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WO2019071795A1 - Procédé de fabrication utilisant un laitier contenant du cuivre - Google Patents

Procédé de fabrication utilisant un laitier contenant du cuivre Download PDF

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Publication number
WO2019071795A1
WO2019071795A1 PCT/CN2017/115650 CN2017115650W WO2019071795A1 WO 2019071795 A1 WO2019071795 A1 WO 2019071795A1 CN 2017115650 W CN2017115650 W CN 2017115650W WO 2019071795 A1 WO2019071795 A1 WO 2019071795A1
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WIPO (PCT)
Prior art keywords
slag
copper
smelting
iron
furnace
Prior art date
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PCT/CN2017/115650
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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 WO2019071795A1 publication Critical patent/WO2019071795A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • C22B11/02—Obtaining noble metals by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/06—Obtaining bismuth
    • 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
    • C22B58/00—Obtaining gallium or indium
    • 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
    • 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 producing copper slag.
  • the copper slag includes copper-containing smelting slag, copper-containing blowing slag, fire-depleted slag, copper slag flotation tailings, and wet copper slag.
  • 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 slag has a copper content of 20% and an iron content of up to 55%. Copper smelting slag is an important secondary resource.
  • the molten copper smelting slag discharged from the smelting furnace of the "smelting smelting” process is higher than 1100 ° C, and is an important physical heat resource.
  • 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.
  • Copper-containing smelting slag and copper-containing blowing slag are returned to the smelting furnace or electric furnace depletion or beneficiation method. Only the recovery of copper components is considered, the depletion or ore dressing effect is not good, and the flotation brings serious environmental pollution.
  • the slag contains more than 0.4% copper, which is higher than the recoverable grade of copper by 0.15%. Iron ore allows the copper content to not exceed 0.15%, and the higher slag contains copper, which is not conducive to subsequent direct reduction iron or smelting reduction iron. Copper is easy to restore into 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.
  • 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. It is a thermal metallurgical clinker. It is a mature metallurgical slag system.
  • Pyrometallurgical lead and wet zinc smelting produce a large amount of copper-containing iron materials containing copper, iron, lead, zinc, gold, silver and other components, which are important secondary resources.
  • Lead smelting slag and volatile kiln slag are also important physical thermal resources.
  • the existing copper pyrometallurgical process is suitable for treating copper sulfide ore, but it is difficult to treat copper oxide ore.
  • the present invention provides a method of producing from copper-containing slag.
  • the method is a method for producing copper, iron, lead, zinc, gold and silver by using a hot copper-containing slag and a slag metallurgy process; the invention adopts the existing fire method copper smelting process, ironmaking process and slag metallurgy Based on theory, large-scale simultaneous processing of copper oxide ore/copper sulfide minerals and copper-containing slag to achieve production and recovery of copper, iron, lead, zinc, gold, silver, indium, antimony, sodium and potassium, the present invention
  • the method is a new slag metallurgy process and a new copper smelting method and iron making process.
  • the main technical solutions adopted by the present invention include:
  • a method for producing smelting slag from nickel comprising the steps of:
  • S1 slag mixing: adding copper slag to the reaction device, adding calcium minerals and additives at the same time; heating the slag to a molten state as reaction slag, adding one of copper oxide mineral, copper sulfide mineral and copper-containing material Kind or several; mixing evenly, and monitoring the reaction slag in real time, by adjusting the reaction slag to satisfy the condition a and the condition b at the same time, obtaining the slag after the reaction, or pouring the slag after the reaction into the heat preservation device;
  • condition a is controlling the slag temperature to be 1100 to 1450 ° C;
  • the slag after the reaction in the step S1 is kept for 5 to 50 minutes, and the molten copper-rich phase at the bottom, the molten iron-rich phase in the middle and lower portions, and the molten iron-containing silicate mineral in the middle and upper portions are obtained by sedimentation.
  • the soot containing the zinc component and the lead component is simultaneously formed, and the gold and silver components migrate and enrich and enter the copper-rich phase; the phases are recovered.
  • the method for regulating the condition a is:
  • the temperature of the reaction slag ⁇ lower limit of the set temperature range is 1100 ° C
  • the heating function of the reaction device itself is used, or fuel or molten molten copper slag is added to the reaction slag (containing copper smelting slag and/or Copper blowing slag), the temperature of the reaction slag is brought to a set temperature of 1100 to 1450 ° C, and when the fuel is injected, the preheated oxidizing gas is simultaneously injected;
  • the copper-containing material, the metallurgical flux, the iron-containing material, the copper oxide mineral, the gold-silver-containing material, or the fluorine-containing material are added to the reaction slag.
  • the method for regulating the condition b is:
  • an alkaline material, an alkali copper oxide mineral, a copper sulfide mineral, a copper-containing material, and an alkaline iron-containing material are added to the reaction slag.
  • an acidic material an acidic copper oxide mineral, an acidic copper sulfide mineral, an acidic iron-containing material or an acidic gold-containing silver material is added to the reaction slag.
  • an acidic material an acidic copper oxide mineral, an acidic copper sulfide mineral, an acidic iron-containing material or an acidic gold-containing silver material is added to the reaction slag.
  • 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.
  • the copper slag and the iron oxide in the slag are controlled to be reduced to metallic copper and FeO.
  • the metal iron content in the slag is ⁇ 3%.
  • the carbon-containing iron-containing material is steel dust and soot, iron concentrate carbon-containing pre-reduction pellets, iron concentrate carbon-containing metallized pellets, and wet zinc-smelting zinc volatilization Kiln slag or coke oven dust and soot.
