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WO2019071793A1 - Procédé permettant de récupérer un composant de valeur à partir d'un laitier contenant du cuivre - Google Patents

Procédé permettant de récupérer un composant de valeur à partir d'un laitier contenant du cuivre Download PDF

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Publication number
WO2019071793A1
WO2019071793A1 PCT/CN2017/115648 CN2017115648W WO2019071793A1 WO 2019071793 A1 WO2019071793 A1 WO 2019071793A1 CN 2017115648 W CN2017115648 W CN 2017115648W WO 2019071793 A1 WO2019071793 A1 WO 2019071793A1
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Prior art keywords
slag
copper
smelting
iron
reaction
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English (en)
Chinese (zh)
Inventor
张力
张武
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Northeastern University China
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Northeastern University China
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Publication of WO2019071793A1 publication Critical patent/WO2019071793A1/fr
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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
    • 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
    • C22B7/04—Working-up slag
    • 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
    • C22B11/00—Obtaining noble metals
    • 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
    • C22B13/00—Obtaining lead
    • 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
    • C22B15/00—Obtaining copper
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B7/001—Dry processes
    • 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 invention belongs to the technical field of slag metallurgy, and in particular relates to a method for recovering valuable components from copper-containing slag.
  • the copper slag includes copper-containing smelting slag, copper-containing blowing slag, copper-fired depleted slag, and copper slag flotation tailings.
  • the copper-containing smelting slag is produced in the process of “smelting and smelting” of the pyrometallurgical process of copper. It emits more than 20 million tons per year, and currently accumulates more than 200 million tons. With the continuous development of "smelting smelting” technology, such as flash smelting furnace, Noranda furnace, Vanukov furnace, Isa furnace, Osmet furnace, Mitsubishi furnace, Jinfeng furnace, bottom blowing furnace, etc. The content of Cu, Fe and other metals in the copper smelting slag is increased, the copper content in the slag reaches 20%, and the iron content is as high as 55%. Copper smelting slag is an important secondary resource.
  • the molten copper smelting slag discharged from the smelting smelting furnace of the "smelting smelting" process is higher than 1100 ° C, and the molten copper smelting slag is also an important physical heat resource.
  • the main utilization method of copper smelting slag is fire depletion and flotation recovery of copper components.
  • the copper-containing blowing slag is produced in the "copper smelting" process of the fire smelting process of copper, such as converter blowing slag, flash blowing slag, top blowing furnace blowing slag, bottom blowing furnace blowing slag, etc.
  • the copper content in the slag reaches 35% and the iron content is as high as 55%.
  • Molten copper-containing blowing slag is also an important physical thermal resource.
  • the copper component is mainly recovered by a return smelting furnace or an electric furnace depletion or beneficiation method.
  • Copper slag is not only an important secondary resource, but also contains a large amount of metallurgical fluxes such as SiO 2 , CaO, MgO, Al 2 O 3 , etc., which has strong chemical reaction activity and is a slag system with excellent physical and chemical properties, and is a thermal metallurgical clinker. It is a mature metallurgical slag system.
  • the copper-containing smelting slag and the copper-containing blowing slag are returned to the smelting furnace or the electric furnace depletion or beneficiation method, and only the recovery of the copper component is considered, the depletion or beneficiation effect is not good, and the flotation brings serious environmental pollution.
  • the slag contains more than 0.3% copper, which is 0.2% higher than the recoverable grade of copper.
  • copper In general, iron ore is allowed to contain no more than 0.2% copper.
  • the higher slag contains copper, which is not conducive to the subsequent direct reduction of iron or smelting reduction of iron. The reason is that during the reduction process, copper is easily reduced and enters pig iron. When it exceeds 0.3%, the weldability of the steel is lowered, and the "hot brittleness" phenomenon of the steel is caused, causing cracks during rolling.
  • the present invention provides a method of recovering valuable components using copper-containing slag.
  • the method of the invention is a new slag metallurgy process, which not only reduces the copper content of the slag, but also makes the slag contain copper ⁇ 0.1 wt%, and realizes efficient recovery of components such as copper, iron, gold, silver, lead and zinc, and obtains low efficiency.
  • Copper-containing iron materials such as iron concentrates and pig iron, and solve the problems of large accumulation of slag, environmental pollution and heavy metal elements.
  • the main technical solutions adopted by the present invention include:
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • S1 slag mixing: adding copper slag to the smelting reaction device, adding calcium minerals and additives to form mixed slag, heating the mixed slag to a molten state as reaction slag, mixing uniformly, and monitoring the reaction slag in real time,
  • the slag after the reaction is obtained by adjusting the mixed reaction slag to satisfy the condition a and the condition b, or the slag after the reaction is poured into the heat preservation device;
  • condition a is that the temperature of the reaction slag is from 1100 to 1450 ° C;
  • the slag after the reaction in the step S1 is kept for 5 to 50 minutes, and the bottom copper-rich phase layer, the middle iron-rich phase and the upper iron-containing silicate mineral phase are obtained by sedimentation separation, and the zinc-containing component is formed at the same time.
  • Lead-containing component Smoke, dust, gold and silver components enter the copper-rich phase; the phases are recycled.
  • the method for regulating the condition a is:
  • the temperature of the reaction slag is >1450 ° C
  • one or more of the copper-containing material, the metallurgical flux, the iron-containing material or the fluorine-containing material is added to the reaction slag, and the mixture is uniformly mixed to make the temperature of the mixed slag Up to 1100 ⁇ 1450 ° C;
  • the method for regulating the condition b is:
  • the reaction device is a heat preservation device or a rotatable smelting reaction device or a smelting reaction device with slag or iron slag flowing out; wherein the heat preservation device is pourable Smelting reaction slag irrigation or insulation pit;
  • the rotatable smelting reaction device is a converter and a smelting reaction slag tank;
  • the smelting reaction device with slag or iron slag can flow out is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola furnace, a side blowing molten pool smelting furnace, Bottom-blow pool smelting furnace, top-blow pool smelting furnace, reverberatory furnace, Osmet furnace, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing rotary furnace The electric heating bed of the copper melting furnace.
  • step S1 while satisfying the conditions a and b, it should be simultaneously satisfied to control the reduction of copper oxide and iron oxide in the slag holding slag to metallic copper. And FeO, the metal iron content in the slag is ⁇ 3%.
  • a reducing agent By adding one or both of a reducing agent, a carbon-containing iron-containing material, wherein the reducing agent and/or the carbon-containing iron-containing material is used in an amount such that copper and iron oxides in the slag are reduced to metal
  • the theoretical amount of copper and FeO is 110-140%; the carbon-containing iron-containing material is steel dust and soot, iron concentrate carbon-containing pre-reduction pellet, iron concentrate carbon-containing metallized pellet, wet zinc smelting Volatile kiln residue or coke oven dust and soot.
  • the copper slag is one or more of a copper-containing smelting slag, a copper-containing blowing slag, a copper-fired depleted slag, a flotation tailings, and a wet copper slag.
