utilization method of the present invention is used to treat industrial solid waste (red mud, fly ash, steel slag, and coal gangue in a mass ratio of 5:1:1:1).
  • the treatment steps are as follows:
  • step (2) The liquid slag water separated in step (1) is cooled to 30°C, then sent to a reaction tank, sodium nitrate accounting for 40% of the mass of the slag water is added, and the reaction is carried out at a temperature of 100°C for 24 hours to obtain a reaction liquid and a sludge; the reaction liquid is sequentially passed into a calcium salt precipitation tank, an aluminum salt precipitation tank, and a silicate tank, and CO2 is respectively passed into the tank for acidification reaction.
  • the acidification reaction temperature is set to 10°C, and the CO2 injection amount and reaction time are adjusted according to the reaction progress in the tank.
  • a detection instrument and a control instrument are installed in the calcium salt precipitation tank.
  • the CO2 injection amount and the acidity value are controlled by detecting the calcium ion value.
  • the calcium ion detection content is 0, the CO2 injection is stopped, the calcium salt is accurately separated, and the product purity is ensured to be free of silicon and aluminum inclusions; a detection instrument and a control instrument are installed in the aluminum salt precipitation tank.
  • the CO2 injection amount and the acidity value are controlled by detecting the aluminum ion value.
  • the CO2 injection is stopped. , accurately separate aluminum salts to ensure product purity without silicon inclusions; install detection instruments and control instruments in the silicate tank to detect the acidity value.
  • step (3) The alkaline solution obtained by filtering in step (2) is concentrated and crystallized, and potassium salt and sodium salt are crystallized separately by utilizing different saturated solubilities.
  • step (2) The sludge obtained in step (2) is dried, heated to 600°C, and Cl2 accounting for 200% of the mass of the sludge is introduced for reaction to obtain gaseous TiCl4 and residue, and the gaseous TiCl4 is cooled to below 120°C, condensed and collected, and purified by distillation to obtain high-purity TiCl4 liquid, which is directly used as a product or further treated by known methods to obtain titanium dioxide.
  • step (4) The residue obtained in step (4) is washed with water in a circulating manner, and then separated by sedimentation to obtain a de-magnesiumized residue and a magnesium chloride solution.
  • the magnesium chloride solution is filtered and passed into a magnesium hydroxide precipitation tank, and sodium hydroxide is added to react to obtain a magnesium hydroxide precipitate.
  • the upper liquid is concentrated by evaporation to produce sodium chloride.
  • the magnesium hydroxide precipitate is dried to obtain magnesium oxide.
  • the de-magnesiumized residue is a rare earth raw material rich in heavy metals.
  • the resource comprehensive utilization method of the present invention is used to treat industrial solid waste (red mud and fly ash in a mass ratio of 1:1).
  • the treatment steps are as follows:
  • step (2) The liquid slag water separated in step (1) is cooled to 100°C, then sent to a reaction tank, sodium nitrate accounting for 10.2% of the mass of the slag water is added, and the reaction is carried out at a temperature of 300°C for 72 hours to obtain a reaction liquid and a sludge; the reaction liquid is sequentially passed into a calcium salt precipitation tank, an aluminum salt precipitation tank, and a silicate tank, and CO2 is respectively passed into the tank for acidification reaction.
  • the acidification reaction temperature is set to 50°C, and the CO2 injection amount and reaction time are adjusted according to the reaction progress in the tank.
  • a detection instrument and a control instrument are installed in the calcium salt precipitation tank.
  • the CO2 injection amount and the acidity value are controlled by detecting the calcium ion value.
  • the calcium ion detection content is 0, the CO2 injection is stopped, the calcium salt is accurately separated, and the product purity is ensured to be free of silicon and aluminum inclusions; a detection instrument and a control instrument are installed in the aluminum salt precipitation tank.
  • the CO2 injection amount and the acidity value are controlled by detecting the aluminum ion value.