  • the copper slag is one or more of a copper-containing smelting slag, a copper-containing smelting slag, a depleted slag, a flotation tailings, and a wet copper slag, wherein
  • the copper-containing smelting slag is produced in the "smelting and smelting" process of the copper smelting process, including the Osmet furnace smelting slag, the flash furnace smelting slag, the Noranda furnace smelting slag, the Isa furnace smelting slag, Vanukov furnace smelting slag, Mitsubishi smelting slag, Caldo furnace smelting slag, silver furnace smelting slag, Shuikoushan smelting slag, Tennite smelting slag, reverberatory furnace smelting slag, electric furnace smelting slag, closed blast furnace smelting slag,
  • the copper smelting slag, the copper smelting slag, and the copper fire depleting slag are in a molten state or a cold state, wherein: the molten copper smelting slag is obtained from a slag-containing smelting furnace of the “smelting smelting” process.
  • the molten copper blowing slag is obtained from a copper smelting furnace slag opening of the "copper smelting" process, or heating the copper smelting slag to a molten state;
  • the molten copper fire method The depleted waste is obtained from the slag outlet of the depleted furnace, or the depleted slag of the fire method is heated to a molten state;
  • the calcium-based mineral is specifically 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 , P 2 O 5 , Fe or Na 2 O;
  • the copper oxide mineral comprises one or more of a cuprite, a black copper ore, a malachite, a blue copper ore, a chrysocolla, a cholesterium; the copper sulfide mineral comprises a copper ore, copper blue, brass One or more of ore, porphyrite, sulphur arsenic, or bismuth.
  • the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead-zinc tailings, lead smelting slag, Lead ice copper, arsenic matte copper, crude lead fire refining slag, vertical tank zinc slag, lead smelting soot and dust, lead acid battery, copper smelting soot and dust, copper, copper containing garbage, copper-containing circuit board One or more of tin smelting slag, nickel smelting slag, tin tailings; wherein the zinc smelting slag comprises slag produced by wet zinc smelting and slag produced by pyrometallurgical smelting, wherein wet zinc smelting is produced
  • the slag is zinc leaching slag, volatile kiln slag, iron slag slag, copper cadmium slag, lead
  • 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 pre-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, zinc smelting slag, tin smelting slag, red mud, high calcium after sodium removal One or more of red mud, coal dust ash, copper tailings, sulfuric acid slag; the steel soot and dust including blast furnace gas, converter dust, electric furnace dust, hot (cold) rolling sludge , sintering dust, pellet dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale;
  • the copper-containing material and the iron-containing material are in a hot state or a cold state, wherein the hot material is directly obtained from the metallurgical furnace discharge port or the slag outlet; the wet zinc slag, the wet copper slag and the dust are dehydrated ,dry.
  • the fluorine-containing material is one or more of fluorite, CaF 2 or fluorine-containing blast furnace slag;
  • the fuel and reducing agent are one or more of solid, liquid or gaseous fuels for injection or feeding Sprayed in a manner, loaded with a gas of 0 to 1200 ° C, the gas is one or more of oxidizing gas, argon gas, nitrogen;
  • the alkaline material is lime powder, red mud, desodium One or more of post-high calcium red mud, calcium carbide slag, dolomite powder or quicklime powder;
  • the basic iron-containing material is a CaO/SiO 2 >1 iron-containing material, an alkaline sintered ore, an alkaline iron concentrate, an iron alloy slag, a steel slag, an alkaline pre-reduction pellet, an alkali metallized pellet, and a steel slag. Or one or more of blast furnace slag;
  • 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 smelting slag, zinc smelting slag, and nickel smelting slag.
  • the copper-rich phase, the iron-rich phase and the iron-containing silicate mineral phase may be separately treated, or the two phases may be combined, gold
  • the component and the silver component migrate and enrich into the copper-rich phase, and the zinc-containing component and the lead-containing component volatilize, and enter the soot recovery as an oxide.
