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WO2019071794A1 - Procédé de récupération de composants de valeur à partir de scories mélangées contenant du cuivre et du fer - Google Patents

Procédé de récupération de composants de valeur à partir de scories mélangées contenant du cuivre et du fer Download PDF

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Publication number
WO2019071794A1
WO2019071794A1 PCT/CN2017/115649 CN2017115649W WO2019071794A1 WO 2019071794 A1 WO2019071794 A1 WO 2019071794A1 CN 2017115649 W CN2017115649 W CN 2017115649W WO 2019071794 A1 WO2019071794 A1 WO 2019071794A1
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Prior art keywords
slag
smelting
copper
iron
furnace
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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 WO2019071794A1 publication Critical patent/WO2019071794A1/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
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C21B3/06—Treatment of liquid 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
    • 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
    • C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • the invention belongs to the technical field of slag metallurgy, and in particular relates to a method for recovering valuable components from a mixed slag containing copper and iron.
  • the copper smelting process “smelting smelting - copper smelting” produces copper slag, which is the first solid waste in heavy ferrous metallurgy.
  • the lead smelting process “sintering - blast furnace reduction - smelting furnace” or direct smelting process “oxidation blowing - high lead slag reduction - smelting furnace” and other processes have produced lead smelting slag.
  • blast furnace slag, steel slag, and iron alloy slag are produced, which is the first solid waste.
  • the copper slag includes copper-containing smelting slag, copper-containing blowing slag, copper-fired depleted slag, copper slag flotation tailings, and wet copper slag.
  • the copper-containing smelting slag is produced in the process of “smelting and smelting”. It contains not only copper, iron, zinc, nickel, precious metals, but also high-level SiO 2 , CaO and other metallurgical fluxes. It emits more than 20 million tons per year. More than 200 million tons of deposits.
  • the copper content is up to 20%, which is much higher than the current 0.2%% copper ore grade.
  • the iron content is as high as 50%, which is much larger than the average grade of 29% by weight of smelting iron ore.
  • the slag also contains precious metals, which are an important secondary resource.
  • the molten copper smelting slag discharged from the melting furnace is higher than 1100 ° C and is an important physical heat resource.
  • “Bronze crucible blowing” produces copper-containing blowing slag (converter blowing slag, flash blowing slag, top blowing furnace blowing slag, low blowing furnace blowing slag, etc.), the copper content in the slag reaches 35%, iron content Up to 55%, it also contains valuable components such as zinc, lead and precious metals. Molten copper-containing blowing slag is also an important physical thermal resource.
  • the copper-containing smelting slag and the copper-containing blowing slag are returned to the smelting furnace or the depletion or ore dressing method.
  • the depletion or beneficiation effect is not good.
  • the copper slag contains a large amount of heavy metals, and a large amount of long When time accumulates, it will pollute the surrounding environment.
  • the copper slag method is depleted or ore-selected, the slag contains more than 0.4% copper, which is higher than the recoverable grade of copper by 0.2%.
  • the higher slag contains copper, which is not conducive to the subsequent reduction of iron.
  • 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, and cracks occur during rolling.
  • Lead smelting slag is produced in the process of lead smelting process "sintering-blast furnace reduction-smoke furnace” or "oxidation blowing-high lead slag reduction-smoke furnace".
  • Lead smelting slag includes lead smelting slag and smelting furnace slag.
  • "Sintering blast furnace reduction” or “solid high lead slag reduction” or “liquid high lead slag reduction process” reduction process produces lead-containing smelting slag
  • lead smelting slag is smelted by smelting furnace to produce smelting furnace slag
  • lead smelting slag contains copper Components such as gold, silver, iron, zinc and lead are important secondary resources.
  • Lead smelting slag temperature is ⁇ 1050 °C, which is an important physical thermal resource.
  • Blast furnace slag, steel slag and iron alloy slag contain high content of metal iron, iron oxide, SiO 2 , CaO, MgO and other valuable components are important secondary resources; molten slag is discharged from blast furnace, steelmaking furnace and ferroalloy furnace At ⁇ 1300 °C, molten blast furnace slag, molten steel slag and molten iron alloy slag are also important physical thermal resources. These physical thermal resources are not well utilized, and the accumulation of large amounts of slag not only occupies a relatively large space, but also brings serious environmental pollution.
  • the present invention provides a method for recovering valuable components from a mixed slag containing copper and iron.
  • the method has the advantages of short reaction time, short process flow, high metal recovery rate, low production cost, large processing capacity, environmental friendliness and high economic benefit, and can effectively solve the problem of efficient recycling of metallurgical resources and thermal energy; and environmental pollution problems.
  • the invention provides a new slag metallurgy process, which not only reduces the copper content of the slag, but also contains copper ⁇ 0.1wt% in the slag, and realizes copper, gold, silver, iron, zinc, lead, indium, antimony, sodium, Efficient recovery of potassium components to obtain low copper iron Materials (iron concentrate and pig iron).
  • the main technical solutions adopted by the present invention include:
  • a method for recovering valuable components from slag containing copper and iron comprising the steps of:
  • S1 slag mixing: adding copper slag to the smelting reaction device, adding one or more of lead smelting slag, blast furnace slag, steel slag and iron alloy slag to form mixed slag; heating the mixed slag to a molten state to form a reaction
  • the slag is uniformly mixed, the reaction slag is monitored in real time, the reaction slag is controlled by regulation, and the condition s and condition b are satisfied, the slag after the reaction is obtained, or the slag after the reaction is poured into the heat preservation device;
  • condition a is a slag temperature of 1050 to 1450 ° C;
  • the slag after the reaction in the step S1 is kept for 5 to 50 minutes, and settled, and the copper-rich phase at the bottom, the iron-rich phase in the middle and the iron-containing silicate mineral phase in the upper portion are separated, and zinc is formed at the same time.
