CN107699700A - A kind of method that valuable component is reclaimed by slag containing nickel fibers - Google Patents

Abstract

The present invention relates to a kind of method that valuable component is reclaimed by slag containing nickel fibers, it includes adding nickel fibers slag in reaction unit, and add calcium system mineral and additive, form mixing slag, mixing slag is heated to molten condition as reaction slag, is well mixed, monitors the reaction slag in real time, make mixed reaction slag by regulation and control while meet condition a and condition b, obtain reacted slag；S2, separation and recovery.The present invention can both make full use of melting nickel slag physics thermal resource and hot flux for metallurgy, cold conditions clinker can be handled again, by adding additive, it is well mixed, control slag oxygen position, realize slag metallurgy, realize copper in nickel fibers slag, iron separated in synchronization technology, and solve current clinker bulk deposition, problem of environmental pollution, and heavy metal contamination problem.

Description

A method for recovering valuable components from nickel-containing smelting slag

technical field

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

Background technique

During the nickel pyro-smelting process, a large amount of nickel smelting slag is produced. The nickel smelting slag includes the nickel smelting slag produced by the "matte smelting" process, the depleted slag produced by the "copper matte nickel blowing" process, and the top-blown smelting process. The nickel precipitated slag. my country's Jinchuan Company adopts "flash smelting" and "top blowing smelting" for nickel concentrate smelting, and produces 1 million tons of nickel smelting slag every year, and the accumulated storage capacity currently exceeds 10 million tons. Copper, iron, nickel, cobalt, zinc, lead, gold, silver and other valuable components in nickel smelting slag are piled up for a long time, which not only wastes resources but also pollutes the environment.

The iron content in the nickel smelting slag is as high as 50wt%, far exceeding the current mineable grade of 26wt%, and the copper content in the slag is as high as 0.2wt%, and the iron component mainly exists in the fayalite phase. At present, the research and utilization of nickel smelting slag mainly focus on direct reduction for iron extraction or smelting ironmaking. During the reduction process, copper, nickel, and cobalt components are reduced into molten iron, which is not conducive to the subsequent steelmaking process.

Nickel smelting slag is not only an important secondary resource, but also contains a large amount of metallurgical fluxes such as SiO ₂ , CaO, MgO, Al ₂ O ₃ , etc. It has strong chemical reactivity and is a slag system with excellent physical and chemical properties. The material is a mature metallurgical slag system. How to effectively use nickel smelting slag as the reaction slag system to realize the synchronous separation technology of copper and iron in nickel smelting slag is currently required by the market.

Contents of the invention

(1) Technical problems to be solved

In order to solve the above-mentioned problems in the prior art, the present invention provides a method for recovering valuable components from nickel-containing smelting slag. The method of the invention is a new slag metallurgical process, which not only reduces the copper content of slag to make the copper content of the slag <0.1wt%, but also realizes copper, nickel, cobalt, iron, gold, silver, lead, zinc, indium, bismuth, and sodium , Potassium and other components are efficiently recovered to obtain low-copper iron-containing materials (iron concentrate and pig iron), and to solve the current problems of massive accumulation of slag, environmental pollution, and heavy metal element pollution.

(2) Technical solution

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

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

S1. Slag mixing: Add nickel smelting slag into the smelting reaction device, and add calcium minerals and additives to form mixed slag, heat the mixed slag to a molten state as reaction slag, mix evenly, and monitor the reaction slag in real time , the mixed reaction slag satisfies condition a and condition b at the same time through regulation and control to obtain the reacted slag;

Wherein, the condition a is to control the temperature of the reaction slag to be 1100-1500°C;

The condition b is to control the basicity of the reaction slag CaO/SiO ₂ ratio=0.15～1.5;

S2. Separation and recovery: the molten slag after the reaction in step S1 is kept warm for 5 to 50 minutes, settled and separated to obtain the copper-rich nickel phase at the bottom, the iron-rich phase layer at the middle and lower part, and the iron-containing silicate mineral phase layer at the middle and upper part, At the same time, the soot of zinc-containing components and lead-containing components is generated, gold components and silver components enter the copper-rich nickel phase, nickel-containing components and cobalt-containing components enter the copper-rich nickel phase and iron-rich phase respectively; for each phase For recycling.

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

When the temperature of the reaction slag is less than 1100°C, use the heating function of the reaction device itself, or add fuel and preheated oxidizing air to the slag, so that the temperature of the reaction slag reaches the set temperature range, so that The temperature of the reaction slag reaches 1100-1500°C;

When the temperature of the reaction slag is greater than 1500°C, one or more of nickel smelting slag, blast furnace slag, ferroalloy slag, steel slag, metallurgical flux, iron-containing material or fluorine-containing material is added to the reaction slag, so that The temperature of the mixed slag reaches 1100-1500°C;

The method for the regulation of condition b is:

When the basicity CaO/ _SiO2 ratio in the reaction slag is less than 0.15, adding alkaline materials and/or basic iron-containing materials to the reaction slag;

When the basicity CaO/SiO ₂ ratio in the reaction slag is greater than 1.5, acidic materials and/or acidic iron-containing materials are 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 a slag hole or a slag hole that can flow out; wherein, the heat preservation device is a pourable Smelting reaction slag irrigation or heat preservation pit;

The rotatable smelting reaction device is a converter and a smelting reaction slag tank;

The smelting reaction device with a slag port or an iron port where the slag can flow out is a plasma furnace, a DC electric arc furnace, an AC electric arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola, a side-blown molten pool melting furnace, Bottom-blown molten pool melting furnace, top-blown molten pool melting furnace, reverberatory furnace, Osmet furnace, Isa furnace, Vanukov molten pool melting furnace, side-blown rotary furnace, bottom-blown rotary furnace, top-blown rotary furnace .

