WO2019071794A1

WO2019071794A1 - Method for recovering valuable components from mixed slag containing copper and iron

Info

Publication number: WO2019071794A1
Application number: PCT/CN2017/115649
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: CN107699704A

Abstract

Provided is a method for recovering valuable components from mixed slag containing copper and iron, which comprises S1, mixing slag; adding copper slag into a smelting reaction device, and simultaneously adding one or more of lead smelting slag, blast furnace slag, steel slag and ferroalloy slag to form mixed slag; heating the molten slag to a molten state to form reaction molten slag, mixing evenly, meeting the requirements that the temperature of the molten slag is 1050-1450℃ and the alkalinity CaO/SiO2 ratio of the molten slag is equal to 0.15-1.5, to obtain the reacted molten slag; S2, separating and recycling. The recovery of copper, iron, zinc, lead, gold and silver in non-ferrous metallurgical slag and iron and steel metallurgical slag is realized, and the problems of large accumulation of slag and environmental pollution at present are solved.

Description

Method for recovering valuable components from mixed slag containing copper and iron

Technical field

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

Background technique

China is the world's largest producer of metallic copper, metal lead, steel and ferroalloys. The copper smelting process "smelting smelting - copper smelting" produces copper slag, which is the first solid waste in heavy ferrous metallurgy. The lead smelting process "sintering - blast furnace reduction - smelting furnace" or direct smelting process "oxidation blowing - high lead slag reduction - smelting furnace" and other processes have produced lead smelting slag. In the steel production process, blast furnace slag, steel slag, and iron alloy slag are produced, which is the first solid waste.

The copper slag includes copper-containing smelting slag, copper-containing blowing slag, copper-fired depleted slag, copper slag flotation tailings, and wet copper slag. The copper-containing smelting slag is produced in the process of “smelting and smelting”. It contains not only copper, iron, zinc, nickel, precious metals, but also high-level SiO ₂ , CaO and other metallurgical fluxes. It emits more than 20 million tons per year. More than 200 million tons of deposits. With the continuous development of copper metallurgy technology, the traditional copper smelting process is gradually being replaced by new technologies such as flash smelting, Noranda, Vanukov, Aisa, Osmet, Mitsubishi, Jinfeng and Bottom. The copper content is up to 20%, which is much higher than the current 0.2%% copper ore grade. The iron content is as high as 50%, which is much larger than the average grade of 29% by weight of smelting iron ore. The slag also contains precious metals, which are an important secondary resource. The molten copper smelting slag discharged from the melting furnace is higher than 1100 ° C and is an important physical heat resource.

"Bronze crucible blowing" produces copper-containing blowing slag (converter blowing slag, flash blowing slag, top blowing furnace blowing slag, low blowing furnace blowing slag, etc.), the copper content in the slag reaches 35%, iron content Up to 55%, it also contains valuable components such as zinc, lead and precious metals. Molten copper-containing blowing slag is also an important physical thermal resource.

The copper-containing smelting slag and the copper-containing blowing slag are returned to the smelting furnace or the depletion or ore dressing method. The depletion or beneficiation effect is not good. After the depletion of the fire or after the flotation, the copper slag contains a large amount of heavy metals, and a large amount of long When time accumulates, it will pollute the surrounding environment. After the copper slag method is depleted or ore-selected, the slag contains more than 0.4% copper, which is higher than the recoverable grade of copper by 0.2%. The higher slag contains copper, which is not conducive to the subsequent reduction of iron. 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, and cracks occur during rolling.

Lead smelting slag is produced in the process of lead smelting process "sintering-blast furnace reduction-smoke furnace" or "oxidation blowing-high lead slag reduction-smoke furnace". Lead smelting slag includes lead smelting slag and smelting furnace slag. "Sintering blast furnace reduction" or "solid high lead slag reduction" or "liquid high lead slag reduction process" reduction process produces lead-containing smelting slag, lead smelting slag is smelted by smelting furnace to produce smelting furnace slag, lead smelting slag contains copper Components such as gold, silver, iron, zinc and lead are important secondary resources. Lead smelting slag temperature is ≥1050 °C, which is an important physical thermal resource.

Blast furnace slag, steel slag and iron alloy slag contain high content of metal iron, iron oxide, SiO ₂ , CaO, MgO and other valuable components are important secondary resources; molten slag is discharged from blast furnace, steelmaking furnace and ferroalloy furnace At ≥1300 °C, molten blast furnace slag, molten steel slag and molten iron alloy slag are also important physical thermal resources. These physical thermal resources are not well utilized, and the accumulation of large amounts of slag not only occupies a relatively large space, but also brings serious environmental pollution.

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 for recovering valuable components from a mixed slag containing copper and iron. The method has the advantages of short reaction time, short process flow, high metal recovery rate, low production cost, large processing capacity, environmental friendliness and high economic benefit, and can effectively solve the problem of efficient recycling of metallurgical resources and thermal energy; and environmental pollution problems. The invention provides a new slag metallurgy process, which not only reduces the copper content of the slag, but also contains copper <0.1wt% in the slag, and realizes copper, gold, silver, iron, zinc, lead, indium, antimony, sodium, Efficient recovery of potassium components to obtain low copper iron Materials (iron concentrate and pig iron).

(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 slag containing copper and iron, comprising the steps of:

S1, slag mixing: adding copper slag to the smelting reaction device, adding one or more of lead smelting slag, blast furnace slag, steel slag and iron alloy slag to form mixed slag; heating the mixed slag to a molten state to form a reaction The slag is uniformly mixed, the reaction slag is monitored in real time, the reaction slag is controlled by regulation, and the condition s and condition b are satisfied, the slag after the reaction is obtained, or the slag after the reaction is poured into the heat preservation device;

Wherein the condition a is a slag temperature of 1050 to 1450 ° C;

The condition b is the 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 settled, and the copper-rich phase at the bottom, the iron-rich phase in the middle and the iron-containing silicate mineral phase in the upper portion are separated, and zinc is formed at the same time. The components and the lead-containing component of the soot, the gold and silver components are enriched into the copper-rich phase; the phases are recovered.

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 <1050 ° C, a heating function of the reaction device itself, or a fuel or molten copper slag, molten lead smelting slag, molten blast furnace slag, molten steel slag or molten iron alloy slag is added to the slag. One or more kinds, when the fuel is injected, the oxidizing gas is simultaneously injected, so that the temperature of the reaction slag reaches 1050 to 1450 ° C;

When the temperature of the reaction slag is >1450 ° C, one of a copper-containing material, a nickel smelting slag, a blast furnace slag, a steel slag, a ferroalloy slag, a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag or Several, so that the temperature of the mixed slag reaches 1050 ~ 1450 ° C;

The method for regulating the condition b is:

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, Osmeite furnace, copper smelting furnace electric heating bed, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing Rotary furnace, top blowing rotary furnace.

In the method as described above, preferably, in the step S1, while satisfying the conditions a and b, it is simultaneously satisfied that the slag is controlled to maintain copper oxide and iron oxide reduced to metallic copper and FeO, The metal iron content in the slag is less than 3%, by adding one or two of a reducing agent and a carbon-containing iron-containing material, wherein the reducing agent and/or the carbon-containing iron-containing material is used in the slag The theoretical amount of copper and iron oxide reduced to metallic copper and FeO is 110-140%; the carbon-containing iron-containing material is steel dust and soot, iron concentrate carbon-containing pre-reduction pellet, iron concentrate carbon-containing metal Pellet, wet zinc smelting kiln slag or coke oven dust and soot.

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. Copper-containing smelting slag is produced in the “smelting and smelting” process of copper pyrometallurgical smelting process, including Osmet furnace smelting slag, flash furnace smelting slag, Noranda furnace smelting slag, Isa furnace smelting slag, Kraft furnace smelting slag, Mitsubishi smelting slag, Caldo furnace smelting slag, silver furnace smelting slag, Shuikoushan smelting slag, Tennite smelting slag, reverberatory furnace smelting slag, electric furnace smelting slag, closed blast furnace smelting slag, low Blowing furnace Smelting slag, side-blown furnace smelting slag; the copper-containing blowing slag is produced in the "copper smelting" process of copper pyrometallurgical smelting process, including converter blowing copper slag, flash furnace blowing copper slag, Nolan Continuously blowing copper slag in a furnace, blowing copper slag in a top blowing furnace, blowing copper slag in a side blowing furnace, blowing copper slag in a bottom blowing furnace, continuously blowing copper slag in a top blowing furnace, continuously blowing copper slag in a side blowing furnace, The bottom blowing furnace continuously blows the copper slag; the copper fire depleted waste slag is a copper smelting slag and a copper-containing blowing slag, and the waste slag is a copper-containing smelting slag and a copper-containing blowing slag. After tailing, the wet smelting copper slag is the waste slag produced by the wet copper smelting; the copper smelting slag and the copper smelting slag are in a molten state or a cold state, wherein: the molten copper smelting slag is processed by the “smelting smelting” process The copper smelting furnace obtains the slag opening, or heats the copper-containing smelting slag to a molten state, and the molten copper blowing slag is obtained from the copper smelting furnace slag opening of the "copper smelting" process, or the copper blowing slag is heated In the molten state, the depleted waste is obtained from the slag outlet of the depleted furnace, and the depleted slag is heated to a molten state;

The lead smelting slag comprises a smelting furnace slag and a lead smelting slag, and the lead smelting slag is in a molten state or a cold state, wherein the molten slag is discharged from the slag outlet or the slag slag outlet of the reduction stage of the pyrometallurgical lead process Obtained; the blast furnace slag, steel slag and iron alloy slag are in a molten state, or in a cold state, wherein: molten slag (including blast furnace slag, steel slag and iron alloy slag) is obtained from a slag outlet, or cold slag (including blast furnace slag, Steel slag and iron alloy slag are heated to a molten state; the steel slag is molten iron pre-desulfurization slag (including desulfurization slag, desiliconization slag, dephosphorization slag), converter slag, electric furnace slag, VOD/VAD slag, VD slag, and intermediate package waste slag; The iron alloy slag is slag generated in the production process of iron alloy, including slag produced by smelting carbon ferromanganese, slag produced by smelting ferrochrome, slag produced by smelting ferronickel, slag produced by smelting ferrovanadium, slag produced by smelting ferrosilicon Smelting slag from smelting iron and slag from smelting ferromolybdenum

The lead smelting slag is produced by a smelting furnace slag and lead-containing smelting slag, "ISP lead-zinc blast furnace reduction" or "sinter blast furnace reduction" or "solid high-lead slag reduction" or "liquid high-lead slag reduction process" reduction process Lead-containing smelting slag, lead-containing smelting slag is smelted by a fuming furnace to produce lead-containing smelting furnace slag.