  • the components and the lead-containing component of the soot, the gold and silver components are enriched into the copper-rich phase; the phases are recovered.
  • the method for regulating the condition a is:
  • the temperature of the reaction slag is ⁇ 1050 ° C
  • a heating function of the reaction device itself, or a fuel or molten copper slag, molten lead smelting slag, molten blast furnace slag, molten steel slag or molten iron alloy slag is added to the slag.
  • the fuel is injected, the oxidizing gas is simultaneously injected, so that the temperature of the reaction slag reaches 1050 to 1450 ° C;
  • the temperature of the reaction slag is >1450 ° C
  • one of a copper-containing material, a nickel smelting slag, a blast furnace slag, a steel slag, a ferroalloy slag, a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag or Several, so that the temperature of the mixed slag reaches 1050 ⁇ 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, Osmeite furnace, copper smelting furnace electric heating bed, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing Rotary furnace, top blowing rotary furnace.
  • the slag is controlled to maintain copper oxide and iron oxide reduced to metallic copper and FeO
  • the metal iron content in the slag is less than 3%, by adding one or two of a reducing agent and a carbon-containing iron-containing material, wherein the reducing agent and/or the carbon-containing iron-containing material is used in the slag
  • the theoretical amount of copper and iron oxide reduced to 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 metal Pellet, wet zinc smelting kiln slag 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.
  • Copper-containing smelting slag is produced in the “smelting and smelting” process of copper pyrometallurgical smelting process, including Osmet furnace smelting slag, flash furnace smelting slag, Noranda furnace smelting slag, Isa furnace smelting slag, Kraft 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-blown furnace smelting slag; the copper-containing blowing slag is produced in the "copper smelting" process of copper pyrometallurgical smelting process, including converter blowing copper slag, flash furnace
  • the wet smelting copper slag is the waste slag produced by the wet copper smelting; the copper smelting slag and the copper smelting slag are in a molten state or a cold state, wherein: the molten copper smelting slag is processed by the “smelting smelting” process
  • the copper smelting furnace obtains the slag opening, or heats the copper-containing smelting slag to a molten state, and the molten copper blowing slag is obtained from the copper smelting furnace slag opening of the "copper smelting" process, or the copper blowing slag is heated
  • the depleted waste is obtained from the slag outlet of the depleted furnace, and the depleted slag is heated to a molten state;
  • the lead smelting slag comprises a smelting furnace slag and a lead smelting slag, and the lead smelting slag is in a molten state or a cold state, wherein the molten slag is discharged from the slag outlet or the slag slag outlet of the reduction stage of the pyrometallurgical lead process Obtained; the blast furnace slag, steel slag and iron alloy slag are in a molten state, or in a cold state, wherein: molten slag (including blast furnace slag, steel slag and iron alloy slag) is obtained from a slag outlet, or cold slag (including blast furnace slag, Steel slag and iron alloy slag are heated to a molten state; the steel slag is molten iron pre-desulfurization slag (including desulfurization slag, desiliconization slag, dephosphorization slag), converter slag,
  • the lead smelting slag is produced by a smelting furnace slag and lead-containing smelting slag, "ISP lead-zinc blast furnace 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, lead-containing smelting slag is smelted by a fuming furnace to produce lead-containing smelting furnace slag.
  • the fuel is one or more of a solid, liquid or gaseous fuel, which is sprayed or fed, loaded with a gas at 0-1200 ° C, the gas Is one or more of an oxidizing gas, argon gas, and nitrogen gas;
  • 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.
  • copper slag includes slag produced by "smelting smelting” and slag generated by "copper smelting", pyrolysis slag, copper slag flotation tail Slag, flotation tailings, wet copper slag; the lead smelting slag is smelting furnace slag and lead smelting slag, "ISP lead-zinc blast furnace reduction” or “sinter blast furnace reduction” or "solid high-lead slag reduction Or the "liquid high-lead slag reduction process” reduction process produces lead-containing smelting
  • 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 containing Carbon pre-reduction pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dusty nickel smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high after de-sodium One or more of calcium red mud, lead smelting slag, high calcium red peat ash, copper tailings, sulfuric acid slag; the steel soot and dust including blast furnace gas, converter dust, Electric furnace dust, hot or cold-rolled sludge, sintered dust, pellet 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 alkaline material is lime powder, red mud, high-calcium red mud after desodiumification, calcium carbide slag, dolomite powder Or one or more of the quicklime powder;
  • the alkaline iron-containing material is a CaO/SiO 2 >1 iron-containing material, an alkaline sintered ore, an alkaline iron concentrate, an alkaline pre-reduction pellet, and a base.
  • a metallized pellet, steel slag or blast furnace slag One or more of a metallized pellet, steel slag or blast furnace slag.
  • the acidic material is one or more of silica, lead smelting slag containing gold silver silica, fly ash, coal gangue;
  • the acidic iron-containing material is CaO / SiO2 ⁇ 1 Iron-containing material, acidic sinter, acid iron concentrate, acid pre-reduction pellet, acid metallized pellet, copper slag, lead smelting lead smelting slag, zinc smelting slag, nickel smelting slag
  • 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.
  • Wet zinc slag, wet copper slag and dust must be dehydrated and dried.
  • the solid fuel is one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite coal, and the shape is granular or powder, and the granular material has a particle size of 5 to 25 mm, and the granular material particle size ⁇ 150 ⁇ m; the liquid fuel is heavy oil, and the gaseous fuel is gas and/or natural gas.
  • the mixing is uniform for natural mixing or stirring mixing, wherein the stirring and mixing is performed by argon stirring, nitrogen stirring, nitrogen-argon gas mixture stirring, reduction.