In the above-mentioned method, preferably, in the step S1, while satisfying the conditions a and b, they should be satisfied at the same time, and control the copper oxide, nickel oxide, cobalt oxide and iron oxide in the reaction slag The oxides are respectively reduced to metal copper, metal nickel, metal cobalt and FeO, and the content of metal iron in the slag is less than 3%. It can be controlled by adding one or both of reducing agent and carbon-containing iron-containing material, wherein the amount of the reducing agent is the reduction of copper oxide, nickel oxide, cobalt oxide and iron oxide in the slag. The theoretical amount of metallic copper, metallic nickel, metallic cobalt and FeO is 110-140%; the carbon-containing iron-containing materials are steel dust and soot, iron concentrate carbon-containing pre-reduced pellets, iron concentrate carbon-containing metal Pelletization, zinc hydrometallurgy volatilization kiln slag, coke furnace dust sludge and soot.

In the method as described above, preferably, the nickel smelting slag is nickel smelting slag produced by the "matte-making smelting" process, blowing slag after blowing by the "copper matte converting" process, or "copper matte converting" process. One or more of the depleted slag produced by blowing blowing slag after blowing, the nickel smelting slag produced by top blowing smelting, and the sedimentation slag produced by sedimentation of nickel smelting slag produced by top blowing smelting; the nickel smelting The slag is in a molten state or a cold state, wherein the molten nickel smelting slag is obtained from the slag outlet of the nickel smelting furnace, or the nickel smelting slag is heated to a molten state;

The calcium minerals are one or more of lime, limestone, dolomite, calcium carbide slag, red mud or red mud after desodium and high calcium; the additives are SiO ₂ , MgO, FeO, Fe ₂ O ₃ , One or more of MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O.

In the method as described above, preferably, the copper-containing material is blister copper pyro-refining slag, copper beneficiation tailings, copper slag, zinc smelting slag, zinc smelting soot and sludge, lead smelting slag, lead-zinc tailings , lead matte, arsenic matte, crude lead pyro-refining slag, lead smelting soot and soot, lead-acid battery, copper smelting soot and dust sludge, miscellaneous copper, copper-containing waste, copper-containing circuit boards, tin smelting slag, tin One or more of the tailings; wherein, the zinc smelting slag is the zinc smelting slag produced by hydrometallurgy and pyrometallurgy, including leaching slag, alum slag, copper cadmium slag, goethite slag, Hematite slag, volatilized kiln slag, vertical tank zinc smelting slag, blast furnace slag, fuming slag, vortex smelting slag, electric furnace zinc smelting slag, the zinc smelting slag of the wet method needs to be dried and dehydrated before entering the furnace; Lead-containing smelting slags are fuming furnace slags and lead-containing smelting slags. Lead smelting slag, lead-containing smelting slag is smelted by fuming furnace to produce lead-containing fuming slag; the copper slag is copper-containing smelting slag, copper-containing blowing slag, depleted waste slag, flotation tailings, wet copper smelting One or more of the slags, the copper-containing smelting slag is produced in the "matte smelting" process of the copper pyro-smelting process; the copper-containing blowing slag is produced in the "copper matte blowing" process of the copper pyro-smelting process "Process; the depleted waste slag is copper-containing smelting slag and copper-containing blowing slag depleted waste slag, and the flotation tailings is copper-containing smelting slag and copper-containing blowing slag after beneficiation.

In the above-mentioned method, preferably, the fuel and the reducing agent are one or more of solid, liquid or gaseous fuels, and are injected in the form of injection or feeding, and the injection is performed with 0 to 1200 A gas loading of °C, the gas being an oxidizing gas;

The alkaline material is one or more of lime powder, red mud, high-calcium red mud after desodiumization, calcium carbide slag, dolomite powder or quicklime powder; the alkaline iron-containing material is alkaline sintered ore, alkali One or more of alkaline iron concentrate, alkaline pre-reduced pellets, alkaline metallized pellets or steel slag;

In the above-mentioned method, preferably, the acidic material is one or more of silica, gold and silver-containing silica, fly ash, and coal gangue; the acidic iron-containing material is CaO/SiO ₂ ≤ 1 containing One or more of iron materials, acid sinter, acid iron concentrate, acid pre-reduced pellets, acid metallized pellets, copper slag, lead-containing slag, zinc smelting slag, nickel smelting slag, ferroalloy slag, blast furnace slag kind.

In the above-mentioned method, preferably, 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 ball Carbon-containing pre-reduction pellets of ordinary iron ore concentrate, steel slag, zinc smelting slag, coke smelting dust and sludge, steel soot and dust sludge, nickel-containing smelting slag, copper slag, lead smelting slag, copper smelting slag, tin smelting slag , red mud, high-calcium red mud after sodium removal, coal fly ash, sulfuric acid slag; the steel soot and dust sludge include blast furnace gas sludge, converter dust sludge, electric furnace dust sludge, heat (cold ) Rolling sludge, sintering dust, pellet dust, cast iron dust, blast furnace gas ash, electric furnace dust, steel rolling oxide scale;

The fluorine-containing material is one or more of fluorite, _CaF2 or fluorine-containing blast furnace slag;

The zinc hydrometallurgy slag and dust sludge need to be dehydrated and dried.

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

Preferably, in the step S1, the uniform mixing is natural mixing or stirring mixing, and the stirring method is argon stirring, nitrogen stirring, nitrogen-argon mixed gas stirring, reducing gas stirring, oxidizing gas stirring, electromagnetic stirring One or more of stirring or mechanical stirring.

In the above-mentioned method, preferably, the copper-containing material, iron-containing material and fluorine-containing material are all pelletized or powdered materials or granulated; wherein, the particle size of the powdered material is ≤150 μm, and the particle size of the granular material is 5 to 5 μm. 25mm, the powdery material is injected in the way of injection, and the granular material is added in the way of injection or feeding. The loading gas used in the injection is preheated argon, nitrogen, reducing gas (coal gas and/or One or more of natural gas), oxidizing gas, and the temperature of the preheating is 0-1200°C.