  • the copper-containing smelting slag is produced in a "smelting smelting" process of a copper pyrometallurgical smelting process
  • the copper-containing smelting slag is produced in a "copper smelting” process of a copper pyrometallurgical process
  • the copper fire method depleted waste slag is a copper smelting slag and a copper-containing smelting slag
  • the slag is depleted
  • the flotation tailing slag is a copper smelting slag and a copper-containing smelting slag, and a tailing slag after beneficiation
  • the copper-containing smelting slag, the copper-containing smelting slag and the depleted slag are in a molten state or a cold state, wherein: the molten copper smelting slag is obtained from a slag-containing smelting furnace slag
  • the calcium-based mineral is one or more of lime, limestone, dolomite, calcium carbide slag, red mud or high-calcium red mud after de-sodium; the additive is SiO 2 , MgO, FeO, Fe 2 O 3 , One or more of MnO 2 , Al 2 O 3 , TiO 2 , Fe or Na 2 O.
  • the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead smelting slag, lead-zinc tailings, Nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag, lead-containing smelting furnace slag, lead smelting soot and soot, lead-acid battery, copper smelting soot and dust, copper, copper-containing garbage, containing One or more kinds of copper circuit board, tin smelting slag, tin tailings; wherein the copper slag includes slag produced by "smelting smelting” and slag generated by "copper smelting", depletion by fire method Slag and copper slag flotation tailings; lead-containing slag is smelting furnace slag and lead smelting slag
  • the metallurgical flux is a mineral containing CaO or SiO 2 , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone;
  • the iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon-bearing pre- Reducing pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag, copper slag, lead smelting slag, copper slag, tin smelting slag, red mud, high calcium after desodium One or more of red mud, coal dust ash, sulfuric acid slag; the steel dust and dust including blast furnace gas mud, converter dust mud, electric furnace dust, hot or cold rolling sludge, sintering dust, pellets Dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale;
  • the fluorine-containing material is one or more of fluorite, CaF 2 or fluorine-containing blast furnace slag;
  • the copper-containing material, the iron-containing material and the fluorine-containing material are all pellets or powdery materials or granulation; wherein, the granular material has a particle size of ⁇ 150 ⁇ m, the granular material has a particle size of 5 to 25 mm, and the powdery material is sprayed. Injecting in a manner, the granular material is added by spraying or feeding, and the gas is loaded into one or more of argon gas, nitrogen gas, reducing gas and oxidizing gas at 0 to 1200 ° C; One or more of the slag inserted into the slag or placed in the upper or side or bottom of the reaction slag.
  • the alkaline material is one or more of lime powder, red mud, decalcified high calcium red mud, calcium carbide slag, dolomite powder or quicklime powder;
  • the iron-containing material is CaO/SiO 2 >1 iron-containing material, alkaline sintered ore, alkaline iron concentrate, iron alloy slag, steel slag, alkaline pre-reduction pellet, alkaline metallized pellet, steel slag or blast furnace slag
  • the iron-containing material is CaO/SiO 2 >1 iron-containing material, alkaline sintered ore, alkaline iron concentrate, iron alloy slag, steel slag, alkaline pre-reduction pellet, alkaline metallized pellet, steel slag or blast furnace slag
  • the oxidizing gas is one of air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen at 0 to 1200 °C;
  • the acidic material is one or more of silica, fly ash and coal gangue;
  • the acidic iron-containing material is iron-containing material with CaO/SiO 2 ⁇ 1, acid sinter, acid iron concentrate, acid pre- One or more of reducing pellets, acid metallized pellets, copper slag, lead-containing slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, and blast furnace slag.
  • the copper-rich phase, the iron-rich phase, and the iron-containing silicate mineral phase are separately treated, or any two phases are combined.
  • the separation and recovery in the step S2 is performed by any one of the following methods 1 to 5:
  • Method 1 When the slag can be used to flow out of the smelting reaction device, after the slag separation after the reaction is completed, the following steps are performed:
  • Method A directly used as a cement raw material after water quenching or air cooling;
  • Method B part or all of the iron-containing silicate mineral phase is returned to the reaction slag as a hot metallurgical flux
  • Method C for pouring glass ceramics or as slag wool
  • Method D slag containing iron silicate mineral phase is oxidized after air cooling or water quenching, the method comprises: slag remaining in the smelting reaction device or melting The slag is poured into the heat preservation device, and the preheated oxidizing gas having a temperature of 0 to 1200 ° C is blown into the slag containing iron silicate, and the slag temperature of the silicate is ensured to be >1450 ° C; The weight percentage of iron is ⁇ 1%, and the slag after oxidation is obtained; the slag after oxidation is directly air-cooled or water-quenched, and is used as a slag cement, a cement conditioner, and a cement production. Additive or cement clinker;
  • the preheated fuel and the preheated oxidizing gas are injected, the heat is burned, the heat is supplemented, or the device itself is heated to make the temperature of the iron-containing silicate slag >1450 ° C;
  • Method E The iron-containing silicate mineral phase is used to produce high value-added cement clinker, including the following steps:
  • the iron-containing silicate mineral phase is retained in the smelting reaction device or the slag is poured into the heat preservation device, and molten slag, lime, limestone, iron alloy slag, and molten slag are added to the slag containing the iron silicate mineral phase.
  • molten slag, lime, limestone, iron alloy slag, and molten slag are added to the slag containing the iron silicate mineral phase.
  • fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, red mud after desoda or calcium carbide slag thoroughly mixed to obtain a slag mixture;
  • the slag mixture is blown into the oxidizing gas with a preheating temperature of 0 to 1190 ° C, and the temperature of the slag mixture is >1450 ° C; when the weight percentage of ferrous oxide is ⁇ 1%, the oxidation is obtained.
  • the oxidized slag is subjected to air cooling or water quenching to obtain a high value-added cement clinker;
  • Method F the slag containing the iron silicate mineral phase as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: after the iron-containing silicate slag is air-cooled, water-quenched or slowly cooled, used as blast furnace ironmaking or Direct reduction of ironmaking raw materials, after direct reduction, magnetic separation or electric furnace melting, magnetic separation products are metal iron and tailings, electric furnace melting, the product is molten iron and slag;
  • the slag is modified and magnetically separated, including: preheating the oxidizing gas at 0 to 1200 ° C into the slag in the heat preservation device, and ensuring the slag temperature thereof. >1250 ° C;
  • the slag temperature is ⁇ 1250 ° C
  • the preheated fuel and the preheated oxidizing gas are injected, the heat is burned, the heat is supplemented, or the device itself is heated to make the slag temperature >1250 ° C;
  • the oxidized slag is slowly cooled to room temperature, crushed and magnetically selected, and the product is magnetite concentrate and tailings, and tailings are used as building materials;
  • Method G The iron-containing silicate mineral phase is subjected to reduction ironmaking, comprising the following steps:
  • the iron-containing silicate mineral phase is retained in the smelting reaction device or the slag is poured into the heat preservation device, or the iron-containing material is added, and the reducing agent is added at the same time to perform smelting reduction, and the reaction slag is monitored in real time, and the slag is controlled.