  • the CO2 injection is stopped. , accurately separate aluminum salts to ensure product purity without silicon inclusions; install detection instruments and control instruments in the silicate tank to detect the acidity value.
  • step (3) The alkaline solution obtained by filtering in step (2) is concentrated and crystallized, and potassium salt and sodium salt are crystallized separately by utilizing different saturated solubilities.
  • step (2) The sludge obtained in step (2) is dried, heated to 1300°C, and Cl2 accounting for 50% of the mass of the sludge is introduced for reaction to obtain gaseous TiCl4 and residue.
  • the gaseous TiCl4 is cooled to below 120°C, condensed and collected, and purified by distillation to obtain high-purity TiCl4 liquid, which is directly used as a product or further processed by known methods to obtain titanium dioxide.
  • step (4) The residue obtained in step (4) is washed with water in a circulating manner, and then separated by sedimentation to obtain a de-magnesiumized residue and a magnesium chloride solution.
  • the magnesium chloride solution is filtered and passed into a magnesium hydroxide precipitation tank, and sodium hydroxide is added to react to obtain a magnesium hydroxide precipitate.
  • the upper liquid is concentrated by evaporation to produce sodium chloride.
  • the magnesium hydroxide precipitate is dried to obtain magnesium oxide.
  • the de-magnesiumized residue is a rare earth raw material rich in heavy metals.
  • the resource comprehensive utilization method of the present invention is used to treat industrial solid waste (red mud and coal gangue with a mass ratio of 3:2).
  • the treatment steps are as follows:
  • step (2) The liquid slag water separated in step (1) is cooled to 50°C, then sent to a reaction tank, sodium nitrate accounting for 32.8% of the mass of the slag water is added, and the reaction is carried out at a temperature of 200°C for 36 hours to obtain a reaction liquid and a sludge; the reaction liquid is sequentially passed into a calcium salt precipitation tank, an aluminum salt precipitation tank, and a silicate tank, and CO2 is respectively passed into the tank for acidification reaction.
  • the acidification reaction temperature is set to 25°C, and the CO2 injection amount and reaction time are adjusted according to the reaction progress in the tank.
  • a detection instrument and a control instrument are installed in the calcium salt precipitation tank.
  • the CO2 injection amount and the acidity value are controlled by detecting the calcium ion value.
  • the calcium ion detection content is 0, the CO2 injection is stopped, the calcium salt is accurately separated, and the product purity is ensured to be free of silicon and aluminum inclusions; a detection instrument and a control instrument are installed in the aluminum salt precipitation tank.
  • the CO2 injection amount and the acidity value are controlled by detecting the aluminum ion value.
  • the CO2 injection is stopped. , accurately separate aluminum salts to ensure product purity without silicon inclusions; install detection instruments and control instruments in the silicate tank to detect the acidity value.
  • step (3) The alkaline solution obtained by filtering in step (2) is concentrated and crystallized, and potassium salt and sodium salt are crystallized separately by utilizing different saturated solubilities.
  • step (2) The sludge obtained in step (2) is dried, heated to 1000°C, and Cl2 accounting for 150% of the mass of the sludge is introduced for reaction to obtain gaseous TiCl4 and residue, and the gaseous TiCl4 is cooled to below 120°C, condensed and collected, and purified by distillation to obtain high-purity TiCl4 liquid, which is directly used as a product or further treated by known methods to obtain titanium dioxide.
  • step (4) The residue obtained in step (4) is washed with water in a circulating manner, and then separated by sedimentation to obtain a de-magnesiumized residue and a magnesium chloride solution.
  • the magnesium chloride solution is filtered and passed into a magnesium hydroxide precipitation tank, and sodium hydroxide is added to react to obtain a magnesium hydroxide precipitate.
  • the upper liquid is concentrated by evaporation to produce sodium chloride.
  • the magnesium hydroxide precipitate is dried to obtain magnesium oxide.
  • the de-magnesiumized residue is a rare earth raw material rich in heavy metals.