  • gas agitation oxidative gas agitation, electromagnetic agitation or mechanical agitation;
  • the copper-rich phase settled at the bottom, the iron-rich phase in the middle portion, and the upper iron-containing silicate mineral phase may be separately treated, or
  • the upper middle iron is combined with the iron-containing silicate mineral, the gold component and the silver component migrate and enrich and enter the copper-rich phase, and the zinc-containing component and the lead-containing component volatilize, and enter the dust 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 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 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;
  • 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, decalcified high calcium red mud or calcium carbide slag fully mixed to obtain 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 is used 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, it is used as a blast furnace ironmaking or direct reduction ironmaking raw material, and after direct reduction, magnetic separation or electric furnace melting is used, and the magnetic separation product is metal iron and tail. Mine, 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 conditions are satisfied: the temperature of the reaction slag is 1350 ⁇ 1650 ° C and the ratio of alkalinity CaO / SiO 2 of the reaction slag is 0.6-2.4, and the slag after completion of the reaction is obtained;
  • 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 1650 ° 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 desoda, 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 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 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 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, and the copper concentrate is returned. Copper smelting system, iron concentrate as raw material for blast furnace ironmaking or direct reduction of ironmaking raw materials or smelting reduction of ironmaking raw materials;
  • 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 device, and the gas-based or coal-based reduction technology is used to reduce the gas base to natural gas and/or gas, and the coal base is reduced to 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 iron-rich phase and the iron-containing silicate mineral phase treatment method are treated by one or more of the methods A to G described in the first method, Or pour into the copper-rich phase after the slow cooling of the heat preservation device, send it to the converter or the smelting furnace for copper smelting, or pulverize and separate the metal iron, then send it to the converter or the smelting furnace to smelt copper, or magnetically separate the metal iron or After 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 the slag rotatable converter and the reaction slag tank, obtaining the molten 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 step of containing the iron-rich phase is carried out by a method S2-1-05; the molten state or the copper-rich phase after being poured into the heat-insulating device to be cooled, sent to a converter or a blowing furnace for copper smelting, or crushed magnetic separation After separating the metal iron, it is sent to the converter or the blowing furnace for copper smelting, or the metal iron is separated by magnetic separation or the metal iron is separated without magnetic separation, and then directly reduced, and the reduced product is separated by magnetic separation and then sent to the converter or Blowing furnace copper smelting.
  • Method 4 using a molten slag rotatable converter and a reaction slag tank, the obtained molten iron-containing silicate mineral phase and the iron-rich phase are obtained, and the treatment method is one or more of the methods A to G described in the first method.
  • the molten copper-rich phase is poured into a heat preservation device to be cooled, and then sent to a converter or a blowing furnace for copper smelting, or after slow cooling, the metal iron is separated by crushing and then sent to a converter or a smelting furnace for copper smelting.
  • magnetic separation of metal iron or magnetic separation without metal separation direct reduction, reduction products after magnetic separation of metal iron, and then sent to the converter or blowing furnace copper.
  • 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;
  • smelting reduction ironmaking raw materials or smelting reduction ironmaking raw materials or flotation copper extraction raw materials or magnetic separation of metallic irons as raw materials for copper smelting or direct reduction ironmaking in direct reduction process, after reduction products are magnetically separated and separated, metal is obtained Iron and tailings, tailings return to copper smelting system; flotation products are copper-bearing concentrates and iron concentrates, copper concentrates are returned to copper smelting system, iron concentrates are used as blast furnace ironmaking raw materials or direct reduction of ironmaking raw materials or smelting reduction Ironmaking raw materials;
  • the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, nitrogen-air, argon-air, oxygen-nitrogen, oxygen-argon.
  • the mixing is a natural mixing or a stirring mixing, wherein the stirring and mixing is performed by argon stirring, nitrogen stirring, nitrogen-argon gas mixture stirring, reducing gas stirring, oxidizing gas stirring, and electromagnetic stirring.
  • stirring or mechanical agitation in the step S2, the sedimentation is natural sedimentation or spin sedimentation or centrifugal sedimentation; the cooling mode when performing cooling sedimentation is natural cooling or rotary cooling or centrifugal cooling.
  • the gravity sorting method is a shaker sorting, a chute sorting, or a combination of the two.
  • the method for recovering valuable components from a mixed slag containing copper and iron which can treat hot slag and make full use of molten copper slag and molten metallurgical slag (melted lead smelting slag, molten blast furnace slag, One or more of molten steel slag and molten iron alloy slag) physical thermal resources and hot metallurgical flux, which can also process cold slag, and realize slag metallurgical modification by slag mixing or cold mixing;
  • the iron-rich phase includes various kinds of metal iron, FeO phase and fayalite phase.
  • metal iron component in the mixed slag is aggregated, grown and settled; (3) copper component and gold and silver components in the mixed slag are separately enriched In the copper-rich phase, and to achieve growth and sedimentation, the copper-rich phase includes copper, white copper, matte, white copper, iron-containing components, or part of the copper component into the iron-rich phase, rich
  • the copper phase is sent to the converter or the converter to smelt copper; (4) the zinc component in the mixed slag
  • the lead component is separately enriched in soot and recovered; (5) part of the indium-containing component, antimony component, potassium-containing component, and sodium-containing component are volatilized into the dust for recovery; (6) free calcium oxide in the mixed slag With magnesium oxide disappearing, mixed slag to achieve quenching and tempering; (7) manual sorting, magnetic separation, re-election,
  • the iron-containing silicate phase wherein the iron-rich phase and the iron-containing silicate phase have a copper content of less than 0.1%, and the iron can be obtained by direct reduction or smelting reduction to obtain metallic iron and molten iron; (10) the present invention adopts mixed melting Slag, the whole process does not require heating or a small amount of compensation for heat.
  • the entire process can be processed without cold metallurgical flux or a small amount of metallurgical flux.
  • the process of the invention can be carried out continuously or intermittently to meet the needs of industrial production.