  • the method of controlling the temperature of the reaction slag is:
  • a metallurgical flux is added to the reaction slag, so that the temperature of the reaction slag reaches 1350 to 1670 ° C, wherein
  • the metallurgical flux is a mineral containing CaO or SiO 2 , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desodiumification, calcium carbide slag, dolomite or limestone;
  • the method of controlling the alkalinity of the reaction slag is:
  • Method I Pour the mixed slag after reduction into a heat preservation slag tank, and slowly cool to room temperature to obtain slow cooling slag; wherein, the metal iron settles to the bottom of the reaction device to form iron slag, and the remaining slow slag contains metal iron Layer, broken to a particle size of 20 ⁇ 400 ⁇ m, grinding, magnetic separation to separate the remaining metal iron and tailings;
  • Method II mixed slag after reduction, sedimentation, slag-gold separation, obtaining molten iron and reduced slag; and the reduced slag is slag according to one or several methods of methods A to E Processing; the molten iron is sent to a converter or an electric furnace for steel making;
  • the copper-rich phase sent to a converter or a blowing furnace for copper smelting or slow cooling and magnetic separation to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting, or magnetic separation of metal iron or After the metal iron is separated by magnetic separation, the reduction product is directly separated, and the reduced product is separated by magnetic separation, and then sent to a converter or a blowing furnace for copper smelting;
  • the iron-rich phase layer is obtained by water quenching or air cooling or pouring into a heat preservation device, or after being manually sorted and re-selected, as a raw material for blast furnace ironmaking or directly reducing ironmaking raw materials or smelting reduction Ironmaking raw materials or flotation copper extraction raw materials or magnetic separation of metal iron as a raw material for copper smelting or direct reduction ironmaking; in the direct reduction process, after reduction and magnetic separation of the reduction products, metal iron and tailings are obtained, and tailings are returned to the refining Copper system; during the flotation process, the flotation product is a copper-bearing concentrate and iron concentrate, the copper concentrate is returned to the copper-smelting system, and the iron concentrate is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material or a smelting reduction ironmaking raw material;
  • the direct reduction process uses a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary
  • the red mud contains potassium, sodium, dust, and steel soot containing lead, zinc, antimony, and indium silver, when these materials are added, some indium, antimony, potassium, and sodium groups are added. It is volatilized and enters the soot as an oxide.
  • Method 2 When the smelting reaction device through which the slag can flow out is used, the obtained molten iron-rich phase and the iron-containing silicate mineral phase treatment method are performed by one or more of the methods A to G described in the first method. Treat, or pour into the copper-rich phase after the slow cooling of the heat preservation device, send it to the converter or the converter to smelt copper, or separate the metal iron by crushing and then send it to the converter or the converter to smelt the copper, or separate the metal by magnetic separation. After the iron or the metal iron is separated by magnetic separation, it is directly reduced, and the reduced product is magnetically separated to separate the metal iron, and then sent to a converter or a blowing furnace for copper smelting.
  • Method 3 using a slag rotatable converter and a reaction slag tank, obtaining an iron-containing silicate mineral phase, and the treatment method is treated by one or more of the methods A to G described in the first method; or
  • the iron-rich phase is treated by the step S2-1-05 in the first method;
  • the molten state is poured into the copper-rich phase after the slow cooling of the heat preservation device, sent to the converter or the blowing furnace for copper smelting, or the magnetic separation is used to separate the metallic iron.
  • the metal After being sent to converter or blowing furnace for copper smelting, or magnetic separation to separate metal iron or without magnetic separation, the metal is directly reduced, and the reduced product is separated by magnetic separation and then sent to a converter or a converting furnace. Copper smelting.
  • Method 4 When the slag rotatable converter and the reaction slag tank are used, the molten iron-containing silicate mineral phase and the iron-rich phase are obtained, and the treatment method is one of the methods A to G described in the first method or Several kinds of processing; the molten copper-rich phase or poured into the heat preservation device after slow cooling, sent to a converter or a blowing furnace for copper smelting, or slow cooling, then magnetic separation to separate the metal iron and then sent to the converter or the converting furnace Copper is smelted, or metal iron is separated by magnetic separation or metal iron is separated by magnetic separation, and the reduction product is subjected to magnetic separation to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting.
  • Method 5 When using a heat preservation device, or using a smelting reaction device through which slag can flow out, when pouring the slag into the heat preservation device, perform the following steps:
  • the slag is slowly cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to the bottom of the reaction device to form a copper-rich strontium; the iron-containing silicate mineral phase floats; the middle is slow cooling slag
  • a zinc-containing component and a lead-containing component are simultaneously formed; wherein the nickel, cobalt, gold, and silver components migrate to the copper-rich phase;
  • the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, nitrogen-air, argon-air, oxygen-nitrogen, oxygen-argon.
  • the reducing agent and the fuel are one or more of a solid, liquid or gaseous fuel, which is sprayed or fed, and the injected gas is a preheated oxidizing gas, nitrogen or argon.
  • the preheating temperature is 0 to 1200 ° C;
  • the solid fuel and the reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite
  • the shape is granular or powdery, the granular material has a particle size of 5 to 25 mm, the powdery material has a particle size of ⁇ 150 ⁇ m, the liquid fuel and the reducing agent are heavy oil, and the gaseous fuel and the reducing agent are gas and/or natural gas.
  • the mixing is uniformly a natural mixing or a stirring mixing, and the stirring mixing is performed by argon stirring, nitrogen stirring, nitrogen-argon gas mixture stirring, reducing property.
  • gas agitation oxidative gas agitation, electromagnetic agitation or mechanical agitation;
  • the sedimentation is natural sedimentation or spin sedimentation or centrifugal sedimentation;
  • the cooling mode when cooling sedimentation is natural cooling or rotary cooling or centrifugal cooling, and the gravity sorting method is a shaker. Sorting, chute sorting or a combination of the two.
  • the method for recovering valuable components from copper-containing slag of the present invention can treat hot slag, make full use of molten copper slag physical heat resources and hot metallurgical flux, and can treat cold slag by adjusting The physical and chemical properties of the slag, using the physical and chemical properties of the copper-containing slag to achieve the metallurgical process of containing copper slag;
  • the slag metallurgical reaction in the slag is added with calcium minerals to disintegrate the olivine, and the iron oxide is fully released to form free iron oxide, which realizes the growth and settlement of the iron-rich phase, and the slag
  • the iron-containing components aggregate, grow up and settle; at the same time, the calcium-based minerals effectively modify the viscosity to lower the viscosity and contribute to the sedimentation of the copper-containing component;
  • the copper-rich phase Including copper, white copper, matte phase, a variety of iron-containing components, or part of the copper component into the iron-rich phase, the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phase, as a blast furnace Iron or steel or direct reduction or smelting reduction of ironmaking raw materials;
  • part of the indium-containing component, the antimony component, the potassium-containing component, and the sodium-containing component are volatilized into the soot for recycling;
  • the method of the present invention can be carried out continuously or intermittently to meet the needs of industrial production.