Among them, the copper-containing material and the iron-containing material are in a hot state or a cold state, and the hot state material is directly obtained from the discharge port or the slag discharge port of the metallurgical furnace.

In the above-mentioned method, preferably, in the separation and recovery in the step S2, the copper-nickel-rich phase settled at the bottom, the iron-rich phase in the middle and the iron-containing silicate mineral phase in the upper layer can be treated separately, Or the combination of iron-rich and iron-containing silicate minerals in the middle and upper part, the gold component and silver component migrate and enrich into the copper-nickel-rich phase, part of the nickel-cobalt component enters the iron-rich phase, and the zinc-containing component and the The lead components volatilize and enter the dust recovery in the form of oxides.

Specifically, the separation and recovery in the step S2 is handled by any one of the following methods 1 to 5:

Method 1. When the slag can flow out of the smelting reaction device, the following steps are carried out after the slag is separated after the reaction is completed:

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 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: used for pouring glass ceramics or as slag wool; method D: air-cooling or water quenching the slag of the iron-containing silicate mineral phase after oxidation, the method includes: keeping the slag in the smelting reaction device or making the slag The slag is poured into the heat preservation device, and the preheated oxidizing gas with a temperature of 0-1200°C is blown into the slag containing iron silicate, and the temperature of the slag of the silicate is guaranteed to be >1450°C; when the slag is oxidized The weight percentage of iron is less than 1%, and oxidized slag is obtained; the oxidized slag is directly air-cooled or water-quenched, and used as slag cement, cement regulator, additive or cement clinker in cement production;

Further, when the temperature of iron-containing silicate slag is <1450°C, inject preheated fuel and preheated oxidizing gas, burn heat, supplement heat, or heat the device itself, so that the temperature of iron-containing silicate slag >1450℃;

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

E-1. The iron-containing silicate mineral phase is kept in the smelting reaction device or the slag is poured into the heat preservation device, and molten steel slag, lime, limestone, ferroalloy slag, One or more of fly ash, alkaline lean iron ore, bauxite, molten blast furnace slag, red mud, red mud after desodination or carbide slag are fully mixed to obtain a slag mixture material;

E-2. Blow into the upward slag mixture material an oxidizing gas with a preheating temperature of 0-1200°C, and ensure that the temperature of the slag mixture material is >1450°C; when the weight percentage of ferrous oxide is less than 1%, after oxidation is obtained of slag;

E-3. The oxidized slag is air-cooled or water-quenched to produce high value-added cement clinker;

Method F: The slag of the iron-containing silicate mineral phase is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: after air cooling, water quenching or slow cooling, the iron-containing silicate slag is used as a blast furnace ironmaking or Direct reduction of raw materials for ironmaking. After direct reduction, magnetic separation or electric furnace melting is used. Magnetic separation products are metallic iron and tailings. Electric furnace melting produces molten iron and slag;

Or after pouring the slag into the heat preservation device, the slag is modified and separated by magnetic separation, including: blowing into the slag in the heat preservation device a preheated oxidizing gas at 0-1200°C, and ensuring the temperature of the slag >1250℃;

Further, when the slag temperature is <1250°C, inject preheated fuel and preheated oxidizing gas, burn heat, supplement heat, or heat the device itself, so that the slag temperature is >1250°C;

The oxidized slag is slowly cooled to room temperature, crushed, and magnetically separated, and the products are magnetite concentrate and tailings, and the tailings are used as building materials;

Method G: the iron-containing silicate mineral phase is reduced to ironmaking, including 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 iron-containing materials are added, and a reducing agent is added at the same time to carry out melting reduction. Real-time monitoring of the reaction slag, through regulation At the same time, the conditions are met: the temperature of the reaction slag is 1350-1670° C. and the basicity of the reaction slag CaO/SiO ₂ ratio = 0.6-2.4, and the slag after the reaction is completed;

Wherein, the method for controlling the temperature of reaction slag is:

When the temperature of the reaction slag is less than 1350°C, the temperature of the reaction slag reaches 1350-1670°C by heating the reaction device itself, or adding fuel and preheated oxidizing gas to the slag;

When the temperature of the reaction slag is higher than 1670°C, one or more of metallurgical flux, iron-containing material or fluorine-containing material is added to the reaction slag, so that the temperature of the reaction slag reaches 1350-1670°C, wherein, the The metallurgical flux is a mineral containing CaO or _SiO2 , specifically one or more of quartz sand, gold and silver-containing quartz sand, red mud, high-calcium red mud after desodiumization, carbide slag, dolomite or limestone;

The method of controlling the basicity of reaction slag is:

When the basicity CaO/ _SiO2 ratio in the reaction slag is <0.6, add alkaline materials and/or basic iron-containing materials to the slag;

When the basicity CaO/ _SiO2 ratio in the reaction slag is >2.4, add acidic materials and/or acidic iron-containing materials to the slag;

G-2. During the smelting reduction in G-1, it is necessary to spray oxidizing gas preheated at 0-1200°C into the slag for smelting reduction to form reduced slag;

G-3. Separation and recovery: use one of the following two methods:

Method Ⅰ: Pour the reduced mixed slag into the thermal insulation slag tank, and slowly cool to room temperature to obtain slow-cooled slag; among them, metallic iron settles to the bottom of the reaction device to form iron lumps, and the remaining slowly-cooled slag containing metallic iron layer, crushed to a particle size of 20-400 μm, ore grinding, and magnetic separation to separate the remaining metal iron and tailings;

Method II: The reduced mixed slag is cooled and settled, and the slag-gold is separated to obtain molten iron and reduced slag; the reduced slag is smelted according to one or more methods in methods A to E Slag treatment; the molten iron is sent to converter or electric furnace for steelmaking;

S2-1-02. The copper-nickel-rich phase is sent to a converter or converting furnace or used as a raw material for the separation of copper, cobalt and nickel;