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Abstract

本发明属于工业固废回收利用技术领域，具体涉及一种赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺。所述资源化综合利用工艺，将工业固废加入Na2CO3、O2和还原剂进行反应，分离出铁水和液态渣水；液态渣水加入钠盐反应，得到反应液和沉渣；将反应液依次通入钙盐沉淀槽、铝盐沉淀槽、硅酸槽，分别通入CO2进行酸化反应，过滤后依次得到钙盐、铝盐、硅酸和碱液；将碱液进行浓缩结晶，得到钾盐和钠盐；把沉渣烘干通入Cl2反应，得到气态TiCl4和残渣；残渣加入氢氧化钠反应得到氢氧化镁。本发明的固废资源化综合利用方法，处理流程短，能耗低，产品附加值高，且处理过程中无废水废渣排放，绿色环保。

Description

赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺 技术领域
 本发明属于工业固废回收利用技术领域，具体涉及一种赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺。
 背景技术
 氧化铝生产过程中的赤泥、电力行业的粉煤灰、冶金行业的冶金钢渣、能源采矿行业的煤矸石等都面临产生量大，处理难度高的问题。目前，针对上述固废常见的处理方法如下：（1）大规模防渗膜填埋厂堆存、填埋；（2）极少量经处理后用作建材砂石料、透水砖、保温棉、保温渣等小型产品，但是由于固废大多具有强碱性，同时富含大量的重金属，导致制品附加值低，对固废的消化量较小；（3）用于做路基夯土垫层，但是同样由于固废具有强碱性，且夹杂的重金属元素未分离出来，会造成一定的环保与安全隐患。
 针对固废的资源化利用，虽然各高校、研究院、企业等都投入了大量精力和资金进行研究，但均是针对固废中的一种或几种组分进行提取利用，并未对固废进行资源化综合利用。
 例如专利CN107083485A中公开了一种氧化铝赤泥的综合利用方法，采用真空热还原法处理赤泥，以碳或铝为还原剂，在真空条件下使赤泥中的氧化铁还原为金属铁，然后通过磁选将还原渣中的铁分离出来用于生产还原铁粉，使化合态的氧化钠还原为金属钠，并被蒸馏出来，从而达到赤泥除碱和回收碱的目的，同时使赤泥中的其它有价物质（如：钪、铌、铯等）被还原为金属态并与铝形成合金，从而与主要成分为氧化硅和氧化铝的渣相分离，实现氧化铝赤泥的无害化处理和有价元素的综合回收利用的效果。该技术方案只是对赤泥中含量较高的铁、氧化铝、氧化硅进行了提取利用，氧化铝赤泥中还含有一定量的钙、镁、钛等具有较高经济价值的金属元素并未被提取利用，且其回收的氧化硅和氧化铝成分纯度不高，限制了其应用范围。
 专利CN102586613A中公开了一种从含钒钢渣中回收钒的方法，将含钒钢渣在质量浓度为10~50%的NaOH溶液中进行反应，得到反应浆料，用稀释剂将反应浆料稀释得到混合浆料，再将混合浆料进行固液分离，得到富钙尾渣和溶出液，将溶出液加入脱硅剂进行除杂，然后固液分离，得到除杂后液和含硅渣，将除杂后液冷却结晶，即得到钒酸钠产品。本方法使钒浸出率达到99%，但其只是对含钒钢渣中的钒进行提取利用，对钢渣中含有的其他元素没有进行***的回收利用，在提取过程中会产生新的固废和废液，并未实现固废的资源化利用，经济价值不高。
 由此可见，上述技术都没有对固废中所含的化学组分进行综合提取利用，固废综合利用率较低，经济效益不高，甚至在处理固废时会产生新的固废组分。因此，需要设计一种流程短、经济性盈亏平衡的工艺路线。