  • the invention realizes comprehensive utilization of the valuable components of the copper component, the iron component, the zinc component, the lead component, the gold, the silver, the phosphorus, the calcium and the silicon component in the nonferrous metallurgical slag and the iron and steel metallurgical slag, and solves the problem At present, a large amount of slag is accumulated and environmental pollution problems;
  • the invention can treat iron alloy slag, steel slag, blast furnace slag, lead smelting slag and copper-containing slag on a large scale, can solve the problem of heavy metal element pollution, and realize the recovery of heavy metal components;
  • the invention can treat a small amount of cold copper-containing and iron-containing materials;
  • the raw material of the invention can be liquid molten copper slag and molten metallurgical slag (melted lead smelting slag, molten blast furnace slag, molten steel slag, One or more of the molten iron alloy slags have the characteristics of high temperature
  • the slag system realizes the efficient utilization of metallurgical resources and thermal resources; fully utilizes the characteristics of high reaction chemical activity of mixed slag, and realizes slag metallurgy; (5) the invention is mixed by slag, heat preservation The gas is blown, the oxygen potential is controlled, and the copper group, the gold component and the silver component in the slag are enriched to the copper-rich phase to achieve aggregation, growth and sedimentation, and the iron component is concentrated in the copper-rich phase to achieve aggregation.
  • the lead component and the zinc component are enriched in the soot to be recovered; the zinc component, the lead component, the indium component, the strontium component, the sodium component, and the potassium component in the slag are volatilized and enter the soot (6)
  • 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 be processed Liquid Slag, and can handle a small amount of cold materials, the material is highly adaptable; the addition of cold materials realizes the efficient use of chemical heat released by the slag metallurgical reaction and the physical heat of the slag; (7) during the sedimentation process of the method of the present invention, The copper component and the gold and silver components in the slag are respectively concentrated in the copper-rich phase, and the aggregation, growth and sedimentation are realized, and the
  • the copper-rich phase is sent to the converter or the smelting furnace for copper smelting, and the low copper rich iron phase is used as the blast furnace ironmaking.
  • the copper-rich phase comprises a plurality of copper phase, white copper, matte phase, iron-containing components, or partially into the iron-rich phase, and the iron-rich phase includes metallic iron, FeO a plurality of phases, the olivine phase;
  • the slag-containing heat preservation device is rotated on the rotating platform to accelerate the accumulation, growth and sedimentation of the copper-rich phase and the iron-rich phase;
  • the addition of the fluorine-containing material accelerates the copper-rich phase, Aggregation, growth and sedimentation of the iron-rich phase;
  • the method of the invention passes through a copper-rich phase
  • 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 iron, to obtain metal iron and
  • the copper-rich phase, the iron-rich phase in the middle and the iron-containing silicate mineral phase in the upper part enable efficient recovery of valuable components in the mixed slag.
  • 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 effectively solve the problem of efficient recycling of metallurgical resources and thermal energy.
  • a method for recovering valuable components from a mixed slag containing copper and iron according to the present invention comprises the following steps:
  • Step 1 slag mixing:
  • copper slag containing copper smelting slag, copper-containing blowing slag, copper fire depleted slag, copper slag flotation tailings, wet copper slag slag, one or more
  • copper slag containing copper smelting slag, copper-containing blowing slag, copper fire depleted slag, copper slag flotation tailings, wet copper slag slag, one or more
  • lead smelting slag smoke furnace slag and/or lead smelting slag
  • blast furnace slag steel slag
  • iron alloy slag may be added to the molten smelting reaction device to form mixed slag
  • the mixed slag is heated to a molten state to form a reaction slag containing copper and iron; the mixture is uniformly mixed, and the reaction slag is monitored in real time, and the following two parameters (a) and (b) are ensured by the control to obtain the melting after completion of the reaction. Slag, or pour the slag after the reaction is completed into the heat preservation device;
  • the control method is:
  • the heating function of the reaction device itself is added, or fuel or molten copper slag, molten lead smelting slag, molten blast furnace slag, or molten slag are added to the slag.
  • One or more of molten steel slag or molten iron alloy slag when injected into the fuel, simultaneously injected into the preheated oxidizing gas, so that the temperature of the slag reaches a set temperature range of 1050 to 1450 ° C;
  • the slag is kept for 5 to 50 minutes, and settled to obtain a bottom molten state of the 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 lead component of the soot, the gold and silver components migrate to the copper-rich phase,
  • Each phase is processed using one of the following methods:
  • 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;
  • Method 3 When the slag rotatable converter and the reaction slag tank are used, the slag after the completion of the reaction is subjected to the following steps: (1) 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 of the second step are subjected to slag treatment; and the iron-rich phase is treated by the step (4) in the first method;
  • Method 4 When the slag rotatable converter and the reaction slag tank are used, the slag after the completion of the reaction is subjected to the following steps: (1) the molten iron-containing silicate mineral phase and the iron-rich phase are subjected to slag treatment, and the specific manner The treatment is carried out by one or more of the methods A to G in the separation and recovery method 1 of the step 2;
  • 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 one of copper-containing smelting slag, copper-containing blowing slag, depleted slag, flotation tailings, and wet copper slag.
  • copper smelting slag produced in the "smelting and smelting" process of copper smelting process, including Osmet furnace smelting slag, flash furnace smelting slag, Noranda furnace smelting slag, 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, low-smelting furnace smelting slag, side-smelting furnace smelting slag; copper-containing blowing slag is produced in the copper smelting process of copper smelting process, including converter blowing copper slag, flash furnace blowing copper Slag, Noranda furnace continuous
  • the lead smelting slag is a smelting furnace slag and a lead-containing smelting slag
  • ISP lead-zinc blast furnace reduction or “sinter blast furnace reduction” or “solid high-lead slag reduction” or “liquid high lead”
  • the slag reduction process "reduction process produces lead-containing smelting slag, and the lead-containing smelting slag is smelted by a smelting furnace to produce lead-containing smelting furnace slag;
  • the smelting reaction device through which the slag can flow out is a rotatable 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 heat preservation pit
  • 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 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.