  • the raw material of the present invention may be cold slag, cold slag treatment, not only can realize copper component, gold component, silver component, iron component, zinc component, lead component, indium component in slag
  • the comprehensive utilization of strontium components, sodium components, potassium components and valuable components can effectively solve the problems of large accumulation of slag, environmental pollution problems and heavy metal pollution.
  • the raw material of the present invention may be liquid molten copper slag ( ⁇ 1100 ° C) flowing out from the slag outlet, which contains abundant thermal energy resources, has the characteristics of high temperature and high heat, and fully utilizes the slag physical heat resource and is highly efficient. Energy saving; liquid molten copper slag contains a large amount of hot metallurgical flux, which is a slag system with excellent physical and chemical properties, which realizes slag metallurgy.
  • the invention adjusts the physical and chemical properties of the slag, injects a gas, controls the oxygen potential, and causes the copper component and the gold and silver component in the slag to migrate and enrich to the copper-rich phase to achieve aggregation, growth and sedimentation.
  • the cold material and the molten copper slag are added to avoid the slag temperature being too high, and the life of the heat preservation device is increased; adding the cold material and the molten copper slag improves the processing amount of the raw material, and can not only treat the liquid slag Moreover, it can process a small amount of cold materials, and the raw materials have strong adaptability; the addition of cold materials realizes the efficient use of the chemical heat released by the reaction and the physical heat of the slag.
  • the invention adjusts the physical and chemical properties of the slag, controls the oxygen potential, and simultaneously adds the calcium-based minerals to release the iron oxides in the olivine phase, enriched in the iron-rich phase, and realizes aggregation, growth and sedimentation;
  • the zinc component, the lead component, the indium component, the bismuth component, the sodium component, and the potassium component are volatilized, and are collected into the soot to be recovered.
  • the copper component and the gold and silver components in the slag are enriched in the copper-rich phase, and the aggregation, growth and sedimentation are realized, and the iron component in the slag is enriched in the iron-rich phase.
  • the slag-containing insulation device is placed on the rotating platform to rotate, accelerate the accumulation of copper-rich phase, iron-rich phase, growth and sedimentation; the addition of fluorine-containing materials accelerates the copper-rich phase, The growth and precipitation of the iron-rich phase shortens the settling time; the copper-rich phase is sent to the converter or the converter to smelt copper, and the low-copper iron-rich phase is used as the raw material for blast furnace ironmaking or direct reduction or smelting reduction ironmaking.
  • the method of the present invention increases the grindability of the slag mineral, and the slag achieves quenching and tempering.
  • the method of the invention separates the silicate mineral phase, the iron-rich phase and the copper-rich phase distributed in the upper part, the middle part and the bottom part by manual sorting, magnetic separation and re-election, respectively, to realize the slag High-efficiency recovery of copper component, gold-silver component, iron component, zinc component, indium component, antimony component, lead component, sodium component and potassium component; due to copper-rich phase and iron-rich phase sedimentation Middle and lower parts, wherein the copper-rich phase comprises a plurality of copper phases, white ice copper, amber phase, and iron-containing components, and the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phases, and therefore,
  • the amount of slag is small, the cost of grinding, magnetic separation and re-election is low; the subsequent separation process uses magnetic separation or re-election, and there is no environmental pollution during the separation process.
  • the slag treatment process has short process, simple operation and recovery rate. High, high-efficiency, clean
  • the iron-containing silicate phase and the iron-rich component have a copper content of less than 0.1%, and can be used as a raw material for blast furnace ironmaking or direct reduction or smelting reduction of ironmaking to obtain metallic iron and molten iron.
  • the invention fully utilizes the molten copper slag physical heat resource and the hot metallurgical flux, and can also treat the cold slag, realizes slag metallurgy, and the copper component and the gold and silver component in the slag are enriched in the copper-rich phase.
  • iron components are enriched in the iron-rich phase, to achieve aggregation, growth and sedimentation, using manual sorting, magnetic separation and re-election methods to separate and deposit copper in different parts
  • Phase, iron-rich phase and iron-containing silicate phase to achieve efficient recovery of copper and iron components in slag can process solid copper-containing materials, the process is short, metal High recovery rate, low production cost, strong adaptability of raw materials, large processing capacity, environmental friendliness and high economic returns can solve the problem of efficient recycling of metallurgical resources and thermal energy.
  • a method for recovering valuable components containing copper slag comprising the following steps:
  • Step 1 slag mixing:
  • copper slag containing one or more of copper smelting slag, copper-containing blowing slag, copper fire depleted slag, flotation tailings, and wet copper slag
  • the mixed slag is heated to a molten state to form a copper-containing reaction slag; the mixture is uniformly mixed, and the copper-containing reaction slag is monitored in real time, and the following parameters (a) and (b) are simultaneously controlled to obtain the slag after completion of the reaction. , or pour the slag after the reaction into the heat preservation device;
  • the control method is:
  • the method for controlling the temperature of the reaction slag in the set temperature range is:
  • the heating function of the reaction device itself or the addition of fuel to the copper-containing reaction slag causes the temperature of the reaction slag to reach a set temperature range;
  • a preheated oxidizing gas is simultaneously injected;
  • the temperature of the copper-containing reaction slag is lower than the upper limit of the set temperature range, one or more of the copper-containing material, the metallurgical flux, the iron-containing material or the fluorine-containing material is added to the copper-containing reaction slag to make the mixed slag The temperature reaches the set temperature range;
  • the slag is kept for 5 to 50 minutes, and the sedimentation is separated to obtain a bottom molten copper-rich phase layer, a central molten iron-rich phase and an upper molten iron-containing silicate mineral phase, and simultaneously form a zinc-containing component and
  • the soot containing lead component, the gold and silver components migrate to the copper-rich phase, and the items are treated as follows;
  • the iron-rich phase is obtained by water quenching or air cooling or pouring into a heat preservation device, or by manual sorting and re-election, as a raw material for blast furnace ironmaking or direct reduction of ironmaking raw materials or smelting reduction of ironmaking raw materials or flotation Copper raw material or magnetic separation to separate metal iron as raw material for copper smelting or direct reduction ironmaking; flotation products are copper-containing concentrates and iron concentrates, copper concentrates are returned to copper smelting system, iron concentrates are used as blast furnace ironmaking materials or Directly reducing the ironmaking raw material or the smelting reduction ironmaking raw material; wherein, in the direct reduction process, the reduction product is magnetically separated and separated, the metal iron and the tailings are obtained, and the tailings are returned to the copper smelting system; the direct reduction process adopts a rotary hearth furnace , tunnel kiln, vehicle bottom road, shaft furnace, rotary kiln or induction furnace as reducing equipment, using gas-based or coal-based reduction technology
  • the iron-containing silicate mineral phase in the step (1) is subjected to slag treatment, and one of the methods A to G is adopted:
  • Iron-containing silicate mineral phase as cement raw material Iron-containing silicate mineral phase as cement raw material
  • the iron-containing silicate mineral phase is directly quenched or air-cooled as a cement raw material or further processed into a high value-added cement raw material.