  • 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 partially or completely returning the iron-containing silicate mineral phase to the copper-containing slag
  • Method C the iron-containing silicate mineral phase is used for pouring glass ceramics or as slag wool;
  • Method D blowing a preheated oxidizing gas at a temperature of 0 to 1200 ° C into the iron-containing silicate slag in the smelting reaction device, and ensuring that the silicate slag temperature is >1450 ° C;
  • the iron weight percentage is ⁇ 1%, and the oxidized slag is obtained;
  • the oxidized slag is directly air-cooled or water-quenched, and is used as a slag cement, a cement conditioner, an additive in cement production or a cement clinker;
  • Method E The iron-containing silicate mineral phase is used to produce high value-added cement clinker:
  • 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 molten iron-containing silicate is subjected to reduction ironmaking, comprising the following steps:
  • the temperature of the reaction slag is 1350-1660 ° C and The alkalinity CaO/SiO 2 ratio of the reaction slag is 0.6 to 2.4, and the slag after completion of the reaction is obtained;
  • the method of controlling the temperature of the reaction slag is:
  • the temperature of the reaction slag is ⁇ 1350 ° C, the heating of the reaction device itself, or the addition of fuel and preheated oxidizing gas to the slag, so that the temperature of the reaction slag reaches a set temperature range;
  • reaction slag When the temperature of the reaction slag 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 make the temperature of the reaction slag reach a set temperature range;
  • 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 cool to room temperature to obtain slow cooling slag; wherein, the metal iron is settled to the bottom of the reaction device to form iron slag, and the remaining chilled slag contains metal iron layer , crushed to a particle size of 20 to 400 ⁇ m, grinding, magnetic separation to separate the remaining metal iron and tailings;
  • Method II the mixed slag after reduction, cooling and sedimentation, separation of slag-gold, obtaining molten iron and reduced slag; and the slag after reduction is melted according to one or several methods of methods A to E Slag treatment; the molten iron is sent to a converter or an electric furnace for steelmaking;
  • 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 copper in a converter or a blowing furnace, or to separate metal iron by magnetic separation or to separate metal iron without magnetic separation, directly reduce, and the reduced product is magnetically separated to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting;
  • the iron-rich phase layer is subjected to water quenching or air cooling or poured into a heat preservation device for slow cooling, and is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material or a smelting reduction ironmaking raw material or a flotation copper extraction raw material or Magnetic separation of metal iron as a raw material for copper smelting or direct reduction of iron; in the direct reduction process, after reduction and magnetic separation of the reduction product, metal iron and tailings are obtained, and tailings are returned to the copper smelting system; during flotation, flotation
  • the 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, and a slewing
  • the kiln or induction furnace is used as a reduction equipment, using gas-based or coal-based reduction technology, gas-based reduction using natural gas and/or gas, and coal-based reduction using one or more of anthracite, bituminous coal, lignite, coking coal, coke breeze or coke
  • 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;
  • the iron 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 followed by separation of the metallic iron. Then send it to converter or blowing furnace for copper smelting, or magnetic separation to separate metal iron or without magnetic separation to separate metal iron, directly reduce, the reduction product is magnetically separated to separate metal iron, and then sent to converter or blowing furnace copper.
  • 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.
  • 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 producing copper-containing slag of the present invention can treat both hot slag and cold slag, and fully utilizes molten copper slag physical heat resources and hot metallurgical flux to treat copper oxide minerals. It can realize the treatment of copper-containing slag and copper oxide mineral. It is a new copper smelting process to realize the production of copper and iron.
  • 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 and settle, and the iron-rich phase includes various kinds of metal iron, FeO phase, and fayalite phase, and is used as a raw material for blast furnace ironmaking or direct reduction or smelting reduction ironmaking; Viscosity, which lowers the viscosity and contributes to the sedimentation of the copper-containing component;
  • the copper component and the gold and silver components in the slag migrate and enrich in the copper-rich phase, respectively, and achieve growth and sedimentation; wherein the copper-rich phase includes copper, white ice copper, matte phase, and a plurality of iron components, or a portion of the copper component entering the iron-rich phase;
  • the zinc component and the lead component in the slag are enriched in the soot and recovered; some of the indium-containing component, the antimony component, the potassium-containing component, and the sodium-containing component are volatilized into the soot for recovery;
  • the slag can be tempered and can be used as cement raw material or building material or instead of crushed stone as aggregate and road material.
  • the utilization value of tail slag is large, and no solid waste is generated in the whole process;
  • the copper content with the iron-containing silicate phase is less than 0.1%, and can be used as a raw material for blast furnace ironmaking or direct reduction or smelting reduction ironmaking to obtain metal iron and molten iron;
  • the method of the invention can be carried out continuously or intermittently, has a short process flow, is clean and environmentally friendly, and has high metal recovery rate.
  • the invention consists of a copper-containing slag or slag, which constitutes a mature slag system.
  • slag metallurgy not only the copper component, the gold component, the silver component, the strontium component, the sodium component, but also the slag can be realized.
  • Comprehensive utilization of potassium, iron, zinc and lead components to solve the problem of large accumulation of slag, and large-scale treatment of copper oxide minerals, simultaneous production of copper and iron, and oxidation The two major problems of copper mineral refractory and iron-containing component recovery; at the same time, the problem of environmental pollution and heavy metal pollution has been solved.
  • the copper-containing slag of the present invention may be a liquid molten copper slag ( ⁇ 1100 ° C) flowing out of 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. 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, and realizes slag metallurgy.
  • the invention controls the oxygen potential by slag metallurgy, so that the copper component and the gold and silver component in the slag migrate and enrich the copper-rich phase to achieve aggregation, growth and sedimentation, lead component and zinc component. Volatilized into the soot and recovered.
  • the copper-rich phase includes copper, blister copper, matte, white copper, and iron-containing components, or part of the copper component enters the iron-rich phase, and the copper-rich phase is sent to the converter. Or blowing furnace copper,
  • the invention controls the oxygen potential by slag metallurgy, disintegrates the iron olivine, fully releases the iron oxide, enters the iron-rich phase, and realizes growth and sedimentation.
  • the iron-rich phase includes metal iron, FeO phase and fayalite phase. A variety of materials, as a raw material for blast furnace ironmaking or direct reduction or smelting reduction iron.
  • adding cold material and molten copper slag avoids excessive slag temperature and improves the service life of the heat preservation device; adding cold material and molten copper slag improves the processing amount of the raw material, and can not only process liquid slag
  • the raw material adaptability is strong; the addition of the cold material realizes the efficient use of the chemical heat released by the slag oxidation reaction and the physical heat of the slag.
  • the copper component, the gold component and the silver component in the slag are respectively migrated and enriched in the copper-rich phase, and the aggregation, growth and sedimentation are realized, and the iron component in the slag migrates and is rich.
  • 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 deposition of fluorine-containing materials.
