WO2019071793A1

WO2019071793A1 - Method for recovering valuable component from slag containing copper

Info

Publication number: WO2019071793A1
Application number: PCT/CN2017/115648
Authority: WO
Inventors: 张力; 张武
Original assignee: 东北大学
Priority date: 2017-10-10
Filing date: 2017-12-12
Publication date: 2019-04-18
Also published as: CN107699702A

Abstract

A method for recovering a valuable component from slag containing copper, comprising: S1. mixing furnace slag: adding copper slag into a smelting reaction device, adding a calcium-series mineral and an additive, forming mixed slag, heating the mixed slag to a molten state to act as reaction slag, mixing well, monitoring the reaction slag in real time, and obtaining slag after a reaction by means of adjusting the mixed reaction slag to simultaneously satisfy conditions a and b; S2. separation and recovery. Hot slag may be processed by means of the method, fully using the physical thermal resources and hot metallurgical flux of smelting copper slag, while cold furnace slag may also be processed; by means of adjusting the physical and chemical properties of slag, and by using the mature physical and chemical properties of slag containing copper, a metallurgical process for slag containing copper is implemented.

Description

Method for recovering valuable components from copper-containing slag

Technical field

The invention belongs to the technical field of slag metallurgy, and in particular relates to a method for recovering valuable components from copper-containing slag.

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, copper-fired depleted slag, and copper slag flotation tailings.

The copper-containing smelting slag is produced in the process of “smelting and smelting” of the pyrometallurgical process of copper. It emits more than 20 million tons per year, and currently accumulates more than 200 million tons. With the continuous development of "smelting smelting" technology, such as flash smelting furnace, Noranda furnace, Vanukov furnace, Isa furnace, Osmet furnace, Mitsubishi furnace, Jinfeng furnace, bottom blowing furnace, etc. The content of Cu, Fe and other metals in the copper smelting slag is increased, the copper content in the slag reaches 20%, and the iron content is as high as 55%. Copper smelting slag is an important secondary resource. The molten copper smelting slag discharged from the smelting smelting furnace of the "smelting smelting" process is higher than 1100 ° C, and the molten copper smelting slag is also an important physical heat resource. The main utilization method of copper smelting slag is fire depletion and flotation recovery of copper components.

The copper-containing blowing slag is produced in the "copper smelting" process of the fire smelting process of copper, such as converter blowing slag, flash blowing slag, top blowing furnace blowing slag, bottom blowing furnace blowing slag, etc. The copper content in the slag reaches 35% and the iron content is as high as 55%. Molten copper-containing blowing slag is also an important physical thermal resource. The copper component is mainly recovered by a return smelting furnace or an electric furnace depletion or beneficiation method.

Copper slag is not only an important secondary resource, but also contains a large amount of metallurgical fluxes such as SiO ₂ , CaO, MgO, Al ₂ O _{3 ,} etc., which has strong chemical reaction activity and is a slag system with excellent physical and chemical properties, and is a thermal metallurgical clinker. It is a mature metallurgical slag system. However, the copper-containing smelting slag and the copper-containing blowing slag are returned to the smelting furnace or the electric furnace depletion or beneficiation method, and only the recovery of the copper component is considered, the depletion or beneficiation effect is not good, and the flotation brings serious environmental pollution. After depletion or beneficiation, the slag contains more than 0.3% copper, which is 0.2% higher than the recoverable grade of copper. In general, iron ore is allowed to contain no more than 0.2% copper. The higher slag contains copper, which is not conducive to the subsequent direct reduction of iron or smelting reduction of iron. The reason is that during the reduction process, copper is easily reduced and enters pig iron. When it exceeds 0.3%, the weldability of the steel is lowered, and the "hot brittleness" phenomenon of the steel is caused, causing cracks during rolling.

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 recovering valuable components using copper-containing slag. The method of the invention is a new slag metallurgy process, which not only reduces the copper content of the slag, but also makes the slag contain copper <0.1 wt%, and realizes efficient recovery of components such as copper, iron, gold, silver, lead and zinc, and obtains low efficiency. Copper-containing iron materials such as iron concentrates and pig iron, and solve the problems of large accumulation of slag, environmental pollution and heavy metal elements.

(2) Technical plan

In order to achieve the above object, the main technical solutions adopted by the present invention include:

A method for recovering valuable components from copper-containing slag, comprising the steps of:

S1, slag mixing: adding copper slag to the smelting reaction device, adding calcium minerals and additives to form mixed slag, heating the mixed slag to a molten state as reaction slag, mixing uniformly, and monitoring the reaction slag in real time, The slag after the reaction is obtained by adjusting the mixed reaction slag to satisfy the condition a and the condition b, or the slag after the reaction is poured into the heat preservation device;

Wherein the condition a is that the temperature of the reaction slag is from 1100 to 1450 ° C;

The condition b is the alkalinity CaO / SiO ₂ ratio of the reaction 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 bottom copper-rich phase layer, the middle iron-rich phase and the upper iron-containing silicate mineral phase are obtained by sedimentation separation, and the zinc-containing component is formed at the same time. Lead-containing component Smoke, dust, gold and silver components enter the copper-rich phase; the phases are recycled.

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 is <1100 ° C, using the heating function of the reaction device itself, or adding fuel and preheated oxidizing air to the slag, so that the temperature of the reaction slag reaches 1100 ~ 1450 ° C;

When the temperature of the reaction slag is >1450 ° C, one or more of the copper-containing material, the metallurgical flux, the iron-containing material or the fluorine-containing material is added to the reaction slag, and the mixture is uniformly mixed to make the temperature of the mixed slag Up to 1100 ~ 1450 ° C;

The method for regulating the condition b is:

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is <0.15, an alkaline material and/or an alkaline iron-containing material is added to the reaction slag;

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >1.5, an acidic material and/or an acidic iron-containing material is added to the reaction slag. 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 method as described above, preferably, in the step S1, while satisfying the conditions a and b, it should be simultaneously satisfied to control the reduction of copper oxide and iron oxide in the slag holding slag to metallic copper. And FeO, the metal iron content in the slag is <3%. 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 method as described above, preferably, the copper slag is one or more of a copper-containing smelting slag, a copper-containing blowing slag, a copper-fired depleted slag, a flotation tailings, and a wet copper slag. Wherein, the copper-containing smelting slag is produced in a "smelting smelting" process of a copper pyrometallurgical smelting process, and the copper-containing smelting slag is produced in a "copper smelting" process of a copper pyrometallurgical process, The copper fire method depleted waste slag is a copper smelting slag and a copper-containing smelting slag, and the slag is depleted, and the flotation tailing slag is a copper smelting slag and a copper-containing smelting slag, and a tailing slag after beneficiation; wherein The copper-containing smelting slag, the copper-containing smelting slag and the depleted slag are in a molten state or a cold state, wherein: the molten copper smelting slag is obtained from a slag-containing smelting furnace slag opening process of the smelting smelting process, or The copper-containing smelting slag is heated to a molten state, and the molten copper slag is obtained from a copper smelting furnace slag tapping port of the "copper smelting" process, or the copper smelting slag is heated to a molten state, and is depleted The waste slag is obtained from the slag outlet of the depleted furnace, and the depleted slag is heated to a molten state;

The calcium-based mineral is one or more of lime, limestone, dolomite, calcium carbide slag, red mud or high-calcium red mud after de-sodium; the additive is SiO ₂ , MgO, FeO, Fe ₂ O ₃ , One or more of MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O.

