WO2019071795A1 - Manufacturing method using copper-containing slag - Google Patents

Abstract

A manufacturing method using a copper-containing slag, comprising the following steps: S1, slag mixing: putting a copper slag into a reaction device and adding calcium-based minerals and additives, heating the slag into a molten state and adding one or more of a copper oxide mineral, a copper sulphide mineral and a copper-containing material, homogeneously mixing the materials to be used as a reaction slag, and monitoring the reaction slag in real-time, enabling through regulation the reaction slag to meet condition a: the temperature of the reaction slag is controlled to be between 1100 to 1450℃ and also condition b: a CaO/SiO2 basicity ratio of the reaction slag is controlled to be 0.15-1.5, and obtaining a post-reaction slag; and S2, separation and recovery.

Description

Method for producing copper-containing slag Technical field

The invention belongs to the technical field of slag metallurgy, and in particular relates to a method for producing copper slag.

Background technique

During the pyrometallurgical process of copper, a large amount of copper slag is produced. 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. After depletion or flotation dressing, 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. At present, there is no large-scale simultaneous treatment of copper oxide minerals, copper sulfide minerals and other copper-containing iron materials to achieve simultaneous production of copper and iron, which can solve the problem of a large amount of slag accumulation.

Summary of the invention

(1) Technical problems to be solved

In order to solve the above problems of the prior art, 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.

(2) Technical plan

In order to achieve the above object, 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;

Wherein the condition a is controlling the slag temperature to be 1100 to 1450 ° C;

The condition b is a control alkalinity CaO / SiO ₂ ratio of the slag = 0.15 ~ 1.5;

S2, separation and recovery: 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. At the same time, 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.

In the method as described above, preferably, in the step S1, the method for regulating the condition a is:

When 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;

When the temperature of the reaction slag > the upper limit of the set temperature range is 1450 ° C, 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. One or several, so that the temperature of the mixed slag reaches a set temperature of 1100 ~ 1450 ° C;

The method for regulating the condition b is:

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is less than or equal to 0.15, 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. One or several

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >1.5, 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. One or several.

In the method as described above, preferably, 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.

In the above-described method, preferably, in the step S1, while satisfying the conditions a and b, 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%. By adding one or both of a reducing agent, a carbon-containing iron-containing material, wherein the amount of the reducing agent and/or the carbon-containing iron-containing material is reduced to copper and iron oxide in the slag to metal copper And the theoretical amount of FeO is 110-140%; 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.

Preferably, 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 , low-blown furnace smelting slag, side-blown furnace smelting slag, the copper-containing blowing slag is produced in the copper smelting process of the copper smelting process, including converter blowing copper slag, flash furnace blowing copper Slag, Noranda furnace continuous blowing copper slag, top blowing furnace blowing copper slag, side blowing furnace blowing copper slag, bottom blowing furnace blowing copper slag, top blowing furnace continuous blowing copper slag, side blowing furnace continuous blowing The copper slag and the bottom blowing furnace continuously blow copper slag; the depleted waste slag is a copper smelting slag and a copper-containing blowing slag, and then the waste slag is depleted. Is selected from copper smelting slag tailings and the copper-containing slag blowing after beneficiation tailings, wet copper hydrometallurgical slag is waste slag;

Preferably, 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. Or heating the copper-containing smelting slag to a molten state, 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.

Preferably, 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, pickled iron slag, goethite slag, hematite slag, one or more; the lead smelting slag is a smelting furnace Lead-containing smelting slag, "raw furnace 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 to produce lead-containing smelting slag The lead-containing smelting slag is smelted by a smelting furnace to produce a lead-containing smelting furnace slag; the nickel smelting slag is a smelting smelting One or more of the nickel smelting slag produced by the process, the depleted slag after the "copper ice nickel blowing" process, and the nickel slag slag produced by the top blowing smelting; the pyrometallurgical slag is a vertical tank smelting slag, One or more kinds of vortex melting furnace slag, blast furnace slag, smelting furnace slag and electric furnace slag;

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.

In the method as described above, preferably, in the separation and recovery in the step S2, 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.

Specifically, 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:

S2-1-01, the iron-containing silicate mineral phase, is subjected to any one of the following methods A-G;

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:

E-1, adding molten steel slag, lime, limestone, iron alloy slag, fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud to the slag containing iron silicate mineral phase One or more of high calcium red mud or calcium carbide slag after sodium removal, fully mixed to obtain a slag mixture;

E-2, blowing an oxidizing gas with a preheating temperature of 0-1200 ° C into the upward slag mixture, and ensuring that the slag mixture temperature is >1450 ° C; when the weight percentage of ferrous oxide is <1%, oxidation is obtained. After the slag;

E-3, 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;

After the slag is poured into the heat preservation device, 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;

Further, when 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:

G-1, adding iron-containing material and reducing agent to the molten iron-containing silicate slag, performing smelting reduction, monitoring the reaction slag in real time, and satisfying the condition by regulation: 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;

Among them, the method of controlling the temperature of the reaction slag is:

When 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;

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:

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is less than 0.6, an alkaline material and/or an alkaline iron-containing material is added to the slag;

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >2.4, an acidic material and/or an acidic iron-containing material is added to the slag;

G-2, in the G-1, in the smelting reduction, the oxidizing gas preheated by 0 to 1200 ° C is sprayed into the slag to be smelted and reduced to form a reduced slag;

G-3, separation and recovery: use one of the following methods:

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 μm, 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;

S2-1-02, 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;

S2-1-03, part of the zinc-containing component and the lead-containing component volatilize, and enter the soot recovery in the form of oxide;

S2-1-04, part of the gold-containing component and the silver-containing component enter the copper-rich phase;

S2-1-05, 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;

Wherein, in the direct reduction process, after 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 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 , control reduction temperature is 900 ~ 1400 ° C, control alkalinity CaO / SiO ₂ ratio = 0.8 ~ 1.5; the gas produced by reduction is burned on the surface of the slag, providing heat, and the gas flowing out of the furnace can be used as drying The heat source of the charge and the heat preservation device.