  • Method B Part or all of the iron-containing silicate mineral phase is returned to the copper-containing reaction slag:
  • Some or all of the iron-containing silicate mineral phase is returned to the copper-containing reaction slag, and as a hot metallurgical flux, the copper-containing reaction slag component is adjusted to control the copper-containing reaction slag temperature.
  • Method C pouring a glass-ceramic with a ferrite-containing mineral phase or as a slag wool.
  • Method D Air-cooling or water quenching after oxidation of iron-containing silicate slag:
  • the preheated fuel and the preheated oxidizing gas are injected, the heat is burned, the heat is supplemented, or the device is heated by itself, so that the silicate slag temperature is >1450 ° C;
  • the slag after oxidation is directly air-cooled or water-quenched, and used as slag cement, cement conditioner, additive in cement production or cement clinker.
  • Method E Treatment of high value-added cement clinker by treatment with iron silicate slag:
  • the temperature is 0 ⁇ 1190°C; and during the whole process, the (d) slag mixture temperature is >1440° C.; the temperature control method is the same as the silicate slag temperature control method in the method D step (1);
  • Method F the iron-containing silicate mineral phase slag is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: the slag containing the iron silicate mineral phase is air-cooled, water quenched or slowly cooled, and used as a blast furnace Iron or direct reduction of ironmaking raw materials, after direct reduction, magnetic separation or electric furnace melting, magnetic separation products are metal iron and tailings, electric furnace melting, the product is molten iron and slag;
  • the separation is performed by the following method: magnetic separation after slag modification: slag flowing into the heat preservation device, blowing 0-1200 ° C Preheating the oxidizing gas, and ensuring that the slag temperature is >1250 ° C, completing the transformation of magnetite in the slag; slowly cooling the oxidized slag to room temperature, crushing, magnetic separation, and the product is magnetite Mines and tailings, tailings as building materials.
  • the control method is:
  • the method for controlling the temperature of the reaction slag in the set temperature range is:
  • the temperature of the reaction slag ⁇ lower limit of the set temperature range is 1350 ° C
  • the temperature of the reaction slag reaches the set temperature range by the heating function of the reaction device itself or by adding the fuel and the preheated oxidizing gas to the slag.
  • the upper limit of the set temperature range is 1650 ° C
  • one or more of a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag to bring the temperature of the reaction slag to a set temperature.
  • the range is from 1350 to 1650 ° C;
  • the temperature range and the alkalinity control method are the same as the method G step (1);
  • Method I Perform the following steps:
  • Method II Perform the following steps:
  • the specific method is: using one or more of the methods A to E in the separation and recovery method 1 of the step 2, the slag treatment;
  • the gas produced by the reduction is secondarily burned on the surface of the slag to provide heat, and the gas flowing out of the furnace can be used as a heat source for the drying furnace material and the heat preservation device;
  • the molten iron-containing silicate mineral phase is subjected to slag treatment, and the specific treatment method is: one or more of the methods A to G in the separation and recovery method 1 of the step 2 is used for slag treatment;
  • the iron-rich phase is treated by the step (4) in the first method;
  • the molten iron-containing silicate mineral phase and the iron-rich phase are subjected to slag treatment in a specific manner: one or more of the methods A to G in the separation and recovery method 1 of the step 2 are used;
  • Method 5 When using a heat preservation device, or using a smelting reaction device through which slag can flow out, when the slag is poured into the heat preservation device, the slag after the reaction is completed is as follows:
  • the direct reduction process adopts a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary kiln or an in
  • the copper slag is a copper-containing smelting slag, a copper-containing blowing slag, a copper fire-depleted slag, a flotation tailings, a wet process
  • the copper-containing smelting slag is produced in a "smelting smelting" process of copper pyrometallurgical smelting process, and the copper-containing blowing slag is produced in a copper smelting process"
  • the depleted waste slag is a copper smelting slag and a copper smelting slag
  • the flotation tailing slag is a copper smelting slag and a copper smelting slag.
  • the slag, the wet copper slag is produced in a wet copper smelting process;
  • the copper smelting slag, the copper smelting slag and the depleted slag are in a molten state or a cold state, wherein: the molten copper smelting slag is from the smelting smelting furnace of the smelting smelting process Obtaining, or heating the copper-containing smelting slag to a molten state, the molten copper blowing slag is obtained from the copper smelting furnace slag opening of the "copper smelting" process, or heating the copper smelting slag to a molten state, depleted and discarded The slag is obtained from the slag outlet of the depleted furnace, and the depleted slag is heated to a molten state.
  • the smelting reaction device through which the slag can flow out can be a smelting reaction device or a smelting reaction device with a slag port or an iron port;
  • the heat preservation device is a pourable smelting reaction slag irrigation and insulation pit
  • the rotatable smelting reaction device is a converter and a smelting reaction slag tank;
  • the smelting reaction device with slag or iron slag can flow out is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola furnace, a side blowing molten pool smelting furnace, Bottom-blow pool smelting furnace, top-blow pool smelting furnace, reverberatory furnace, Osmet furnace, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing rotary furnace The electric heating bed of the copper melting furnace.
  • the calcium-based mineral is specifically one or more of lime, limestone, dolomite, calcium carbide slag, red mud or post-sodium high calcium red mud; Is one or more of SiO 2 , MgO, FeO, Fe 2 O 3 , MnO 2 , Al 2 O 3 , TiO 2 , Fe or Na 2 O;
  • the two parameters (a) and (b) are ensured at the same time, and at the same time, the copper oxide and the iron oxide in the slag are reduced to metal copper and FeO, and the metal iron content in the slag is ⁇ 3. %.
  • a reducing agent and a carbon-containing iron-containing material By adding one or both of a reducing agent and a carbon-containing iron-containing material, wherein the amount of the reducing agent and/or the carbon-containing iron-containing material in the slag is reduced to copper and iron oxide in the slag
  • the theoretical amount of metallic copper and FeO is 110-140%;
  • the carbon-containing iron-containing material is steel dust and soot, iron concentrate carbon-containing pre-reduction pellet, iron concentrate carbon-containing metallized pellet, wet process Zinc volatilization slag or coke oven dust and soot.
  • the fuel and the reducing agent are one or more of a solid, liquid or gaseous fuel, which is sprayed or charged, and the loaded gas is preheated and oxidized.
  • solid fuel and reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite
  • the shape is granular or powdery, the granular material has a particle size of 5 to 25 mm, the powdery material has a particle size of ⁇ 150 ⁇ m, the liquid fuel and the reducing agent are heavy oil, and the gaseous fuel and the reducing agent are gas and/or natural gas;
  • the copper-containing materials in steps 1 and 2 are copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, lead-containing slag, nickel smelting slag, lead ice copper, arsenic matte, and crude lead fire.