  • gas, nitrogen, and argon, preheating temperature is 0-1200 ° C
  • solid fuel and reducing agent is one of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite a variety of shapes, granular or powdery, granular material size of 5 ⁇ 25mm, powder material size of ⁇ 150 ⁇ m, liquid fuel and reducing agent for heavy oil, gaseous fuel and reducing agent for gas and / or natural gas
  • the copper material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, lead smelting slag, nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag containing lead fuming furnace slag,
  • the fluorine-containing material described in the high calcium red mud after desulfurization of the lead smelting slag is one or more of fluorite, CaF 2 or fluorine-containing blast furnace slag; the copper-containing material and the iron-containing material are hot or cold.
  • the hot material is directly obtained from the metallurgical furnace discharge port or the slag outlet; the wet zinc slag and dust sludge are dehydrated and dried.
  • 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 method of controlling the temperature of the mixed slag in the set temperature range is:
  • 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 preheating temperature is 0 to 1200 ° C;
  • the blowing method is one or more of using a refractory spray gun to insert slag or placing it on the upper part or side or bottom of the reaction slag;
  • 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 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 iron-containing material, the blast furnace slag, the steel slag, the iron alloy slag, the metallurgical flux or the fluorine-containing material are added to avoid the temperature being too high.
  • protective refractory Another effect of adding fluorine-containing materials is to reduce the viscosity, accelerate the copper-rich phase, the ice-rich copper phase, the iron-rich phase aggregation, growth and sedimentation in the slag, which is beneficial to the silicate floating;
  • the copper component and the gold and silver component in the slag are enriched in the copper-rich phase, and aggregate, grow and settle, or partially enriched in the iron-rich phase, iron
  • the components are released from the olivine, enriched in the iron-rich phase, and achieve aggregation, growth and sedimentation.
  • the zinc component and the lead component in the slag respectively enter the soot and are recovered as oxides;
  • 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 or an alkali metallized pellet.
  • 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 or an alkali metallized pellet.
  • the acidic material is one or more of silica, fly ash and coal gangue;
  • the acidic iron-containing material is CaO/SiO 2 ⁇ 1 acid sintering.
  • the copper-rich phase, the ice-rich copper phase, the iron-rich phase in the slag are aggregated, grown and settled, which is favorable for the silicate to float, and the copper-rich phase includes copper, white copper, and matte. a plurality of white copper or iron-containing components, or a portion of the copper component entering the iron-rich phase, the iron-rich phase comprising a plurality of metal iron, FeO phase, and fayalite phase;
  • the mixed slag is sufficiently mixed while ensuring the two parameters (a) and (b), and the mixing mode is natural mixing or stirring mixing, and the stirring mode is one of the following modes: argon One or more of gas agitation, nitrogen agitation, argon-nitrogen gas mixture, reducing gas (gas and/or natural gas), electromagnetic stirring, mechanical agitation, gas preheating temperature is 0 to 1200 ° C;
  • 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 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 metallic copper and
  • the theoretical amount of FeO is 110-140%;
  • the carbon-containing iron-containing materials are steel dust and soot, iron concentrate carbon-containing pre-reduction pellets, iron concentrate carbon-containing metallized pellets, and wet zinc smelting kiln Slag or coke oven dust and soot.
  • the direct reduction process uses a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary kiln, an induction furnace as a reduction device, and a gas-based or coal-based reduction technology
  • the gas base is natural gas and/or Gas
  • coal-based reduction to one or more of anthracite, bituminous coal, lignite, coking coal, coke breeze, coke reduction temperature of 900 ⁇ 1400 ° C
  • alkalinity CaO / SiO 2 ratio 0.7 ⁇ 1.9
  • 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 spraying method is one or several types of inserting slag into the molten slag or placing it in the upper part or side or bottom of the reaction slag;
  • cooling and sedimentation are required for separation and recovery, wherein the cooling mode is natural cooling or rotary cooling or centrifugal cooling, and the sedimentation mode is natural sedimentation or rotary sedimentation or centrifugal cooling;
  • the specific operation of the rotation and the centrifugal cooling is: the device containing the slag after the reaction is completed is placed on the rotating platform, and is rotated according to a certain speed, and the rotation speed is determined according to the quality of the slag and the height or depth of the heat preservation device, and the rotation is performed.
  • the 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 a rotating platform for the purpose of accelerating the accumulation of copper-rich phase, iron-rich phase, growth and sedimentation, and is beneficial to
  • the silicate (phosphorus-rich phase) floats, shortens the settling time, improves the sedimentation effect, and improves production efficiency;
  • step 2 in 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 and the ice-rich copper phase, and realize growth and sedimentation; the iron component in the mixed slag Continue to migrate and enrich in the iron-rich phase, And to achieve growth and settlement.
  • the finally obtained slag contains copper ⁇ 0.1%, the iron recovery rate is ⁇ 90%, the zinc recovery rate is ⁇ 91%, the lead recovery rate is ⁇ 92%, and the gold enrichment rate is ⁇ 94%, silver enrichment rate is ⁇ 94%, indium recovery rate is ⁇ 94%, strontium recovery rate is ⁇ 94%, sodium recovery rate is ⁇ 95%, and potassium recovery rate is ⁇ 95%.
  • reaction slag basicity CaO / SiO 2 ratio of copper and iron 0.15 ⁇ 1.5;
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 slag mixing: the copper-containing smelting slag obtained from the slag smelting furnace slag outlet and the copper-containing blowing slag (converter slag) obtained from the slag outlet of the converter are added to the DC arc furnace, and simultaneously added to the cold state.