In the method as described above, preferably, the fuel is one or more of a solid, liquid or gaseous fuel, which is sprayed or fed, loaded with a gas at 0-1200 ° C, the gas Is one or more of an oxidizing gas, argon gas, and nitrogen gas;

Preferably, the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead-zinc tailings, lead smelting slag. Lead smelting slag, nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag containing lead fuming furnace slag, lead smelting soot and dust, lead acid battery, copper smelting soot and dust, copper, Copper-containing garbage, copper-containing circuit board, tin smelting slag, tin tailings; copper slag includes slag produced by "smelting smelting" and slag generated by "copper smelting", pyrolysis slag, copper slag flotation tail Slag, flotation tailings, wet copper slag; the lead smelting slag is smelting furnace slag and lead smelting slag, "ISP lead-zinc blast furnace reduction" or "sinter blast furnace reduction" or "solid high-lead slag reduction Or the "liquid high-lead slag reduction process" reduction process produces lead-containing smelting slag, which is smelted by a smelting furnace to produce lead-containing smelting furnace slag; the nickel smelting slag is a smelting smelting process produced by the "smelting smelting" process Depleted slag and top blow smelting after slag and "copper ice nickel blowing" process One or more of nickel slag slag; the smelting slag comprises slag produced by wet zinc smelting and slag produced by pyrometallurgical slag, wherein slag produced by wet zinc smelting is zinc leaching slag, volatile kiln slag, iron One or more kinds of slag, copper cadmium slag, pickled iron slag, goethite slag, hematite slag, fire smelting slag is vertical tank zinc slag, vortex smelting slag, blast furnace slag, smouldering One or more kinds of slag and 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 containing Carbon pre-reduction pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dusty nickel smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high after de-sodium One or more of calcium red mud, lead smelting slag, high calcium red peat ash, copper tailings, sulfuric acid slag; the steel soot and dust including blast furnace gas, converter dust, Electric furnace dust, hot or cold-rolled sludge, sintered dust, pellet dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale;

The fluorine-containing material is one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag; the alkaline material is lime powder, red mud, high-calcium red mud after desodiumification, calcium carbide slag, dolomite powder Or one or more of the quicklime powder; the alkaline iron-containing material is a CaO/SiO ₂ >1 iron-containing material, an alkaline sintered ore, an alkaline iron concentrate, an alkaline pre-reduction pellet, and a base. One or more of a metallized pellet, steel slag or blast furnace slag.

Preferably, the acidic material is one or more of silica, lead smelting slag containing gold silver silica, fly ash, coal gangue; the acidic iron-containing material is CaO / SiO2 ≤ 1 Iron-containing material, acidic sinter, acid iron concentrate, acid pre-reduction pellet, acid metallized pellet, copper slag, lead smelting lead smelting slag, zinc smelting slag, nickel smelting slag One or more of tin smelting slag, iron alloy slag, and blast furnace slag

The copper-containing material and the iron-containing material are in a hot or cold state, wherein the hot material is directly obtained from a metallurgical furnace discharge port or a slag outlet. Wet zinc slag, wet copper slag and dust must be dehydrated and dried.

Further, the solid fuel is one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite coal, and the shape is granular or powder, and the granular material has a particle size of 5 to 25 mm, and the granular material particle size ≤ 150 μm; the liquid fuel is heavy oil, and the gaseous fuel is gas and/or natural gas.

In the method as described above, preferably, in the step S1, the mixing is uniform for natural mixing or stirring mixing, wherein the stirring and mixing is performed by argon stirring, nitrogen stirring, nitrogen-argon gas mixture stirring, reduction. One or more of gas agitation, oxidative gas agitation, electromagnetic agitation or mechanical agitation;

The method as described above, preferably, in the separation and recovery in the step S2, the copper-rich phase settled at the bottom, the iron-rich phase in the middle portion, and the upper iron-containing silicate mineral phase may be separately treated, or The upper middle iron is combined with the iron-containing silicate mineral, the gold component and the silver component migrate and enrich and enter the copper-rich phase, and the zinc-containing component and the lead-containing component volatilize, and enter the dust recovery as an oxide. .

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 iron weight percentage is <1%, and the oxidized slag is obtained; the oxidized slag is directly air-cooled or water-quenched, and is used as a slag cement, a cement conditioner, an additive in cement production or a cement clinker;

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, decalcified high calcium red mud or calcium carbide slag, fully mixed to obtain 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 is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: After the iron-containing silicate slag is air-cooled, water-quenched or slowly cooled, it is used as a blast furnace ironmaking or direct reduction ironmaking raw material, and after direct reduction, magnetic separation or electric furnace melting is used, and the magnetic separation product is metal iron and tail. Mine, electric furnace melting, the product is molten iron and slag;

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 1350~1650 ° C and the ratio of alkalinity CaO / SiO _{2 of the} reaction slag is 0.6-2.4, and the slag after completion of the reaction is obtained;

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 >1650 ° 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 1650 ° C, wherein The metallurgical flux is a mineral containing CaO or SiO ₂ , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone;

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

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 cool to room temperature to obtain slow cooling slag; wherein, the metal iron is settled to the bottom of the reaction device to form iron slag, and the remaining chilled slag contains metal iron layer , crushed to a particle size of 20 to 400 μm, grinding, magnetic separation to separate the remaining metal iron and tailings;

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

S2-1-02, the copper-rich phase, sent to a converter or a blowing furnace for copper smelting or slow cooling and magnetic separation to separate metal iron, and then sent to 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 subjected to water quenching or air cooling or poured into a heat preservation device for slow cooling, and is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material or a smelting reduction ironmaking raw material or a flotation copper extraction raw material or Magnetic separation of metal iron as a raw material for copper smelting or direct reduction of iron; in the direct reduction process, after reduction and magnetic separation of the reduction product, metal iron and tailings are obtained, and tailings are returned to the copper smelting system; during flotation, flotation The product is a copper-bearing concentrate and iron concentrate, and the copper concentrate is returned. Copper smelting system, iron concentrate as raw material for blast furnace ironmaking or direct reduction of ironmaking raw materials or smelting reduction of ironmaking raw materials;

Wherein, in the direct reduction process, after the reduction product is magnetically separated and separated, the metal iron and the tailings are obtained, and the tailings are returned to the copper smelting system; the direct reduction process uses a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, and a slewing The kiln or induction furnace is used as a reduction device, and the gas-based or coal-based reduction technology is used to reduce the gas base to natural gas and/or gas, and the coal base is reduced to one or more of anthracite, bituminous coal, lignite, coking coal, coke breeze or coke. The reduction temperature is 900-1400 ° C, the alkalinity CaO / SiO ₂ ratio = 0.8 ~ 1.5; the gas produced by the reduction is secondarily burned on the surface of the slag, providing heat, and the gas flowing out of the furnace can be used as a drying charge and Heat source of the heat preservation device;

In addition, since the red mud contains potassium, sodium, dust, and steel soot containing lead, zinc, antimony, and indium silver, when these materials are added, some indium, antimony, potassium, and sodium groups are added. It is volatilized and enters the soot as an oxide.

Method 2: When the smelting reaction device through which the slag can flow out is used, the obtained iron-rich phase and the iron-containing silicate mineral phase treatment method are treated by one or more of the methods A to G described in the first method, Or pour into the copper-rich phase after the slow cooling of the heat preservation device, send it to the converter or the smelting furnace for copper smelting, or pulverize and separate the metal iron, then send it to the converter or the smelting furnace to smelt copper, or magnetically separate the metal iron or After the metal iron is separated by magnetic separation, it is directly reduced, and the reduced product is magnetically separated to separate the metal iron, and then sent to a converter or a blowing furnace for copper smelting.

Method 3, using the slag rotatable converter and the reaction slag tank, obtaining the molten iron-containing silicate mineral phase, and the treatment method is treated by one or more of the methods A to G described in the first method; The step of containing the iron-rich phase is carried out by a method S2-1-05; the molten state or the copper-rich phase after being poured into the heat-insulating device to be cooled, sent to a converter or a blowing furnace for copper smelting, or crushed magnetic separation After separating the metal iron, it is sent to the converter or the blowing furnace for copper smelting, or the metal iron is separated by magnetic separation or the metal iron is separated without magnetic separation, and then directly reduced, and the reduced product is separated by magnetic separation and then sent to the converter or Blowing furnace copper smelting.