Preferably, the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead smelting slag, lead-zinc tailings, Nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag, lead-containing smelting furnace slag, lead smelting soot and soot, lead-acid battery, copper smelting soot and dust, copper, copper-containing garbage, containing One or more kinds of copper circuit board, tin smelting slag, tin tailings; wherein the copper slag includes slag produced by "smelting smelting" and slag generated by "copper smelting", depletion by fire method Slag and copper slag flotation tailings; lead-containing slag is smelting furnace slag and lead smelting slag, “ISP lead-zinc blast furnace reduction” or “sinter blast furnace reduction” or “solid high-lead slag reduction” or “liquid high lead” Slag reduction process" reduction process produces lead-containing melting The slag and the lead smelting slag are smelted by the smelting furnace to produce lead-containing smelting furnace slag; the nickel smelting slag is the nickel smelting slag produced by the "smelting smelting" process, and the depleted slag after the "copper ice nickel blowing" process is blown One or more of the nickel settling slag produced by top-blown smelting; the zinc smelting slag includes slag produced by wet zinc smelting and slag produced by wet zinc smelting, wherein the slag produced by the wet zinc smelting is zinc leaching residue and volatilized One or more kinds of kiln slag, iron slag, pickled iron slag, goethite slag, hematite slag, vertical tank zinc smelting is vertical tank zinc slag, vortex smelting slag, blast furnace slag, electric furnace slag One or more

The metallurgical flux is a mineral containing CaO or SiO ₂ , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone;

The iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon-bearing pre- Reducing pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag, copper slag, lead smelting slag, copper slag, tin smelting slag, red mud, high calcium after desodium One or more of red mud, coal dust ash, sulfuric acid slag; the steel dust and dust including blast furnace gas mud, converter dust mud, electric furnace dust, hot or cold rolling sludge, sintering dust, pellets Dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale;

The fluorine-containing material is one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag;

The copper-containing material, the iron-containing material and the fluorine-containing material are all pellets or powdery materials or granulation; wherein, the granular material has a particle size of ≤150 μm, the granular material has a particle size of 5 to 25 mm, and the powdery material is sprayed. Injecting in a manner, the granular material is added by spraying or feeding, and the gas is loaded into one or more of argon gas, nitrogen gas, reducing gas and oxidizing gas at 0 to 1200 ° C; One or more of the slag inserted into the slag or placed in the upper or side or bottom of the reaction slag. Preferably, the alkaline material is one or more of lime powder, red mud, decalcified high calcium red mud, calcium carbide slag, dolomite powder or quicklime powder; The iron-containing material is CaO/SiO ₂ >1 iron-containing material, alkaline sintered ore, alkaline iron concentrate, iron alloy slag, steel slag, alkaline pre-reduction pellet, alkaline metallized pellet, steel slag or blast furnace slag One or several

The oxidizing gas is one of air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen at 0 to 1200 °C;

The acidic material is one or more of silica, fly ash and coal gangue; the acidic iron-containing material is iron-containing material with CaO/SiO ₂ ≤ 1, acid sinter, acid iron concentrate, acid pre- One or more of reducing pellets, acid metallized pellets, copper slag, lead-containing slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, and blast furnace slag.

In the above-described method, 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 are separately treated, or any two phases are combined.

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: part or all of the iron-containing silicate mineral phase is returned to the reaction slag as a hot metallurgical flux;

Method C: for pouring glass ceramics or as slag wool; Method D: slag containing iron silicate mineral phase is oxidized after air cooling or water quenching, the method comprises: slag remaining in the smelting reaction device or melting The slag is poured into the heat preservation device, and the preheated oxidizing gas having a temperature of 0 to 1200 ° C is blown into the slag containing iron silicate, and the slag temperature of the silicate is ensured to be >1450 ° C; The weight percentage of iron is <1%, and the slag after oxidation is obtained; the slag after oxidation is directly air-cooled or water-quenched, and is used as a slag cement, a cement conditioner, and a cement production. Additive or cement clinker;

Further, 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 itself is heated to make the temperature of the iron-containing silicate slag >1450 ° C;

Method E: The iron-containing silicate mineral phase is used to produce high value-added cement clinker, including the following steps:

E-1. The iron-containing silicate mineral phase is retained in the smelting reaction device or the slag is poured into the heat preservation device, and molten slag, lime, limestone, iron alloy slag, and molten slag are added to the slag containing the iron silicate mineral phase. One or more of fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, red mud after desoda or calcium carbide slag, thoroughly mixed to obtain a slag mixture;

E-2, the slag mixture is blown into the oxidizing gas with a preheating temperature of 0 to 1190 ° C, and the temperature of the slag mixture is >1450 ° C; when the weight percentage of ferrous oxide is <1%, the oxidation is obtained. 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 iron-containing silicate mineral phase is subjected to reduction ironmaking, comprising the following steps:

G-1, the iron-containing silicate mineral phase is retained in the smelting reaction device or the slag is poured into the heat preservation device, or the iron-containing material is added, and the reducing agent is added at the same time to perform smelting reduction, and the reaction slag is monitored in real time, and the slag is controlled. At the same time, the conditions are satisfied: the temperature of the reaction slag is 1350～1670° C. and the alkalinity of the reaction slag is CaO/SiO ₂ ratio=0.6-2.4, and the slag after the 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 1350 ~ 1670 ° C;

When the temperature of the reaction slag is >1670 ° C, one or more of a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag, so that the temperature of the reaction slag reaches 1350 to 1670 ° C, wherein The metallurgical flux is a mineral containing CaO or SiO ₂ , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desodiumification, calcium carbide slag, dolomite or limestone;

The method of controlling the alkalinity of the reaction slag is:

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: using one of the following two methods:

Method I: Pour the mixed slag after reduction into a heat preservation slag tank, and slowly cool to room temperature to obtain slow cooling slag; wherein, the metal iron settles to the bottom of the reaction device to form iron slag, and the remaining slow slag contains metal iron Layer, broken to a particle size of 20 ~ 400μm, grinding, magnetic separation to separate the remaining metal iron and tailings;

Method II: mixed slag after reduction, sedimentation, slag-gold separation, obtaining molten iron and reduced slag; and the reduced slag is slag according to one or several methods of methods A to E Processing; the molten iron is sent to a converter or an electric furnace for steel making;

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 a converter or a blowing furnace for copper smelting, or magnetic separation of metal iron or After the metal iron is separated by magnetic separation, the reduction product is directly separated, and the reduced product is separated by magnetic separation, and then sent to a converter or a blowing furnace for copper smelting;

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 obtained by water quenching or air cooling or pouring into a heat preservation device, or after being manually sorted and re-selected, as a raw material for blast furnace ironmaking or directly reducing ironmaking raw materials or smelting reduction Ironmaking raw materials or flotation copper extraction raw materials or magnetic separation of metal iron as a raw material for copper smelting or direct reduction ironmaking; in the direct reduction process, after reduction and magnetic separation of the reduction products, metal iron and tailings are obtained, and tailings are returned to the refining Copper system; during the flotation process, the flotation product is a copper-bearing concentrate and iron concentrate, the copper concentrate is returned to the copper-smelting system, and the iron concentrate is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material or a smelting reduction ironmaking raw material; Wherein, 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 gas. The coal base is reduced to one or more of anthracite, bituminous coal, lignite, coking coal, coke powder or coke, the reduction temperature is 900-1400 ° C, the alkalinity CaO / SiO ₂ ratio = 0.8 ~ 1.5; the gas produced by reduction is melting Secondary combustion of slag surface, provided Heat, and the gas flowing out of the furnace as a heat source can heat and dry the charge 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; or The iron-rich phase is treated by the step S2-1-05 in the first method; the molten state is poured into the copper-rich phase after the slow cooling of the heat preservation device, sent to the converter or the blowing furnace for copper smelting, or the magnetic separation is used to separate the metallic iron. After being sent to converter or blowing furnace for copper smelting, or magnetic separation to separate metal iron or without magnetic separation, the metal is directly reduced, and the reduced product is separated by magnetic separation and then sent to a converter or a converting furnace. Copper smelting.

Method 4: When the slag rotatable converter and the reaction slag tank are used, the molten iron-containing silicate mineral phase and the iron-rich phase are obtained, and the treatment method is one of the methods A to G described in the first method or Several kinds of processing; the molten copper-rich phase or poured into the heat preservation device after slow cooling, sent to a converter or a blowing furnace for copper smelting, or slow cooling, then magnetic separation to separate the metal iron and then sent to the converter or the converting furnace Copper is smelted, or metal iron is separated by magnetic separation or metal iron is separated by magnetic separation, and the reduction product is subjected to magnetic separation to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting.