  • the method of the invention adopts the methods of manual sorting, magnetic separation, re-election or slag-gold separation to respectively carry out the iron-containing silicate mineral phase, the iron-rich phase and the copper-rich phase distributed in the upper, middle and bottom portions. Separation, high-efficiency recovery of copper component and iron component in slag; since the copper-rich phase and iron-rich phase settle in the middle and lower parts, the amount of slag to be sorted is small, the slag is tempered, and the mineral grindability is increased.
  • the production cost is low; the subsequent separation process uses physical beneficiation, the separated medium is water, and no environmental pollution occurs during the separation process, so that the entire slag treatment process has short process, simple operation, high recovery rate, high efficiency, cleanliness and environmental protection.
  • the characteristics of tailings as cement raw materials, building materials, instead of crushed stone for aggregates, road materials.
  • the present invention is precipitated by the copper-rich phase, and the iron content of the iron-containing silicate phase and the iron-rich component is less than 0.1%, and metal iron and molten iron are obtained as raw materials for blast furnace ironmaking or direct reduction or smelting reduction;
  • the invention utilizes a copper-containing slag or slag to form a mature slag system, and utilizes slag metallurgy to realize not only efficient recovery of copper, gold, silver, iron, zinc and lead in the slag, but also realization of copper oxide minerals.
  • Large-scale production, simultaneous production of copper and iron, is a new copper smelting process and a new ironmaking process.
  • the method has the advantages of short process flow, high metal recovery rate, low production cost, strong adaptability of raw materials, large processing capacity, environmental friendliness and high economic benefit, and can solve the problem of metallurgical resources and heat energy recycling.
  • a method for producing copper-containing slag according to the present invention comprises the following steps:
  • Step 1 slag mixing:
  • the copper slag is added to the heat preservation device or the smelting reaction device through which the slag can flow out, and the calcium-based minerals and additives are added, the slag is heated to a molten state to form a reaction slag containing copper and iron, and copper oxide mineral is added at the same time.
  • Vulcanization One or more of copper minerals and copper-containing materials; uniformly mix and monitor the reaction slag in real time, and ensure the slag after the completion of the reaction by controlling the two parameters (a) and (b) as follows, or Pour the slag after the reaction is completed 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 fuel or molten copper slag (containing copper smelting slag and/or copper) is added to the copper-containing reaction slag by the heating function of the reaction device itself. Blowing slag), so that the temperature of the reaction slag reaches a set temperature range of 1100 to 1450 ° C; when the fuel is added, the preheated oxidizing gas is simultaneously injected;
  • the copper-containing material, metallurgical flux, iron-containing material, copper oxide mineral, gold-silver-containing material, or fluorine-containing material is added to the copper-containing reaction slag.
  • an alkaline material, an alkali copper oxide mineral, a copper sulfide mineral, a copper-containing material, and an alkaline iron-containing material are added to the reaction slag.
  • an acidic material an acidic copper oxide mineral, an acidic copper sulfide mineral, an acidic iron-containing material or an acidic gold-containing silver material is added to the reaction slag.
  • an acidic material an acidic copper oxide mineral, an acidic copper sulfide mineral, an acidic iron-containing material or an acidic gold-containing silver material is added to the reaction slag.
  • the slag is kept for 5 to 50 minutes, and the slag-gold is separated to obtain a molten copper-rich phase at the bottom, a molten iron-rich phase in the middle and lower portions, and a molten iron-containing silicate mineral phase in the middle and upper portions, and simultaneously
  • the zinc-containing component and the lead-containing component of the soot, the gold-silver component migrates 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 employed:
  • 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:
  • Part or all of the iron-containing silicate mineral phase is returned to the copper-containing reaction slag, as a hot metallurgical flux, the copper-containing reaction slag component is adjusted, and the copper-containing reaction slag temperature is controlled;
  • Method C pouring a glass ceramic with a silicate 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;
  • Method E Treatment of high value-added cement clinker by treatment with iron silicate slag:
  • Iron-containing silicate mineral phase slag as blast furnace ironmaking raw material or direct reduction ironmaking raw material Iron-containing silicate mineral phase slag as blast furnace ironmaking raw material or direct reduction ironmaking raw material: slag containing iron silicate mineral phase is air-cooled, water quenched or slowly cooled, used as blast furnace ironmaking or direct reduction After the direct reduction of the iron raw material, magnetic separation or electric furnace melting is used, the magnetic separation product is metal iron and tailings, and the electric furnace is melted, and the product is molten iron and molten 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 Mine and tailings, tailings as building materials; during the reduction process, the zinc-containing component and the lead-containing component volatilize and enter the soot as oxides;
  • 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 is added, or the fuel and the preheated oxidizing gas are added to the slag to make the temperature of the reaction slag reach the set temperature range;
  • reaction slag When the temperature of the reaction slag is lower than the upper limit of the set temperature range, 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 range. ;
  • 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 F in the separation and recovery method 1 of the step 2, the slag treatment outside the furnace;
  • 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 method is treated by one or more of the methods A to G described in the first method;
  • the iron-containing silicate mineral phase is subjected to slag treatment, and the specific treatment method is: using one or more of the methods A to G in the separation and recovery method 1 of the step 2 to carry out the slag treatment outside the furnace;
  • the molten iron-containing silicate mineral phase and the iron-rich phase are subjected to slag treatment, and the specific treatment method is: using one or several of the methods A to G in the separation and recovery method 1 of the step 2 External slag treatment;
  • 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 depleted slag, a flotation tailings, and a wet copper slag.