Method 4, using a molten slag rotatable converter and a reaction slag tank, the obtained molten iron-containing silicate mineral phase and the iron-rich phase are obtained, and the treatment method is one or more of the methods A to G described in the first method. The molten copper-rich phase is poured into a heat preservation device to be cooled, and then sent to a converter or a blowing furnace for copper smelting, or after slow cooling, the metal iron is separated by crushing and then sent to a converter or a smelting furnace for copper smelting. , 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 the converter or blowing furnace copper.

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

S201, sedimentation cooling: the slag is slowly cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to the bottom of the reaction device to form a copper-rich strontium; the iron-containing silicate mineral phase floats; the middle is slow cooling slag For the iron-rich phase, a zinc-containing component and a lead-containing component are simultaneously formed; wherein the nickel, cobalt, gold, and silver components migrate to the copper-rich phase;

S202. Separation: manually extracting the copper-rich bismuth deposited at the bottom, or separating the metal iron by the copper-filled mash, and then sending it to the converter or the smelting furnace for copper smelting, or separating the metal iron by magnetic separation or separating the metal without magnetic separation. After iron, direct reduction, the reduction product is separated by magnetic separation and then sent to a converter or a rotary furnace for copper smelting; the iron-rich phase and the iron-containing silicate phase are used as raw materials for blast furnace ironmaking or direct reduction of ironmaking raw materials. Or smelting reduction ironmaking raw materials or smelting reduction ironmaking raw materials or flotation copper extraction raw materials or magnetic separation of metallic irons as raw materials for copper smelting or direct reduction ironmaking; in direct reduction process, after reduction products are magnetically separated and separated, metal is obtained Iron and tailings, tailings return to copper smelting system; flotation products are copper-bearing concentrates and iron concentrates, copper concentrates are returned to copper smelting system, iron concentrates are used as blast furnace ironmaking raw materials or direct reduction of ironmaking raw materials or smelting reduction Ironmaking raw materials;

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.

As described above, preferably, the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, nitrogen-air, argon-air, oxygen-nitrogen, oxygen-argon.

Preferably, the mixing is a natural mixing or a stirring mixing, wherein the stirring and mixing is performed by argon stirring, nitrogen stirring, nitrogen-argon gas mixture stirring, reducing gas stirring, oxidizing gas stirring, and electromagnetic stirring. One or more of stirring or mechanical agitation; in the step S2, the sedimentation is natural sedimentation or spin sedimentation or centrifugal sedimentation; the cooling mode when performing cooling sedimentation is natural cooling or rotary cooling or centrifugal cooling. When separating, the gravity sorting method is a shaker sorting, a 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 a mixed slag containing copper and iron according to the present invention, which can treat hot slag and make full use of molten copper slag and molten metallurgical slag (melted lead smelting slag, molten blast furnace slag, One or more of molten steel slag and molten iron alloy slag) physical thermal resources and hot metallurgical flux, which can also process cold slag, and realize slag metallurgical modification by slag mixing or cold mixing; (2) Metallurgical reaction of slag in mixed slag, disintegration of fayalite, iron oxide is fully released, enters iron-rich phase, and grows and settles. The iron-rich phase includes various kinds of metal iron, FeO phase and fayalite phase. As a raw material for blast furnace ironmaking or direct reduction or smelting reduction of iron; metal iron component in the mixed slag is aggregated, grown and settled; (3) copper component and gold and silver components in the mixed slag are separately enriched In the copper-rich phase, and to achieve growth and sedimentation, the copper-rich phase includes copper, white copper, matte, white copper, iron-containing components, or part of the copper component into the iron-rich phase, rich The copper phase is sent to the converter or the converter to smelt copper; (4) the zinc component in the mixed slag The lead component is separately enriched in soot and recovered; (5) part of the indium-containing component, antimony component, potassium-containing component, and sodium-containing component are volatilized into the dust for recovery; (6) free calcium oxide in the mixed slag With magnesium oxide disappearing, mixed slag to achieve quenching and tempering; (7) manual sorting, magnetic separation, re-election, slag gold separation method, separation of copper-rich phase at the bottom, iron-rich phase in the middle and upper silicon Acid salt mineral phase, which realizes copper component, gold component, silver component, indium component, bismuth component, sodium component, potassium component, iron component, zinc component and lead component in the mixed slag (8) It can process solid copper and iron materials to achieve efficient and comprehensive utilization of resources; (9) The invention uses mixed slag to help the copper-rich phase settle, so that the sedimentation and separation can be obtained as low-copper iron-rich phase. The iron-containing silicate phase, wherein the iron-rich phase and the iron-containing silicate phase have a copper content of less than 0.1%, and the iron can be obtained by direct reduction or smelting reduction to obtain metallic iron and molten iron; (10) the present invention adopts mixed melting Slag, the whole process does not require heating or a small amount of compensation for heat. The entire process can be processed without cold metallurgical flux or a small amount of metallurgical flux. The process of the invention can be carried out continuously or intermittently to meet the needs of industrial production.

(3) Beneficial effects

The beneficial effects of the invention are:

(1) The invention realizes comprehensive utilization of the valuable components of the copper component, the iron component, the zinc component, the lead component, the gold, the silver, the phosphorus, the calcium and the silicon component in the nonferrous metallurgical slag and the iron and steel metallurgical slag, and solves the problem At present, a large amount of slag is accumulated and environmental pollution problems; (2) The invention can treat iron alloy slag, steel slag, blast furnace slag, lead smelting slag and copper-containing slag on a large scale, can solve the problem of heavy metal element pollution, and realize the recovery of heavy metal components; The invention can treat a small amount of cold copper-containing and iron-containing materials; (4) the raw material of the invention can be liquid molten copper slag and molten metallurgical slag (melted lead smelting slag, molten blast furnace slag, molten steel slag, One or more of the molten iron alloy slags have the characteristics of high temperature and high heat, and make full use of the slag physical heat resources; the mixed slag contains a large amount of hot metallurgical flux, which are all excellent in physical and chemical properties. The slag system realizes the efficient utilization of metallurgical resources and thermal resources; fully utilizes the characteristics of high reaction chemical activity of mixed slag, and realizes slag metallurgy; (5) the invention is mixed by slag, heat preservation The gas is blown, the oxygen potential is controlled, and the copper group, the gold component and the silver component in the slag are enriched to the copper-rich phase to achieve aggregation, growth and sedimentation, and the iron component is concentrated in the copper-rich phase to achieve aggregation. Growing up and sedimentation, the lead component and the zinc component are enriched in the soot to be recovered; the zinc component, the lead component, the indium component, the strontium component, the sodium component, and the potassium component in the slag are volatilized and enter the soot (6) 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 be processed Liquid Slag, and can handle a small amount of cold materials, the material is highly adaptable; the addition of cold materials realizes the efficient use of chemical heat released by the slag metallurgical reaction and the physical heat of the slag; (7) during the sedimentation process of the method of the present invention, The copper component and the gold and silver components in the slag are respectively concentrated in the copper-rich phase, and the aggregation, growth and sedimentation are realized, and the iron component in the slag is enriched in the iron-rich phase, and aggregation, growth and sedimentation are achieved, and melting The phosphorus component, silicon component and calcium component in the slag are respectively concentrated in the silicate mineral phase and floated up. The copper-rich phase is sent to the converter or the smelting furnace for copper smelting, and the low copper rich iron phase is used as the blast furnace ironmaking. Or direct reduction or smelting reduction of ironmaking raw materials, the copper-rich phase comprises a plurality of copper phase, white copper, matte phase, iron-containing components, or partially into the iron-rich phase, and the iron-rich phase includes metallic iron, FeO a plurality of phases, the olivine phase; the slag-containing heat preservation device is rotated on the rotating platform to accelerate the accumulation, growth and sedimentation of the copper-rich phase and the iron-rich phase; the addition of the fluorine-containing material accelerates the copper-rich phase, Aggregation, growth and sedimentation of the iron-rich phase; (8) The method of the invention passes through a copper-rich phase The iron-containing silicate phase and the iron-rich component have a copper content of less than 0.1%, and can be used as a raw material for blast furnace ironmaking or direct reduction or smelting reduction of iron, to obtain metal iron and molten iron; (9) the method of the invention adopts Manual sorting, magnetic separation, re-election, slag-gold sedimentation method, respectively separating the silicate mineral phase, iron-rich phase and copper-rich phase distributed in the upper, middle and bottom to realize the copper component in the slag High-efficiency recovery of gold, silver, iron component, silicon component, calcium component and phosphorus component; since the iron-rich phase and copper-rich phase settle in the middle and lower parts, the amount of slag to be sorted is small, and the sorting cost is low; The separation process adopts magnetic separation or re-election, and does not cause environmental pollution; since the slag is subjected to quenching and tempering treatment, tailings are used as cement raw materials, building materials, instead of crushed stone as aggregates and road materials; (10) It can process hot slag, make full use of the physical heat resources of molten metallurgical slag and hot metallurgical flux, and can process cold slag and materials. It can realize metallurgical reaction of molten slag and metal migration in slag. Enriched in copper-rich phase and achieved aggregation and length Large and sedimentation, iron component migration, enrichment in the iron-rich phase, to achieve aggregation, growth and sedimentation, migration of silicon, calcium and phosphorus components, enrichment in the silicate mineral phase, to achieve floating, separation and settlement at the bottom The copper-rich phase, the iron-rich phase in the middle and the iron-containing silicate mineral phase in the upper part enable efficient recovery of valuable components in the mixed slag. The method has the advantages of short process flow, high metal recovery rate, low production cost, strong adaptability of raw materials, large processing capacity, environmental friendliness and high economic benefit, and can effectively solve the problem of efficient recycling of metallurgical resources and thermal energy.