Method 5: When using a heat preservation device, or using a smelting reaction device through which slag can flow out, when pouring the slag into the heat preservation device, perform the following steps:

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 taking out copper-rich bismuth deposited at the bottom, or copper-filled ruthenium after magnetic separation to separate metal 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; the iron-rich phase and the iron-containing silicate phase as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material or a smelting 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 ironmaking; in the direct reduction process, after the magnetic separation of the reduction product, metal iron and tailings are obtained, and the tailings are returned to the copper smelting system; the flotation product is a copper-bearing concentrate and iron concentrate. The copper concentrate is returned to the copper smelting system, and the iron concentrate is used as a raw material for blast furnace ironmaking or directly reducing ironmaking raw materials or smelting reduction ironmaking raw materials;

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, oxidative 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.

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

(1) The method for recovering valuable components from copper-containing slag of the present invention can treat hot slag, make full use of molten copper slag physical heat resources and hot metallurgical flux, and can treat cold slag by adjusting The physical and chemical properties of the slag, using the physical and chemical properties of the copper-containing slag to achieve the metallurgical process of containing copper slag;

(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 up and settle; at the same time, the calcium-based minerals effectively modify the viscosity to lower the viscosity and contribute to the sedimentation of the copper-containing component;

(3) The copper component and the gold and silver components in the slag are separately migrated and enriched in the copper-rich phase, and the growth and sedimentation are realized, and the copper-rich phase is sent to the converter or the smelting furnace for copper smelting; wherein, the copper-rich phase Including copper, white copper, matte phase, a variety of iron-containing components, or part of the copper component into the iron-rich phase, the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phase, as a blast furnace Iron or steel or direct reduction or smelting reduction of ironmaking raw materials;

(4) The zinc component and the lead component in the mixed slag are separately migrated, enriched in the soot, and recovered;

(5) part of the indium-containing component, the antimony component, the potassium-containing component, and the sodium-containing component are volatilized into the soot for recycling;

(6) Separating the copper-rich phase at the bottom, the iron-rich phase in the middle, and the iron-containing silicate phase in the upper part by manual sorting, magnetic separation, re-election, and slag-gold separation to realize the copper group in the slag Efficient recovery of fractions and iron components; can process solid copper-containing materials to achieve efficient and comprehensive utilization of resources;

(7) Adding an additive to the method of the present invention, one is for reducing the viscosity, the other is for lowering the melting point, and at a certain temperature (1100-1450 ° C), the copper-rich phase is precipitated, and the sedimentation is separated and obtained low. Copper rich iron phase and iron a silicate phase, wherein the iron-rich phase and the iron-containing silicate phase have a copper content of less than 0.1%, and the iron can be obtained by direct reduction or smelting reduction to obtain metallic iron and molten iron;

(9) The method of the present invention can be carried out continuously or intermittently to meet the needs of industrial production.

(3) Beneficial effects

The beneficial effects of the invention are:

(1) The raw material of the present invention may be cold slag, cold slag treatment, not only can realize copper component, gold component, silver component, iron component, zinc component, lead component, indium component in slag The comprehensive utilization of strontium components, sodium components, potassium components and valuable components can effectively solve the problems of large accumulation of slag, environmental pollution problems and heavy metal pollution.

(2) The raw material of the present invention may be liquid molten copper slag (≥1100 ° C) flowing out from the slag outlet, which contains abundant thermal energy resources, has the characteristics of high temperature and high heat, and fully utilizes the slag physical heat resource and is highly efficient. Energy saving; liquid molten copper slag contains a large amount of hot metallurgical flux, which is a slag system with excellent physical and chemical properties, which realizes slag metallurgy.

(3) The invention adjusts the physical and chemical properties of the slag, injects a gas, controls the oxygen potential, and causes the copper component and the gold and silver component in the slag to migrate and enrich to the copper-rich phase to achieve aggregation, growth and sedimentation.

(4) In the method of the invention, the cold material and the molten copper slag are added to avoid the slag temperature being too high, and the life of the heat preservation device is increased; adding the cold material and the molten copper slag improves the processing amount of the raw material, and can not only treat the liquid slag Moreover, it can process a small amount of cold materials, and the raw materials have strong adaptability; the addition of cold materials realizes the efficient use of the chemical heat released by the reaction and the physical heat of the slag.

(5) The invention adjusts the physical and chemical properties of the slag, controls the oxygen potential, and simultaneously adds the calcium-based minerals to release the iron oxides in the olivine phase, enriched in the iron-rich phase, and realizes aggregation, growth and sedimentation; The zinc component, the lead component, the indium component, the bismuth component, the sodium component, and the potassium component are volatilized, and are collected into the soot to be recovered.

(6) During the natural sedimentation process of the method of the invention, the copper component and the gold and silver components in the slag are enriched in the copper-rich phase, and the aggregation, growth and sedimentation are realized, and the iron component in the slag is enriched in the iron-rich phase. And to 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 sedimentation; the addition of fluorine-containing materials accelerates the copper-rich phase, The growth and precipitation of the iron-rich phase shortens the settling time; the copper-rich phase is sent to the converter or the converter to smelt copper, and the low-copper iron-rich phase is used as the raw material for blast furnace ironmaking or direct reduction or smelting reduction ironmaking.

(7) The method of the present invention increases the grindability of the slag mineral, and the slag achieves quenching and tempering.

(8) The method of the invention separates the silicate mineral phase, the iron-rich phase and the copper-rich phase distributed in the upper part, the middle part and the bottom part by manual sorting, magnetic separation and re-election, respectively, to realize the slag High-efficiency recovery of copper component, gold-silver component, iron component, zinc component, indium component, antimony component, lead component, sodium component and potassium component; due to copper-rich phase and iron-rich phase sedimentation Middle and lower parts, wherein the copper-rich phase comprises a plurality of copper phases, white ice copper, amber phase, and iron-containing components, and the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phases, and therefore, The amount of slag is small, the cost of grinding, magnetic separation and re-election is low; the subsequent separation process uses magnetic separation or re-election, and there is no environmental pollution during the separation process. The slag treatment process has short process, simple operation and recovery rate. High, high-efficiency, clean and environmentally friendly; tailings are used as cement raw materials, building materials, instead of crushed stone for aggregates and road materials.

(9) The iron-containing silicate phase and the iron-rich component have a copper content of less than 0.1%, and can be used as a raw material for blast furnace ironmaking or direct reduction or smelting reduction of ironmaking to obtain metallic iron and molten iron.

(10) The invention fully utilizes the molten copper slag physical heat resource and the hot metallurgical flux, and can also treat the cold slag, realizes slag metallurgy, and the copper component and the gold and silver component in the slag are enriched in the copper-rich phase. And achieve aggregation, growth and settlement, iron components are enriched in the iron-rich phase, to achieve aggregation, growth and sedimentation, using manual sorting, magnetic separation and re-election methods to separate and deposit copper in different parts Phase, iron-rich phase and iron-containing silicate phase to achieve efficient recovery of copper and iron components in slag; can process solid copper-containing materials, the process is short, metal High recovery rate, low production cost, strong adaptability of raw materials, large processing capacity, environmental friendliness and high economic returns can solve the problem of efficient recycling of metallurgical resources and thermal energy.