 发明内容
 本发明要解决的技术问题是：提供一种赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，处理流程短，能耗低，产品附加值高，能够连续化、规模化处理固废，且处理过程中无废水废渣排放，绿色环保。
 本发明所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，步骤如下：
（1）将工业固废加热至1800～2400℃，然后加入Na2CO3、O2和还原剂进行反应，分离出铁水和液态渣水；
（2）将步骤（1）分离出的液态渣水冷却至30～100℃，然后送入反应罐，加入钠盐，在30～300℃温度下进行反应，得到反应液和沉渣；将反应液依次通入钙盐沉淀槽、铝盐沉淀槽、硅酸槽，分别通入CO2进行酸化反应，过滤后依次得到钙盐、铝盐、硅酸和碱液；
（3）将步骤（2）过滤得到的碱液进行浓缩结晶，利用饱和溶解度不同分别结晶得到钾盐和钠盐；
（4）把步骤（2）得到的沉渣烘干，加热至600-1300℃，通入Cl2进行反应，得到气态TiCl4和残渣，将气态TiCl4冷却至120℃以下冷凝收集，得到固体TiCl4；
（5）步骤（4）中得到的残渣用水循环洗涤后，沉降分离得到脱镁残渣和氯化镁溶液，将氯化镁溶液通入氢氧化镁沉淀槽，加入氢氧化钠进行反应，得到氢氧化镁沉淀。
 步骤（1）中，所述固废为赤泥、粉煤灰、钢渣、煤矸石中的一种或多种。
 优选的，所述赤泥为拜耳法赤泥，以质量百分比计，包括以下主要化学成分：Al2O310～20%，SiO25～50%，Fe2O35～45%，CaO1～5%，Na2O 8～14%，K2O0.2～3%，MgO0.5～5%，TiO21～7%。
 优选的，所述粉煤灰以质量百分比计，包括以下主要化学成分：Al2O33～40%，SiO220～40%，Fe2O32～20%，CaO2～8%，Na2O 0.2～3%，K2O0.1～1%，MgO0.2～3%，TiO20.2～5%。
 优选的，所述钢渣以质量百分比计，包括以下主要化学成分：Al2O3 6～24%，SiO2 20～45%，Fe2O3 0.05～1%，CaO 20～50%，Na2O 0.2～4%，S 0.2～3%，MgO 1～13%，TiO2 0.5～15%。
 优选的，所述煤矸石以质量百分比计，包括以下主要化学成分：C20～30%，Al2O310～25%，SiO233～43%，Fe2O31.5～12%，CaO0.3～2%，Na2O 1～3%，S0.3～3%，MgO0.3～2%，TiO20.6～2%。
 步骤（1）中，工业固废加热时，优选使用氢气炉、煤焦炉或电弧炉进行加热。
 步骤（1）中，Na2CO3的加入量为工业固废质量的20～80%。
 步骤（1）中，O2的加入量为工业固废质量的3～20%。
 步骤（1）中，还原剂为C、CO、H2中的一种或多种，还原剂的加入量为工业固废质量的5～30%。
 步骤（2）中，钠盐优选为硝酸钠；钠盐的加入量为渣水质量的10～40%。
 步骤（2）中，酸化反应温度均为10～50℃。
 步骤（2）中，在钙盐沉淀槽内安装有检测仪表和控制仪表，通过检测钙离子数值，控制CO2通入量和酸度值，精确分离钙盐，保证产品纯度无硅铝夹杂。CO2的加入量和酸化反应时间以钙盐的反应终点计。
 步骤（2）中，在铝盐沉淀槽内安装有检测仪表和控制仪表，通过检测铝离子数值，控制  CO2通入量和酸度值，精确分离铝盐，保证产品纯度无硅夹杂。CO2的加入量和酸化反应时间以铝盐的反应终点计。