  • One or more of the copper-containing smelting slags are produced in the "smelting and smelting" process of the copper smelting process, including the Osmet furnace smelting slag, the flash furnace smelting slag, the Noranda furnace Smelting slag, Aisa furnace smelting slag, Vanukov furnace smelting slag, Mitsubishi smelting slag, Caldo furnace smelting slag, silver furnace smelting slag, Shuikoushan smelting slag, Tennite smelting slag, reverberatory furnace smelting slag , electric furnace smelting slag, closed blast furnace smelting slag, low blowing furnace smelting slag, side blowing furnace smelting slag, the copper-containing blowing slag is produced in the copper smelting process of copper smelting process, including converter blowing Copper slag, flash furnace blowing
  • the copper smelting slag, the copper smelting slag, and the copper fire depleting slag are in a molten state or a cold state, wherein: the molten copper smelting slag is obtained from a slag-containing smelting furnace of the “smelting smelting” process.
  • the molten copper blowing slag is obtained from a copper smelting furnace slag opening of the "copper smelting" process, or heating the copper smelting slag to a molten state;
  • the molten copper fire method The depleted waste is obtained from the slag outlet of the depleted furnace, or the depleted slag of the fire method is heated to a molten state;
  • the heat preservation device is a pourable smelting reaction slag irrigation and heat preservation pit;
  • the smelting reaction device through which the slag can flow is a rotatable smelting reaction device or with a slag or iron Smelting reaction device;
  • the rotatable smelting reaction device is a converter and a smelting reaction slag tank;
  • the smelting reaction device with the slag port or the iron slag flowing 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, and a side blowing molten pool melting furnace.
  • the calcium-based mineral is specifically 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 One or more of 2 O 3 , MnO 2 , Al 2 O 3 , TiO 2 , P 2 O 5 , Fe or Na 2 O;
  • the copper oxide mineral comprises one or more of a cuprite, a black copper ore, a malachite, a azurite, a chrysocolla, a cholesterium;
  • the copper sulfide mineral comprises a chalcopyrite, One or more of copper blue, chalcopyrite, porphyrite, arsenic arsenide, or bismuth copper;
  • 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 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 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.
  • One or more of gas, nitrogen and argon, preheating temperature is 0-1200 ° C;
  • solid fuel and reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite Species, in the form of granules or powders, the granular material has a particle size of 5 to 25 mm, the powdery material has a particle size of ⁇ powdery material particles, the liquid fuel and the reducing agent are heavy oil, and the gaseous fuel and 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, zinc smelting soot and dust, lead-zinc tailings, lead smelting slag, lead copper , arsenic matte, coarse lead fire refining slag, vertical tank zinc slag, lead smelting soot and dust, lead acid battery, copper smelting soot and dust, copper, copper-containing garbage, copper-containing circuit board, tin smelting One or more of slag, nickel smelting slag and tin tailings; wherein the zinc smelting slag comprises slag produced by wet zinc smelting and slag produced by pyrometallurgical smelting, wherein slag produced by wet zinc smelting is One or more of zinc leaching residue, volatile kiln residue, iron slag residue, copper cadmium slag, pickled
  • the metallurgical flux in the step 1 is a mineral containing CaO or SiO 2 , specifically one or more of quartz sand, gold-silver-sand quartz sand, red mud, 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 pre-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, zinc smelting slag, tin smelting slag, red mud, high calcium after sodium removal One or more of red mud, coal dust ash, copper tailings, sulfuric acid slag; the steel soot and dust including blast furnace gas, converter dust, electric furnace dust, hot or cold rolling sludge, Sintered dust, pellet dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale;
  • the copper-containing material and the iron-containing material are in a hot or cold state, wherein the hot material is directly obtained from a metallurgical furnace discharge port or a slag outlet; the wet zinc slag, wet copper slag and dust are required Dehydrated and dried.
  • zinc smelting slag and soot, lead smelting slag and soot contain indium and antimony, lead, silver, zinc, ⁇ ; red mud contains sodium and potassium, steel dust and dust contain indium, antimony, silver, sodium and potassium, the above materials have iron, lead smelting slag and zinc smelting slag contain copper, copper soot and dust contain indium And bismuth, therefore, in the method of the invention, indium, bismuth, sodium, potassium, zinc, and lead enter the soot in the form of an oxide, thereby being recovered.
  • 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 a mixture of one or more of argon gas, nitrogen gas or reducing gas (gas and/or natural gas). ;
  • 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 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 are realized, and the zinc component and the lead component in the slag respectively enter the soot, wherein the smoke and dust are recovered in the form of zinc oxide and lead oxide.
  • the copper-containing material and the iron-containing material are in a hot state or a cold state, and the hot material is a hot material directly produced from a metallurgical furnace, and the temperature of the hot material is 200 to 1750. °C.
  • the step 1 described is a method for controlling the temperature of the mixed slag in a set temperature range:
  • 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, red mud after desoda, calcium carbide slag, dolomite powder or quicklime powder;
  • the alkaline iron-containing material is one of 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-reduced pellet or an alkali metallized pellet. kind or several.
  • 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-argon gas.
  • the mixing mode is natural mixing or stirring mixing
  • the stirring mode is argon stirring, nitrogen stirring, nitrogen-argon gas.
  • One or more of mixed gas agitation, reducing gas agitation, oxidizing gas, electromagnetic stirring, mechanical agitation, gas preheating temperature is 0 to 1200 ° C;
  • the copper-containing material and the iron-containing material may be in a hot state or a cold state, and the hot material is a hot material directly produced from a metallurgical furnace, and the temperature of the hot material is 200 ⁇ . 1750 ° C.