In addition, since 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:

S201, sedimentation cooling: 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 For the iron-rich phase, 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;

S202. Separation: manually extracting the copper-rich bismuth deposited at the bottom, or separating the metal iron by the copper-filled mash, and then sending it to the converter or the smelting furnace for copper smelting, or separating the metal iron by magnetic separation or separating the metal without magnetic separation. After iron, direct reduction, the reduction product is separated by magnetic separation and then sent to a converter or a rotary furnace for copper smelting; the iron-rich phase and the iron-containing silicate phase are used as raw materials for blast furnace ironmaking or direct reduction of ironmaking raw materials. Or 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 With iron concentrate, copper concentrate returns to copper smelting system, iron concentrate as blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material;

S203, manually taking out the upper iron-containing silicate mineral phase, obtaining a silicate phase as a blast furnace ironmaking raw material or directly reducing ironmaking raw materials or smelting reduction ironmaking raw materials or cement raw materials;

S204, part of the zinc component and the lead component are volatilized, and enter the soot recovery in the form of oxide;

S205. When adding raw materials such as red mud or dust mud and steel soot, part of the indium component, the strontium component, the potassium component and the sodium component are volatilized and enter the soot recovery.

Preferably, 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. One or more of 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 μm, the liquid fuel and the reducing agent are heavy oil, and the gaseous fuel and the reducing agent are gas and/or natural gas.

In the above method, preferably, in the step S1, 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. One or more of gas agitation, oxidizing gas, electromagnetic stirring or mechanical agitation;

In the step S2, 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.

Compared with the prior art, the features of the invention are:

(1) 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.

(2) 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;

(3) 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;

(4) 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;

(6) Separating and accumulating copper-rich phase and iron-rich phase in different parts by manual sorting, magnetic separation, re-election or slag-gold separation to achieve efficient recovery of copper and iron components in the slag;

(7) 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;

(8) Adding an additive to the method of the present invention, one for reducing the viscosity, the other for lowering the melting point, and contributing to the precipitation of the copper-rich phase at a certain temperature (1100-1450 ° C), and the iron-rich phase after sedimentation and separation 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;

(9) 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.

(3) Beneficial effects

The beneficial effects of the invention are:

(1) The invention consists of a copper-containing slag or slag, which constitutes a mature slag system. Through 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.

(2) 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.

(3) 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,

(4) 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.

(5) In the method of the invention, 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.

(6) During the natural cooling process of the method of the present invention, 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. Set in the iron-rich phase, and achieve aggregation, growth and settlement, 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. Accelerate the accumulation, growth and sedimentation of the copper-rich phase and the iron-rich phase; 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 are collected into the dust to be recovered.

(7) 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.

(8) 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;

(9) 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.

Detailed ways

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;

(a) the temperature of the copper-containing reaction slag is 1100 ~ 1450 ° C;

(b) alkalinity CaO / SiO ₂ ratio of copper-containing reaction slag = 0.15 ~ 1.5;

The control method is:

Corresponding to (a):

The method for controlling the temperature of the reaction slag in the set temperature range is:

When the temperature of the copper-containing reaction slag < the lower limit of the set temperature range is 1100 ° C, 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;

When the temperature of the copper-containing reaction slag is higher than the upper limit of the set temperature range of 1450 ° C, 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. One or more of the materials, so that the temperature of the mixed slag reaches a set temperature range of 1100 to 1450 ° C;

Corresponding to (b):

When the ratio of alkalinity CaO/SiO ₂ in the copper-containing reaction slag is less than or equal to 0.15, 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. One or several

When the ratio of alkalinity CaO/SiO ₂ in the copper-containing reaction slag is >1.5, 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. One or several

Step 2, separate and recycle:

After the reaction is completed, 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;

Use one of the following methods:

Method 1: When the slag can flow out of the smelting reaction device, the slag after the completion of the reaction is subjected to the following steps:

(1) a molten iron-containing silicate mineral phase, which is subjected to slag treatment;

(2) molten copper-rich phase, sent to converter or blowing furnace for copper smelting or crushing magnetic separation of metal iron and then sent to converter or blowing furnace for copper smelting, or magnetic separation to separate metal iron or without magnetic separation After the metal iron is directly reduced, the reduced product is separated by magnetic separation and then sent to a converter or a blowing furnace for copper smelting;

(3) part of the lead component, the zinc component, the indium component, the strontium component, the sodium component, and the potassium component are volatilized into the soot recovery oxide into the soot;

(4) 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, gas-based reduction to natural gas and / or gas, coal-based reduction to anthracite, bituminous coal, lignite, coking coal One or more of coke powder or coke, the reduction temperature is 900-1400 ° C, and the alkalinity CaO/SiO ₂ ratio is 0.8-1.5.