S2-1-03. Part of the zinc-containing components and lead-containing components volatilize and enter the dust recovery in the form of oxides;

S2-1-04. Part of the gold-containing component and the silver-containing component enter the copper-nickel-rich phase, and the nickel and cobalt components enter the copper-nickel-rich phase and the iron-rich phase, respectively;

S2-1-05. The iron-rich phase layer is obtained by water quenching or air cooling, or pouring into a heat preservation device for slow cooling, or by combining manual sorting and gravity selection, and is used as a raw material for blast furnace ferronickel smelting or direct reduction ferronickel smelting or Smelting reduction ferronickel smelting raw materials or flotation copper extraction raw materials; in the flotation process, the flotation products are copper concentrates, nickel concentrates, nickel-containing alloys and iron concentrates, and iron concentrates are used as blast furnace ironmaking raw materials or direct reduction smelting Iron raw materials or smelting reduction ironmaking raw materials; wherein, the direct reduction process uses rotary hearth furnaces, tunnel kilns, car bottom roads, shaft furnaces, rotary kilns or induction furnaces as reduction equipment, using gas-based or coal-based reduction technology, gas-based Natural gas and/or coal gas are used for base reduction, one or more of anthracite, bituminous coal, lignite, coking coal, coke powder or coke are used for coal base reduction, the reduction temperature is controlled at 900-1400 °C, and the alkalinity CaO/ _SiO2 ratio is controlled ＝0.8～1.5; the gas produced by the reduction is burned on the surface of the slag for the second time, which provides heat, and the gas flowing out of the furnace can be used as a heat source for drying the charge and the heat preservation device;

In addition, because red mud contains potassium and sodium, and dust sludge and steel soot contain lead, zinc, bismuth, and indium, when adding these raw materials, some indium components, bismuth components, potassium-containing components, and sodium-containing components Volatilizes and enters the dust in the form of oxides.

Method 2. When using a smelting reaction device in which slag can flow out, the obtained iron-rich phase and iron-containing silicate mineral phase are treated with one or more of the steps A to G described in method 1. , pour into the copper-nickel-rich phase after slow cooling in the heat preservation device, and send it to the converter or blowing furnace or as the raw material for the separation of copper, cobalt and nickel.

Method 3. When using a slag-rotatable converter and a reaction slag tank, the iron-containing silicate mineral phase is obtained in a molten state, and the treatment method is treated with one or more of the steps A to G in the method 1. ; or contain the iron-rich phase in step S2-1-05 of method 1 for processing; the molten state or the copper-nickel-rich phase after being poured into the heat preservation device and slowly cooled is sent to the converter or blowing furnace or used as copper-cobalt Raw material for nickel separation.

Method 4. When using a slag-rotatable converter and a reaction slag tank, the iron-containing silicate mineral phase and iron-rich phase obtained in the molten state are treated with one of the steps A to G in method 1. or several kinds of processing; the molten copper-nickel-rich phase is sent to a converter or blowing furnace for copper smelting, or after slow cooling, it is crushed and magnetically separated to separate metal iron and then sent to a converter or blowing furnace or separated as copper, cobalt and nickel raw materials.

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

S201. Settling cooling: the molten slag is cooled to room temperature to obtain slow cooling slag; the nickel-rich copper phase settles to the bottom of the reaction device to form copper-rich nickel lump; the iron-containing silicate mineral phase floats; the middle is slow cooling The slag is an iron-rich phase, and simultaneously generates zinc-containing components and lead-containing components; among them, the gold and silver components migrate to the copper-rich nickel phase, and the nickel and cobalt components migrate to the copper-nickel-rich phase and iron-rich phase, respectively;

S202. Separation: Manually remove the copper-nickel lump that settled at the bottom, and send it to a converter or blowing furnace or as a raw material for copper-cobalt-nickel separation; the iron-rich phase is used as a raw material for blast furnace ironmaking or direct reduction ironmaking raw material or smelting reduction Ironmaking raw materials or smelting reduction ironmaking raw materials or flotation copper extraction raw materials; flotation products are copper-containing concentrates, nickel concentrates, nickel alloys and iron concentrates, and iron concentrates are used as blast furnace ironmaking raw materials or direct reduction ironmaking raw materials Or smelting reduction ironmaking raw materials;

S203. Manually remove the upper iron-containing silicate mineral phase to obtain the silicate phase as a raw material for blast furnace ironmaking or direct reduction ironmaking raw material or smelting reduction ironmaking raw material or cement raw material;

S204. Part of the zinc and lead components volatilize and enter the dust recovery in the form of oxides;

S205. When raw materials such as red mud or dust sludge and iron and steel soot are added, part of the indium component, bismuth component, potassium-containing component, and sodium-containing component volatilize and enter the dust recovery.

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

As described above, preferably, in the step S1, the uniform mixing is natural mixing and stirring mixing, and the stirring and mixing methods are argon stirring, nitrogen stirring, nitrogen-argon mixed gas stirring, reducing One or more of gas stirring, oxidizing gas stirring, electromagnetic stirring or mechanical stirring;

In the step S2, the settling is natural settling or rotary settling or centrifugal settling; the cooling mode when carrying out cooling settling is natural cooling or rotary cooling or centrifugal cooling, and during the separation, gravity separation is shaker sorting, chute sorting or a combination of both.