 步骤（2）中，在硅酸槽内安装有检测仪表和控制仪表，通过检测酸度值，精确分离硅酸。CO2的加入量和酸化反应时间以硅酸的反应终点计。
 步骤（2）中，将得到的钙盐、铝盐、硅酸分别进行干燥，进一步处理可以得到钙粉、氧化铝、二氧化硅。
 步骤（4）中，Cl2的加入量为沉渣干质量的50～200%。
 步骤（4）中，固体TiCl4进一步处理可以得到钛白粉。
 步骤（5）中，氢氧化镁沉淀槽内沉淀完全后，将上层液体通过蒸发浓缩设备产出氯化钠。
 步骤（5）中，氢氧化镁沉淀烘干后可以得到氧化镁。
 步骤（5）中，脱镁残渣为富含重金属的稀土原料。
 与现有技术相比，本发明的有益效果如下：
本发明的工业固废资源化综合利用方法，采用化学、物理、高温焚烧相结合的方式，把赤泥、粉煤灰、钢渣、煤矸石固废中含量占比99.85%左右的8种主要化学成分依次进行分离，得到铁、铝、钾、钠、硅、钙、钛、镁等产物；处理流程短，能耗低，产品附加值高，能够连续化、规模化处理固废，且处理过程中无废水废渣排放，绿色环保。
 具体实施方式
 下面结合实施例对本发明作进一步说明。
 实施例中所用到的原料，如无特别说明，均为市售常规产品；实施例中所采用的工艺方法，如无特别说明，均为本领域常规方法。
 实施例中所采用的赤泥为拜耳法赤泥，以质量百分比计，包括以下主要化学成分：Al2O3 18.4%，SiO2 38.2%，Fe2O3 21.8%，CaO 2.4%，Na2O 9.5%，K2O 0.8%，MgO 3.1%，TiO2 5.5%，其他组分0.3%。
 实施例中所采用的粉煤灰以质量百分比计，包括以下主要化学成分：Al2O333.6%，SiO235.8%，Fe2O315.7%，CaO5.3%，Na2O 2.2%，K2O0.3，MgO2.8%，TiO23.5%，其他组分0.5%。
 实施例中所采用的钢渣以质量百分比计，包括以下主要化学成分：Al2O318.3%，SiO223.1%，Fe2O30.5%，CaO32.4%，Na2O2.5%，S0.3%，MgO12.4%，TiO210.1%，其他组分0.4%。
 实施例中所采用的煤矸石以质量百分比计，包括以下主要化学成分：C 23.6%，Al2O3 20.3%，SiO2 40.8%，Fe2O3 8.9%，CaO 1.2%，Na2O 1.8%，S 0.4%，MgO 1.0%，TiO2 1.2%，其他组分0.8%。
 实施例1
采用本发明的资源化综合利用方法对工业固废赤泥进行处理。处理步骤如下：
（1）将工业固废利用氢气炉加热至2400℃，然后加入占工业固废质量32.4%的Na2CO3、12.5%的O2和14.8%的C，反应180min，然后分离出铁水和液态渣水。
 （2）将步骤（1）分离出的液态渣水冷却至80℃，然后送入反应罐，加入占渣水质量24.6%的硝酸钠，在200℃温度下反应24h，得到反应液和沉渣；将反应液依次通入钙盐沉淀槽、铝盐沉淀槽、硅酸槽，分别通入CO2进行酸化反应，酸化反应温度均设置为30℃，CO2通入量和反应时间根据槽内反应进度调整，在钙盐沉淀槽内安装有检测仪表和控制仪表，通过检测钙离子数值，控制CO2通入量和酸度值，当钙离子检测含量为0时，结束通入CO2，精确分离钙盐，保证产品纯度无硅铝夹杂；在铝盐沉淀槽内安装有检测仪表和控制仪表，通过检测铝离子数值，控制CO2通入量和酸度值，当铝离子检测含量为0时，结束通入CO2，精确分离铝盐，保证产品纯度无硅夹杂；在硅酸槽内安装有检测仪表和控制仪表，通过检测酸度值，当酸度值开始增大时，结束通入CO2，精确分离硅酸；当各槽内酸化反应完毕后，经过滤后依次得到钙盐、铝盐、硅酸和碱液，将得到的钙盐、铝盐、硅酸分别进行干燥，直接作为产品或者通过已知方法进一步处理得到钙粉、氧化铝、二氧化硅。