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:

Method A: 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:

(1) blowing a preheated oxidizing gas into the iron-containing silicate slag in the smelting reaction device, and when the slag oxidized ferrous oxide content is less than 1%, the oxidation of the slag is completed to obtain oxidation. After the slag, wherein the preheating temperature of the oxidizing gas is 0 to 1200 ° C; and throughout the process, to ensure (c) silicate slag temperature > 1450 ° C;

Corresponding to (c) the control method adopted:

When the temperature of the iron-containing silicate slag is <1450 ° C, 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;

(2) The slag after oxidation is directly air-cooled or water-quenched, 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:

(1) adding molten steel slag, lime, limestone, iron alloy slag, fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, to the iron-containing silicate slag in the smelting reaction device. One or more of red mud or calcium carbide slag after de-sodium removal, thoroughly mixed to obtain a slag mixture;

(2) blowing a preheated oxidizing gas into the slag mixture, and when the weight percentage of the ferrous oxide is <1%, the oxidation of the slag is completed to obtain the oxidized slag, wherein the oxidizing gas is preheated. The temperature is 0-1200 ° C; and in the whole process, ensure (d) slag mixture temperature > 1450 ° C; temperature control method and method D step (1) silicate slag temperature control method;

(3) slag after oxidation, air cooling or water quenching, to obtain high value-added cement clinker;

Method F:

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;

Or after pouring the slag containing the iron silicate mineral phase into the heat preservation device, 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;

Method G: Iron-containing silicate slag smelting reduction ironmaking:

(1) The iron-containing silicate slag in the smelting reaction device, or the iron-containing material is added, the reducing agent is added to the slag, and the smelting reduction is performed, and the reaction slag is monitored in real time, and the following (a) and (b) are ensured through regulation. ) two parameters to obtain the slag after the completion of the reaction;

(a) the temperature of the reaction slag is 1350 ~ 1450 ° C;

(b) the alkalinity of the reaction slag CaO / SiO ₂ ratio = 0.6 ~ 2.4;

The control method is:

Corresponding to (a):

The method for controlling the temperature of the reaction slag in the set temperature range is:

When the temperature of the reaction slag is lower than the lower limit of the set temperature range, 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;

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. ;

Corresponding to (b):

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is less than 0.6, an alkaline material and/or an alkaline iron-containing material is added to the slag;

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >2.4, an acidic material and/or an acidic iron-containing material is added to the slag;

(2) smelting and reducing the oxidizing gas after preheating into the slag to form a reduced slag, wherein: the oxidizing gas is preheated at a temperature of 0 to 1200 ° C, and is passed during the blowing process. Regulation also guarantees two parameters (a) and (b):

(a) the temperature of the slag after completion of the reaction is 1350 ~ 1650 ° C;

(b) the alkalinity of the slag after the completion of the reaction CaO / SiO ₂ ratio = 0.6 ~ 2.4;

Wherein, the temperature range and the alkalinity control method are the same as the method G step (1);

(3) Separation and recovery:

Use one of the following methods:

Method I: Perform the following steps:

(a) cooling: the reduced mixed slag is poured into a holding slag pot, and cooled to room temperature to obtain a slow cooling slag;

(b) Separation: metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out;

Containing a metal iron layer, crushed to a particle size of 20-400 μm, grinding, magnetic separation to separate the remaining metal iron and tailings;

(c) recycling of tailings, used as cement raw materials, building materials, instead of crushed stone as aggregates and road materials;

Method II: Perform the following steps:

(a) the mixed slag after reduction, cooling and sedimentation, separation of slag-gold, obtaining molten iron and reduced slag;

(b) the slag after the reduction, the slag treatment outside the furnace, 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;

(c) molten iron, sent to converter or electric furnace steelmaking;

(d) the zinc-containing component and the lead-containing component are volatilized, and are collected into the dust as an oxide;

(e) part of the indium component, the bismuth component, the sodium component, and the potassium component are volatilized into the soot;

(f) 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 2: When the smelting reaction device through which the slag can flow out is used, the slag after the completion of the reaction is subjected to the following steps:

(1) molten copper-rich phase, sent to converter copper or bake furnace for copper smelting, or crushed magnetic separation of metal iron and then sent to converter or blowing furnace for copper smelting, or magnetic separation of metal iron or not After magnetic separation and separation of metallic iron, the reduction product is directly separated by magnetic separation, and then sent to a converter or a rotary furnace for copper smelting; (2) the molten iron-rich phase layer and the iron-containing silicate mineral phase are treated. The method is treated by one or more of the methods A to G described in the first method;

(3) part of the zinc-containing component and the lead-containing component volatilize, and enter the soot recovery in the form of oxide;

(4) Some of the indium, antimony, sodium and potassium components are volatilized into the soot.

Method 3: When the smelting reaction device through which the slag can flow out is used, the slag after the completion of the reaction is subjected to the following steps:

After the completion of the reaction, the slag is cooled and settled, and the slag-gold is separated to obtain a copper-rich phase iron-rich phase and a middle-upper molten iron-containing silicate mineral phase, thereby forming a zinc-containing component and a lead-containing component, as follows: step:

(1) 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;

(2) After the molten copper-rich phase is poured into the heat preservation device and slowly cooled, it is sent to a converter or a blowing furnace for copper smelting, or the metal iron is separated by crushing and magnetic separation, and then sent to a converter or a blowing furnace for copper smelting, or magnetic separation. Separating metal iron or separating metal iron without magnetic separation, directly reducing, reducing product by magnetic separation to separate metal iron, and then sending it to converter or blowing furnace for copper smelting;

(3) The iron-rich phase is treated by the step (4) in the first method;

(4) Part of the indium, antimony, sodium and potassium components volatilize and enter the soot;

Method 4: When the smelting reaction device through which the slag can flow out is 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 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;

(2) molten copper-rich phase, sent to converter or blowing furnace for copper smelting, or slow cooling, crushed magnetic separation of metal iron and then sent to converter or blowing furnace for copper smelting or magnetic separation to separate metal iron or not After magnetic separation of metal iron, direct reduction, reduction products are separated by magnetic separation and then sent to converter or blowing furnace for copper smelting

(3) Some lead, zinc, indium, antimony, sodium and potassium components are volatilized into the soot; Method 5:

When the heat preservation device is used, or when the slag is poured into the heat preservation device by using the smelting reaction device through which the slag can flow out, the slag after the reaction is completed is as follows:

(1) Settling cooling: the slag after the reaction is 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 bismuth; the iron-containing silicate mineral phase floats; copper-rich white ice The slow cooling slag between the copper phase metal lanthanum and the iron-containing silicate mineral is an iron-rich phase, and at the same time, a zinc-containing component and a lead-containing component are formed; the gold-silver component migrates to the copper-rich phase;

(2) Separation: manually take out the copper-rich bismuth deposited at the bottom, magnetically separate the metal iron and then send it to the converter or the smelting furnace for copper smelting, or separate the metal iron by crushing and then send it to the converter or the smelting furnace for copper smelting. , or 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 converter or blowing furnace copper; the iron-rich phase layer in the middle as a blast furnace The ironmaking raw material or the direct reduction ironmaking raw material or the smelting reduction ironmaking raw material or the flotation copper extraction raw material or the magnetic separation and separation of the metallic iron is used as a raw material for copper smelting or direct reduction; in the flotation process, the flotation product is copper-containing fine Mine and iron concentrate, copper concentrate returned to copper smelting system, iron concentrate as blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, after the reduction product is magnetically separated, Obtaining metal iron and tailings, and tailings returning to the copper smelting system; the direct reduction process adopts 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 uses a gas-based or coal-based reduction Technology, gas-based reduction using days Gas and / or gas, coal-based reduced using one or more of anthracite, bituminous coal, lignite, coke, coke breeze or coke, controlled reduction temperature is 900 ~ 1400 ℃, controlling basicity CaO / SiO ₂ ratio = 0.8 1.5;

(3) Manually take out the upper iron-containing silicate mineral phase as a blast furnace ironmaking raw material or directly reduce ironmaking raw materials or smelting reduction ironmaking raw materials or as cement raw materials, building materials, instead of crushed stone as aggregates and road materials. ;

(4) Part of the lead component, the zinc component, the indium component, the bismuth component, the sodium component, and the potassium component are volatilized into the soot oxide.

In the method as described above, preferably, in the steps 1 and 2, 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 copper slag, Noranda furnace continuous blowing copper slag, top blowing furnace blowing copper slag, side blowing furnace blowing copper slag, bottom blowing furnace blowing copper slag, top blowing furnace continuous blowing The copper slag and the side blowing furnace continuously blow copper slag, and the bottom blowing furnace continuously blows copper slag; the depleted waste slag is copper smelting slag and copper After refining slag depleted waste slag flotation tailings of copper smelting slag and copper slag blowing after beneficiation tailings, wet copper hydrometallurgical slag is waste slag;

Preferably, 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. Or heating the copper-containing smelting slag to a molten state, 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;

In the steps 1 and 2, 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. Bottom blowing pool melting furnace, top blowing molten pool melting furnace, reverberatory furnace, Osmet furnace, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing back Electric heating front bed of converter and copper melting furnace.

In the step 1, 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;

In the step 1, 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;

In the step 1, 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. %. 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.

In the steps 1 and 2, 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 iron slag, goethite slag, and hematite slag; the lead smelting slag is smelting furnace slag and Lead smelting slag, "raw furnace Zn blast furnace reduction" or "sinter blast furnace reduction" or "solid high lead slag reduction" or "liquid high lead slag reduction process" reduction process to produce lead-containing smelting slag, said lead smelting The slag is smelted by a smelting furnace to produce a lead-containing smelting furnace slag; the nickel smelting slag is produced by a "smelting smelting" process One or more of smelting slag, depleted slag after blowing in "copper ice nickel blowing" process, and nickel slag slag generated by top blowing smelting; vertical smelting zinc slag is pyrometallurgical slag, vortex melting furnace slag, One or more of blast furnace slag, smelting furnace slag and electric furnace slag;

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.

Among the above raw materials, zinc smelting slag and soot, lead smelting slag and soot contain indium and antimony, lead, silver, zinc, 赤; 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.

In the steps 1 and 2, 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 μm, 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). ;

In the steps 1 and 2, 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;

In the steps 1 and 2, during the slag reaction, 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.

In the steps 1 and 2, 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:

When 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.

In the steps 1 and 2, when the alkalinity is adjusted, 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.

In the steps 1 and 2, when the alkalinity is adjusted, the acidic material is one or more of silica, fly ash and coal gangue; the acidic iron-containing material is CaO/SiO ₂ ≤1. One or more of iron-containing materials, acid sinter, acid iron concentrate, acid pre-reduction pellets, acid metallized pellets, copper slag, lead smelting slag, zinc smelting slag, and nickel smelting slag;

In the step 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. One or more of mixed gas agitation, reducing gas agitation, oxidizing gas, electromagnetic stirring, mechanical agitation, gas preheating temperature is 0 to 1200 ° C;

In the steps S1 and S2, 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.

In the steps 1 and 2, 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;

In the steps 1 and 2, the oxidizing gas is one of air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen, and 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;

In the step 2, 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;

In the step 2, the cooling mode is natural cooling or rotary cooling or centrifugal cooling, and the sedimentation mode is natural sedimentation or rotary sedimentation or centrifugal sedimentation;

In the step 2, 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.

In the step 2 described above, 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.

In the step 2, 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.

In the step 2 described, 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.

The invention will be described in detail by way of specific embodiments in order to explain the invention. Wherein, the detection methods and raw materials used in the following examples are not specifically indicated, and the conventional techniques in the art can be employed. Unless otherwise stated, the percentages used in the present invention are all by weight.