  • the molten slag is reacted, and the reaction slag is electromagnetically stirred to achieve natural mixing; 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); corresponding to (a):
  • the reaction slag containing copper and iron has a temperature of 1,660 ° C, and is inserted into the reaction slag by using a refractory spray gun, and nitrogen gas is used as a loading gas, and is sprayed with copper slag, copper-containing soot, copper-containing and copper containing a powder particle size of ⁇ 150 ⁇ m at normal temperature.
  • Step 2 separation and recovery method 1:
  • the slag After 6 min of heat preservation, the slag 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 a zinc component and a lead component are simultaneously formed, and the following steps are performed: (1) The iron-containing silicate mineral phase is treated by the external slag, and the method F is used. After the iron-containing silicate slag is air-cooled, it is used as a direct reduction ironmaking raw material, and the rotary kiln is used for direct reduction, and the gas-based reduction technology is utilized.
  • 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 after reduction, the metal iron and slag are obtained by melting in a magnetic furnace, and the melting temperature is 1550 ° C; (2) melting The 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 is used as the blast furnace ironmaking raw material after air cooling; (4) the zinc component, the indium component, the lead component, and the bismuth group The fractions, potassium components and sodium components volatilized oxides are recycled into the soot.
  • the final slag contains copper ⁇ 0.1%, zinc recovery rate is 92%, lead recovery rate is 92%, iron recovery rate is 93%, gold
  • the enrichment rate is 96%
  • the silver enrichment rate is 94%
  • the indium recovery rate is 94%
  • the ruthenium recovery rate is 95%.
  • Sodium recovery The rate was 95% and the potassium recovery was 97%.
  • 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 a mixed slag containing copper and iron comprising the steps of:
  • Step 1 slag mixing: the copper smelting slag of the Isa furnace obtained from the slag outlet of the smelting smelting furnace and the copper-containing smelting slag (converter slag) obtained from the tapping port of the converter are added to the pourable smelting reaction slag, Adding iron alloy slag produced by molten smelting ferrochrome obtained from the slag outlet to form mixed slag; using oxygen-enriched air, blowing natural gas, aniseous coal with a particle size of 20 mm and coke particles, heating the mixed slag to a molten state, forming a
  • the reaction slag between copper and iron, and the reaction slag is electromagnetically stirred to achieve mixing; the reaction slag is monitored in real time, and the two parameters of (a) and (b) are simultaneously controlled to obtain the slag after completion of the reaction;
  • the reaction temperature of slag containing copper and iron is 1660 °C, and it is
  • the argon gas is used as carrier gas, and sprayed into the room temperature powder particle size ⁇ 150 ⁇ m copper slag, steel sintered dust, sintered pellet dust, iron Factory dust, copper-containing circuit board, ordinary iron concentrate, ordinary iron concentrate direct reduced iron and ordinary iron concentrate sinter, the temperature is reduced to 1360 ° C; (b) copper and iron reaction slag basicity CaO / SiO 2 ratio is 2.7, added to the reaction slag Acidic sinter, acid iron concentrate and acid pre-reduction pellets, the ratio of alkalinity of slag containing copper to iron is reduced to 1.3; the content of metal iron in slag is 2.9%;
  • the zinc recovery rate is 92%
  • the slag contains copper ⁇ 0.1%
  • the lead recovery rate is 92%
  • the iron recovery rate is 91%
  • the indium recovery rate is 96%.
  • the recovery rate of ruthenium is 96%
  • the recovery rate of sodium is 97%
  • the recovery rate of potassium is 98%
  • the enrichment rate of gold is 94%
  • the enrichment rate of silver is 95%.
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 slag mixing: the copper smelting slag of the Osmite furnace obtained from the slag smelting furnace slag and the copper-containing smelting slag (converter slag) obtained from the slag outlet of the converter are added to the induction furnace, and simultaneously added by the converter
  • the steel slag obtained from the steel slag outlet forms a mixed slag; the oxygen is sprayed at a temperature of 600 ° C, and the particle size is 20 mm anthracite, coke and pulverized coal, and the mixed slag is heated to a molten state to form copper and iron.
  • reaction slag is reacted and the slag is mixed; the slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling both parameters (a) and (b); corresponding to (a): reaction with copper and iron
  • the temperature of the slag is 1685 ° C, and quartz sand, red mud, dolomite, limestone, wet zinc smelting kiln slag is added to the reaction slag, and copper-containing materials, ordinary iron concentrate pellets, and ordinary iron fines are simultaneously added.
  • Step 2 separation and recovery method 2: heat preservation 15min, slag natural sedimentation, slag-gold separation, obtain molten copper-rich phase, iron-rich phase and iron-containing silicate mineral phase, and simultaneously produce zinc-containing components and lead
  • the slag contains copper ⁇ 0.08%, the iron recovery rate is 93%, the zinc recovery rate is 93%, and the lead recovery rate is 94%, sodium recovery rate was 93%, potassium recovery rate was 94%, gold enrichment rate was 95%, silver enrichment rate was 96%, indium recovery rate was 96%, and hydrazine recovery rate was 95%.
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 Mixing slag: adding cold smelting slag of copper in the Nolanda furnace and copper depleted slag to the plasma furnace, and adding the steel slag obtained by the converter steel slag, the electric furnace steel slag and the smelting ferronic steel obtained by the slag outlet, Forming mixed slag; heating the mixed slag to a molten state, forming a reaction slag containing copper and iron, and reacting the slag with a temperature of 1200 ° C to achieve mixing; real-time monitoring of the reaction slag, through regulation and control
  • the two parameters (a) and (b) are guaranteed to obtain the slag after the completion of the reaction; corresponding to (a) the temperature of the reaction slag containing copper and iron is 1,650 ° C, and red mud and coal dust are added to the reaction slag.
  • reaction slag basicity containing copper and iron The ratio of CaO/SiO 2 is 2.9, and copper-containing blowing slag is added to the reaction slag to reduce the alkalinity ratio of copper-iron reaction slag to 1.1; natural gas is sprayed, and coke particles having a particle size of 20 mm are sprayed with air.