 （3）将步骤（2）过滤得到的碱液进行浓缩结晶，利用饱和溶解度不同分别结晶得到钾盐和钠盐。
 （4）把步骤（2）得到的沉渣烘干，加热至 800 ℃，通入占沉渣质量100%的 Cl2 进行反应，得到气态TiCl4 和残渣，将气态TiCl4 冷却至120℃以下冷凝收集，精馏净化，得到高纯TiCl4 液体，直接作为产品或者通过已知方法进一步处理得到钛白粉。
 （5）步骤（4）中得到的残渣用水循环洗涤后，沉降分离得到脱镁残渣和氯化镁溶液，将氯化镁溶液过滤后通入氢氧化镁沉淀槽，加入氢氧化钠进行反应，得到氢氧化镁沉淀，上层液体通过蒸发浓缩设备产出氯化钠，氢氧化镁沉淀烘干后可以得到氧化镁，脱镁残渣为富含重金属的稀土原料。
 实施例2
采用本发明的资源化综合利用方法对工业固废（质量比为5:1:1:1的赤泥、粉煤灰、钢渣、煤矸石）进行处理。处理步骤如下：
（1）将工业固废利用氢气炉加热至1800℃，然后加入占工业固废质量78.9%的Na2CO3、19.6%的O2和29.5%的CO，反应200min，然后分离出铁水和液态渣水。
 （2）将步骤（1）分离出的液态渣水冷却至30℃，然后送入反应罐，加入占渣水质量40%的硝酸钠，在100℃温度下反应24h，得到反应液和沉渣；将反应液依次通入钙盐沉淀槽、铝盐沉淀槽、硅酸槽，分别通入CO2进行酸化反应，酸化反应温度均设置为10℃，CO2通入量和反应时间根据槽内反应进度调整，在钙盐沉淀槽内安装有检测仪表和控制仪表，通过检测钙离子数值，控制CO2通入量和酸度值，当钙离子检测含量为0时，结束通入CO2，精确分离钙盐，保证产品纯度无硅铝夹杂；在铝盐沉淀槽内安装有检测仪表和控制仪表，通过检测铝离子数值，控制CO2通入量和酸度值，当铝离子检测含量为0时，结束通入CO2，精确分离铝盐，保证产品纯度无硅夹杂；在硅酸槽内安装有检测仪表和控制仪表，通过检测酸度值，当酸度值开始增大时，结束通入CO2，精确分离硅酸；当各槽内酸化反应完毕后，经过滤后依次得到钙盐、铝盐、硅酸和碱液，将得到的钙盐、铝盐、硅酸分别进行干燥，直接作为产品或者通过已知方法进一步处理得到钙粉、氧化铝、二氧化硅。
 （3）将步骤（2）过滤得到的碱液进行浓缩结晶，利用饱和溶解度不同分别结晶得到钾盐和钠盐。
 （4）把步骤（2）得到的沉渣烘干，加热至 600 ℃，通入占沉渣质量200%的 Cl2 进行反应，得到气态TiCl4 和残渣，将气态TiCl4 冷却至120℃以下冷凝收集，精馏净化，得到高纯TiCl4 液体，直接作为产品或者通过已知方法进一步处理得到钛白粉。
 （5）步骤（4）中得到的残渣用水循环洗涤后，沉降分离得到脱镁残渣和氯化镁溶液，将氯化镁溶液过滤后通入氢氧化镁沉淀槽，加入氢氧化钠进行反应，得到氢氧化镁沉淀，上层液体通过蒸发浓缩设备产出氯化钠，氢氧化镁沉淀烘干后可以得到氧化镁，脱镁残渣为富含重金属的稀土原料。
 实施例3
采用本发明的资源化综合利用方法对工业固废（质量比为1:1的赤泥和粉煤灰）进行处理。处理步骤如下：
（1）将工业固废利用氢气炉加热至2000℃，然后加入占工业固废质量20.2%的Na2CO3、3.2%的O2和5.4%的H2，反应60min，然后分离出铁水和液态渣水。