Detailed ways

A method for recovering valuable components from a mixed slag containing copper and iron according to the present invention comprises the following steps:

Step 1, slag mixing:

Adding copper slag (containing copper smelting slag, copper-containing blowing slag, copper fire depleted slag, copper slag flotation tailings, wet copper slag slag, one or more) to heat preservation transposition or slag One or more of lead smelting slag (smoke furnace slag and/or lead smelting slag), blast furnace slag, steel slag and iron alloy slag may be added to the molten smelting reaction device to form mixed slag;

The mixed slag is heated to a molten state to form a reaction slag containing copper and iron; the mixture is uniformly mixed, and the reaction slag is monitored in real time, and the following two parameters (a) and (b) are ensured by the control to obtain the melting after completion of the reaction. Slag, or pour the slag after the reaction is completed into the heat preservation device;

(a) The temperature of the reaction slag containing copper and iron is 1050 ~ 1450 ° C;

(b) The alkalinity CaO/SiO ₂ ratio of the reaction slag containing copper and iron = 0.15 to 1.5;

The control method is:

Corresponding to (a): The method of controlling the temperature of the reaction slag containing copper and iron in the set temperature range is:

When the temperature of the reaction slag containing copper and iron is less than 1050 ° C of the set temperature range, the heating function of the reaction device itself is added, or fuel or molten copper slag, molten lead smelting slag, molten blast furnace slag, or molten slag are added to the slag. One or more of molten steel slag or molten iron alloy slag, when injected into the fuel, simultaneously injected into the preheated oxidizing gas, so that the temperature of the slag reaches a set temperature range of 1050 to 1450 ° C;

When the temperature of the reaction slag containing copper and iron is higher than the upper limit of the set temperature range of 1450 ° C, copper-containing materials, nickel smelting slag, blast furnace slag, steel slag, iron alloy slag, metallurgical flux are added to the reaction slag containing copper and iron. One or more of the iron-containing material or the fluorine-containing material, so that the temperature of the mixed slag reaches a set temperature range of 1050 to 1450 ° C;

Corresponding to (b):

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag containing copper and iron 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 containing copper and iron is >1.5, an acidic material and/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 settled to obtain a bottom molten state of the copper-rich phase layer, a central molten iron-rich phase and an upper molten iron-containing silicate mineral phase, and simultaneously form a zinc-containing component and The lead component of the soot, the gold and silver components migrate to the copper-rich phase,

Each phase is processed using one of the following methods:

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) Copper in molten state, sent to converter or blowing furnace for copper smelting or crushing magnetic separation to separate metal iron, then sent to converter or blowing furnace for copper smelting, or magnetic separation of metal iron or separation of metal without magnetic separation After iron, direct reduction, the reduction 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, zinc component, indium component, strontium component, sodium component, and potassium component are volatilized into soot recovery;

(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 into the iron-containing silicate slag in the smelting reaction device One or more of gold furnace slag, fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, red mud after desoda or calcium carbide slag, fully mixed to obtain 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):

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

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 completion of the reaction is subjected to the following steps: (1) the molten iron-containing silicate mineral phase is subjected to slag treatment, and the specific treatment method is: One or more of the methods A to G in the separation and recovery method of the second step are subjected to slag treatment; and the iron-rich phase is treated by the step (4) in the first method;

(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 completion of the reaction is subjected to the following steps: (1) the molten iron-containing silicate mineral phase and the iron-rich phase are subjected to slag treatment, and the specific manner The treatment is carried out by one or more of the methods A to G in the separation and recovery method 1 of the step 2;

(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 reduction using one or several of anthracite, bituminous coal, lignite, coking coal, coke powder or coke, control reduction temperature of 900 ~ 1400 ° C, control alkalinity 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 aggregate, Road material use;

(4) Some lead components, zinc components, indium components, antimony components, sodium components, and potassium components are volatilized into the soot, and oxides are introduced into the soot.

In the method as described above, preferably, in the steps 1 and 2, the copper slag is one of copper-containing smelting slag, copper-containing blowing slag, depleted slag, flotation tailings, and wet copper slag. Or several kinds of copper smelting slag produced in the "smelting and smelting" process of copper smelting process, including Osmet furnace smelting slag, flash furnace smelting slag, Noranda furnace smelting slag, Isa furnace smelting Slag, Vanukov furnace smelting slag, Mitsubishi smelting slag, Caldo furnace smelting slag, silver furnace smelting slag, Shuikoushan smelting slag, Tennite smelting slag, reverberatory furnace smelting slag, electric furnace smelting slag, closed blast furnace Smelting slag, low-smelting furnace smelting slag, side-smelting furnace smelting slag; copper-containing blowing slag is produced in the copper smelting process of copper smelting process, including converter blowing copper slag, flash furnace blowing copper Slag, Noranda furnace continuous blowing copper slag, top blowing furnace blowing copper slag, side blowing furnace blowing copper slag, bottom blowing furnace blowing copper slag, top blowing furnace continuous blowing copper slag, side blowing furnace continuous blowing Copper slag and bottom blowing furnace continuously blow copper slag; depleted waste slag is copper smelting slag and copper-containing blowing slag, and then waste slag, flotation tail The copper smelting slag and the copper-containing smelting slag after the beneficiation, the wet smelting copper slag is produced in a wet copper smelting process; the copper smelting slag and the copper smelting slag are in a molten state or a cold state, wherein: molten copper The smelting slag is obtained from the slag slag of the copper smelting furnace in the process of "smelting smelting", or the smelting slag containing copper is heated to a molten state, and the slag slag of the molten copper smelting slag is "copper smelting" Obtaining, or heating the copper blowing slag to a molten state, obtaining the depleted slag from the slag outlet of the depleted furnace, and heating the depleted slag to a molten state; the lead smelting slag comprises a smelting furnace slag and a lead-containing smelting slag, The lead smelting slag is in a molten state or a cold state, wherein the molten slag is obtained from a tapping port of a reduction stage of a pyrometallurgical lead process or a slag tapping port of a fumigating furnace; the blast furnace slag, the steel slag and the iron alloy slag are in a molten state, or a cold state , wherein: molten slag (blast slag, steel slag and iron alloy slag) is obtained from the slag outlet, or the cold slag (blast slag, steel slag and iron alloy slag) is heated to a molten state; the steel slag is molten iron pre-desulfurization slag (desulfurization slag) , desiliconization slag, dephosphorization slag), converter slag, electric furnace slag, VOD/VAD VD slag, tundish waste slag; the iron alloy slag is slag produced in the production process of iron alloy, including slag produced by smelting carbon ferromanganese, slag produced by smelting ferrochrome, slag produced by smelting ferronickel, smelting of ferrovanadium The slag, the slag produced by smelting ferrosilicon, the slag produced by smelting ferroniobium, and the slag produced by smelting ferromolybdenum.

In the steps 1 and 2, the lead smelting slag is a smelting furnace slag and a lead-containing smelting slag, "ISP lead-zinc blast furnace reduction" or "sinter blast furnace reduction" or "solid high-lead slag reduction" or "liquid high lead" The slag reduction process "reduction process produces lead-containing smelting slag, and the lead-containing smelting slag is smelted by a smelting furnace to produce lead-containing smelting furnace slag;

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

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

The smelting reaction device with the slag port or the iron slag flowing out is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola, and a side blowing molten pool melting furnace. Bottom-blow pool smelting furnace, top-blow pool smelting furnace, reverberatory furnace, Osmite furnace, copper smelting furnace electric heating bed, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom Blowing rotary furnace, top blowing rotary furnace.

In the steps 1 and 2, the fuel and the reducing agent are one or more of a solid, liquid or gaseous fuel, which is sprayed or charged, and the loaded gas is preheated and oxidized. One or more of gas, nitrogen, and argon, preheating temperature is 0-1200 ° C; solid fuel and reducing agent is one of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite a variety of shapes, granular or powdery, granular material size of 5 ~ 25mm, powder material size of ≤ 150μm, liquid fuel and reducing agent for heavy oil, gaseous fuel and reducing agent for gas and / or natural gas; The copper material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, lead smelting slag, nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag containing lead fuming furnace slag, One or more of lead-containing soot, lead-acid batteries, copper-containing soot, copper-rich, copper-containing garbage or copper-containing circuit boards; copper slag includes slag produced by "smelting smelting" and "copper smelting" Slag, fire depleted slag, copper slag flotation tailings; lead smelting slag is smelting furnace slag and lead Smelting slag, "ISP lead-zinc blast furnace reduction" or "sinter blast furnace reduction" or "solid high-lead slag reduction" or "liquid high-lead slag reduction process" reduction process to produce lead-containing smelting slag, lead-containing smelting slag through the smelting furnace Smelting produces lead-containing smelting furnace slag; nickel smelting slag is 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 One or more kinds; zinc smelting slag includes slag produced by wet zinc smelting and slag produced by pyrometallurgical slag, wherein slag produced by wet zinc smelting is zinc leaching residue, volatile kiln residue, iron slag residue, iron after pickling One or more kinds of 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-sand quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone; The material is ordinary iron concentrate, ordinary iron concentrate, direct reduced iron, Iron concentrate sinter, ordinary iron concentrate pellets, ordinary iron concentrate metallized pellets, ordinary iron concentrates containing carbon pre-reduction pellets, steel slag, zinc smelting slag, coke smelting dust and dust, steel smoke and dust Dust, nickel smelting slag, copper slag,

One or more of lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high-calcium red mud after desodiumification, coal ash ash, sulfuric acid slag; the steel soot and dust including blast furnace gas mud, Converter dust, electric furnace dust, hot (cold) rolling sludge, sintering dust, pellet dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, steel oxide scale;

The fluorine-containing material described in the high calcium red mud after desulfurization of the lead smelting slag is one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag; the copper-containing material and the iron-containing material are hot or cold. The hot material is directly obtained from the metallurgical furnace discharge port or the slag outlet; the wet zinc slag and dust sludge are dehydrated and dried.