  • 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 copper-rich phase includes copper, white ice copper, matte phase, and a plurality of iron components, or a portion of the copper component enters the iron-rich phase, and the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phase;
  • the oxidizing gas is one of air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen
  • the spraying method is a fire-resistant spray gun. Inserting slag or one or more of the upper or side or bottom blowing 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, and the gas-based or coal-based reduction technology is used to reduce the gas base to natural gas and/or Or gas
  • coal-based reducing agent is one or more of anthracite, bituminous coal, lignite, coking coal, coke powder or coke
  • the reduction temperature is 900-1400 ° C
  • the alkalinity CaO / SiO 2 ratio 0.8 ⁇ 1.5;
  • 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: placing the device containing the slag after the reaction is completed On the rotating platform, the rotation is performed 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, and the rotation time depends on the quality of the slag and the solidification of the slag; the device that contains the slag after the reaction is completed Rotating on a rotating platform, the purpose is to accelerate the accumulation of copper-rich phase, ice-rich copper phase, iron-rich phase, growth and settlement, which 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 iron-rich phase and the copper-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 are continuously enriched in the copper-rich phase, or partially enriched in the iron-rich phase to achieve growth and sedimentation; the iron group in the mixed slag The fraction continues to be enriched in the iron-rich phase and achieves growth and sedimentation.
  • the gravity sorting method is a shaker sorting, a chute sorting, or a combination of the two.
  • the nickel smelting slag is treated by the method of the invention, and the slag finally produced contains ⁇ 0.1% of copper, the recovery of iron is ⁇ 91%, the recovery of zinc is ⁇ 92%, the recovery of lead is ⁇ 92%, gold
  • the enrichment rate is ⁇ 94%, and the enrichment rate of silver is ⁇ 94%, which is lower than the copper content in the slag after treatment in the prior art, and at the same time, iron and copper can be simultaneously recovered.
  • a method of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing:
  • the molten copper smelting slag obtained from the slag outlet of the Osmet furnace furnace and the molten converter copper slag obtained from the slag outlet of the converter are added to the DC arc furnace, and lime, SiO 2 , MgO and Al 2 O 3 are added to form a mixed melting.
  • the slag is added with copper sulfide concentrate; the mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is naturally mixed; the reaction slag is monitored in real time, and both (a) and (b) are ensured through regulation.
  • the slag after the completion of the reaction is obtained; corresponding to (a): the temperature of the copper-containing reaction slag is 1660 ° C, and the refractory spray gun is inserted into the reaction slag, and the nitrogen gas is used as the loading gas, and the normal temperature powder particle size is sprayed.
  • Step 2 separation and recovery method 1:
  • the slag after the completion of the reaction settles naturally, and the slag-gold separation, obtaining a molten copper-rich phase layer, a molten iron-rich phase and a molten iron-containing silicate mineral phase, and simultaneously forming a zinc component and a lead component.
  • the following steps are carried out: (1) the iron-containing silicate mineral phase is subjected to the slag treatment outside the furnace, and the method F is used, and the iron-containing silicate slag is used for direct reduction after air cooling.
  • rotary kiln is used as reduction equipment, and 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 used after reduction.
  • the melting 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 iron-rich phase is poured into the heat preservation device, and the air-cooled is used as the blast furnace ironmaking (4) zinc component indium component, lead component, antimony component, potassium component, sodium component volatilization, enters soot recovery in the form of oxide; slag contains copper ⁇ 0.1%, zinc recovery rate is 92% The lead recovery rate is 92%; the iron recovery rate is 92%, and the indium recovery rate is 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, and 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 of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing:
  • the molten copper-containing smelting slag obtained from the slag outlet of the Isa copper smelting furnace is added to the pourable smelting reaction slag, and limestone, dolomite, red mud, FeO and Fe 2 O 3 are added to form mixed slag, and copper oxide is added.
  • copper-containing reaction slag temperature is 1660 ° C, using refractory spray gun inserted into the reaction slag, using argon as carrier gas, spraying into normal temperature powder particle size ⁇ using refractory copper slag, copper-containing soot, copper and Copper-containing garbage, copper-containing circuit board, ordinary iron concentrate direct reduced iron, the temperature is lowered to 1380 ° C;
  • copper-containing reaction slag basicity CaO / SiO 2 ratio of 2.4 adding acid iron to the reaction slag Concentrate, acid pre-reduction pellets, lead-containing smelting slag, wet zinc smelting kiln slag, and lead-containing slag slag mixture, the alkalinity ratio of copper-containing reaction slag is reduced to 1.1; the metal iron content in slag is 1.2%;
  • Step 2 separation and recovery method 2:
  • the temperature of the reaction slag is 1480, in the temperature range;
  • the zinc component and the lead component volatilize and enter the soot recovery in the form of oxide; the slag contains copper ⁇ 0.1%, the zinc recovery rate is 92%, the lead recovery rate is 92%; the iron recovery rate is 91%, 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 of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing: the copper-containing smelting slag obtained from the slag outlet of the Jinfeng copper smelting furnace, the copper-containing blowing slag (converter slag) obtained from the slag outlet of the converter is added to the induction furnace, and limestone and red mud after de-sodium removal are added at the same time.