  • the copper slag is copper-containing smelting slag, One or more of copper-containing blowing slag, copper fire depleted slag, flotation tailings, and wet copper slag; lead-containing slag as smelting furnace slag and lead-containing smelting slag, "ISP lead-zinc blast furnace Lead-containing smelting slag produced by reduction or "sinter blast furnace reduction” or “solid high-lead slag reduction” or "liquid high-lead slag reduction process” reduction process, lead-containing smelting slag is smelted by a smelting furnace to produce lead-containing smelting furnace slag Nickel smelting slag is one or more of nickel smelting slag produced by "smelting
  • the metallurgical flux in the steps 1 and 2 is a mineral containing CaO or SiO 2 , specifically quartz sand, gold-silver-sand quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone. One or several.
  • the iron-containing materials in the 1 and 2 are ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron.
  • the wet zinc slag and dust are subjected to dehydration and drying.
  • zinc smelting slag and soot, lead smelting slag and soot contain indium and antimony, lead, silver, zinc and antimony; red mud contains sodium and potassium, and steel soot and dust contain indium, antimony and silver.
  • Sodium and potassium the above materials all have iron, lead smelting slag and zinc smelting slag contain copper, copper soot and dust contain indium and antimony, so in the method of the invention, indium, antimony, sodium, potassium, zinc, lead will The fumes are entered in the form of oxides for recycling.
  • the fluorine-containing materials in 1 and 2 are one or more of fluorite, CaF 2 or fluorine-containing blast furnace slag;
  • the copper-containing material, the iron-containing material and the fluorine-containing material are pellets or powdery materials or granulation; wherein, the granular material has a particle size of ⁇ 150 ⁇ m, and the granular material has a particle size of 5 to 25 mm.
  • the powdery material is sprayed by spraying, and the granular material is added by spraying or feeding, and the loading gas is preheated argon gas, nitrogen gas, reducing gas (gas and/or natural gas), oxidizing gas.
  • the blowing method is one or more of inserting slag into a slag by using a refractory lance or placing it in an upper portion or a side or bottom of the reaction slag.
  • the copper component and the gold and silver components in the slag are enriched in the copper-rich phase, and aggregation, growth and sedimentation are achieved, and the iron component is concentrated in the iron-rich phase.
  • the phase, the aggregation, the growth and the sedimentation, the zinc component and the lead component in the slag respectively enter the soot, wherein the soot is recovered in the form of zinc oxide and lead oxide, wherein the copper-rich phase includes copper, white ice copper, ice.
  • the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phase, as blast furnace ironmaking or direct reduction or smelting reduction Iron raw material;
  • the method of controlling the temperature of the mixed slag in the set temperature range is as follows:
  • the temperature of the mixed slag is > the upper limit of the set temperature
  • one or more of the copper-containing material, the metallurgical flux, the iron-containing material or the fluorine-containing material is added, in order to avoid the excessive temperature and protect the refractory material;
  • Another function of the material is to reduce the viscosity and accelerate the accumulation, growth and sedimentation of the copper-rich phase, the ice-rich copper phase, and the iron-rich phase in the slag.
  • the alkaline material is one or more of lime powder, red mud, high calcium red mud after desoda, calcium carbide slag, dolomite powder or quicklime powder;
  • the alkaline iron-containing material is a CaO/SiO 2 >1 iron-containing material, an alkaline sintered ore, an alkaline iron concentrate, a ferroalloy slag, a steel slag, an alkaline pre-reduction pellet, an alkali metallized pellet, One or more of steel slag or blast furnace slag.
  • the acidic material is one or more of silica, fly ash and coal gangue;
  • the acidic iron-containing material is CaO/SiO 2 ⁇ 1.
  • the two parameters of (a) and (b) are ensured, and the slag is thoroughly mixed, and the mixing mode is natural mixing or stirring mixing, and the stirring mode is argon stirring, nitrogen stirring, nitrogen- One or more of argon gas mixture agitation, reducing gas agitation, oxidizing gas, electromagnetic stirring, and mechanical agitation;
  • the copper-rich phase and the iron-rich phase in the slag are aggregated, grown and settled, which is favorable for the silicate to float;
  • the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen, and the preheating temperature is 0. ⁇ 1200°C
  • the blowing method is one or several types in which a refractory spray gun is inserted into the slag or placed in the upper part or the side or bottom of the reaction slag.
  • the direct reduction process uses a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary kiln or an induction furnace as a reduction device, using a gas-based or coal-based reduction technique.
  • the gas base is reduced to natural gas and/or gas
  • the coal base is reduced to one or more of anthracite, bituminous coal, lignite, coking coal, coke breeze or coke
  • the cooling mode is natural cooling or rotary cooling or centrifugal cooling
  • the sedimentation mode is natural sedimentation or rotary sedimentation or centrifugal sedimentation
  • the specific operation of the rotation and the centrifugation is: the device containing the slag after the reaction is completed is placed on the rotating platform and rotated according to a certain speed, and the rotation speed depends on the quality of the slag and the height or depth of the heat preservation device.
  • the rotation time depends on the quality of the slag and the solidification of the slag; the device containing the slag after the completion of the reaction is placed on the rotating platform for the purpose of accelerating the accumulation of the copper-rich phase, the iron-rich phase, growth and sedimentation, It is beneficial to silicate floating, shortening settlement time, improving sedimentation effect and improving production efficiency.
  • step 2 during the slag cooling process after the completion of the reaction, most of the copper-rich phase and the iron-rich phase settle in the middle and lower portions due to the difference in density and the size of the mineral.
  • the copper component and the gold and silver component in the slag after the reaction is completed to migrate, enriched in the copper-rich phase, to achieve growth and sedimentation, or partially enriched in the iron-rich phase; iron in the mixed slag
  • the components continue to migrate, enrich in the iron-rich phase, and achieve growth and sedimentation.
  • the gravity sorting method is a shaker sorting, a chute sorting, or a combination of the two.
  • the finally obtained slag contains copper ⁇ 0.1%, the iron recovery rate is ⁇ 91%, the zinc recovery rate is ⁇ 92%, the lead recovery rate is ⁇ 92%, and the gold enrichment rate is ⁇ 94%, the silver enrichment rate is ⁇ 94%.
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 slag mixing:
  • the copper-containing smelting slag obtained from the slag smelting of the smelting process of the smelting process and the copper-containing slag obtained by the slag slag of the "copper smelting" process blowing furnace are added to the DC arc furnace, and lime and SiO are simultaneously added.
  • Step 2 separation and recovery method 1:
  • the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase layer, an iron-rich phase and an iron-containing silicate mineral phase, and at the same time, a zinc component and a lead component are formed, and the smoke is entered. Recycling in the form of oxides, the following steps are carried out: (1) molten iron-containing silicate mineral phase, for external slag treatment, method F, iron silicate slag air cooling, used as direct reduction ironmaking In the direct reduction process, the rotary kiln is used as the reduction equipment, and the gas-based reduction technology is used.