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.

In the method as described above, preferably, in the steps 1 and 2, the method of controlling the temperature of the mixed slag in the set temperature range is:

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, the preheating temperature is 0 to 1200 ° C; the blowing method is one or more of using a refractory spray gun to insert slag or placing it on the upper part or side or bottom of the reaction slag;

In the steps 1 and 2, the copper-containing material and the iron-containing material are in a hot state or a cold state, and the hot material is a hot material directly produced from a metallurgical furnace, and the temperature of the hot material is 200 to 1750. °C.

In the step 1 described, 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 iron-containing material, the blast furnace slag, the steel slag, the iron alloy slag, the metallurgical flux or the fluorine-containing material are added to avoid the temperature being too high. , protective refractory Another effect of adding fluorine-containing materials is to reduce the viscosity, accelerate the copper-rich phase, the ice-rich copper phase, the iron-rich phase aggregation, growth and sedimentation in the slag, which is beneficial to the silicate floating;

In the step 1, in the slag reaction process, the copper component and the gold and silver component in the slag are enriched in the copper-rich phase, and aggregate, grow and settle, or partially enriched in the iron-rich phase, iron The components are released from the olivine, enriched in the iron-rich phase, and achieve aggregation, growth and sedimentation. The zinc component and the lead component in the slag respectively enter the soot and are recovered as oxides;

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 or an alkali metallized pellet. One or several.

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

In the steps 1 and 2, the copper-rich phase, the ice-rich copper phase, the iron-rich phase in the slag are aggregated, grown and settled, which is favorable for the silicate to float, and the copper-rich phase includes copper, white copper, and matte. a plurality of white copper or iron-containing components, or a portion of the copper component entering the iron-rich phase, the iron-rich phase comprising a plurality of metal iron, FeO phase, and fayalite phase;

In the steps 1 and 2, the mixed slag is sufficiently mixed while ensuring the two parameters (a) and (b), and the mixing mode is natural mixing or stirring mixing, and the stirring mode is one of the following modes: argon One or more of gas agitation, nitrogen agitation, argon-nitrogen gas mixture, reducing gas (gas and/or natural gas), electromagnetic stirring, mechanical agitation, gas preheating temperature is 0 to 1200 ° C;

In the step 1, the two parameters (a) and (b) are ensured at the same time, and at the same time, the copper oxide and the iron oxide in the slag are reduced to metal copper and FeO, and the metal iron content in the slag is <3. %. By adding one or both of a reducing agent, a carbon-containing iron-containing material, wherein the reducing agent and/or the carbon-containing iron-containing material is used in an amount such that copper and iron oxides in the slag are reduced to metallic copper and The theoretical amount of FeO is 110-140%; the carbon-containing iron-containing materials are steel dust and soot, iron concentrate carbon-containing pre-reduction pellets, iron concentrate carbon-containing metallized pellets, and wet zinc smelting kiln Slag or coke oven dust and soot.

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, an induction furnace as a reduction device, and a gas-based or coal-based reduction technology, the gas base is natural gas and/or Gas, coal-based reduction to one or more of anthracite, bituminous coal, lignite, coking coal, coke breeze, coke, reduction temperature of 900 ~ 1400 ° C, alkalinity CaO / SiO ₂ ratio = 0.7 ~ 1.9,

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 spraying method is one or several types of inserting slag into the molten slag or placing it in the upper part or side or bottom of the reaction slag;

In the step 2, cooling and sedimentation are required for separation and recovery, wherein the cooling mode is natural cooling or rotary cooling or centrifugal cooling, and the sedimentation mode is natural sedimentation or rotary sedimentation or centrifugal cooling;

Further, the specific operation of the rotation and the centrifugal cooling is: the device containing the slag after the reaction is completed is placed on the rotating platform, and is rotated according to a certain speed, and the rotation speed is determined according to the quality of the slag and the height or depth of the heat preservation device, and the rotation is performed. The time depends on the quality of the slag and the solidification of the slag; the device containing the slag after the completion of the reaction is placed on a rotating platform for the purpose of accelerating the accumulation of copper-rich phase, iron-rich phase, growth and sedimentation, and is beneficial to The silicate (phosphorus-rich phase) floats, shortens the settling time, improves the sedimentation effect, and improves production efficiency;

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

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 and the ice-rich copper phase, and realize growth and sedimentation; the iron component in the mixed slag Continue to migrate and enrich in the iron-rich phase, And to achieve growth and settlement.

The method for recovering valuable components from the slag containing copper and iron of the present invention, and finally the mineral grindability obtained is increased.

In the method described above, the finally obtained slag contains copper ≤ 0.1%, the iron recovery rate is ≥ 90%, the zinc recovery rate is ≥ 91%, the lead recovery rate is ≥ 92%, and the gold enrichment rate is ≥94%, silver enrichment rate is ≥94%, indium recovery rate is ≥94%, strontium recovery rate is ≥94%, sodium recovery rate is ≥95%, and potassium recovery rate is ≥95%.

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:

(b) reaction slag basicity CaO / SiO ₂ ratio of copper and iron = 0.15 ~ 1.5;

Example 1

A method for recovering valuable components from a mixed slag containing copper and iron, comprising the steps of:

Step 1, slag mixing: the copper-containing smelting slag obtained from the slag smelting furnace slag outlet and the copper-containing blowing slag (converter slag) obtained from the slag outlet of the converter are added to the DC arc furnace, and simultaneously added to the cold state. Blast furnace slag, VOD/VAD slag and iron alloy slag produced by smelting carbon ferromanganese, lead smelting slag of liquid high lead slag reduction furnace, forming mixed slag; heating slag to molten state to form copper and iron The molten slag is reacted, and the reaction slag is electromagnetically stirred to achieve natural mixing; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling both parameters (a) and (b); corresponding to (a): The reaction slag containing copper and iron has a temperature of 1,660 ° C, and is inserted into the reaction slag by using a refractory spray gun, and nitrogen gas is used as a loading gas, and is sprayed with copper slag, copper-containing soot, copper-containing and copper containing a powder particle size of ≤150 μm at normal temperature. Copper garbage and copper-containing circuit boards, at the same time adding blast furnace gas mud, electric furnace dust, converter dust, ordinary iron concentrate direct reduced iron and blast furnace gas ash, so that the temperature is reduced to 1380 ° C; (b): containing copper and iron the reaction slag basicity CaO / SiO ₂ ratio = 2.8, the reverse Added silica slag, fly ash and gangue mixture, the reaction with copper slag basicity ratio to 1.3 iron; slag content of metal iron of 0.8%;

Step 2, separation and recovery method 1:

After 6 min of heat preservation, the slag is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase layer, an iron-rich phase and an iron-containing silicate mineral phase, and a zinc component and a lead component are simultaneously formed, and the following steps are performed: (1) The iron-containing silicate mineral phase is treated by the external slag, and the method F is used. After the iron-containing silicate slag is air-cooled, it is used as a direct reduction ironmaking raw material, and the rotary kiln is used for direct reduction, and the gas-based reduction technology is utilized. The gas-based reducing agent is natural gas and gas, the reduction temperature is 900 ° C, the alkalinity CaO / SiO ₂ ratio is 0.8, and after reduction, the metal iron and slag are obtained by melting in a magnetic furnace, and the melting temperature is 1550 ° C; (2) melting The copper-rich phase is sent to the continuous blowing furnace for copper smelting; (3) the iron-rich phase is poured into the heat preservation device, and is used as the blast furnace ironmaking raw material after air cooling; (4) the zinc component, the indium component, the lead component, and the bismuth group The fractions, potassium components and sodium components volatilized oxides are recycled into the soot. The final slag contains copper <0.1%, zinc recovery rate is 92%, lead recovery rate is 92%, iron recovery rate is 93%, gold The enrichment rate is 96%, the silver enrichment rate is 94%, the indium recovery rate is 94%, and the ruthenium recovery rate is 95%. Sodium recovery The rate was 95% and the potassium recovery was 97%. 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 copper smelting slag of the Isa furnace obtained from the slag outlet of the smelting smelting furnace and the copper-containing smelting slag (converter slag) obtained from the tapping port of the converter are added to the pourable smelting reaction slag, Adding iron alloy slag produced by molten smelting ferrochrome obtained from the slag outlet to form mixed slag; using oxygen-enriched air, blowing natural gas, aniseous coal with a particle size of 20 mm and coke particles, heating the mixed slag to a molten state, forming a The reaction slag between copper and iron, and the reaction slag is electromagnetically stirred to achieve mixing; the reaction slag is monitored in real time, and the two parameters of (a) and (b) are simultaneously controlled to obtain the slag after completion of the reaction; The reaction temperature of slag containing copper and iron is 1660 °C, and it is inserted into the reaction slag by refractory spray gun. The argon gas is used as carrier gas, and sprayed into the room temperature powder particle size ≤150μm copper slag, steel sintered dust, sintered pellet dust, iron Factory dust, copper-containing circuit board, ordinary iron concentrate, ordinary iron concentrate direct reduced iron and ordinary iron concentrate sinter, the temperature is reduced to 1360 ° C; (b) copper and iron reaction slag basicity CaO / SiO ₂ ratio is 2.7, added to the reaction slag Acidic sinter, acid iron concentrate and acid pre-reduction pellets, the ratio of alkalinity of slag containing copper to iron is reduced to 1.3; the content of metal iron in slag is 2.9%;