Detailed ways

A method for recovering valuable components containing copper slag, comprising the following steps:

Step 1, slag mixing:

Adding copper slag (containing one or more of copper smelting slag, copper-containing blowing slag, copper fire depleted slag, flotation tailings, and wet copper slag) to the heat preservation device or slag Calcining the reaction device and adding calcium minerals and additives to form a mixed slag;

The mixed slag is heated to a molten state to form a copper-containing reaction slag; the mixture is uniformly mixed, and the copper-containing reaction slag is monitored in real time, and the following parameters (a) and (b) are simultaneously controlled to obtain the slag after completion of the reaction. , or pour the slag after the reaction into the heat preservation device;

(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 is lower than the lower limit of the set temperature range, the heating function of the reaction device itself or the addition of fuel to the copper-containing reaction slag causes the temperature of the reaction slag to reach a set temperature range; When fuel is injected, a preheated oxidizing gas is simultaneously injected;

When the temperature of the copper-containing reaction slag is lower than the upper limit of the set temperature range, one or more of the copper-containing material, the metallurgical flux, the iron-containing material or the fluorine-containing material is added to the copper-containing reaction slag to make the mixed slag The temperature reaches the set temperature range;

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, one or more of an alkaline material or an alkaline iron-containing material is added to the reaction slag;

When the ratio of alkalinity CaO/SiO ₂ in the copper-containing reaction slag is >1.5, one or more of an acidic material or an acidic iron-containing material is added to the reaction slag;

Step 2, separate and recycle:

After the reaction is completed, the slag is kept for 5 to 50 minutes, and the sedimentation is separated to obtain a bottom molten copper-rich phase layer, a central molten iron-rich phase and an upper molten iron-containing silicate mineral phase, and simultaneously form a zinc-containing component and The soot containing lead component, the gold and silver components migrate to the copper-rich phase, and the items are treated as follows;

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, and are collected into the dust as an oxide;

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

Wherein, the iron-containing silicate mineral phase in the step (1) is subjected to slag treatment, and one of the methods A to G is adopted:

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:

Some or all of the iron-containing silicate mineral phase is returned to the copper-containing reaction slag, and as a hot metallurgical flux, the copper-containing reaction slag component is adjusted to control the copper-containing reaction slag temperature.

Method C: pouring a glass-ceramic with a ferrite-containing mineral phase or as a slag wool.

Method D: Air-cooling or water quenching after oxidation of iron-containing silicate slag:

(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 slag is oxidized to obtain an oxidized 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, and used as slag cement, cement conditioner, additive in cement production or cement clinker.

Method E: Treatment of high value-added cement clinker by treatment with iron silicate slag:

(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 0～1190°C; and during the whole process, the (d) slag mixture temperature is >1440° C.; the temperature control method is the same as the silicate slag temperature control method in the method D step (1);

(3) The slag after oxidation is subjected to air cooling or water quenching to obtain a high value-added cement clinker.

Method F: the iron-containing silicate mineral phase slag is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: the slag containing the iron silicate mineral phase is air-cooled, water quenched or slowly cooled, and used as a blast furnace Iron or direct reduction of ironmaking raw materials, after direct reduction, magnetic separation or electric furnace melting, magnetic separation products are metal iron and tailings, electric furnace melting, the product is molten iron and slag;

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 Mines and tailings, tailings as building materials.

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

(1) Retaining the iron-containing silicate slag in the smelting reaction device or pouring the slag into the heat preservation device, adding the iron-containing material to the molten slag, reducing the agent, performing the smelting reduction, and monitoring the reaction slag in real time. The control simultaneously ensures the following two parameters (a) and (b), and obtains the slag after the completion of the reaction;

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

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

The control method is:

Corresponding to (a):

When the temperature of the reaction slag < lower limit of the set temperature range is 1350 ° C, the temperature of the reaction slag reaches the set temperature range by the heating function of the reaction device itself or by adding the fuel and the preheated oxidizing gas to the slag. Within 1350 ~ 1650 ° C;

When the temperature of the reaction slag > the upper limit of the set temperature range is 1650 ° C, one or more of a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag to bring the temperature of the reaction slag to a set temperature. The range is from 1350 to 1650 ° C;

Corresponding to (b):

(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; the metal ferrous layer in the remaining slow slag is crushed to a particle size of 20 to 400 μm, and the remaining metal is separated by magnetic separation. 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 E in the separation and recovery method 1 of the step 2, the slag treatment;

(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 of metal iron, direct reduction, the reduction product is magnetically separated to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting;

(2) The molten iron-rich phase layer and the iron-containing silicate mineral phase are 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 slag rotatable converter and the reaction slag tank are used, the slag after the reaction is completed is carried out as follows:

(1) The molten iron-containing silicate mineral phase is subjected to slag treatment, and the specific treatment method is: one or more of the methods A to G in the separation and recovery method 1 of the step 2 is used for slag treatment; The iron-rich phase is treated by the step (4) in the first method;

(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) Part of the indium, antimony, sodium and potassium components are volatilized into the soot recovery;

Method 4: When the slag rotatable converter and the reaction slag tank are used, the slag after the reaction is completed is as follows:

(1) The molten iron-containing silicate mineral phase and the iron-rich phase are subjected to slag treatment in a specific manner: one or more of the methods A to G in the separation and recovery method 1 of the step 2 are used;

(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, the reduction product is magnetically separated to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting;

(3) part of the indium, antimony, sodium and potassium components volatilize into the soot oxide into the soot;

Method 5: When using a heat preservation device, or using a smelting reaction device through which slag can flow out, when the slag is poured into the heat preservation device, the slag after the reaction is completed is as follows:

(1) Settling cooling: the slag after the completion of the reaction is cooled to room temperature to obtain slow cooling slag; the copper-rich phase is settled to the bottom of the reaction device to form a copper-rich bismuth; the iron-containing silicate mineral phase is floated; the copper-rich phase and the The slow cooling slag in the middle of the iron silicate mineral is an iron-rich phase, and simultaneously forms a zinc-containing component and a lead-containing component; 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) Some lead components, zinc components, indium components, antimony components, sodium components, and potassium components volatilize into soot oxides and enter the soot.

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 copper fire-depleted slag, a flotation tailings, a wet process One or more of copper slag, wherein the copper-containing smelting slag is produced in a "smelting smelting" process of copper pyrometallurgical smelting process, and the copper-containing blowing slag is produced in a copper smelting process" In the process of copper blasting, the depleted waste slag is a copper smelting slag and a copper smelting slag, and the slag is depleted, and the flotation tailing slag is a copper smelting slag and a copper smelting slag. The slag, the wet copper slag is produced in a wet copper smelting process;

In the steps 1 and 2, the copper smelting slag, the copper smelting slag and the depleted slag are in a molten state or a cold state, wherein: the molten copper smelting slag is from the smelting smelting furnace of the smelting smelting process Obtaining, or heating the copper-containing smelting slag to a molten state, the molten copper blowing slag is obtained from the copper smelting furnace slag opening of the "copper smelting" process, or heating the copper smelting slag to a molten state, depleted and discarded The slag is obtained from the slag outlet of the depleted furnace, and the depleted slag is heated to a molten state.

In the steps 1 and 2, the smelting reaction device through which the slag can flow out can be a smelting reaction device or a smelting reaction device with a slag port or an iron port; wherein:

The heat preservation device is a pourable smelting reaction slag irrigation and insulation pit;

In the method as described above, preferably, in the step 1, the calcium-based mineral is specifically one or more of lime, limestone, dolomite, calcium carbide slag, red mud or post-sodium high calcium red mud; Is one or more of SiO ₂ , MgO, FeO, Fe ₂ O ₃ , MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O;

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 and a carbon-containing iron-containing material, wherein the amount of the reducing agent and/or the carbon-containing iron-containing material in the slag is reduced to copper and iron oxide in the slag The theoretical amount of metallic copper and FeO is 110-140%; the carbon-containing iron-containing material is steel dust and soot, iron concentrate carbon-containing pre-reduction pellet, iron concentrate carbon-containing metallized pellet, wet process Zinc volatilization slag or coke oven dust and soot.