  • the metal iron content in the slag is 2.9%;
  • Step 2 separation and recovery method 3: heat preservation for 19 min, the slag is naturally settled after the reaction is completed, and the slag-gold separation, obtaining a molten copper-rich phase, an iron-rich phase and an iron-containing silicate mineral phase, and a zinc-containing and lead-containing phase
  • the components are subjected to the following steps: (1) the molten copper-rich phase and the molten iron-rich phase are sent to the converter for copper smelting; (2) the iron-containing silicate mineral phase is subjected to the method A of the first method, after water quenching, As a cement raw material; (3) part of the zinc-containing component bismuth component, indium component and lead-containing component volatilize, enter the soot recovery as oxide, slag contains copper ⁇ 0.1%, iron recovery rate is 90%, zinc The recovery rate is 92%, the lead recovery rate is 92%, the indium recovery rate is 93%, the ruthenium recovery rate is 94%, the gold enrichment rate is 95%, the silver enrichment rate is
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 Slag mixing: the copper-containing smelting slag of the cold Mitsubishi method and the copper slag flotation tailings and the wet copper slag are added to the slag slag tank, and the molten steel slag obtained from the slag outlet is added to form the mixed slag.
  • the reaction slag is obtained by controlling two parameters (a) and (b) to obtain the slag after completion of the reaction; corresponding to (a): the reaction slag temperature of copper and iron is 1210 ° C; (b): The ratio of copper to iron reaction slag basicity CaO / SiO 2 is 0.75, both within the required range; the metal iron content in the slag is 1.4%;
  • Step 2 separation and recovery of heat preservation for 16 min, using method nine: the slag after the completion of the reaction is carried out as follows: (1) sedimentation cooling: the slag after the reaction is rotated and cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to The bottom of the reaction device forms a metal copper crucible; the iron-containing silicate mineral phase floats; the copper-rich phase metal antimony and the iron-containing silicate mineral intermediate slow-cooling slag are iron-rich phases, and at the same time, a zinc-containing and lead-containing component is formed; (2) Separation: manually extracting the copper-rich strontium deposited at the bottom, directly reducing, magnetically separating the iron, and then sending the product to the converter; the iron-rich phase layer in the middle is directly sent to the converter for iron making; (3) manually taking out the upper part Iron silicate mineral phase, obtained as silicate tailings, used as cement raw material; (4) Part of zinc component and lead component volatilized, entered into soot as oxide,
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 slag mixing: the copper-containing blowing slag (converter slag) obtained from the slag outlet of the converter is added to the alternating current electric arc furnace, and the iron alloy slag produced by the cold smelting of vanadium iron and the ferroalloy slag produced by smelting the ferrosilicon are added to form a mixed melting.
  • the slag is heated to a molten state to form a reaction slag containing copper and iron, and the reaction slag is sprayed with an argon-nitrogen gas mixture having a preheating temperature of 400 ° C, and mixed; the reaction slag is monitored in real time.
  • the two parameters of (a) and (b) are guaranteed to obtain the slag after completion of the reaction; corresponding to (a): the temperature of the molten slag containing copper and iron is 1040 ° C, and oxygen-enriched air, heavy oil and molten content are added to the reaction slag. Copper blowing slag, the temperature is raised to 1330 ° C; (b): copper and iron reaction slag basicity CaO / SiO 2 ratio of 0.1, adding basic iron concentrate and alkaline pre-reduction ball to the reaction slag Group, the ratio of alkalinity of slag containing copper to iron is raised to 0.4; the content of metallic iron in slag is 1.8%;
  • Step 2 separation and recovery method 1: heat preservation for 21 min, the slag after the completion of the reaction is naturally settled, slag-gold separation, obtaining a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and zinc-containing
  • the lead-containing component is subjected to the following steps: (1) the molten iron-containing silicate mineral phase is subjected to the step 2 separation and recovery method method A, and the water quenching is directly used as the cement raw material; (2) the molten copper-rich phase is sent to the converter (3) After the iron-rich phase is poured into the heat preservation device, the iron is directly reduced; (4) part of the zinc-containing and lead-containing components are volatilized, and the fumes are recovered as oxides, and the slag contains copper ⁇ 0.1%, iron.
  • the recovery rate was 91%, the zinc recovery rate was 94%, the lead recovery rate was 92%, the gold enrichment rate was 94%, and the silver enrichment rate was 96%.
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 slag mixing: the silver furnace smelting slag obtained from the slag smelting furnace slag tapping and the copper-containing blowing slag (converter slag) obtained by the converter smelting slag outlet, and the copper slag flotation tailings are added to the submerged arc furnace At the same time, the slag produced by the smelting of the slag iron and the slag produced by the smelting of the ferromolybdenum are added to form a mixed slag; the mixed slag is heated to a molten state to form a reaction slag containing copper and iron, and the reaction is melted.
  • the silver furnace smelting slag obtained from the slag smelting furnace slag tapping and the copper-containing blowing slag (converter slag) obtained by the converter smelting slag outlet, and the copper slag flotation tailings are added to the submerged arc furnace
  • the slag is blown with nitrogen to achieve mixing; the reaction slag is monitored in real time, and the slag after completion of the reaction is obtained by controlling both parameters (a) and (b); corresponding to (a): reaction slag containing copper and iron The temperature of the reaction is 1320 ° C; (b): the ratio of alkalinity CaO / SiO 2 of the reaction slag containing copper and iron is 0.8; the natural gas is sprayed, the content of metal iron in the slag is 2.5%;
  • Step 2 separation and recovery method 4: heat preservation for 15 min, after the completion of the reaction, the slag is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase, a ferrosilicate-containing mineral phase, a zinc component and lead.