  • the gas-based reducing agent is natural gas and gas, the reduction temperature is 900 ° C, the alkalinity CaO / SiO 2 ratio is 0.8, and the electric furnace is melted after reduction.
  • the temperature is 1550 ° C, the product is metal molten iron and slag; (2) the molten copper-rich phase is sent to the continuous blowing furnace for copper smelting; (3) the molten iron-rich phase is poured into the insulating slag tank, and the air is cooled as a blast furnace Ironmaking raw materials; (4) zinc component, indium component, lead component, antimony component, potassium component, sodium component volatilization, and enter the soot recovery in the form of oxide; the final obtained slag contains copper ⁇ 0.1%, The zinc recovery rate was 92%, the lead recovery rate was 93%, and the iron recovery rate was 92%.
  • the slag-containing copper refers to the slag phase after the copper-rich phase separation, specifically the copper content in the iron-rich phase and the silicate mineral phase
  • the gold and silver enrichment ratio is Refers to the content of gold and silver in the copper-rich phase as a percentage of the total amount of gold and silver in the raw material.
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 slag mixing:
  • the molten copper-containing smelting slag obtained from the smelting port of the smelting process of the smelting process and the molten depleted slag obtained from the slag outlet of the depleted furnace are added to the pourable smelting reaction slag, and limestone, dolomite, and the like are added simultaneously.
  • Red mud and FeO and Fe 2 O 3 form mixed slag; use oxygen-enriched air with a preheating temperature of 800 °C to spray anthracite and coke with a particle size of 20 mm, while injecting natural gas to heat the mixed slag to a molten state.
  • copper-containing reaction slag temperature is 1660 ° C, using a refractory spray gun to insert into the reaction slag, using argon as carrier gas, spraying normal temperature powder particle size ⁇ 150 ⁇ m copper slag, copper-containing soot, copper-copper steel sintered dust , sintering pellet dust, iron plant dust, ordinary iron concentrate direct reduced iron, the temperature is reduced to 1350 ° C;
  • copper containing reaction slag basicity CaO / SiO 2 ratio of 2.4 added to the reaction slag a mixture of acidic iron concentrate, acidic pre-reduction pellets, lead-containing smelting slag, and lead-containing smelting furnace slag, so that the alkalinity ratio of the copper-containing reaction slag is reduced to 1.6; the metal iron content in the slag is 1.5%;
  • Step 2 separation and recovery method 2:
  • the slag is poured into a rotatable converter, and an oxygen-enriched air with a preheating temperature of 600 ° C is used to add anthracite and bituminous coal with a particle size of 20 mm to the slag for smelting reduction, and the reaction slag is monitored in real time. At the same time, it is ensured that the temperature of the reaction slag is 1350 ⁇ 1650 ° C, and (b) the ratio of alkalinity CaO / SiO 2 of the reaction slag is 0.6-2.4, and the slag after the reaction is obtained;
  • the temperature of the reaction slag is 1480 ° C, in the temperature range;
  • the zinc component and the lead component volatilize and enter the soot recovery in the form of oxide; the zinc recovery rate is 94%, the slag contains copper ⁇ 0.1%, the lead recovery rate is 92%; the iron recovery rate is 93%, indium recovery The rate was 96%, the recovery rate of cesium was 96%, the recovery rate of sodium was 97%, the recovery rate of potassium was 98%, the enrichment rate of gold was ⁇ 94%, and the enrichment rate of silver was ⁇ 95%.
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 slag mixing: copper-containing smelting slag obtained from the slag smelting slag of the smelting process, and copper-containing blowing slag and copper slag flotation obtained from the slag outlet of the "copper smelting" process blowing furnace
  • the tailings are added to the induction furnace, and limestone and high-calcium red mud after de-sodium are added to form mixed slag;
  • the slag is sprayed with 20 g of anthracite, coke and pulverized coal with a preheating temperature of 400 ° C. Heating to a molten state, forming a copper-containing reaction slag, mechanically stirring and mixing; monitoring the reaction slag in real time, and simultaneously controlling the two parameters (a) and (b) to obtain the slag after completion of the reaction;
  • Step 2 separation and recovery method 2:
  • the soot is recovered as an oxide and the following steps are carried out:
  • the zinc-containing component, the indium component, the antimony component and the lead-containing component volatilize, and enter the soot recovery in the form of an oxide to obtain zinc oxide and lead oxide.
  • the slag contains copper ⁇ 0.05%, the iron recovery rate is 91%, the zinc recovery rate is 93%, the lead recovery rate is 92%, the indium recovery rate is 93%, the ruthenium recovery rate is 94%, and the gold enrichment rate is At 95%, the silver enrichment rate is 96%.
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 Slag mixing: adding the copper-containing smelting slag obtained in the cold state from the smelting port of the smelting process to the plasma furnace, adding dolomite, MgO, Al 2 O 3 , and Fe to form mixed slag.
  • the mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is electromagnetically stirred to achieve mixing; the reaction slag is monitored in real time, and two parameters (a) and (b) are obtained through regulation and control.
  • the slag after the reaction is completed;
  • the temperature of the copper-containing reaction slag is 1670 ° C, and red mud, coal dust ash, sulfuric acid slag, fluorite, lead ice copper, lead-containing soot, zinc-containing soot, arsenic matte copper are added to the reaction slag.
  • the temperature is lowered to 1440 ° C;
  • the copper-containing reaction slag has a basicity CaO / SiO 2 ratio of 2.0, and the copper-containing blowing slag is added to the reaction slag to melt the copper-containing reaction
  • the slag alkalinity ratio is reduced to 1.2; the air is sprayed with natural gas, the coke grain having a particle size of 20 mm, and the metal iron content in the slag is 2%;
  • the slag after the completion of the reaction is naturally cooled and settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and at the same time, a zinc-containing component and a lead-containing component are formed.