Compared with prior art, the characteristics of the present invention are:

(1) The method for recovering valuable components from nickel-containing smelting slag of the present invention can handle hot slag, make full use of the physical heat resources and hot metallurgical flux of molten nickel smelting slag, and can handle cold slag again, By adjusting the physical and chemical properties of slag and utilizing the mature physical and chemical properties of nickel-containing slag, the metallurgical process of nickel-containing slag has been realized; and the current problems of massive accumulation of slag, environmental pollution, and heavy metal element pollution have been solved;

(2) The slag metallurgical reaction in the slag, adding calcium minerals, disintegrates the fayalite, fully releases the iron oxides, forms free iron oxides, and realizes the growth and settlement of the iron-rich phase. The iron-containing components of the iron-containing components gather, grow and settle, and the iron-rich phase includes a variety of metallic iron, FeO phase, and fayalite phase, which are used as raw materials for blast furnace ironmaking or direct reduction or smelting reduction ironmaking; at the same time, calcium-based minerals can effectively transform Viscosity, which is a reduction in viscosity, helps copper-containing components to settle,

(3) The copper components, nickel components, cobalt components, and gold and silver components in the mixed slag migrated and enriched in the copper-rich nickel phase respectively, and realized growth and settlement. Among them, the copper-rich nickel phase includes copper , white matte, copper matte, copper-nickel-cobalt-rich phase, multiple iron-containing components, or some copper-nickel-cobalt components enter the iron-rich phase;

(4) The zinc and lead components in the mixed slag migrate and enrich in the soot respectively, and realize recovery; some components containing indium, bismuth, potassium and sodium volatilize into the soot to recycle;

(6) Separating the copper-rich nickel phase and iron oxides that settled in different parts to realize the efficient recovery of copper components and iron components in the slag. The copper content in the slag is less than 0.1wt%, and solid copper-containing materials can be processed;

(7) The slag can be quenched and tempered, and can be used as cement raw material or building material or instead of gravel as aggregate and road material;

(8) The method of the present invention adds additives, one is used to reduce the viscosity, the other is used to reduce the melting point, and at a certain temperature (1100-1450 ° C), it is helpful for the precipitation of the copper-rich nickel phase, so that the iron-rich phase can be obtained after sedimentation and separation. The phases are low-copper iron-rich phase and iron-containing silicate phase, wherein the copper content of the iron-rich phase and iron-containing silicate phase is less than 0.1%. Iron concentrate and metal can be obtained by direct reduction or smelting reduction ironmaking iron;

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

(3) Beneficial effects

The beneficial effects of the present invention are:

(1) The raw material of the present invention can be cold state slag, and cold state slag is handled, and not only can realize copper component, nickel component, cobalt component, gold component, silver component, bismuth component, sodium component in slag The comprehensive utilization of valuable components of , potassium, iron, zinc, and lead can solve the current problem of massive accumulation of slag and environmental pollution.

(2) The raw material of the present invention can be liquid molten nickel smelting slag flowing out of the slag outlet, which contains abundant thermal energy resources, has the characteristics of high temperature and high heat, makes full use of the physical heat resources of molten slag, and saves energy efficiently; liquid Molten copper slag contains a large amount of hot metallurgical flux, is a slag system with excellent physical and chemical properties, and realizes slag metallurgy.

(3) The present invention adjusts the physical and chemical properties of the slag, injects gas, and controls the oxygen potential, so that the copper components, nickel components, cobalt components, and gold and silver components in the slag migrate and enrich to the copper-nickel-rich phase , to achieve aggregation, growth and settlement.

(4) In the inventive method, adding cold state material and molten nickel smelting slag has avoided slag temperature too high, improves the life-span of heat preservation device; Adding cold state material and nickel smelting slag improves raw material handling capacity, not only can handle slag, and can handle a small amount of cold materials, and the raw materials have strong adaptability; adding cold materials realizes the efficient use of the chemical heat released by the reaction and the physical heat of slag.

(5) The present invention adjusts the physical and chemical properties of slag, controls the oxygen potential, and adds calcium minerals at the same time, so that iron oxides in the olivine phase are released and enriched in the iron-rich phase to achieve aggregation, growth and settlement, and iron-rich The phase includes many kinds of metallic iron, FeO phase, and fayalite phase, which are used as raw materials for blast furnace ironmaking or direct reduction or smelting reduction ironmaking; zinc components, lead components, indium components, bismuth components, sodium components in slag Components and potassium components volatilize and enter the dust for recovery.

(6) During the natural cooling process of the method of the present invention, with the addition of additives, the copper components, nickel components, cobalt components, and gold and silver components in the slag are enriched in the copper-nickel-rich phase, and realize aggregation, growth and settlement , the copper-nickel-rich phase includes copper, white matte, copper matte, copper-nickel-cobalt phase, and various iron-containing components, or part of the copper-nickel-cobalt component enters the iron-rich phase, and the iron component in the slag is enriched In the iron-rich phase, and realize the aggregation, growth and settlement, the heat preservation device with slag is placed on the rotating platform to rotate, to accelerate the aggregation, growth and settlement of the copper-nickel-rich phase and iron-rich phase; the addition of fluorine-containing materials , to accelerate the growth and settlement of copper-nickel-rich phase and iron-rich phase.

(7) The iron oxides in the molten slag of the method of the present invention almost disappear, the grindability of minerals increases, and the molten slag is tempered.

(8) The method of the present invention adopts the method for artificial sorting, magnetic separation, gravity separation or slag-gold separation, respectively to the low-iron silicate mineral phase, iron-rich phase, copper-nickel-rich phase distributed in the upper, middle and bottom Separation to achieve efficient recovery of copper components, nickel components, cobalt components, gold and silver components, indium components, bismuth components, and iron components in the slag, and the obtained iron-containing silicate phase and iron-rich The slag of the components contains less than 0.1wt% copper. Since the copper-nickel-rich phase and the iron-rich phase settle in the middle and lower parts, the amount of slag to be sorted is small, the grindability of minerals increases, and the cost of grinding, magnetic separation and gravity separation Low; the subsequent separation process adopts physical beneficiation (magnetic separation or gravity separation), and the separation medium is water, which will not cause environmental pollution during the separation process. The slag treatment process has short process, simple operation, high recovery rate, high efficiency, Clean and environmentally friendly; tailings are used as cement raw materials, building materials, aggregates and road materials instead of crushed stones.