Example 1

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. Two parameters, 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. ≤ Refractory sprayed copper slag, copper-containing soot, copper and copper-containing garbage and copper-containing circuit boards, and added blast furnace gas mud, electric furnace dust, converter dust, ordinary iron concentrate direct reduced iron and blast furnace gas ash, The temperature is lowered to 1380 ° C; (b): the alkalinity CaO / SiO ₂ ratio of the copper-containing reaction slag = 2.6, a mixture of silica, fly ash and coal gangue is added to the reaction slag to make the copper-containing reaction slag base Degree ratio decreased to 1.3; metal iron content in slag 0.6%;

Step 2, separation and recovery method 1:

After 48 min of heat preservation, 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. To enter the soot recovery in the form of oxides, 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. In the process of direct reduction of iron raw materials, 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%. Bismuth recovery was 94%, 95% recovery of sodium, potassium recovery was 96%, 96% enrichment of gold, silver was 94% enrichment. In all the embodiments of the present invention, 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.

Example 2

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. Concentrate; with 600 ° C of oxygen-enriched air, natural gas, 20 mm anthracite and coke particles, the mixed slag is heated to a molten state to form a copper-containing reaction slag; real-time monitoring of the reaction slag, through regulation and assurance ( a) and (b) two parameters, obtaining the slag after the completion of the reaction;

Corresponding to (a) 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; (b) 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:

After 10 min of heat preservation, the slag after the reaction is completed, and the slag-gold separation, the molten copper-rich phase layer, the molten iron-rich phase and the molten iron-containing silicate mineral phase are obtained, and the zinc component and the lead component are simultaneously formed. With the indium component, enter the soot and recover as oxide, proceed as follows:

(1) melting the iron-containing silicate mineral phase and the iron-rich phase, pouring into the thermal insulation slag tank, using the method G in the first method to carry out the external slag treatment, and the iron-containing silicate slag smelting and reducing the ironmaking, the specific steps as follows:

(1-1) adding anthracite and bituminous coal with a particle size of 20mm to the iron-containing silicate slag, performing smelting reduction, monitoring the reaction slag in real time, and ensuring the following (a) the temperature of the reaction slag is 1450 to 1450 ° C by regulation. And (b) the ratio of the alkalinity CaO/SiO ₂ ratio of the reaction slag = 0.6 to 2.4, and the slag after completion of the reaction is obtained;

Corresponding to (a): the temperature of the reaction slag is 1480, in the temperature range;

Corresponding to (b): when the ratio of alkalinity CaO/SiO ₂ in the reaction slag is 0.8, in the range of alkalinity;

(1-2) Spraying an oxidizing gas (oxygen-enriched air) preheated at 200 ° C into the slag to perform smelting reduction to form a mixed slag after reduction, and ensuring (a) during the blowing process The temperature of the reaction slag is 1450 to 1450 ° C, and (b) the ratio of alkalinity CaO / SiO _{2 of the} reaction slag = 0.6 to 2.4,

(1-3) Separation and recovery:

(a) the mixed slag after reduction, natural cooling and sedimentation, separation of slag-gold, obtaining molten iron and reduced slag;

(b) The slag after reduction is processed into a high value-added cement raw material by the method A in the method of the second step;

(c) molten iron, sent to converter or electric furnace steelmaking;

(d) the zinc-containing component, the lead-containing component, the antimony component and the indium component are volatilized, and are collected into the soot as an oxide;

(e) The sodium-containing component and the potassium-containing component are volatilized and enter the soot recovery;

(2) molten copper-rich phase, sent to converter copper smelting;

(3) 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%.

Example 3

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;

Corresponding to (a): 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; (b): alkalinity CaO / SiO containing copper reaction slag ₂ ratio = 1.3, adding quartz sand, red mud, wet zinc smelting kiln slag mixture to the reaction slag, so that the alkalinity ratio of the copper-containing reaction slag is reduced to 1.6; the copper oxide content in the slag is less than 0.1% slag metal iron content (wt%) = 0.8%; slag metal iron content is 3%;

Step 2, separation and recovery method 4:

After 20 min of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold separation, obtaining a molten copper-rich phase, a molten iron-rich phase and a molten iron-containing silicate mineral phase, and simultaneously forming a zinc-containing component and a lead-containing group Divide into the soot and recycle it in the form of oxides. Perform the following steps:

(1) molten copper-rich phase, sent to converter copper smelting;

(2) The iron-rich phase and the iron-containing silicate mineral phase are separated by the step (4) in the first method:

After magnetic separation of metal iron, as a direct reduction ironmaking raw material, the reduction product is magnetically separated to obtain metallic iron and tailings; during the reduction process, part of the zinc component and lead component volatilize to form fumes into the soot; direct reduction process In the middle, the rotary hearth furnace is used, the reduction temperature is 1200 ° C, the alkalinity CaO / SiO ₂ ratio = 1.0, and the reducing agent is the coal powder having the particle size ≤ reducing agent as granule;

(3) 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% .

Example 4

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. And (b) two parameters to obtain the slag after completion of the reaction;

Corresponding to (a) 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; (b) 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:

After 35 minutes of heat preservation, 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 a zinc-containing component and a lead-containing group are simultaneously formed. Divide into the soot and recycle it in the form of oxides. Perform the following steps:

(1) molten copper-rich phase, sent to converter copper smelting;

(2) The iron-rich phase and the iron-containing silicate mineral phase are subjected to the method I in the first method, oxidatively modified magnetic separation; 1 the slag is poured into the thermal insulation slag tank, and the oxygen-rich preheating temperature is 900 ° C. Air, complete magnetite conversion; 2 slow cooling to room temperature, magnetic separation to obtain iron concentrate and tailings;

(3) Some zinc-containing components, antimony components, indium components and lead-containing components volatilize and enter the soot recovery in the form of oxides. 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%.