  • Forming a mixed slag adding a copper-containing material (wet zinc leaching slag); spraying an anthracite, coke granules and pulverized coal having a particle size of 20 mm with a preheating temperature of 300 ° C, and heating the mixed slag 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;
  • a copper-containing material wet zinc leaching slag
  • the temperature of the copper-containing reaction slag is 1685 ° C, adding acid metallized pellets, copper smelting slag and copper-containing blowing slag to the reaction slag, and adding copper-containing materials, lead-containing smelting furnace slag, Ordinary iron concentrate pellets, ordinary iron concentrate metallized pellets and ordinary iron concentrates containing carbon pre-reduction pellets, the temperature is lowered to 1620 ° C;
  • Step 2 separation and recovery method 4:
  • 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 95%, the zinc recovery rate is 93%, and the lead recovery rate is 94%, indium recovery rate is 96%, hydrazine recovery rate is 97%, sodium recovery rate is 97%, potassium recovery rate is 97%, gold enrichment rate is ⁇ 95%, silver enrichment rate is ⁇ 96% .
  • a method of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing: adding cold varnished slag of the Vaughankov furnace to the DC arc 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, a copper oxide concentrate and a copper sulfide concentrate are added, and the reaction slag is electromagnetically stirred to achieve mixing;
  • the reaction slag is monitored in real time, and the (a) is ensured through regulation.
  • (b) two parameters to obtain the slag after completion of the reaction are monitored in real time, and the (a) is ensured through regulation.
  • the temperature of the copper-containing reaction slag is 1670 ° C, and adding red mud, sulfuric acid slag, lead ice copper, lead-containing soot, zinc-containing soot, arsenic matte and wet zinc slag, to the reaction slag, CaF 2 and fluorine-containing blast furnace slag, the temperature is lowered to 1440 ° C;
  • the alkalinity CaO / SiO 2 ratio of the copper-containing reaction slag is 2.0, and the copper-containing blowing slag is added to the reaction slag to make the copper-containing reaction
  • the slag basicity ratio is reduced to 1.4; the natural gas and the coke particles having a particle size of 20 mm are sprayed with air at 800 ° C, and the metal iron content in the slag is 2.4%;
  • Step 2 separation and recovery method 2:
  • the slag contains copper ⁇ 0.1%, the iron recovery rate is 91%, and the zinc recovery rate is 92%, lead recovery rate is 92%, indium recovery rate is 93%, hydrazine recovery rate is 94%, sodium recovery rate is 98%, potassium recovery rate is 97%; gold enrichment rate is 95%, silver The enrichment rate was 97%.
  • a method of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing: molten copper smelting slag flowing out of the slag outlet of the flash furnace and copper containing copper flowing out of the converter
  • the slag (converter slag) is added to the pit, and limestone and Fe are added at the same time to form mixed slag, and copper oxide concentrate and zinc smelting slag (wet zinc smelting kiln slag and iron vanadium slag) are added; the preheating temperature is 800.
  • 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, through regulation and assurance (a) and (b) two parameters, obtaining the slag after completion of the reaction;
  • 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 1.8 %;
  • Settlement cooling heat preservation for 43 min, the slag after the reaction is naturally cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to the bottom of the reaction device to form copper-rich strontium; the iron-containing silicate mineral phase floats; The intermediate phase of the copper phase and the iron-containing silicate mineral is an iron-rich phase, and a zinc-containing component and a lead-containing component are simultaneously formed;
  • the slag contains copper ⁇ 0.15%, the iron recovery rate is 92%, the zinc recovery rate is 94%, and the lead recovery rate is 95%, indium recovery rate is 94%, hydrazine recovery rate is 94%, gold enrichment rate is 94%, and silver enrichment rate is 96%.
  • a method of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing: the copper-containing smelting slag obtained from the slag outlet of the silver smelting furnace and the copper-containing smelting slag (converted slag) obtained by the slag outlet of the converter are added to the alternating current electric arc furnace and simultaneously added.
  • the temperature of the copper-containing reaction slag is 1080 ° C, the electric arc furnace is heated to raise the temperature to 1330 ° C;
  • the alkalinity CaO / SiO 2 ratio of the copper-containing reaction slag is 0.1, to the reaction melt Nickel smelting slag, blast furnace gas mud, alkaline pre-reduction pellets, high-calcium red mud after de-sodium are added to the slag, so that the alkalinity ratio of the copper-containing reaction slag is raised to 0.4; the natural gas is injected into the slag 1.5%;
  • 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, the lead-containing component, the indium-containing component and the cerium-containing component are volatilized, and are collected into the dust as an oxide, the slag contains copper ⁇ 0.1%, the iron recovery rate is 93%, and the zinc recovery The rate was 95%, the lead recovery was 96%, the gold enrichment rate was 94%, and the silver enrichment rate was 96%.
  • a method of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing: adding copper smelting slag of cold Tennant furnace, cold converter containing copper blowing slag (converter slag), depleted slag, copper slag flotation tailings into ore furnace, and adding Limestone, SiO 2 , FeO and MgO form a mixed slag; heating the mixed slag to a molten state to form a copper-containing reaction slag, adding a copper sulfide concentrate and a copper-containing material (lead smelting slag - smelting furnace slag), spraying Blowing argon-nitrogen gas mixture, and mixing the reaction slag; 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 1320 ° C;
  • the ratio of alkalinity CaO / SiO 2 of the copper-containing reaction slag is 0.8, both within the required range; the pulverized coal having the required particle size is required With natural gas, the content of metallic iron in the slag is 2.2%;
  • Step 2 separation and recovery method 4:
  • the slag contains copper ⁇ 0.1%, the iron recovery rate is 91%, the zinc recovery rate is 93%, and the lead recovery rate is 92%, indium recovery rate is 94%, hydrazine recovery rate is 95%, gold enrichment rate is 95%, and silver enrichment rate is 97%.