 （2）将步骤（1）分离出的液态渣水冷却至100℃，然后送入反应罐，加入占渣水质量10.2%的硝酸钠，在300℃温度下反应72h，得到反应液和沉渣；将反应液依次通入钙盐沉淀槽、铝盐沉淀槽、硅酸槽，分别通入CO2进行酸化反应，酸化反应温度均设置为50℃，CO2通入量和反应时间根据槽内反应进度调整，在钙盐沉淀槽内安装有检测仪表和控制仪表，通过检测钙离子数值，控制CO2通入量和酸度值，当钙离子检测含量为0时，结束通入CO2，精确分离钙盐，保证产品纯度无硅铝夹杂；在铝盐沉淀槽内安装有检测仪表和控制仪表，通过检测铝离子数值，控制CO2通入量和酸度值，当铝离子检测含量为0时，结束通入CO2，精确分离铝盐，保证产品纯度无硅夹杂；在硅酸槽内安装有检测仪表和控制仪表，通过检测酸度值，当酸度值开始增大时，结束通入CO2，精确分离硅酸；当各槽内酸化反应完毕后，经过滤后依次得到钙盐、铝盐、硅酸和碱液，将得到的钙盐、铝盐、硅酸分别进行干燥，直接作为产品或者通过已知方法进一步处理得到钙粉、氧化铝、二氧化硅。
 （3）将步骤（2）过滤得到的碱液进行浓缩结晶，利用饱和溶解度不同分别结晶得到钾盐和钠盐。
 （4）把步骤（2）得到的沉渣烘干，加热至1300 ℃，通入占沉渣质量50% 的 Cl2 进行反应，得到气态TiCl4 和残渣，将气态TiCl4 冷却至120℃以下冷凝收集，精馏净化，得到高纯TiCl4 液体，直接作为产品或者通过已知方法进一步处理得到钛白粉。
 （5）步骤（4）中得到的残渣用水循环洗涤后，沉降分离得到脱镁残渣和氯化镁溶液，将氯化镁溶液过滤后通入氢氧化镁沉淀槽，加入氢氧化钠进行反应，得到氢氧化镁沉淀，上层液体通过蒸发浓缩设备产出氯化钠，氢氧化镁沉淀烘干后可以得到氧化镁，脱镁残渣为富含重金属的稀土原料。
 实施例4
采用本发明的资源化综合利用方法对工业固废（质量比为3:2的赤泥和煤矸石）进行处理。处理步骤如下：
（1）将工业固废利用氢气炉加热至2200℃，然后加入占工业固废质量54.8%的Na2CO3、15.4%的O2和10.5%的C，反应120min，然后分离出铁水和液态渣水。
 （2）将步骤（1）分离出的液态渣水冷却至50℃，然后送入反应罐，加入占渣水质量32.8%的硝酸钠，在200℃温度下反应36h，得到反应液和沉渣；将反应液依次通入钙盐沉淀槽、铝盐沉淀槽、硅酸槽，分别通入CO2进行酸化反应，酸化反应温度均设置为25℃，CO2通入量和反应时间根据槽内反应进度调整，在钙盐沉淀槽内安装有检测仪表和控制仪表，通过检测钙离子数值，控制CO2通入量和酸度值，当钙离子检测含量为0时，结束通入CO2，精确分离钙盐，保证产品纯度无硅铝夹杂；在铝盐沉淀槽内安装有检测仪表和控制仪表，通过检测铝离子数值，控制CO2通入量和酸度值，当铝离子检测含量为0时，结束通入CO2，精确分离铝盐，保证产品纯度无硅夹杂；在硅酸槽内安装有检测仪表和控制仪表，通过检测酸度值，当酸度值开始增大时，结束通入CO2，精确分离硅酸；当各槽内酸化反应完毕后，经过滤后依次得到钙盐、铝盐、硅酸和碱液，将得到的钙盐、铝盐、硅酸分别进行干燥，直接作为产品或者通过已知方法进一步处理得到钙粉、氧化铝、二氧化硅。
 （3）将步骤（2）过滤得到的碱液进行浓缩结晶，利用饱和溶解度不同分别结晶得到钾盐和钠盐。
 （4）把步骤（2）得到的沉渣烘干，加热至1000℃，通入占沉渣质量150%的 Cl2 进行反应，得到气态TiCl4 和残渣，将气态TiCl4 冷却至120℃以下冷凝收集，精馏净化，得到高纯TiCl4 液体，直接作为产品或者通过已知方法进一步处理得到钛白粉。
 （5）步骤（4）中得到的残渣用水循环洗涤后，沉降分离得到脱镁残渣和氯化镁溶液，将氯化镁溶液过滤后通入氢氧化镁沉淀槽，加入氢氧化钠进行反应，得到氢氧化镁沉淀，上层液体通过蒸发浓缩设备产出氯化钠，氢氧化镁沉淀烘干后可以得到氧化镁，脱镁残渣为富含重金属的稀土原料。

Claims (10)