Example 5

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. °C oxygen-enriched air, spray particle size ≤ oxygen-enriched air, bituminous coal, 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;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1430 ° C; (b): 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 %;

Step 2, separation and recovery method 5:

The slag after the completion of the reaction is subjected to the following steps:

(1) 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;

(2) Separation: manually extracting the copper-rich strontium deposited at the bottom, directly reducing, magnetically separating the iron, the product is sent to the converter; the iron-rich phase in the middle is directly sent to the converter for copper smelting;

(3) manually taking out the upper iron-containing silicate mineral phase to obtain silicate tailings, which are used as cement raw materials;

(4) Part of the zinc component and the lead component volatilize, and enter the soot as oxide to recover. 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%.

Example 6

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. Lime, MgO, Al ₂ O ₃ , Fe ₂ O ₃ , forming mixed slag, adding copper sulfide concentrate and pyrometallurgical refining slag; heating the mixed slag to a molten state to form copper-containing reaction slag, spraying Argon gas, and the reaction slag is mixed; the reaction slag is monitored in real time, and two parameters (a) and (b) are simultaneously controlled to obtain the slag after completion of the reaction;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1080 ° C, the electric arc furnace is heated to raise the temperature to 1330 ° C; (b): 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:

After immersion for 25 min, 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:

(1) The iron-containing silicate mineral phase is separated and recovered in the first method, Method A, and water quenching is directly used as the cement raw material;

(2) molten copper-rich phase, sent to converter copper smelting;

(3) The iron-rich phase is poured into the heat preservation device to directly reduce the iron-making after cooling;

(4) 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%.

Example 7

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;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1320 ° C; (b): 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:

After 48 minutes of heat preservation, 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 a zinc component and a lead component are simultaneously formed. To enter the soot and recycle it in the form of oxides, proceed as follows:

(1) molten copper-rich phase, sent to converter copper smelting;

(2) the molten iron-rich phase and the iron-containing silicate mineral are subjected to the method B in the first method, and returned to the reaction slag;

(3) Part of the zinc-containing component and the lead-containing component volatilize and enter the soot recovery in the form of oxide. 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%.

Example 8

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);

Corresponding to (a): the temperature of the copper-containing reaction slag is 1330 ° C; (b): 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 %;

Step 2, separation and recovery method 3:

After 30 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-containing silicate mineral phase in the copper-rich phase and the upper middle portion, and at the same time, a zinc-containing component and a lead-containing component are formed, and the dust is entered. To recover as oxide, proceed as follows:

(1) molten iron-containing silicate mineral phase slag, poured into a smelting device, and subjected to slag treatment outside the furnace, specifically using the separation and recovery method B of step 2, and returning all the iron silicate mineral phase slag to the slag Copper-containing reaction slag, as a hot metallurgical flux, adjusting the composition of the copper-containing reaction slag to control the temperature of the copper-containing reaction slag;

(2) molten copper-rich phase, iron-rich phase, sent to converter or blowing furnace for copper smelting;

(3) Some zinc-containing components and lead-containing components volatilize, oxides are recovered into soot, slag contains copper <0.1%, iron recovery rate is 93%, zinc recovery rate is 94%, and lead recovery rate is 95. %, sodium recovery rate is 95%, potassium recovery rate is 96%, gold enrichment rate is 98%, and silver enrichment rate is 96%.

Example 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;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1340 ° C; (b): 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:

After 47 min of heat preservation, the slag after the completion of the reaction was naturally settled, and the slag-gold was separated to obtain a copper-rich phase and a middle-upper portion. 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:

(1) The middle and upper slag is poured into the smelting device, and the medium and upper slag is poured into the glass ceramics by the method C in the separation and recovery method 1 of the step 2;

(2) The lower molten copper-rich phase and the iron-rich phase are sent to the converter for copper smelting;

(3) Part of the zinc-containing component and the lead-containing component enter the smoke as an oxide;

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%.

Example 10

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;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1430 ° C; (b): 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 %;

Step 2, separation and recovery method 5:

The slag after the completion of the reaction is subjected to the following steps:

(1) Settling cooling: After 40 minutes of heat preservation, 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 metal lanthanum and the silicate mineral is an iron-rich phase, and at the same time, a zinc-containing component and a lead-containing component are formed;

(2) Separation: manually extracting the copper-rich strontium deposited at the bottom; after the direct reduction of the iron-rich phase layer in the middle, the metal iron is separated by magnetic separation, and the tailings are returned to the copper system;

(3) manually taking out the upper iron-containing silicate mineral phase to obtain silicate tailings, which are used as cement raw materials;

(4) Some zinc components and lead components volatilize, oxides are recovered into soot, slag contains copper <0.1%, iron recovery is 95%, zinc recovery is 96%, and lead recovery is 94%. The gold enrichment rate is 95%, and the silver enrichment rate is 96%.

The above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any person skilled in the art may use the above-disclosed technical contents to change or modify the equivalent equivalent. Example. However, any simple modifications, equivalent changes and modifications made to the above embodiments in accordance with the technical spirit of the present invention are still within the scope of protection of the technical solutions of the present invention.