  • a method of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing: adding copper smelting slag of cold Mitsubal method and converter copper smelting slag (converter slag) to blast furnace, adding dolomite, red mud, MgO, using preheating temperature of 300 ° C of oxygen, spraying Into the gas and particle size ⁇ oxygen, injected coke powder, the mixed slag is heated to a molten state, forming a copper-containing reaction slag, adding copper oxide concentrate and copper-containing materials (lead smelting slag and zinc smelting 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 both parameters (a) and (b);
  • 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 1.9 %;
  • a method of producing copper-containing slag comprising the following steps:
  • Step 1 slag mixing: the copper-containing smelting slag of the hot bottom blowing smelting furnace slag opening and the copper-containing blowing slag of the hot continuous bottom blowing furnace slag opening are added to the side blowing furnace, and limestone is added to form mixed slag , adding copper sulfide concentrate and copper-containing materials (including copper garbage, copper-containing circuit board); using preheating air with preheating temperature of 800 ° C to spray ⁇ preheated air sprayed coke powder, heating the mixed slag to a molten state Forming a copper-containing reaction slag and mixing the reaction slag; 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 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 2.6 %;
  • Step 2 separation and recovery method 2:
  • the molten state contains the iron silicate mineral phase, and at the same time, the zinc-containing component and the lead-containing component are formed into the soot, and the following steps are performed:
  • the slag in the middle and upper portions is subjected to slag treatment outside the furnace, and one or more of the methods A to G in the separation and recovery method 1 of the step 2 are specifically used to carry out slag treatment outside the furnace.
  • the soot is recovered, the slag contains copper ⁇ 0.1%, the iron recovery rate is 91%, the zinc recovery rate is 92%, the lead recovery rate is 94%, the gold enrichment rate is 94%, and the silver enrichment rate It is 96%.
  • a method of producing copper-containing slag comprising the following steps:
  • Step 1 Slag mixing: the molten copper-containing smelting slag flowing out of the slag outlet of the Noranda melting furnace and the copper-containing blowing slag (converting slag) flowing out of the converter are added to the thermal insulation pit, and limestone and Fe are added to form mixed slag. Adding copper oxide concentrate and copper-containing soot; using oxygen-enriched air to spray anthracite with the required particle size, heating the mixed slag to a molten state, forming a copper-containing reaction slag, and mixing the reaction slag; real-time monitoring The reaction slag is obtained by controlling and simultaneously ensuring two parameters (a) and (b), and obtaining the slag after completion of the reaction;
  • 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 1.7 %;

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Abstract

L'invention concerne un procédé de fabrication utilisant un laitier contenant du cuivre, qui comprend les étapes suivantes : S1, mélange du laitier, qui consiste à mettre un laitier de cuivre dans un dispositif de réaction et à ajouter des minéraux calciques et des additifs, à chauffer le laitier à un état fondu et à ajouter un ou plusieurs éléments du groupe constitué par un minéral d'oxyde de cuivre, un minéral de sulfure de cuivre et un matériau contenant du cuivre, à mélanger de façon homogène les matériaux destinés à être utilisés comme laitier de réaction et à surveiller le laitier de réaction en temps réel afin que celui-ci présente la condition a suivante, obtenue par régulation : température du laitier de réaction réglée de façon à être comprise entre 1100 et 1450 °C, ainsi que la condition b suivante : rapport de basicité CaO/SiO2 du laitier de réaction réglé de façon à être compris entre 0,15 et 1,5, et à obtenir un laitier post-réaction ; et S2, séparation et récupération.
PCT/CN2017/115650 2017-10-10 2017-12-12 Procédé de fabrication utilisant un laitier contenant du cuivre Ceased WO2019071795A1 (fr)

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WO2020093234A1 (fr) * 2018-11-06 2020-05-14 东营金玺铜业有限公司 Mélange combustible pour la fusion de cuivre
CL2019003246A1 (es) * 2019-11-13 2020-04-17 Univ Concepcion Un proceso para producir cobre metálico desde concentrados de cobre sin generación de residuos
CN110845163A (zh) * 2019-12-19 2020-02-28 沈阳有色金属研究院有限公司 一种铜渣集料及其制备方法与应用
CN111334671A (zh) * 2020-04-03 2020-06-26 河南豫光金铅股份有限公司 一种辉铜矿的短流程高回收率冶炼方法
CN112322902B (zh) * 2020-09-18 2021-11-09 中南大学 一种铜冶炼渣的资源化回收方法
CN115141938B (zh) * 2021-03-29 2024-10-22 东北大学 一种利用铜精炼熔渣对铜冶炼熔渣进行贫化的方法
CN115141936B (zh) * 2021-03-29 2024-10-22 东北大学 一种铜镍熔炼熔渣和/或吹炼熔渣的贫化药剂及方法
CN113528743B (zh) * 2021-06-21 2022-08-05 首钢集团有限公司 一种基于用后中间包涂抹料的转炉调渣剂、制备方法及应用
CN115011806B (zh) * 2022-02-09 2025-03-25 昆明理工大学 一种铜熔渣低碳深度贫化的方法
CN114774705A (zh) * 2022-04-22 2022-07-22 昆明理工大学 一种利用铜冶炼渣回收铁、锌并制备耐火原料的方法

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