(9) The present invention obtains metallic iron and molten iron through precipitation of the copper-rich nickel phase, the copper content of the iron-containing silicate phase and the iron-rich component is less than 0.1%, and is used as a raw material for blast furnace ironmaking or direct reduction or smelting reduction.

(10) The present invention not only makes full use of molten slag physical heat resources and hot state metallurgical flux, but also can process cold state slag, realizes slag metallurgy, copper component, nickel component, cobalt component, gold and silver components in molten slag The iron component is enriched in the copper-nickel-rich phase, and realizes aggregation, growth and settlement. The iron component is enriched in the iron-rich phase, and realizes aggregation, growth and settlement. Manual sorting, magnetic separation, gravity separation and slag-gold The method of combination of sedimentation separates the copper-nickel-rich phase and iron-rich phase that settle in different parts, and realizes the efficient recovery of copper components, nickel, cobalt, gold and silver components, and iron components in the slag; it can process solid copper-containing materials , the method has short process flow, high metal recovery rate, low production cost, strong raw material adaptability, large processing capacity, environmental friendliness, high economic returns, and can solve the problem of efficient recovery and utilization of metallurgical resources and thermal energy.

detailed description

A method for recovering valuable components from nickel-containing smelting slag, specifically comprising the following steps:

Step 1, slag mixing:

Put the nickel-containing smelting slag into the heat preservation device or the smelting reaction device where the slag can flow out, and add calcium-based minerals and additives to form a mixed slag;

Heating the mixed slag to a molten state to form a reaction slag; mixing evenly, monitoring the nickel-containing reaction slag in real time, and ensuring the following two parameters (a) and (b) through regulation at the same time to obtain the slag after the reaction is completed;

(a) The temperature of the reaction slag is 1100～1500°C;

(b ₎ basicity CaO/SiO of reaction slag Ratio=0.15～1.5;

The control method is:

Corresponding to (a):

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

When the temperature of the reaction slag is lower than the lower limit of the set temperature range, the temperature of the reaction slag reaches the set temperature range through the heating function of the reaction device itself, or by adding fuel and preheated oxidizing air to the reaction slag;

When the temperature of the reaction slag is higher than the upper limit of the set temperature range, add one of nickel smelting slag, blast furnace slag, ferroalloy slag, steel slag, copper-containing material, metallurgical flux, iron-containing material or fluorine-containing material to the reaction slag or several, so that the temperature of the mixed slag reaches the set temperature range;

Corresponding to (b):

When the ratio of alkalinity CaO/ _SiO2 in the reaction slag is less than 0.15, add one or more of alkaline materials or basic iron-containing materials to the reaction slag;

When the ratio of basicity CaO/ _SiO2 in the reaction slag is >1.5, add one or more of acidic materials or acidic iron-containing materials to the reaction slag;

Step 2, separation and recovery:

Keep warm for 5 to 50 minutes. After the reaction is completed, the molten slag will settle, and the slag-gold will be separated to obtain the copper-rich nickel in the molten state at the bottom, the iron-rich phase in the molten state in the middle and lower parts, and the iron-containing silicate mineral phase in the molten state in the upper and middle parts. Simultaneously generate zinc-containing components and lead-containing components, wherein, indium, bismuth, nickel, cobalt, gold, and silver components migrate to the nickel-rich copper phase, and part of the nickel-cobalt component migrates to the iron-rich phase;

Recycle the phases using one of the following methods:

Method 1: When the slag can flow out of the smelting reaction device, the slag after the reaction is completed carries out the following steps:

(1) The iron-containing silicate mineral phase in molten state is processed with slag;

(2) Copper-rich molten state, sent to converter or blowing furnace or as raw material for separation of copper, cobalt and nickel;

(3) Part of the lead components, zinc components, indium components, bismuth components, sodium components, and potassium components volatilize and enter the dust recovery;

(4) The iron-rich phase is water-quenched or air-cooled or poured into a heat preservation device for slow cooling or combined with manual sorting and gravity selection to be used as raw materials for blast furnace ironmaking or direct reduction of ferronickel smelting raw materials or smelting reduction of ferronickel smelting raw materials or floating Copper and nickel raw materials are extracted; flotation products are copper concentrates, nickel concentrates, nickel-containing alloys and iron concentrates, and iron concentrates are used as blast furnace ironmaking raw materials or direct reduction ironmaking raw materials or smelting reduction ironmaking raw materials; the direct The reduction process uses rotary hearth furnace, tunnel kiln, car bottom road, shaft furnace, rotary kiln or induction furnace as reduction equipment, and uses gas-based or coal-based reduction technology, gas-based reduction to natural gas and/or coal gas, and coal-based reduction to anthracite , Bituminous coal, lignite, coking coal, coke powder or one or more of coke, the reduction temperature is 900-1400°C, and the alkalinity CaO/SiO ₂ ratio = 0.8-1.5.

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

Method A: Iron-containing silicate mineral phase as cement raw material:

The iron-containing silicate mineral phase is water-quenched or air-cooled and directly used as cement raw materials or further processed into high-value-added cement raw materials.

Method B: Part or all of the iron-containing silicate mineral phase is returned to the copper-containing reaction slag:

Part or all of the iron-containing silicate mineral phase is returned to the copper-containing reaction slag as a hot metallurgical flux to adjust the composition of the copper-containing reaction slag and control the temperature of the copper-containing reaction slag.

Method C: Cast glass-ceramic or as slag wool with iron-silicate mineral phase.

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

(1) Blow preheated oxidizing gas into the iron-containing silicate slag in the smelting reaction device. When the content of ferrous oxide in the slag is less than 1%, the oxidation of the slag is completed and the oxidized slag is obtained. , wherein the preheating temperature of the oxidizing gas is 0 to 1200°C; and during the whole process, ensure that (c) the temperature of the silicate slag is >1450°C;

Corresponding to the control method adopted in (c):

When the temperature of iron-containing silicate slag is less than 1450°C, inject preheated fuel and preheated oxidizing gas, burn heat, supplement heat, or heat the device itself, so that the temperature of silicate slag is greater than 1450°C;

(2) The oxidized slag is directly air-cooled or water-quenched and used as slag cement, cement regulator, additive or cement clinker in cement production.