Claims (10)

A method of producing copper-containing slag, characterized in that it comprises the following steps: S1, slag mixing: adding copper slag to the reaction device, adding calcium minerals and additives; heating the slag to a molten state, adding one or more of copper oxide minerals, copper sulfide minerals, and copper-containing materials; Mixing uniformly, as reaction slag, and monitoring the reaction slag in real time, and 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; Wherein the condition a is controlling the reaction slag temperature to be 1100 to 1450 ° C; The condition b is a ratio of alkalinity CaO / SiO ₂ ratio of the reaction slag = 0.15 to 1.5; S2, separation and recovery: the slag after the reaction in the step S1 is kept for 5 to 50 minutes, and the copper-rich phase at the bottom, the iron-rich phase in the middle and lower portions, and the iron-containing silicate mineral phase in the middle and upper portions are obtained by sedimentation and separation, and simultaneously The zinc component and the lead-containing component of the soot, the gold and silver components migrate and enrich into the copper-rich phase; the phases are recovered. The method according to claim 1, wherein in said step S1, said condition a is regulated by: When the temperature of the reaction slag is <1100 ° C, the heating of the reaction device itself is used, or fuel or molten copper slag is added to the reaction slag, so that the temperature of the reaction slag reaches 1100 to 1450 ° C, and the fuel is injected while spraying. Into the preheated oxidizing gas; When the temperature of the reaction slag is >1450 ° C, one or more of a copper-containing material, a metallurgical flux, an iron-containing material, a copper oxide mineral, a gold-silver-containing material, or a fluorine-containing material are added to the reaction slag. , the temperature of the mixed reaction slag is reached 1100 ~ 1450 ° C; The method for regulating the condition b is: When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is less than or equal to 0.15, 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. One or several When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >1.5, 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. One or several. The method according to claim 1, wherein said reaction device is a heat retention device or a rotatable smelting reaction device or a smelting reaction device with slag or iron slag flowing out; wherein said heat retention device Pit filling or insulation pit for pourable smelting reaction; 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 method according to claim 1, wherein in said step S1, while satisfying said conditions a and b, it is simultaneously satisfied to control reduction of copper oxide and iron oxide in said reaction slag to Metallic copper and FeO, the metal iron content in the slag is <3%. The method according to claim 1, wherein the copper slag is one or more of copper-containing smelting slag, copper-containing blowing slag, depleted slag, flotation tailings, and wet copper slag. 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 Nolanda 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 fire smelting process, including converter blowing copper slag, flashing speed Furnace blowing copper slag, Nolanda furnace continuous blowing copper slag, top blowing furnace blowing copper slag, side blowing furnace blowing copper slag, bottom blowing furnace blowing copper slag, top blowing furnace continuous blowing copper slag, side The copper slag is continuously blown by the blowing furnace, and the copper slag is continuously blown by the bottom blowing furnace; the depleted waste slag is copper-containing smelting slag and copper-containing blowing slag After the slag is discarded, the flotation tailings are the tailings after the beneficiation of the copper-containing smelting slag and the copper-containing blowing slag. Wet copper slag is a waste slag of wet copper smelting; 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 copper smelting furnace in the process of “smelting smelting”, or The copper-containing smelting slag is heated 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 to a molten state; the molten copper fire method is depleted and discarded The slag 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 method according to claim 2, wherein the copper-containing material is copper slag, copper-selective 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, coarse lead fire refining slag, lead smelting soot and dust, lead acid battery, copper smelting soot and dust, copper, copper containing garbage, copper-containing circuit board, tin One or more of smelting slag, nickel smelting slag, and tin tailings; wherein the zinc smelting slag comprises slag produced by wet zinc smelting and slag produced by pyrometallurgical slag, wherein slag produced by wet zinc smelting It is one or more of zinc leaching residue, volatile kiln residue, iron slag residue, copper cadmium slag, pickled iron slag, goethite slag, and hematite slag; the lead smelting slag is smelting furnace slag and Lead-containing smelting slag, "raw furnace 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 to produce lead-containing smelting slag, said lead-containing The smelting slag is smelted by a smelting furnace to produce lead-containing smelting furnace slag; the nickel smelting slag is "smelting smelting" One or more of the nickel smelting slag produced by the process, the depleted slag after the "copper ice nickel blowing" process, and the nickel slag slag produced by the top blowing smelting; the pyrometallurgical slag is a vertical tank zinc smelting Slag, vortex smelting slag, smelting furnace slag, blast furnace slag, electric furnace slag one or more; 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 state or a cold state, wherein the hot material is directly obtained from a metallurgical furnace discharge port or a slag outlet; The fluorine-containing material is one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag; The fuel is one or more of a solid, liquid or gaseous fuel, which is injected by spraying or feeding, and is loaded with a gas of 0 to 1200 ° C, which is an oxidizing gas, argon gas, nitrogen gas. One or more of the above; 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 material is one or more of lime powder, red mud, red mud after desoda, calcium carbide slag, dolomite powder or quicklime powder; the basic iron-containing material is CaO/SiO ₂ >1 One or more of iron-containing materials, alkaline sintered ore, alkaline iron concentrate, iron alloy slag, steel slag, alkaline pre-reduction pellets, alkaline metallized pellets, steel slag or blast furnace slag; The acidic material is one or more of silica, fly ash and coal gangue; the acidic iron-containing material is 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 method according to any one of claims 1 to 6, wherein the step S2 is separated and recovered, and the following processing is performed: Containing the copper-rich phase in a hot or cold state, sent to a converter or a blowing furnace for copper smelting or slow cooling and magnetic separation to separate the metal iron, and then sent to a converter or a blowing furnace for copper smelting or magnetic separation to separate metal iron or not After separation of the metal iron by magnetic