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 0～1200°C; solid fuel and reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite The shape is granular or powdery, the granular material has a particle size of 5 to 25 mm, the powdery material has a particle size of ≤150 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;

The copper-containing materials in steps 1 and 2 are copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, lead-containing slag, nickel smelting slag, lead ice copper, arsenic matte, and crude lead fire. Method for refining slag containing lead slag slag, lead-containing soot, lead-acid battery, copper-containing soot, copper-containing, copper-containing garbage or copper-containing circuit board; the copper slag is copper-containing smelting slag, One or more of copper-containing blowing slag, copper fire depleted slag, flotation tailings, and wet copper slag; lead-containing slag as smelting furnace slag and lead-containing smelting slag, "ISP lead-zinc blast furnace Lead-containing smelting slag produced by reduction or "sinter blast furnace reduction" or "solid high-lead slag reduction" or "liquid high-lead slag reduction process" reduction process, lead-containing smelting slag is smelted by a smelting furnace to produce lead-containing smelting furnace slag Nickel smelting slag is one or more of nickel smelting slag produced by "smelting smelting" process, depleted slag after blowing by "copper ice nickel blowing" process, and nickel slag slag produced by top blowing smelting; zinc smelting The slag includes slag produced by wet zinc smelting and slag produced by wet zinc smelting, wherein the furnace produced by wet zinc smelting It is zinc leaching residue, volatile kiln residue, iron slag residue, pickled iron slag, goethite slag, hematite slag one or more, vertical tank zinc smelting is vertical tank zinc slag, vortex melting furnace slag, One or more of blast furnace slag and electric furnace slag;

The metallurgical flux in the steps 1 and 2 is a mineral containing CaO or SiO ₂ , specifically quartz sand, gold-silver-sand quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone. One or several.

In the method as described above, preferably, the iron-containing materials in the 1 and 2 are ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron. Concentrate metallized pellets, ordinary iron concentrates, carbon pre-reduction pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel-containing smelting slag, lead smelting slag, copper slag, tin Smelting slag, red mud, high calcium red mud after desodiumification, coal dust ash, One or more of sulfuric acid slag; the steel dust and dust including blast furnace gas mud, converter dust mud, electric furnace dust mud, hot (cold) rolling sludge, sintering dust, pellet dust, iron pipe factory Dust, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale; the copper-containing material and the iron-containing material are hot or cold, wherein the hot material is directly obtained from the metallurgical furnace discharge port or the slag outlet.

The wet zinc slag and dust are subjected to dehydration and drying.

Among the above raw materials, zinc smelting slag and soot, lead smelting slag and soot contain indium and antimony, lead, silver, zinc and antimony; red mud contains sodium and potassium, and steel soot and dust contain indium, antimony and silver. Sodium and potassium, the above materials all have iron, lead smelting slag and zinc smelting slag contain copper, copper soot and dust contain indium and antimony, so in the method of the invention, indium, antimony, sodium, potassium, zinc, lead will The fumes are entered in the form of oxides for recycling.

The fluorine-containing materials in 1 and 2 are one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag;

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 preheated argon gas, nitrogen gas, reducing gas (gas and/or natural gas), oxidizing gas. One or more preheating temperatures of 0 to 1200 ° C; the blowing method is one or more of inserting slag into a slag by using a refractory lance or placing it in an upper portion or a side or bottom of the reaction slag.

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, the zinc component and the lead component in the slag respectively enter the soot, wherein the soot is recovered in the form of zinc oxide and lead oxide, wherein the copper-rich phase includes copper, white ice copper, ice. a plurality of copper phases, iron-containing components, or part 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, as blast furnace ironmaking or direct reduction or smelting reduction Iron raw material;

In the step 1 described above, the method of controlling the temperature of the mixed slag in the set temperature range is as follows:

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, high calcium red mud after desoda, calcium carbide slag, dolomite powder or quicklime powder; The alkaline iron-containing material is a CaO/SiO ₂ >1 iron-containing material, an alkaline sintered ore, an alkaline iron concentrate, a ferroalloy slag, a steel slag, an alkaline pre-reduction pellet, an alkali metallized pellet, One or more of steel slag or blast furnace slag.

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. Iron-containing materials, acid sinter, acid iron concentrate, acid pre-reduction pellets, acid metallized pellets, copper slag, lead-containing slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, blast furnace slag One or several

In the steps 1 and 2, the two parameters of (a) and (b) are ensured, and the slag is thoroughly mixed, and the mixing mode is natural mixing or stirring mixing, and the stirring mode is argon stirring, nitrogen stirring, nitrogen- One or more of argon gas mixture agitation, reducing gas agitation, oxidizing gas, electromagnetic stirring, and mechanical agitation;

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;

In the steps 1 and 2, the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen, and the preheating temperature is 0. ～1200°C, the blowing method is one or several types in which a refractory spray gun is inserted into the slag or placed in the upper part or the side or bottom of the reaction slag.

In the method as described above, preferably, 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, using a gas-based or coal-based reduction technique. The gas base is reduced to natural gas and/or gas, and the coal base is reduced to one or more of anthracite, bituminous coal, lignite, coking coal, coke breeze or coke, the reduction temperature is 900-1400 ° C, and 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: the device containing the slag after the reaction is completed is placed on the rotating platform and rotated according to a certain speed, and the rotation speed depends on the quality of the slag and the height or depth of the heat preservation device. The rotation time depends on the quality of the slag and the solidification of the slag; the device containing the slag after the completion of the reaction is placed on the rotating platform for the purpose of accelerating the accumulation of the copper-rich phase, the iron-rich phase, growth and sedimentation, It is beneficial to silicate floating, shortening settlement time, improving sedimentation effect and improving production efficiency.

In the step 2, during the slag cooling process after the completion of the reaction, most of the copper-rich phase and the iron-rich phase settle in the middle and lower portions due to the difference in density and the size of the mineral.

In the step 2, the copper component and the gold and silver component in the slag after the reaction is completed to migrate, enriched in the copper-rich phase, to achieve growth and sedimentation, or partially enriched in the iron-rich phase; iron in the mixed slag The components continue to migrate, enrich in the iron-rich phase, and achieve growth and sedimentation.

In the step 2, the gravity sorting method is a shaker sorting, a chute sorting, or a combination of the two.

By adopting the method of the invention, the finally obtained slag contains copper ≤0.1%, the iron recovery rate is ≥91%, the zinc recovery rate is ≥92%, the lead recovery rate is ≥92%, and the gold enrichment rate is ≥ 94%, the silver enrichment rate is ≥94%.

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.

In the following steps (1) in the following examples 1 to 10, when the slag is mixed, the two parameters (a) and (b) which are guaranteed by the regulation are specifically:

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

(b) Reaction slag basicity CaO/SiO ₂ ratio of copper and iron = 0.15 to 1.5.

Example 1

Step 1, slag mixing:

The copper-containing smelting slag obtained from the slag smelting of the smelting process of the smelting process and the copper-containing slag obtained by the slag slag of the "copper smelting" process blowing furnace are added to the DC arc furnace, and lime and SiO are simultaneously added. ₂ , MgO, Al ₂ O ₃ , forming mixed slag; heating the mixed slag to a molten state, forming a copper-containing reaction slag, and allowing the reaction slag to achieve natural mixing; monitoring the reaction slag in real time, and ensuring by regulation ( a) and (b) two parameters, obtain the slag after the completion of the reaction; corresponding (a): the temperature of the copper-containing reaction slag is 1660 ° C, using a refractory spray gun inserted into the reaction slag, with nitrogen as the loading gas, Spraying copper slag, copper-containing soot, copper-containing and copper-containing garbage and copper-containing circuit boards with powder particle size ≤150μm at normal temperature, and adding 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): alkalinity CaO / SiO ₂ ratio of copper-containing reaction slag = 2.6, silica, fly ash and coal gangue mixture is added to the reaction slag to make copper The reaction slag basicity ratio is reduced to 1.1; the slag contains metallic iron 1%;

Step 2, separation and recovery method 1:

After 10 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 layer, an iron-rich phase and an iron-containing silicate mineral phase, and at the same time, a zinc component and a lead component are formed, and the smoke is entered. Recycling in the form of oxides, the following steps are carried out: (1) molten iron-containing silicate mineral phase, for external slag treatment, method F, iron silicate slag air cooling, used as direct reduction ironmaking In the direct reduction process, the rotary kiln is used as the reduction equipment, and the gas-based reduction technology is used. The gas-based reducing agent is natural gas and gas, the reduction temperature is 900 ° C, the alkalinity CaO / SiO ₂ ratio is 0.8, and the electric furnace is melted after reduction. The temperature is 1550 ° C, the product is metal molten iron and slag; (2) the molten copper-rich phase is sent to the continuous blowing furnace for copper smelting; (3) the molten iron-rich phase is poured into the insulating slag tank, and the air is cooled as a blast furnace Ironmaking raw materials; (4) zinc component, indium component, lead component, antimony component, potassium component, sodium component volatilization, and enter the soot recovery in the form of oxide; the final obtained slag contains copper <0.1%, The zinc recovery rate was 92%, the lead recovery rate was 93%, and the iron recovery rate was 92%. The indium recovery rate was 92%, the ruthenium recovery rate was 94%, the sodium recovery rate was 95%, the potassium recovery rate was 96%, the gold enrichment rate was ≥96%, and the silver enrichment rate was ≥94%. 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

Step 1, slag mixing:

The molten copper-containing smelting slag obtained from the smelting port of the smelting process of the smelting process and the molten depleted slag obtained from the slag outlet of the depleted furnace are added to the pourable smelting reaction slag, and limestone, dolomite, and the like are added simultaneously. Red mud and FeO and Fe ₂ O ₃ form mixed slag; use oxygen-enriched air with a preheating temperature of 800 °C to spray anthracite and coke with a particle size of 20 mm, while injecting natural gas to heat the mixed slag to a molten state. Forming a copper-containing 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) copper-containing reaction slag temperature is 1660 ° C, using a refractory spray gun to insert into the reaction slag, using argon as carrier gas, spraying normal temperature powder particle size ≤150μm copper slag, copper-containing soot, copper-copper steel sintered dust , sintering pellet dust, iron plant dust, ordinary iron concentrate direct reduced iron, the temperature is reduced to 1350 ° C; (b) copper containing reaction slag basicity CaO / SiO ₂ ratio of 2.4, added to the reaction slag a mixture of acidic iron concentrate, acidic pre-reduction pellets, lead-containing smelting slag, and lead-containing smelting furnace slag, so that the alkalinity ratio of the copper-containing reaction slag is reduced to 1.6; the metal iron content in the slag is 1.5%;

Step 2, separation and recovery method 2:

After 5 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold separation, the molten copper-rich phase layer, the iron-rich phase and the iron-containing silicate mineral phase are obtained, and the zinc component, the lead component and the indium component are simultaneously formed. To enter the soot and recycle it in the form of oxides, proceed as follows:

(1) The molten iron-containing silicate mineral and the iron-rich phase are treated by the method G, and the slag is smelted to reduce the iron-making. The specific steps are as follows:

(1-1) The slag is poured into a rotatable converter, and an oxygen-enriched air with a preheating temperature of 600 ° C is used to add anthracite and bituminous coal with a particle size of 20 mm to the slag for smelting reduction, and the reaction slag is monitored in real time. At the same time, it is ensured that the temperature of the reaction slag is 1350~1650 ° C, and (b) the ratio of alkalinity CaO / SiO _{2 of the} reaction slag is 0.6-2.4, and the slag after the reaction is obtained;

Corresponding to (a): the temperature of the reaction slag is 1480 ° C, 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 1350 ~ 1650 ° C, and (b) the ratio of alkalinity CaO / SiO ₂ ratio of the reaction slag = 0.6 ~ 2.4,

(1-3) Separation and recovery:

(a) the mixed slag after reduction, natural sedimentation, slag-gold separation, 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 zinc recovery rate is 94%, the slag contains copper <0.1%, the lead recovery rate is 92%; the iron recovery rate is 93%, indium recovery The rate was 96%, the recovery rate of cesium was 96%, the recovery rate of sodium was 97%, the recovery rate of potassium was 98%, the enrichment rate of gold was ≥94%, and the enrichment rate of silver was ≥95%.

Example 3

Step 1, slag mixing: copper-containing smelting slag obtained from the slag smelting slag of the smelting process, and copper-containing blowing slag and copper slag flotation obtained from the slag outlet of the "copper smelting" process blowing furnace The tailings are added to the induction furnace, and limestone and high-calcium red mud after de-sodium are added to form mixed slag; the slag is sprayed with 20 g of anthracite, coke and pulverized coal with a preheating temperature of 400 ° C. Heating to a molten state, forming a copper-containing reaction slag, mechanically stirring and mixing; monitoring the reaction slag in real time, and simultaneously controlling the two parameters (a) and (b) to obtain the slag after completion of the reaction;

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 soot, lead-containing smelting furnace slag, Rolled iron oxide scale, ordinary iron concentrate metallized pellets and ordinary iron concentrate carbon-bearing pre-reduction pellets, the temperature is lowered to 1220 ° C; (b): alkalinity CaO / SiO ₂ ratio of copper-containing reaction slag = 2.3. Adding a mixture of quartz sand, red mud and wet zinc smelting slag to the reaction slag to reduce the alkalinity ratio of the copper-containing reaction slag to 0.6; the slag is a weak reducing atmosphere, and the metallic iron in the slag The content is 1.2%;

Step 2, separation and recovery method 2:

After heat preservation for 45 min, the slag after the completion of the reaction, natural sedimentation, separation of slag-gold, obtaining a molten copper-rich phase, an iron-rich phase and an iron-containing silicate mineral phase, and simultaneously forming a zinc-containing component and a lead-containing component, enter The soot is recovered as an oxide and the following steps are carried out:

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

(2) The molten iron-rich phase layer and the silicate mineral phase act as direct reduction ironmaking raw materials; during the reduction process, the zinc component, the lead component, the antimony component and the indium component volatilize and enter the soot; the direct reduction process In the middle, using a rotary hearth furnace, the reduction temperature is 1200 ° C, the alkalinity CaO / SiO ₂ ratio = 1.0, the particle size is ≤ 150 μm anthracite and coal powder;

(3) The zinc-containing component, the indium component, the antimony component and the lead-containing component volatilize, and enter the soot recovery in the form of an oxide to obtain zinc oxide and lead oxide. The slag contains copper <0.05%, the iron recovery rate is 91%, the zinc recovery rate is 93%, the lead recovery rate is 92%, the indium recovery rate is 93%, the ruthenium recovery rate is 94%, and the gold enrichment rate is At 95%, the silver enrichment rate is 96%.

Example 4

Step 1. Slag mixing: adding the copper-containing smelting slag obtained in the cold state from the smelting port of the smelting process to the plasma furnace, adding dolomite, MgO, Al ₂ O ₃ , and Fe to form mixed slag. The mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is electromagnetically stirred to achieve mixing; the reaction slag is monitored in real time, and two parameters (a) and (b) are obtained through regulation and control. The slag after the reaction is completed;

Corresponding to (a) the temperature of the copper-containing reaction slag is 1670 ° C, and red mud, coal dust ash, sulfuric acid slag, fluorite, lead ice copper, lead-containing soot, zinc-containing soot, arsenic matte copper are added to the reaction slag. And the wet zinc slag, the temperature is lowered to 1440 ° C; (b) the copper-containing reaction slag has a basicity CaO / SiO ₂ ratio of 2.0, and the copper-containing blowing slag is added to the reaction slag to melt the copper-containing reaction The slag alkalinity ratio is reduced to 1.2; the air is sprayed with natural gas, the coke grain having a particle size of 20 mm, and the metal iron content in the slag is 2%;

Step 2, separation and recovery method 3:

After 30 minutes of heat preservation, the slag after the completion of the reaction is naturally cooled and settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and at the same time, a zinc-containing component and a lead-containing component are formed. The soot is recovered as an oxide and the following steps are carried out:

(1) molten iron-containing silicate mineral phase, using the separation and recovery method of step 2; a method of slag-modified magnetic separation: 1 using a spray gun to spray molten slag into a preheating temperature of 600 ° C Oxygen air, to achieve magnetite transformation, 2 slow cooling to room temperature, magnetic separation to obtain iron concentrate and tailings;

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

(3) Part of the zinc-containing component bismuth component, indium component and lead-containing component volatilize, and enter the soot recovery in the form of oxide; slag contains copper <0.1%, iron recovery rate is 94%, and zinc recovery rate 93%, the lead recovery rate was 92%, the indium recovery rate was 93%, the ruthenium recovery rate was 94%, the gold enrichment rate was 95%, and the silver enrichment rate was 97%.