Method E: Iron-containing silicate slag treatment to produce high value-added cement clinker:

(1) Add molten steel slag, lime, limestone, ferroalloy slag, fly ash, basic iron lean ore, bauxite, molten blast furnace slag, red mud, One or more of red mud or calcium carbide slag after desodiumization are fully mixed to obtain slag mixture;

(2) Blow into preheated oxidizing gas in the slag mixture material, when ferrous oxide content＜1%, finish the oxidation of slag, obtain oxidized slag, wherein, the preheating temperature of oxidizing gas is 0～1190 DEG C; And in the whole process, guarantee (d) slag mixture material temperature>1450 DEG C; The temperature control method is the same as the silicate slag temperature control method in method D step (1);

(3) The oxidized slag is air-cooled or water-quenched to produce 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 iron-containing silicate mineral phase slag is air-cooled, water quenched or slowly cooled, and used as a blast furnace smelting slag. Iron or direct reduction ironmaking raw materials, after direct reduction, use magnetic separation or electric furnace melting, magnetic separation products are metallic iron and tailings, electric furnace melting, the products are molten iron and slag;

Or after pouring the slag of the iron-containing silicate mineral phase into the heat preservation device, the following method is used for separation: magnetic separation after modification of the slag: blowing into the slag in the heat preservation device, Preheated oxidizing gas, and ensure that the temperature of the slag is >1250°C to complete the transformation of magnetite in the slag; slowly cool the above-mentioned oxidized slag to room temperature, crush and magnetically separate, and the product is magnetite concentrate Mine and tailings, tailings as construction materials. Method G: Smelting reduction ironmaking of iron-containing silicate slag:

(1) Keep the iron-containing silicate slag in the smelting reaction device or pour the slag into the heat preservation device, add iron-containing materials and reducing agents to the molten slag, carry out melting reduction, monitor the reaction slag in real time, and pass Control and ensure the following two parameters (a) and (b) at the same time to obtain the slag after the reaction is completed;

(a) The temperature of the reaction slag is 1350～1670°C;

(b ₎ basicity CaO/SiO of reaction slag Ratio=0.6～2.4;

The control method is:

Corresponding to (a):

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

When the temperature of the reaction slag is lower than the lower limit of the set temperature range of 1350°C, the temperature of the reaction slag reaches the set temperature range through the heating function of the reaction device itself, or by adding fuel and preheated oxidizing gas to the slag Within 1350～1670℃;

When the temperature of the reaction slag is higher than the upper limit of the set temperature range of 1350°C, add one or more of metallurgical flux, iron-containing material or fluorine-containing material to the reaction slag to make the temperature of the reaction slag reach the set temperature Within the range of 1350～1670℃;

Corresponding to (b):

When the basicity CaO/ _SiO2 ratio in the reaction slag is <0.6, add alkaline materials and/or basic iron-containing materials to the slag;

When the basicity CaO/ _SiO2 ratio in the reaction slag is >2.4, add acidic materials and/or acidic iron-containing materials to the slag;

(2) Spray preheated oxidizing gas into the molten slag for smelting reduction to form reduced slag, wherein: the preheating temperature of the oxidizing gas is 0-1200°C, and during the blowing process, through Regulation guarantees both (a) and (b) parameters at the same time:

(a) the temperature of the molten slag after the reaction is completed is 1350～1670 ℃;

(b ₎ basicity CaO/SiO of the molten slag after the reaction is completed Ratio=0.6～2.4;

Wherein, set temperature range and alkalinity control method with method G step (1);

(3) Separation and recovery:

Use one of the following methods:

Method Ⅰ: Carry out the following steps:

(a) Cooling: Pour the reduced mixed slag into the thermal insulation slag tank, cool to room temperature, and obtain slowly cooled slag;

(b) Separation: Metal iron settles to the bottom of the reaction device to form iron lumps, which are manually removed; the metallic iron layer in the remaining slowly cooled slag is crushed to a particle size of 20-400 μm, ore is ground, and the remaining metals are separated by magnetic separation iron and tailings;

(c) Recycling of tailings, used as cement raw materials, construction materials, instead of crushed stones as aggregates, road materials or phosphate fertilizers;

Method Ⅱ: Carry out the following steps:

(a) The reduced mixed slag is cooled and settled, and the slag-gold is separated to obtain molten iron and reduced slag;

(b) Carry out the slag treatment outside the furnace for the reduced slag, the specific method is: adopt one or more of the methods A to E in the separation and recovery method 1 of step 2 to carry out the slag treatment;

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

(d) Zinc-containing components and lead-containing components volatilize and enter the dust recovery in the form of oxides;

(e) Part of the indium component, bismuth component, sodium component, and potassium component volatilizes into the smoke;

(f) The gas generated by the reduction is burned on the surface of the slag for the second time to provide heat, and the gas flowing out of the furnace can be used as a heat source for drying the charge and the heat preservation device.

Method 2: When using a smelting reaction device in which slag can flow out, the slag after the reaction is completed undergoes the following steps:

(1) The cold copper-nickel-rich phase is sent to converter copper smelting or blowing furnace or as a raw material for copper-cobalt-nickel separation;

(2) The iron-rich phase layer and the iron-containing silicate mineral phase are treated with one or more of the steps A to G described in method one;

(3) Part of the zinc-containing components and lead-containing components volatilize and enter the dust recovery in the form of oxides;

(4) Some indium components, bismuth components, sodium components, and potassium components volatilize into the smoke.