Step 2, separation and recovery method 2: heat preservation for 47 min, slag spin sedimentation, slag-gold separation, obtain molten copper-rich phase layer, iron-rich phase and iron-containing silicate mineral phase, and form zinc-zinc component, lead group Dividing into the indium component and entering the soot, the following steps are carried out: (1) the molten silicate mineral phase and the iron-rich phase are poured into the thermal insulation slag tank, and the slag smelting reduction ironmaking is carried out by the method G, and the specific steps are as follows: (1) -1) adding anthracite and bituminous coal having a particle size of 20 mm to the slag, performing smelting reduction, monitoring the reaction slag, and ensuring the following by (a) the temperature of the reaction slag is 1350 to 1650 ° C, and (b) reacting the slag base Degree CaO / SiO ₂ ratio = 0.6 ~ 2.4 two parameters, the slag after the completion of the reaction; corresponding (a): the temperature of the reaction slag is 1420, in the temperature range; corresponding (b): alkali in the reaction slag When the ratio of CaO/SiO ₂ is 0.8, in the range of alkalinity; (1-2) the oxygen-enriched air preheated at 200 ° C is sprayed into the slag after the completion of the reaction to be smelted and reduced to form a mixed slag after reduction. During the blowing process, the (a) reaction slag temperature is guaranteed to be 1,350 to 1,650 ° C, and (b) Slag basicity CaO / SiO ₂ ratio = 0.6-2.4 two parameters; (1-3) separating and recovering: (a) mixing the slag after reduction, sedimentation slag - metal separation to obtain the hot metal with a reducing slag; (b) After the reduction, the slag is processed into a high value-added cement raw material by the method of the second method and the middle method A; (c) the molten iron is sent to the converter or the electric furnace for steelmaking; (d) the zinc-containing component, the lead-containing component, the antimony component Volatilized with indium components, and entered into soot recovery in the form of oxides; (e) sodium-containing components, potassium-containing components volatilized, and entered into soot recovery; (2) molten copper-rich phase, sent to converter copper smelting; (3) The zinc component and the lead component are volatilized, and the oxide is recovered into the dust. The zinc recovery rate is 92%, the slag contains copper <0.1%, the lead recovery rate is 92%, the iron recovery rate is 91%, and the indium recovery rate is 96%. The recovery rate of ruthenium is 96%, the recovery rate of sodium is 97%, the recovery rate of potassium is 98%, the enrichment rate of gold is 94%, and the enrichment rate of silver is 95%.

Example 3

Step 1, slag mixing: the copper smelting slag of the Osmite furnace obtained from the slag smelting furnace slag and the copper-containing smelting slag (converter slag) obtained from the slag outlet of the converter are added to the induction furnace, and simultaneously added by the converter The steel slag obtained from the steel slag outlet forms a mixed slag; the oxygen is sprayed at a temperature of 600 ° C, and the particle size is 20 mm anthracite, coke and pulverized coal, and the mixed slag is heated to a molten state to form copper and iron. The reaction slag is reacted and the slag is mixed; the slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling both parameters (a) and (b); corresponding to (a): reaction with copper and iron The temperature of the slag is 1685 ° C, and quartz sand, red mud, dolomite, limestone, wet zinc smelting kiln slag is added to the reaction slag, and copper-containing materials, ordinary iron concentrate pellets, and ordinary iron fines are simultaneously added. Mineralized metallized pellets and ordinary iron concentrates containing carbon pre-reduction pellets, the temperature is lowered to 1320 ° C; (b): The ratio of alkalinity CaO / SiO ₂ of the reaction slag containing copper and iron = 3.0, to the reaction melt Adding a mixture of acidic metallized pellets, copper-containing smelting slag and copper-containing blowing slag to the slag The reaction with the slag basicity ratio to 1.2 iron; slag content of metal iron of 2.1%;

Step 2, separation and recovery method 2: heat preservation 15min, slag natural sedimentation, slag-gold separation, obtain molten copper-rich phase, iron-rich phase and iron-containing silicate mineral phase, and simultaneously produce zinc-containing components and lead The components are subjected to the following steps: (1) molten copper-rich phase and sent to converter for copper smelting; (2) molten iron-rich phase and iron-containing silicate mineral phase as direct reduction ironmaking raw materials, direct reduction product magnetic separation Separation, obtaining metal iron and tailings, zinc component, lead component volatilization, entering the soot as oxide; in the reduction process, using a rotary hearth furnace, the reduction temperature is 1200 ° C, the alkalinity CaO / SiO ₂ ratio = 1.0; (3) The zinc-containing component and the lead-containing component volatilize and enter the soot recovery as an oxide. The slag contains copper <0.08%, the iron recovery rate is 93%, the zinc recovery rate is 93%, and the lead recovery rate is 94%, sodium recovery rate was 93%, potassium recovery rate was 94%, gold enrichment rate was 95%, silver enrichment rate was 96%, indium recovery rate was 96%, and hydrazine recovery rate was 95%.

Example 4

Step 1. Mixing slag: adding cold smelting slag of copper in the Nolanda furnace and copper depleted slag to the plasma furnace, and adding the steel slag obtained by the converter steel slag, the electric furnace steel slag and the smelting ferronic steel obtained by the slag outlet, Forming mixed slag; heating the mixed slag to a molten state, forming a reaction slag containing copper and iron, and reacting the slag with a temperature of 1200 ° C to achieve mixing; real-time monitoring of the reaction slag, through regulation and control The two parameters (a) and (b) are guaranteed to obtain the slag after the completion of the reaction; corresponding to (a) the temperature of the reaction slag containing copper and iron is 1,650 ° C, and red mud and coal dust are added to the reaction slag. Sulfuric acid slag, fluorite, lead copper, leaded soot, zinc-containing soot, arsenic matte and wet zinc slag to reduce the temperature to 1340 ° C; (b) reaction slag basicity containing copper and iron The ratio of CaO/SiO ₂ is 2.9, and copper-containing blowing slag is added to the reaction slag to reduce the alkalinity ratio of copper-iron reaction slag to 1.1; natural gas is sprayed, and coke particles having a particle size of 20 mm are sprayed with air. The metal iron content in the slag is 2.9%;

Step 2, separation and recovery method 3: heat preservation for 19 min, the slag is naturally settled after the reaction is completed, and the slag-gold separation, obtaining a molten copper-rich phase, an iron-rich phase and an iron-containing silicate mineral phase, and a zinc-containing and lead-containing phase The components are subjected to the following steps: (1) the molten copper-rich phase and the molten iron-rich phase are sent to the converter for copper smelting; (2) the iron-containing silicate mineral phase is subjected to the method A of the first method, after water quenching, As a cement raw material; (3) part of the zinc-containing component bismuth component, indium component and lead-containing component volatilize, enter the soot recovery as oxide, slag contains copper <0.1%, iron recovery rate is 90%, zinc The recovery rate is 92%, the lead recovery rate is 92%, the indium recovery rate is 93%, the ruthenium recovery rate is 94%, the gold enrichment rate is 95%, the silver enrichment rate is 97%, and the sodium recovery rate. At 95%, the potassium recovery rate is 96%.

Example 5

Step 1. Slag mixing: the copper-containing smelting slag of the cold Mitsubishi method and the copper slag flotation tailings and the wet copper slag are added to the slag slag tank, and the molten steel slag obtained from the slag outlet is added to form the mixed slag. Using air with a preheating temperature of 800 ° C, blowing a particle size of 20 mm bituminous coal and coal powder, heating the mixed slag to a molten state, forming a reaction slag containing copper and iron, and mixing the reaction slag; real-time monitoring The reaction slag is obtained by controlling two parameters (a) and (b) to obtain the slag after completion of the reaction; corresponding to (a): the reaction slag temperature of copper and iron is 1210 ° C; (b): The ratio of copper to iron reaction slag basicity CaO / SiO ₂ is 0.75, both within the required range; the metal iron content in the slag is 1.4%;

Step 2, separation and recovery of heat preservation for 16 min, using method nine: the slag after the completion of the reaction is carried out as follows: (1) sedimentation cooling: the slag after the reaction is rotated and cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to The bottom of the reaction device forms a metal copper crucible; the iron-containing silicate mineral phase floats; the copper-rich phase metal antimony and the iron-containing silicate mineral intermediate slow-cooling slag are iron-rich phases, and at the same time, a zinc-containing and lead-containing component is formed; (2) Separation: manually extracting the copper-rich strontium deposited at the bottom, directly reducing, magnetically separating the iron, and then sending the product to the converter; the iron-rich phase layer in the middle is directly sent to the converter for iron making; (3) manually taking out the upper part Iron silicate mineral phase, obtained as silicate tailings, used as cement raw material; (4) Part of zinc component and lead component volatilized, entered into soot as oxide, slag contains copper <0.15%, iron recovery The rate was 96%, the recovery rate of zinc was 94%, the recovery rate of lead was 93%, the enrichment rate of gold was 94%, and the enrichment rate of silver was 96%.