Example 5

Step 1, slag mixing: the copper-containing smelting slag obtained from the slag smelting port of the smelting process of the smelting process, and the copper-containing smelting slag obtained by the slag discharging port of the "copper smelting" process blowing furnace are added to the slag pot. At the same time, limestone and Fe are added to form mixed slag; the oxygen-enriched air at a temperature of 100 ° C is used to spray the bituminous coal with a particle size of ≤150 μm, and the mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is realized. Mixing; monitoring the reaction slag in real time, and simultaneously controlling the two parameters (a) and (b) to obtain the slag after completion of the reaction;

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 1.4, both within the required range; the metal iron content in the slag is 2.8 %;

Step 2, separation and recovery method 5:

After the temperature was kept for 49 minutes, the slag after the completion of the reaction was spin-cooled, and the following steps were performed:

(1) Settling cooling: After the completion of the reaction, the slag is rotated and cooled to room temperature to obtain slow cooling slag; the copper-rich phase is settled to the bottom of the reaction device to form a copper-rich bismuth; the iron-containing silicate mineral phase is floated; the copper-rich phase and The iron-containing silicate mineral intermediate slow cooling slag 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 bismuth settled at the bottom, directly reducing, magnetically separating the iron, and then sending the product to the converter; the iron-rich phase in the middle is magnetically separated to separate the metal iron, and then sent to the converter for iron making;

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

(4) Some zinc components and lead components volatilize and enter the soot recovery as oxides; the slag contains copper <0.15%, the iron recovery rate is 91%, the zinc recovery rate is 92%, and the lead recovery rate is 95. %, the gold enrichment rate is 94%, and the silver enrichment rate is 96%.

Example 6

Step 1, slag mixing: the copper-containing smelting slag obtained from the slag-containing slag obtained from the smelting smelting furnace of the smelting process, and the copper-containing blowing slag obtained from the slag discharging port of the "copper smelting" process blowing furnace is added to the alternating current arc furnace At the same time, adding lime, MgO, Al ₂ O ₃ , Fe ₂ O ₃ to form a mixed slag; heating the mixed slag to a molten state to form a copper-containing reaction slag, spraying argon gas at a temperature of 1100 ° C, and The reaction slag is mixed; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling both parameters (a) and (b);

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 1350 ° C; (b): the alkalinity CaO / SiO ₂ ratio of the copper-containing reaction slag is 0.1, to the reaction melt Alkaline iron concentrate, blast furnace gas mud, alkaline pre-reduction pellets, converter steel slag are added to the slag to increase the alkalinity ratio of the copper-containing reaction slag to 0.4; natural gas is sprayed, and the metal iron content in the slag is 2.2%. ;

Step 2, separation and recovery method 1:

After 38 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 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 second method, Method A, and water quenched directly as 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 and the lead-containing component volatilize and enter the soot recovery as an oxide; the slag contains copper <0.1%, the iron recovery rate is 91%, the zinc recovery rate is 92%, and the lead recovery rate is 94%, the gold enrichment rate is 94%, and the silver enrichment rate is 96%.

Example 7

Step 1. Slag mixing: adding the cold copper-containing smelting slag of the "smelting smelting" process, the cold copper-containing blowing slag of the "copper smelting" process, and the wet copper slag to the ore furnace, and adding limestone at the same time. , SiO ₂ , FeO and MgO form a mixed slag; the mixed slag is heated to a molten state to form a copper-containing slag, and an argon-nitrogen mixed gas having a temperature of 200 ° C is sprayed, and the slag is mixed; Monitoring the reaction slag, and ensuring the two parameters of (a) and (b) by regulation to obtain the completed slag;

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; adding pulverized coal with a particle size of ≤ 150 μm , the metal iron content in the slag is 2.4%;

Step 2, separation and recovery method 4:

After holding for 39 minutes, the molten slag after the completion of the reaction was poured into the thermal insulation slag tank, and the sediment was sedimented and separated by slag-gold to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and a zinc component and lead were simultaneously formed. The components, which enter the soot and are recovered as oxides, are subjected to the following steps:

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

(2) The molten iron-rich phase and the iron-containing silicate mineral are separated and recovered in the second method, Method C, and the molten slag is cast into the glass ceramics;

(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 At 93%, the gold enrichment rate is 95% and the silver enrichment rate is 97%.

Example 8

Step 1. Slag mixing: adding cold copper-containing smelting slag from the “smelting smelting” process, cold copper-containing blowing slag of the “copper smelting” process, and depleted slag to the blast furnace, and adding dolomite and red Mud, MgO, using 600 ° C oxygen, sprayed into the gas and coke powder with particle size ≤ 150μm, the mixed slag is heated to a molten state, forming a copper-containing reaction slag, and the reaction slag is mixed; real-time monitoring of the reaction slag After the two parameters of (a) and (b) are simultaneously controlled, the completed slag is obtained;

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 2.7 %;

Step 2, separation and recovery method 3:

After 33 min 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 middle-upper portion, and at the same time, a zinc-containing component and a lead-containing component are formed, and the dust is introduced into the dust. To recover as oxide, proceed as follows:

(1) The iron-containing silicate mineral phase, specifically adopting the method B in the separation and recovery method of the second step, and returning the middle and upper slag to the copper-containing reaction slag as a hot metallurgical flux to adjust the slag composition. , controlling the slag temperature;

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

(3) Some of the zinc-containing components and the lead-containing components are volatilized, and are collected into the dust as oxides, and the slag contains copper <0.1%. The recovery of iron was 95%, the recovery of zinc was 93%, the recovery of lead was 94%, the enrichment rate of gold was 98%, and the enrichment rate of silver was 96%.

Example 9

Step 1, slag mixing: copper-containing smelting slag and copper slag obtained from the slag-containing slag obtained by the smelting smelting process of the smelting smelting process and the slag vent of the "copper smelting" process blowing furnace The flotation tailings is added to the side blowing furnace, and limestone is added at the same time to form mixed slag; the preheated air with a temperature of 1100 ° C is sprayed with ≤150 μm coke powder, and the mixed slag is heated to a molten state to form a copper-containing reaction slag. And the reaction slag is mixed; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling and simultaneously ensuring two parameters (a) and (b);

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 1.7 %;

Step 2, separation and recovery method 5:

After 19 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a copper-rich phase and a medium-upper iron-containing silicate mineral phase, and at the same time, a zinc-containing component and a lead-containing component are formed, and the smoke is entered into the dust. To recover the oxide form, proceed as follows:

(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 is sent to the converter;

(3) Part of the zinc-containing component and lead-containing component enter the soot as oxide; the slag contains copper <0.1%, the iron recovery rate is 93%, the zinc recovery rate is 94%, and the lead recovery rate is 95. %, the gold enrichment rate is 94%, and the silver enrichment rate is 96%.