separation, the reduction product is directly separated by magnetic separation, and then sent to a converter or a blowing furnace for copper smelting; The zinc-containing component and the lead-containing component enter the soot as an oxide; The iron-containing silicate mineral phase and/or the iron-rich phase is subjected to any of the following methods A-G; Method A: directly after water quenching or air cooling, used for cement raw materials; Method B: part or all of the iron-containing silicate mineral phase and/or the iron-rich phase is returned to the reaction slag as a hot metallurgical flux; Method C: for pouring glass ceramics or as slag wool; Method D: The iron-containing silicate mineral phase and/or the iron-rich phase remains in the smelting reaction device or is poured into the heat preservation device, and the preheating at a temperature of 0 to 1200 ° C is blown into the slag. Oxidizing gas, and ensure that the slag temperature is >1450 ° C; when the slag oxidized ferrous iron content percentage <1%, the oxidized slag is obtained; the oxidized slag is directly air-cooled or water quenched, used as slag cement , cement conditioner, additive in cement production or cement clinker; Method E, for producing high value-added cement clinker, the method is as follows: E-1, retaining the iron-containing silicate mineral phase and/or the iron-rich phase in the smelting reaction device or pouring the slag into the heat preservation device, and adding molten steel slag, lime, limestone, One or more of ferroalloy slag, fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, red mud after desoda or calcium carbide slag, thoroughly mixed to obtain slag mixture; E-2, the slag mixture mixture is blown into an oxidizing gas having a preheating temperature of 0 to 1190 ° C, and the temperature of the slag mixture is >1440 ° C; when the weight percentage of ferrous oxide is <1%, the oxidation is obtained. Slag E-3, performing air cooling or water quenching on the oxidized slag to obtain a high value-added cement clinker; Method F: the iron-containing silicate mineral phase and/or the iron-rich phase slag as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: an iron-containing silicate mineral phase and/or the iron-rich phase After the slag is air-cooled, water-quenched or slow-cooled, it is used as a blast furnace ironmaking or direct reduction ironmaking raw material. After direct reduction, magnetic separation or electric furnace melting is used, and the magnetic separation product is metal iron and tailings, and the electric furnace is melted. The product is molten iron and slag; Or after pouring the iron-silicate-containing mineral phase and/or the iron-rich phase slag into the heat preservation device, separating by the following method: magnetic separation after slag modification: slag into the heat preservation device , blowing a preheated oxidizing gas at 0-1200 ° C, and ensuring that the slag temperature is >1250 ° C, completing the conversion of magnetite in the slag; slowly cooling the oxidized slag to room temperature, crushing, magnetic Selected, the product is magnetite concentrate and tailings, tailings as building materials; Method G: The iron-containing slag is subjected to reduction ironmaking, comprising the following steps: G-1, retaining the iron-containing silicate mineral phase and/or the iron-rich phase slag in the smelting reaction device or pouring the slag into the heat preservation device, and adding the iron-containing material to the molten slag The reducing agent is subjected to smelting reduction, and the reaction slag is monitored in real time, and the conditions are satisfied by the regulation: the temperature of the reaction slag is 1350 to 1650 ° C and the alkalinity of the reaction slag is CaO / SiO ₂ ratio = 0.6 to 2.4, and the reaction is completed. After the slag; Among them, the method of controlling the temperature of the reaction slag is: When 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 1350 ~ 1650 ° C; When the temperature of the reaction slag is >1350 ° 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 1350 to 1650 ° C; wherein The metallurgical flux is a mineral containing CaO or SiO ₂ ; The method of controlling the alkalinity of the reaction slag is: When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is less than 0.6, an alkaline material and/or an alkaline iron-containing material is added to the slag; When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >2.4, an acidic material and/or an acidic iron-containing material is added to the slag; G-2, in the G-1, in the smelting reduction, the oxidizing gas preheated by 0 to 1200 ° C is sprayed into the slag to be smelted and reduced to form a reduced slag; G-3, separation and recovery: use one of the following methods: 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 μm, 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; Or indium, antimony, sodium and potassium containing components volatilize and enter the soot; Or containing the iron-rich phase layer for water quenching or air cooling or pouring into a heat preservation device for slow cooling or by manual sorting and re-election, as a blast furnace ironmaking raw material or directly reducing ironmaking raw materials or smelting reduction ironmaking raw materials or floating Select copper raw materials 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 return to copper smelting system, iron concentrates as blast furnace ironmaking Raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, the reduced product is magnetically separated and separated, the metal iron and tailings are obtained, and the tailings are returned to the copper smelting system; Bottom furnace, tunnel kiln, undercarriage, shaft furnace, rotary kiln or induction furnace, using gas-based or coal-based reduction, gas-based reduction using natural gas and/or gas, coal-based reduction using anthracite, bituminous coal, lignite, coking coal, coke One or more of the powder or coke, the controlled reduction temperature is 900 to 1400 ° C, and the control alkalinity CaO / SiO ₂ ratio = 0.8 to 1.5. The method of claim 7 wherein said oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, nitrogen-air, argon-air, oxygen-nitrogen, oxygen-argon. The preheating temperature is 0 to 1200 °C. The method according to claim 7, wherein said fuel and reducing agent are one or more of a solid, a liquid or a gas, which is sprayed or fed, said injected gas For one or more of preheating oxidizing gas, nitrogen or argon, the preheating temperature is 0 to 1200 ° C; the solid fuel and reducing agent are coal powder, coke powder, coke, powder One or more of coal ash, bituminous coal or anthracite coal, in the form of granules or powder, granular material having a particle size of 5 to 25 mm, powdery material having a particle size of ≤150 μm, said liquid fuel and reducing agent being heavy oil, gaseous fuel and The reducing agent is gas and/or natural gas. The method according to claim 1, wherein in the step S1, the mixing is uniformly a natural mixing or a stirring mixing, and the stirring mixing is performed by argon stirring, nitrogen stirring, and nitrogen-argon mixing. One or more of gas agitation, reducing gas agitation, oxidizing gas agitation, electromagnetic agitation or mechanical agitation; In the step S2, 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.