Example 6

Step 1, slag mixing: the copper-containing blowing slag (converter slag) obtained from the slag outlet of the converter is added to the alternating current electric arc furnace, and the iron alloy slag produced by the cold smelting of vanadium iron and the ferroalloy slag produced by smelting the ferrosilicon are added to form a mixed melting. The slag is heated to a molten state to form a reaction slag containing copper and iron, and the reaction slag is sprayed with an argon-nitrogen gas mixture having a preheating temperature of 400 ° C, and mixed; the reaction slag is monitored in real time. At the same time, the two parameters of (a) and (b) are guaranteed to obtain the slag after completion of the reaction; corresponding to (a): the temperature of the molten slag containing copper and iron is 1040 ° C, and oxygen-enriched air, heavy oil and molten content are added to the reaction slag. Copper blowing slag, the temperature is raised to 1330 ° C; (b): copper and iron reaction slag basicity CaO / SiO ₂ ratio of 0.1, adding basic iron concentrate and alkaline pre-reduction ball to the reaction slag Group, the ratio of alkalinity of slag containing copper to iron is raised to 0.4; the content of metallic iron in slag is 1.8%;

Step 2, separation and recovery method 1: heat preservation for 21 min, the slag after the completion of the reaction is naturally settled, slag-gold separation, obtaining a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and zinc-containing The lead-containing component is subjected to the following steps: (1) the molten iron-containing silicate mineral phase is subjected to the step 2 separation and recovery method method A, and the water quenching is directly used as the cement raw material; (2) the molten copper-rich phase is sent to the converter (3) After the iron-rich phase is poured into the heat preservation device, the iron is directly reduced; (4) part of the zinc-containing and lead-containing components are volatilized, and the fumes are recovered as oxides, and the slag contains copper <0.1%, iron. The recovery rate was 91%, the zinc recovery rate was 94%, the lead recovery rate was 92%, the gold enrichment rate was 94%, and the silver enrichment rate was 96%.

Example 7

Step 1, slag mixing: the silver furnace smelting slag obtained from the slag smelting furnace slag tapping and the copper-containing blowing slag (converter slag) obtained by the converter smelting slag outlet, and the copper slag flotation tailings are added to the submerged arc furnace At the same time, the slag produced by the smelting of the slag iron and the slag produced by the smelting of the ferromolybdenum are added to form a mixed slag; the mixed slag is heated to a molten state to form a reaction slag containing copper and iron, and the reaction is melted. The slag is blown with nitrogen to achieve mixing; the reaction slag is monitored in real time, and the slag after completion of the reaction is obtained by controlling both parameters (a) and (b); corresponding to (a): reaction slag containing copper and iron The temperature of the reaction is 1320 ° C; (b): the ratio of alkalinity CaO / SiO ₂ of the reaction slag containing copper and iron is 0.8; the natural gas is sprayed, the content of metal iron in the slag is 2.5%;

Step 2, separation and recovery method 4: heat preservation for 15 min, after the completion of the reaction, the slag is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase, a ferrosilicate-containing mineral phase, a zinc component and lead. The components are subjected to the following steps: (1) a molten copper-rich phase, which is sent to a converter to smelt copper; (2) a molten iron-rich phase and a ferrosilicate-containing method using the method D in the first method: (1) into the slag The oxidizing gas with a preheating temperature of 800 ° C is blown, and the slag temperature is controlled to be higher than 1350 ° C; (2) the slag after oxidation is water quenched and used as cement clinker

(3) Some zinc-containing components and lead-containing components volatilize, and oxides are recovered into soot. The slag contains copper <0.1%, the iron recovery rate is 91%, the zinc recovery rate is 93%, and the lead recovery rate is 92. %, the gold enrichment rate is 95%, and the silver enrichment rate is 97%.

Example 8

Step 1, slag mixing: adding cold smelting furnace copper smelting slag and flash blowing copper-containing copper slag to the blast furnace, adding blast furnace slag and electric furnace steel slag obtained from the slag outlet to form mixed slag; The preheating temperature is 600 ° C air, the spray size is 20 mm bituminous coal and coal powder, the mixed slag is heated to a molten state to form a reaction slag containing copper and iron, and the reaction slag is mixed; real-time monitoring reaction melting The slag is obtained by controlling two parameters (a) and (b) to obtain the slag after completion of the reaction; corresponding to (a): the temperature of the reaction slag containing copper and iron is 1330 ° C; (b): copper The ratio of alkalinity CaO/SiO ₂ of the reaction slag with iron is 1.0, which is within the required range; the metal iron content in the slag is 2.9%;

Step 2, separation and recovery method 3: heat preservation for 10 min, after the reaction is completed, the slag is naturally settled, and the slag-gold is separated to obtain a copper-rich phase and a medium-top iron-containing silicate mineral phase, and at the same time, a zinc-containing and lead-containing component is formed. , the following steps are carried out: (1) the molten iron-containing silicate mineral phase, specifically adopting the step 2 separation and recovery method method B, and returning the middle and upper slag to the copper-and iron-containing reaction slag as the hot metallurgical flux. Adjusting the composition of the slag containing copper and iron to control its temperature; (2) enriching the iron phase in the molten copper phase and sending it to the smelting furnace to smelt copper; (3) partially containing the zinc component and volatilizing the lead component, The oxide enters the dust recovery. The slag contains copper <0.1%, the iron recovery rate is 97%, the zinc recovery rate is 95%, the lead recovery rate is 94%, the gold enrichment rate is 98%, and the silver enrichment. The rate is 96%.

Example 9

Step 1, slag mixing: the copper-containing smelting slag obtained by the slag smelting smelting slag of the gold peak side blowing pool and the copper-containing blowing slag (converter slag) obtained by the converter slag mouth, and the wet copper slag are added to the side blowing rotary kiln. At the same time, the molten blast furnace slag and VD slag obtained from the slag outlet are added to form a mixed slag; the mixed slag is heated to a molten state to form a reaction slag containing copper and iron, and the reaction slag is sprayed with argon gas. Mixing; monitoring the reaction slag in real time, obtaining the slag after completion of the reaction by regulating and simultaneously satisfying two parameters (a) and (b); corresponding to (a): the reaction slag temperature containing copper and iron is 1340 ° C; b): The reaction slag basicity CaO/SiO ₂ ratio of copper and iron is 1.2, which meets the requirements; the coke particles with a particle size of 20 mm are sprayed with air with a preheating temperature of 1000 ° C, and the content of metallic iron in the slag is 2.5%;

Step 2, separation and recovery method 5: heat preservation for 10 min, after the completion of the reaction, the slag is naturally settled, and the slag-gold separation, obtaining a molten copper-rich phase, an iron-rich phase and a medium-top iron-containing silicate mineral phase, and zinc-containing With the lead-containing component, the following steps are carried out: (1) the upper middle slag is separated and recovered in step 2, the middle method C, and the glass ceramics are poured; (2) the lower molten copper-rich phase and the iron-rich phase are sent to the converter (3) Partially containing zinc and lead-containing components, which are recovered as fumes in the form of oxides. The slag contains copper <0.1%, the recovery of iron is 93%, the recovery of zinc is 94%, and the recovery of lead is 92%, the gold enrichment rate is 95%, and the silver enrichment rate is 97%.

Example 10

Step 1, slag mixing:

The molten copper-containing smelting slag flowing out from the slag outlet of the bottom-blow pool melting furnace and the copper-containing blowing slag flowing out of the bottom-blown continuous blowing furnace are added to the heat preservation pit, and the molten converter steel slag obtained by adding the slag mouth is formed to form mixed slag Using oxygen-enriched air with a preheating temperature of 800 ° C, blowing bituminous coal with a particle size of ≤150 μm, heating the mixed slag to a molten state, forming a copper-containing reaction slag, and mixing the reaction slag; monitoring the reaction slag in real time, After the two parameters of (a) and (b) are simultaneously controlled, the completed slag is obtained;

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 0.9, both within the required range; the metal iron content in the slag is 1.9 %;

Step 2, separation and recovery method 5:

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

(1) Settling cooling: heat preservation for 48 min, the slag after the reaction is completed and slowly cooled to room temperature to obtain slow cooling slag; the copper-rich copper phase settles to the bottom of the reaction device to form a copper-rich strontium; the iron-containing silicate mineral phase floats; The copper-rich phase metal lanthanum and the silicate mineral intermediate slow-cooling slag are iron-rich phase, and at the same time, a zinc-containing component and a lead-containing component are formed;

(2) Separation: manually extracting the copper-rich strontium deposited at the bottom; directly reducing the iron-rich phase layer in the middle, magnetically separating the metal iron, and returning the tailings to the copper smelting system; (3) manually removing the upper iron-containing silicate Mineral phase, obtaining silicate tailings, used as cement raw materials;

(4) Part of the zinc component and the lead component volatilize, and enter the soot recovery in the form of oxide. The slag contains copper <0.15%, the iron recovery rate is 98%, the zinc recovery rate is 96%, and the lead recovery rate is 94. %, the gold enrichment rate is 95%, and the silver enrichment rate is 96%.