  • the soot is recovered as an oxide and the following steps are carried out:
  • step 2 (1) molten iron-containing silicate mineral phase, using the separation and recovery method of step 2; a method of slag-modified magnetic separation: 1 using a spray gun to spray molten slag into a preheating temperature of 600 ° C Oxygen air, to achieve magnetite transformation, 2 slow cooling to room temperature, magnetic separation to obtain iron concentrate and tailings;
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 slag mixing: the copper-containing smelting slag obtained from the slag smelting port of the smelting process of the smelting process, and the copper-containing smelting slag obtained by the slag discharging port of the "copper smelting" process blowing furnace are added to the slag pot. At the same time, limestone and Fe are added to form mixed slag; the oxygen-enriched air at a temperature of 100 ° C is used to spray the bituminous coal with a particle size of ⁇ 150 ⁇ m, and the mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is realized. Mixing; monitoring the reaction slag in real time, and simultaneously controlling the two parameters (a) and (b) to obtain the slag after completion of the reaction;
  • the temperature of the copper-containing reaction slag is 1330 ° C;
  • the alkalinity CaO / SiO 2 ratio of the copper-containing reaction slag is 1.4, both within the required range;
  • the metal iron content in the slag is 2.8 %;
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 slag mixing: the copper-containing smelting slag obtained from the slag-containing slag obtained from the smelting smelting furnace of the smelting process, and the copper-containing blowing slag obtained from the slag discharging port of the "copper smelting" process blowing furnace is added to the alternating current arc furnace At the same time, adding lime, MgO, Al 2 O 3 , Fe 2 O 3 to form a mixed slag; heating the mixed slag to a molten state to form a copper-containing reaction slag, spraying argon gas at a temperature of 1100 ° C, and The reaction slag is mixed; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling both parameters (a) and (b);
  • the temperature of the copper-containing reaction slag is 1080 ° C, the electric arc furnace is heated to raise the temperature to 1350 ° C;
  • the alkalinity CaO / SiO 2 ratio of the copper-containing reaction slag is 0.1, to the reaction melt Alkaline iron concentrate, blast furnace gas mud, alkaline pre-reduction pellets, converter steel slag are added to the slag to increase the alkalinity ratio of the copper-containing reaction slag to 0.4; natural gas is sprayed, and the metal iron content in the slag is 2.2%. ;
  • Step 2 separation and recovery method 1:
  • the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, a molten iron-rich phase and a molten iron-containing silicate mineral phase, and at the same time, a zinc-containing component and lead are formed.
  • the components, which enter the soot and are recovered as oxides, are subjected to the following steps:
  • the zinc-containing component and the lead-containing component volatilize and enter the soot recovery as an oxide; the slag contains copper ⁇ 0.1%, the iron recovery rate is 91%, the zinc recovery rate is 92%, and the lead recovery rate is 94%, the gold enrichment rate is 94%, and the silver enrichment rate is 96%.
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 Slag mixing: adding the cold copper-containing smelting slag of the "smelting smelting" process, the cold copper-containing blowing slag of the "copper smelting” process, and the wet copper slag to the ore furnace, and adding limestone at the same time.
  • SiO 2 , FeO and MgO form a mixed slag;
  • the mixed slag is heated to a molten state to form a copper-containing slag, and an argon-nitrogen mixed gas having a temperature of 200 ° C is sprayed, and the slag is mixed;
  • Monitoring the reaction slag and ensuring the two parameters of (a) and (b) by regulation to obtain the completed slag;
  • the temperature of the copper-containing reaction slag is 1320 ° C;
  • the ratio of alkalinity CaO / SiO 2 of the copper-containing reaction slag is 0.8, both within the required range; adding pulverized coal with a particle size of ⁇ 150 ⁇ m , the metal iron content in the slag is 2.4%;
  • Step 2 separation and recovery method 4:
  • the molten slag after the completion of the reaction was poured into the thermal insulation slag tank, and the sediment was sedimented and separated by slag-gold to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and a zinc component and lead were simultaneously formed.
  • the components, which enter the soot and are recovered as oxides, are subjected to the following steps:
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 Slag mixing: adding cold copper-containing smelting slag from the “smelting smelting” process, cold copper-containing blowing slag of the “copper smelting” process, and depleted slag to the blast furnace, and adding dolomite and red Mud, MgO, using 600 ° C oxygen, sprayed into the gas and coke powder with particle size ⁇ 150 ⁇ m, the mixed slag is heated to a molten state, forming a copper-containing reaction slag, and the reaction slag is mixed; real-time monitoring of the reaction slag After the two parameters of (a) and (b) are simultaneously controlled, the completed slag is obtained;
  • the temperature of the copper-containing reaction slag is 1330 ° C;
  • the alkalinity CaO / SiO 2 ratio of the copper-containing reaction slag is 1.0, both within the required range;
  • the metal iron content in the slag is 2.7 %;
  • the iron-containing silicate mineral phase specifically adopting the method B in the separation and recovery method of the second step, and returning the middle and upper slag to the copper-containing reaction slag as a hot metallurgical flux to adjust the slag composition. , controlling the slag temperature;
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 slag mixing: copper-containing smelting slag and copper slag obtained from the slag-containing slag obtained by the smelting smelting process of the smelting smelting process and the slag vent of the "copper smelting" process blowing furnace
  • the flotation tailings is added to the side blowing furnace, and limestone is added at the same time to form mixed slag; the preheated air with a temperature of 1100 ° C is sprayed with ⁇ 150 ⁇ m coke powder, and the mixed slag is heated to a molten state to form a copper-containing reaction slag.
  • the reaction slag is mixed; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling and simultaneously ensuring two parameters (a) and (b);
  • the temperature of the copper-containing reaction slag is 1340 ° C;
  • the alkalinity CaO / SiO 2 ratio of the copper-containing reaction slag is 1.2, both within the required range, the metal iron content in the slag is 1.7 %;
  • a method for recovering valuable components from copper-containing slag comprising the steps of:
  • Step 1 slag mixing: the copper-containing smelting slag obtained from the slag smelting port of the smelting process of the smelting process, and the copper-containing smelting slag obtained by the slag discharging port of the "copper smelting" process blowing furnace are added to the heat preservation pit.
  • the temperature of the copper-containing reaction slag is 1430 ° C;
  • the alkalinity CaO / SiO 2 ratio of the copper-containing reaction slag is 1.5, both within the required range;
  • the metal iron content in the slag is 2.2 %;
  • the slag contains copper ⁇ 0.15%
  • the iron recovery rate is 98%
  • the zinc recovery rate is 95%
  • the lead recovery rate is 93.
  • the enrichment rate of % gold is 95%
  • the enrichment rate of silver is 96%.

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Abstract

La présente invention concerne un procédé permettant de récupérer un composant de valeur à partir d'un laitier contenant du cuivre, comprenant : l'étape S1. consistant à mélanger un laitier de four : à ajouter un laitier de cuivre dans un dispositif de réaction de fusion, à ajouter un minéral de série de calcium et un additif, à former un laitier mélangé, à chauffer le laitier mélangé à un état fondu pour servir de laitier de réaction, à bien mélanger, à surveiller le laitier de réaction en temps réel et à obtenir un scories après une réaction au moyen de l'ajustement du laitier de réaction mélangé pour remplir en même temps les conditions a et b ; l'étape S2. de séparation et de récupération. Le laitier chaud peut être traité au moyen du procédé, en utilisant pleinement les ressources thermiques physiques et le flux métallurgique chaud d'un laitier de cuivre de fusion tandis que le laitier de four froid peut également être traité ; au moyen de l'ajustement des propriétés physiques et chimiques du laitier et en utilisant les propriétés physiques et chimiques matures du laitier contenant du cuivre, un procédé métallurgique pour le laitier contenant du cuivre est mis en œuvre.
PCT/CN2017/115648 2017-10-10 2017-12-12 Procédé permettant de récupérer un composant de valeur à partir d'un laitier contenant du cuivre Ceased WO2019071793A1 (fr)

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CN115572837A (zh) * 2022-09-05 2023-01-06 楚雄滇中有色金属有限责任公司 防止艾萨熔炼高砷铜精矿堵塞锅炉烟道的方法
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