  • the components are subjected to the following steps: (1) a molten copper-rich phase, which is sent to a converter to smelt copper; (2) a molten iron-rich phase and a ferrosilicate-containing method using the method D in the first method: (1) into the slag The oxidizing gas with a preheating temperature of 800 ° C is blown, and the slag temperature is controlled to be higher than 1350 ° C; (2) the slag after oxidation is water quenched and used as cement clinker
  • 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. %, the gold enrichment rate is 95%, and the silver enrichment rate is 97%.
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 slag mixing: adding cold smelting furnace copper smelting slag and flash blowing copper-containing copper slag to the blast furnace, adding blast furnace slag and electric furnace steel slag obtained from the slag outlet to form mixed slag;
  • the preheating temperature is 600 ° C air
  • the spray size is 20 mm bituminous coal and coal powder
  • the mixed slag is heated to a molten state to form a reaction slag containing copper and iron
  • the reaction slag is mixed
  • the slag is obtained by controlling two parameters (a) and (b) to obtain the slag after completion of the reaction; corresponding to (a): the temperature of the reaction slag containing copper and iron is 1330 ° C; (b): copper
  • the ratio of alkalinity CaO/SiO 2 of the reaction slag with iron is 1.0, which is within the required range; the metal iron content in the slag is 2.9%;
  • Step 2 separation and recovery method 3: heat preservation for 10 min, after the reaction is completed, the slag is naturally settled, and the slag-gold is separated to obtain a copper-rich phase and a medium-top iron-containing silicate mineral phase, and at the same time, a zinc-containing and lead-containing component is formed.
  • the following steps are carried out: (1) the molten iron-containing silicate mineral phase, specifically adopting the step 2 separation and recovery method method B, and returning the middle and upper slag to the copper-and iron-containing reaction slag as the hot metallurgical flux.
  • the slag contains copper ⁇ 0.1%, the iron recovery rate is 97%, the zinc recovery rate is 95%, the lead recovery rate is 94%, the gold enrichment rate is 98%, and the silver enrichment. The rate is 96%.
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 slag mixing: the copper-containing smelting slag obtained by the slag smelting smelting slag of the gold peak side blowing pool and the copper-containing blowing slag (converter slag) obtained by the converter slag mouth, and the wet copper slag are added to the side blowing rotary kiln.
  • the molten blast furnace slag and VD slag obtained from the slag outlet are added to form a mixed slag; the mixed slag is heated to a molten state to form a reaction slag containing copper and iron, and the reaction slag is sprayed with argon gas.
  • reaction slag temperature containing copper and iron is 1340 ° C
  • reaction slag basicity CaO/SiO 2 ratio of copper and iron is 1.2, which meets the requirements; the coke particles with a particle size of 20 mm are sprayed with air with a preheating temperature of 1000 ° C, and the content of metallic iron in the slag is 2.5%;
  • Step 2 separation and recovery method 5: heat preservation for 10 min, after the completion of the reaction, the slag is naturally settled, and the slag-gold separation, obtaining a molten copper-rich phase, an iron-rich phase and a medium-top iron-containing silicate mineral phase, and zinc-containing With the lead-containing component, the following steps are carried out: (1) the upper middle slag is separated and recovered in step 2, the middle method C, and the glass ceramics are poured; (2) the lower molten copper-rich phase and the iron-rich phase are sent to the converter (3) Partially containing zinc and lead-containing components, which are recovered as fumes in the form of oxides.
  • the slag contains copper ⁇ 0.1%, the recovery of iron is 93%, the recovery of zinc is 94%, and the recovery of lead is 92%, the gold enrichment rate is 95%, and the silver enrichment rate is 97%.
  • a method for recovering valuable components from a mixed slag containing copper and iron comprising the steps of:
  • Step 1 slag mixing:
  • the molten copper-containing smelting slag flowing out from the slag outlet of the bottom-blow pool melting furnace and the copper-containing blowing slag flowing out of the bottom-blown continuous blowing furnace are added to the heat preservation pit, and the molten converter steel slag obtained by adding the slag mouth is formed to form mixed slag Using oxygen-enriched air with a preheating temperature of 800 ° C, blowing bituminous coal with a particle size of ⁇ 150 ⁇ m, 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, 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 0.9, both within the required range; the metal iron content in the slag is 1.9 %;
  • the slag contains copper ⁇ 0.15%, the iron recovery rate is 98%, the zinc recovery rate is 96%, and the lead recovery rate is 94. %, the gold enrichment rate is 95%, and the silver enrichment rate is 96%.

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Abstract

La présente invention concerne un procédé de récupération de composants de valeur à partir de scories mélangées contenant du cuivre et du fer, le procédé comprenant S1, le mélange de scories; l'ajout de scories de cuivre dans un dispositif de réaction par fusion, et l'ajout simultané d'une ou plusieurs scories choisies parmi des scories de fonderie de plomb, des scories de haut fourneau, des scories d'acier et des scories de ferroalliage pour former des scories mélangées; le chauffage des scories fondues jusqu'à un état fondu pour former des scories fondues de réaction, en mélangeant uniformément, en satisfaisant aux exigences selon lesquelles la température des scories fondues est de 1050 à 1450 °C et le rapport d'alcalinité CaO/SiO2 des scories fondues est égal à 0,15 à 1,5, pour obtenir des scories fondues ayant réagi; S2, une séparation et un recyclage. La récupération de cuivre, de fer, de zinc, de plomb, d'or et d'argent dans des scories métallurgiques non ferreuses et des scories métallurgiques de fer et d'acier est réalisée, et les problèmes associés à une forte accumulation de scories et à la pollution environnementale sont résolus.
PCT/CN2017/115649 2017-10-10 2017-12-12 Procédé de récupération de composants de valeur à partir de scories mélangées contenant du cuivre et du fer Ceased WO2019071794A1 (fr)

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TWI840112B (zh) * 2023-02-07 2024-04-21 威致鋼鐵工業股份有限公司 爐渣廢棄物回收再利用的方法

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