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

Claims

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

S1, slag mixing: adding copper slag to the smelting reaction device, adding one or more of lead smelting slag, blast furnace slag, steel slag and iron alloy slag to form mixed slag; heating slag to molten state to form reaction slag , mixing evenly, monitoring the reaction slag in real time, and simultaneously adjusting the reaction slag after mixing, while satisfying the condition a and the condition b, obtaining the slag after the reaction, or pouring the slag after the reaction into the heat preservation device;

Wherein the condition a is controlling the reaction slag temperature to be 1050 to 1450 ° C;

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

S2, separation and recovery: the slag after the reaction in the step S1 is kept for 5 to 50 minutes, and the copper-rich phase at the bottom, the iron-rich phase in the middle and the iron-containing silicate mineral phase in the upper portion are obtained by sedimentation and separation, and a zinc-containing group is formed at the same time. The soot is separated from the lead-containing component, and the gold and silver components are enriched into the copper-rich phase; the phases are treated.
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 <1050 ° C, the heating of the reaction device itself, or the addition of fuel or molten copper slag, molten lead smelting slag, molten blast furnace slag, molten steel slag or molten iron alloy slag to the slag or a plurality of, when the fuel is injected, the preheated oxidizing gas is simultaneously injected, so that the temperature of the reaction slag reaches 1050 to 1450 ° C;

When the temperature of the reaction slag is >1450 ° C, one or more of copper-containing material, nickel smelting slag, blast furnace slag, steel slag, iron alloy slag, metallurgical flux, iron-containing material or fluorine-containing material are added to the reaction slag. Kind, the temperature of the mixed reaction slag is reached 1050 ~ 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, Osmeite furnace, copper smelting furnace electric heating bed, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing Rotary furnace, top blowing rotary furnace.
The method according to claim 1, wherein in said step S1, said conditions a and b are satisfied while satisfying simultaneously, and simultaneous control of copper oxide and iron oxide in said slag is satisfied. It is reduced to metallic copper and FeO, and the content of metallic iron in the 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 kinds of copper smelting slag produced in the "smelting and smelting" process of copper smelting process, including Osmet furnace smelting slag, flash furnace smelting slag, Noranda furnace smelting slag, Isa furnace smelting Slag, Vanukov furnace smelting slag, Mitsubishi smelting slag, Caldo furnace smelting slag, silver furnace smelting slag, Shuikoushan smelting slag, Tennite smelting slag, reverberatory furnace smelting slag, electric furnace smelting slag, closed blast furnace Smelting slag, low-smelting furnace smelting slag, side-blown furnace smelting slag; the copper-containing blowing slag is produced in the "copper smelting" process of copper pyrometallurgical smelting process, including converter blowing copper slag, flash furnace blowing Copper slag, Nolanda furnace continuous Blowing copper slag, top blowing furnace blowing copper slag, side blowing furnace blowing copper slag, bottom blowing furnace blowing copper slag, top blowing furnace continuous blowing copper slag, side blowing furnace continuous blowing copper slag, bottom blowing furnace Continuously blowing copper slag; the copper fire method depleted waste slag is copper smelting slag and copper-containing smelting slag depleted and then slag, flotation tail slag is copper smelting slag and copper-containing blowing slag after tailing The slag and the wet copper slag are wet smelting copper slag; the copper smelting slag and the copper smelting slag are in a molten state or a cold state, wherein: the molten copper smelting slag is discharged from a copper smelting furnace in a process of “smelting and melting” The slag mouth is obtained, or the copper-containing smelting slag is heated to a molten state, and the molten copper blowing slag is obtained from a copper smelting furnace slag tapping port of the "copper smelting" process, or the copper blowing slag is heated to a molten state, which is poor The waste slag is obtained from the slag outlet of the depleted furnace, and the depleted slag is heated to a molten state;

The lead smelting slag comprises a smelting furnace slag and a lead smelting slag, and the lead smelting slag is in a molten state or a cold state, wherein the molten slag is obtained from a slag outlet or a slag slag outlet of a reduction stage of the pyrometallurgical lead process The blast furnace slag, the steel slag and the iron alloy slag are in a molten state or in a cold state, wherein: the molten slag is obtained from the slag outlet, or the cold slag is heated to a molten state; the steel slag is molten iron pre-desulfurization slag, converter slag, Electric furnace slag, VOD/VAD slag, VD slag, tundish waste slag; the iron alloy slag is slag generated in the production process of iron alloy, including smelting smelting of carbon ferromanganese, slag produced by smelting ferrochrome, smelting ferronickel The slag, the slag produced by smelting ferrovanadium, the slag produced by smelting ferrosilicon, the slag produced by smelting ferroniobium, and the slag produced by smelting ferromolybdenum.
The method according to claim 2, wherein the fuel is one or more of a solid, liquid or gaseous fuel, which is sprayed or fed, and loaded with a gas of 0 to 1200 ° C. The gas is one or more of an oxidizing gas, argon gas, and nitrogen gas;

Preferably, the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead-zinc tailings, lead smelting slag. Lead smelting slag nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag containing lead fuming furnace slag, lead smelting soot and dust, lead acid battery, copper smelting soot and dust, copper, containing One or more of copper garbage, copper-containing circuit board, tin smelting slag, tin tailings; the lead smelting slag is smelting furnace slag and lead-containing smelting slag, "ISP lead-zinc blast furnace reduction" or "sinter The blast furnace reduction or the "solid high-lead slag reduction" or "liquid high-lead slag reduction process" reduction process produces lead-containing smelting slag, and the lead-containing smelting slag is smelted by the smelting furnace to produce lead-containing smelting furnace slag; the nickel smelting slag is One or more of the nickel smelting slag produced by the "smelting smelting" process, the depleted slag after the "copper ice nickel blowing" process, and the nickel slag slag produced by the top blowing smelting; the zinc smelting slag includes wet Slag produced by zinc smelting and slag produced by pyrometallurgical smelting, wherein zinc smelting The raw slag is zinc leaching residue, volatile kiln residue, iron slag residue, copper cadmium slag, pickled iron slag, goethite slag, hematite slag one or more, and fire method zinc smelting is vertical tank smelting One or more of zinc furnace slag, vortex smelting furnace slag, blast furnace slag, smelting furnace slag, electric furnace slag; the metallurgical flux is a mineral containing CaO or SiO 2 , specifically quartz sand, gold-silver quartz sand, red mud, One or more of high-calcium red mud, calcium carbide slag, dolomite or limestone after de-sodium; the iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sinter, Ordinary iron concentrate pellets, ordinary iron concentrate metallized pellets, ordinary iron concentrates containing carbon pre-reduction pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag One or more of copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high-calcium red mud after desodiumification, coal dust ash, sulfuric acid slag; Blast furnace gas mud, converter dust, electric furnace dust, hot (cold) rolling sludge, sintered dust, pellet dust, out Dust collecting plant, blast furnace dust, electric furnace dust, rolling mill scale;

The fluorine-containing material described in the high-calcium red mud after desulfurization of the lead smelting slag is one or more of fluorite, CaF 2 or fluorine-containing blast furnace slag;

The alkaline material is one or more of lime powder, red mud, high calcium red mud, calcium carbide slag, dolomite powder or quicklime powder; the basic iron-containing material is CaO/SiO 2 > One or more of an iron-containing material, an alkaline sintered ore, an alkaline iron concentrate, an alkaline pre-reduced pellet, an alkali metallized pellet, or a steel slag;

The acidic material is one or more of silica, lead smelting slag containing gold silver silica, fly ash, coal gangue; the acidic iron-containing material is CaO/SiO 2 ≤ 1 iron-containing material, acid sinter One or more of acid iron concentrate, acid pre-reduction pellet, acid metallized pellet, copper slag, lead smelting slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, and blast furnace slag.
The method according to any one of claims 1 to 6, wherein the step S2 is separated and recovered, and the following processing is performed:

The copper-rich phase in hot or cold state, 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 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 are volatilized, and enter the soot as an oxide;

Containing the iron-containing silicate mineral phase and/or the iron-rich phase, and performing any of the following methods A-G;

Method A: directly after water quenching or air cooling;

Method B: partially or completely returning 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 the production of 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 material is blown into the oxidizing gas with a preheating temperature of 0-1200 ° C, and the slag mixture material temperature is >1450 ° C; when the ferrous oxide weight percentage content 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: performing reduction ironmaking, including 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 >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 1350 to 1650 ° C; wherein The metallurgical flux is a mineral containing CaO or SiO 2 ;

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

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

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

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

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

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

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

Or indium, antimony, sodium and potassium containing components volatilize and enter the soot;

Or containing the iron-rich phase layer for water quenching or air cooling or pouring into a heat preservation device for slow cooling or by manual sorting and re-election, as a blast furnace ironmaking raw material or directly reducing ironmaking raw materials or smelting reduction ironmaking raw materials or floating Select copper raw materials or magnetic separation to separate metal iron as raw material for copper smelting or direct reduction ironmaking; flotation products are copper-containing concentrates and iron concentrates, copper concentrates return to copper smelting system, iron concentrates as blast furnace ironmaking Raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, the reduced product is magnetically separated and separated, the metal iron and tailings are obtained, and the tailings are returned to the copper smelting system; Bottom furnace, tunnel kiln, undercarriage, shaft furnace, rotary kiln or induction furnace, using gas-based or coal-based reduction, gas-based reduction using natural gas and/or gas, coal-based reduction using anthracite, bituminous coal, lignite, coking coal, coke One or more of the powder or coke, the controlled reduction temperature is 900 to 1400 ° C, and the control alkalinity CaO / SiO 2 ratio = 0.8 to 1.5.
The method according to claim 7, wherein said oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, nitrogen-air, argon-air, oxygen-nitrogen, oxygen-argon. The preheating temperature is 0 to 1200 °C.
The method of claim 7 wherein said fuel and reducing agent are one or more of a solid, liquid or gaseous fuel that is injected by injection or feed, said injection loading The gas is one or more of a preheated oxidizing gas, nitrogen or argon, the preheating temperature is 0 to 1200 ° C; the solid fuel and the reducing agent are pulverized coal, coke powder, coke, powder One or more of coal ash, bituminous coal or anthracite coal, the shape is granular or powder, the granular material has a particle size of 5 to 25 mm, the powdery material has a particle size of ≤150 μm, and the liquid fuel and the reducing agent are heavy oil, the gas The fuel and reducing agent are gas and/or natural gas.
The method according to claim 1, wherein in the step S1, the mixing is uniformly natural mixing or stirring mixing, wherein the stirring and mixing is performed by argon stirring, nitrogen stirring, nitrogen-argon. One or more of gas mixture agitation, reducing gas agitation, oxidizing gas agitation, electromagnetic agitation or mechanical agitation;

In the step S2, the sedimentation is natural sedimentation or spin sedimentation or centrifugal sedimentation; the cooling mode when cooling sedimentation is natural cooling or rotary cooling or centrifugal cooling, and the gravity sorting method is a shaker. Sorting, chute sorting or a combination of the two.