Example 10

Step 1, slag mixing: the copper-containing smelting slag obtained from the slag smelting port of the smelting process of the smelting process, and the copper-containing smelting slag obtained by the slag discharging port of the "copper smelting" process blowing furnace are added to the heat preservation pit. At the same time, adding limestone and Fe to form mixed slag; using oxygen-enriched air with a preheating temperature of 600 ° C, blowing bituminous coal with a particle size of ≤150 μm, heating the mixed slag to a molten state, forming a copper-containing reaction slag, and melting the reaction The slag is mixed; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling and simultaneously ensuring two parameters (a) and (b);

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 2.2 %;

Step 2, separation and recovery method 5:

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

(1) Settling cooling: holding for 20 min, the slag after the reaction 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 copper-rich strontium; the silicate mineral phase floats; the copper-rich phase And the iron-silicate silicate mineral phase silicate mineral intermediate slow-cooling slag is iron-rich phase, and at the same time, the zinc-containing component and the lead-containing component are generated;

(2) Separation: manually extracting the copper-rich strontium deposited at the bottom; after the direct reduction of the iron-rich phase 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) Part of the zinc component and the lead component volatilize, and enter the soot recovery as an oxide; the slag contains copper <0.15%, the iron recovery rate is 98%, the zinc recovery rate is 95%, and the lead recovery rate is 93. The enrichment rate of % gold is 95%, and the enrichment rate of silver is 96%.

Claims

A method for recovering valuable components from copper-containing slag, characterized in that it comprises the following steps:

S1, slag mixing: adding copper slag to the smelting reaction device, adding calcium minerals and additives to form mixed slag, heating the mixed slag to a molten state as reaction slag, mixing uniformly, and monitoring the reaction slag in real time, The slag after the reaction is obtained by adjusting the mixed reaction slag to satisfy the condition a and the condition b, or the slag after the reaction is poured into the heat preservation device;

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 bottom copper-rich phase, the middle iron-rich phase and the upper iron-containing silicate mineral phase are obtained by sedimentation and separation, and the zinc-containing component and the The smoke and dust of the lead component migrate and enrich the gold and silver components 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, using the heating of the reaction device itself, or adding fuel and preheated oxidizing air to the slag, so that the temperature of the reaction slag reaches 1100 ~ 1450 ° C;

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 or a fluorine-containing material is added to the reaction slag, and the mixture is uniformly mixed to make the mixed reaction slag The temperature reaches 1100 ~ 1450 ° C;

The method for regulating the condition b is:

When the ratio of alkalinity CaO/SiO 2 in the reaction slag is <0.15, an alkaline material and/or an alkaline iron-containing material is added to the reaction slag;

When the ratio of alkalinity CaO/SiO 2 in the reaction slag is >1.5, an acidic material and/or an acidic iron-containing material is added to the reaction slag.
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, simultaneous control of reduction of copper oxide and iron oxide in said reaction slag to metal is satisfied. Copper and FeO, the metal iron content in the reaction slag is <3%.
The method according to claim 1, wherein the copper slag is one of copper-containing smelting slag, copper-containing blowing slag, copper-fired depleted slag, flotation tailings, and wet copper slag. Or several, wherein the copper-containing smelting slag is produced in a "smelting smelting" process of a copper pyrometallurgical slag, which is produced in a copper smelting process of "copper smelting" a process, the copper fire method depleted waste slag is a copper smelting slag and a copper-containing smelting slag, and the waste slag is a tail slag after the copper-containing smelting slag and the copper-containing smelting slag. The wet copper slag is a waste slag after the wet copper smelting; the copper smelting slag, the copper containing slag and the depleted slag are in a molten state or a cold state, wherein: the molten copper smelting slag Obtained from the slag-out of the copper-containing smelting furnace in the process of "smelting and smelting", or heating the smelting slag containing copper to a molten state, the copper smelting furnace in the molten copper state is blown by the "copper smelting" process Obtaining the slag outlet, or heating the copper blowing slag to a molten state, and obtaining the depleted slag from the slag outlet of the depleted furnace, and heating the depleted slag to a molten state;

The calcium-based mineral is one or more of lime, limestone, dolomite, calcium carbide slag, red mud or high-calcium red mud after de-sodium removal;

The additive is one or more of SiO 2 , MgO, FeO, Fe 2 O 3 , MnO 2 , Al 2 O 3 , TiO 2 , Fe or Na 2 O.
The method according to claim 2, wherein the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead smelting slag, lead Zinc tailings, nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag, lead-containing smelting furnace slag, lead smelting soot and soot, lead-acid battery, copper smelting soot and dust, copper, containing One or more kinds of copper garbage, copper-containing circuit board, tin smelting slag, tin tailings; wherein the copper slag is copper-containing smelting slag, copper-containing blowing slag, copper fire-depleted slag, One or more of flotation tailings and wet copper slag; lead-containing slag is smelting furnace slag and lead smelting slag, “ISP lead-zinc blast furnace reduction” or “sinter blast furnace reduction” or “solid lead” The slag reduction or the liquid high lead slag reduction process produces a lead-containing smelting slag, and the lead smelting slag is smelted by a smelting furnace to produce a lead-containing smelting furnace slag; the nickel smelting slag is a smelting smelting process produced by the smelting smelting process Depleted slag after slag, "copper ice nickel blowing" process, nickel produced by top blowing smelting One or more of the settled slag; the zinc smelting furnace slag includes slag produced by wet zinc smelting and slag produced by wet zinc smelting, wherein the slag produced by the wet zinc smelting is zinc leaching slag, volatile kiln slag, iron slag, After pickling, iron ore slag, goethite slag, hematite slag one or more, vertical tank zinc smelting is one or more of vertical tank zinc slag, vortex smelting slag, blast furnace slag, electric furnace slag;

The metallurgical flux is a mineral containing CaO or SiO 2 , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone;

The iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon-bearing pre- Reducing pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag, copper slag, lead smelting slag, copper slag, tin smelting slag, red mud, high calcium after desodium One or more of red mud, coal dust ash, sulfuric acid slag; the steel dust and dust including blast furnace gas mud, converter dust mud, electric furnace dust, hot or cold rolling sludge, sintering dust, pellets Dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale;

The fluorine-containing material is one or more of fluorite, CaF 2 or fluorine-containing blast furnace slag.
The method according to claim 2, wherein 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 The particle size is 5~25mm, the powdery material is sprayed by spraying, and the granular material is added by spraying or feeding, and the gas is loaded into argon gas, nitrogen gas, reducing gas and oxidizing gas of 0-1200 °C. One or more of the following methods; the injection method is one or several types in which a refractory spray gun is inserted into the slag or placed in the upper portion or the side or bottom of the reaction slag; the alkaline material is lime powder. One or more of red mud, high calcium red mud, calcium carbide slag, dolomite powder or quicklime powder after de-sodium removal; the basic iron-containing material is CaO/SiO 2 >1 iron-containing material, alkaline One or more of sinter, alkaline iron concentrate, iron alloy slag, steel slag, alkaline pre-reduction pellet, alkaline metallized pellet, steel slag or blast furnace slag; the acidic material is silica, fly ash One or more of coal gangue; the acidic iron-containing material is CaO/SiO 2 ≤1 Iron material, acid sinter, acid iron concentrate, acid pre-reduction pellet, acid metallized pellet, copper slag, lead slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, blast furnace slag One or several.
The method according to any one of claims 1 to 7, 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 containing the iron-rich phase layer for water quenching or air cooling or pouring into a heat preservation device, slow cooling by manual sorting and re-election, as a blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material or flotation Copper extraction raw materials or magnetic separation and separation of metal iron as raw materials 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 raw materials Or directly reducing the ironmaking raw material or the smelting reduction ironmaking raw material; wherein, in the direct reduction process, after the magnetic reduction of the reduced product, the metal iron and the tailings are obtained, and the tailings are returned to the copper smelting system; 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 breeze Or one or more of coke, the controlled reduction temperature is 900-1400 ° C, and the control alkalinity CaO / SiO 2 ratio = 0.8 ~ 1.5.
The method of claim 8 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 fuel and the reducing agent are one or more of a solid, a liquid or a gas, which is sprayed or fed, and the injected gas is preheated in an 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.
The method according to claim 1, wherein in the step S1, the mixing is uniformly performed by natural mixing or stirring, and the stirring mode is argon stirring, nitrogen stirring, nitrogen-argon gas mixture stirring, reduction. 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.