  1. 一种赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：包括以下步骤：
    （1）将工业固废加热至1800～2400℃，然后加入Na2CO3、O2和还原剂进行反应，分离出铁水和液态渣水；
    （2）将步骤（1）分离出的液态渣水冷却至30～100℃，然后送入反应罐，加入钠盐，在30～300℃温度下进行反应，得到反应液和沉渣；将反应液依次通入钙盐沉淀槽、铝盐沉淀槽、硅酸槽，分别通入 CO2进行酸化反应，过滤后依次得到钙盐、铝盐、硅酸和碱液；
    （3）将步骤（2）过滤得到的碱液进行浓缩结晶，利用饱和溶解度不同分别结晶得到钾盐和钠盐；
    （4）把步骤（2）得到的沉渣烘干，加热至600-1300℃，通入Cl2进行反应，得到气态TiCl4和残渣，将气态TiCl4冷却至120℃以下冷凝收集，得到固体TiCl4；
    （5）步骤（4）中得到的残渣用水循环洗涤后，沉降分离得到脱镁残渣和氯化镁溶液，将氯化镁溶液通入氢氧化镁沉淀槽，加入氢氧化钠进行反应，得到氢氧化镁沉淀。
  2.  根据权利要求1所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：步骤（1）中，所述固废为赤泥、粉煤灰、钢渣、煤矸石中的一种或多种。
  3.  根据权利要求2所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：所述赤泥为拜耳法赤泥。
  4.  根据权利要求1所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：步骤（1）中，Na2CO3的加入量为工业固废质量的20～80%。
  5.  根据权利要求1所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：步骤（1）中，O2的加入量为工业固废质量的3～20%。
  6.  根据权利要求1所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：步骤（1）中，还原剂为C、CO、H2中的一种或多种，还原剂的加入量为工业固废质量的5～30%。
  7.  根据权利要求1所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：步骤（2）中，钠盐优选为硝酸钠；钠盐的加入量为渣水质量的10～40%。
  8.  根据权利要求1所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：步骤（2）中，酸化反应温度均为10～50℃。
  9.  根据权利要求1所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：步骤（4）中，Cl2的加入量为沉渣干质量的50～200%。
  10.  根据权利要求1所述的赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺，其特征在于：步骤（5）中，氢氧化镁沉淀槽内沉淀完全后，将上层液体通过蒸发浓缩设备产出氯化钠。
PCT/CN2023/123286 2022-10-08 2023-10-08 赤泥、粉煤灰、钢渣、煤矸石固废资源化综合利用工艺 WO2024074144A1 (zh)

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