Method 3: When using a converter with rotatable slag and a reaction slag tank, the slag after the reaction is completed undergoes the following steps:

or The step (4) in method 1 is used to process the iron-rich phase;

(2) After the molten copper-nickel-rich phase is poured into the insulation device for slow cooling, it is sent to the converter or blowing furnace or used as a raw material for the separation of copper, cobalt and nickel;

(3) Some lead components, zinc components, indium components, bismuth components, sodium components, and potassium components volatilize into the smoke;

Method 4: When using a slag-rotatable converter and a reaction slag tank, the slag after the reaction is completed undergoes the following steps:

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

(2) The copper-nickel-rich phase in a molten state is sent to a converter or converting furnace or as a raw material for the separation of copper, cobalt and nickel;

(3) Some lead components, zinc components, indium components, bismuth components, sodium components, and potassium components volatilize into the smoke;

Method 5: When using a heat preservation device, or using a smelting reaction device where slag can flow out, when pouring the slag into the heat preservation device, the slag after the reaction is completed undergoes the following steps:

(1) Settling cooling: After the reaction is completed, the slag is cooled to room temperature to obtain slowly cooled slag; the copper-nickel-rich phase settles to the bottom of the reaction device to form a copper-rich nickel lump; the iron-containing silicate mineral phase floats; the copper-nickel-rich phase The slowly cooled slag between the phase and iron-containing silicate minerals is an iron-rich phase, and simultaneously generates zinc-containing components and lead-containing components; the gold-silver component migrates to the copper-nickel-rich phase;

(2) Separation: Manually remove the copper-nickel-rich lump that settles at the bottom, and send it to the converter or blowing furnace or as a raw material for copper-cobalt-nickel separation; the iron-rich phase layer in the middle is used as a raw material for blast furnace nickel-iron smelting or direct reduction of nickel-iron smelting raw material Or smelting reduction ferronickel smelting raw materials or flotation copper extraction raw materials; in the flotation process, the flotation products are copper concentrate, nickel concentrate, nickel alloy and iron concentrate, iron concentrate is used as blast furnace ironmaking raw material or direct reduction Ironmaking raw materials or smelting reduction ironmaking raw materials;

The direct reduction process adopts rotary hearth furnace, tunnel kiln, car bottom road, shaft furnace, rotary kiln or induction furnace as reduction equipment, and utilizes gas-based or coal-based reduction technology. Gas-based reduction uses natural gas and/or coal gas, and coal-based One or more of anthracite, bituminous coal, lignite, coking coal, coke powder or coke is used for reduction, the reduction temperature is controlled at 900-1400°C, and the alkalinity CaO/ _SiO2 ratio is controlled at 0.8-1.5;

(3) Manually remove the upper iron-containing silicate mineral phase, and use it as raw material for blast furnace ironmaking, direct reduction ironmaking raw material or smelting reduction ironmaking raw material, or as cement raw material, building material, instead of crushed stone as aggregate, and road material ;

(4) Some lead, zinc, indium, bismuth, sodium, and potassium components volatilize into the smoke.

In the above method, preferably, in the steps 1 and 2, the nickel smelting slag is molten or cold, wherein: the molten nickel smelting slag is obtained from the slag outlet of the nickel smelting furnace, or the nickel smelting slag is heated to the molten state; nickel smelting slag is the nickel smelting slag produced by the "matte smelting" process, the blowing slag after blowing by the copper matte nickel blowing process, and the blowing slag after blowing by the "copper matte nickel blowing" process One or more of depleted slag produced by depletion, nickel smelting slag produced by top blowing smelting, and settled slag produced by sedimentation of nickel smelting slag produced by top blowing smelting;

The copper materials in steps 1 and 2 are crude copper pyro-refining slag, copper slag, copper beneficiation tailings, zinc smelting slag, zinc smelting soot and dust, lead smelting slag, lead-zinc tailings, lead matte, Arsenic matte, crude lead pyro-refining slag, lead smelting soot and sludge, lead-acid batteries, copper smelting soot and sludge, miscellaneous copper, copper-containing waste, copper-containing circuit boards, tin smelting slag, tin tailings One or several types; zinc smelting slag is zinc smelting slag produced by hydrometallurgy and pyrometallurgy, including leaching slag, ferrite slag, copper cadmium slag, goethite slag, hematite slag, volatilized kiln slag , vertical tank zinc smelting slag, blast furnace slag, fuming furnace slag, vortex furnace slag, electric furnace zinc smelting slag; 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 through a fuming furnace to produce lead-containing fuming slag;

In the steps 1 and 2, the copper slag is one or more of copper-containing smelting slag, copper-containing blowing slag, depleted waste slag, flotation tailings, and hydrometallurgy copper smelting slag, and copper-containing smelting slag Produced in the "matte smelting" process of the copper pyrometallurgy process; copper-containing blowing slag is produced in the "copper matte blowing" process of the copper pyrometallurgy process; the depleted waste slag is copper-containing smelting slag and copper-containing slag The blowing slag is diluted and discarded, and the flotation tailings are copper-containing smelting slag and copper-containing blowing slag after beneficiation.

In the method described above, preferably, in the steps 1 and 2, the smelting reaction device from which 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 tank and a heat preservation pit;

The rotatable smelting reaction device is a converter and a smelting reaction slag tank;

The smelting reaction device with slag mouth or iron mouth where slag can flow out is plasma furnace, DC electric arc furnace, AC electric arc furnace, submerged arc furnace, blast furnace, blast furnace, induction furnace, cupola, side blowing molten pool melting furnace , Bottom-blown molten pool melting furnace, top-blown molten pool melting furnace, reverberatory furnace, Osmet furnace, Isa furnace, Vanukov molten pool melting furnace, side-blown rotary furnace, bottom-blown rotary furnace, top-blown back Converter.

In the above-mentioned method, preferably, in the step 1, the calcium-series minerals are specifically one or more of lime, limestone, dolomite, carbide slag, red mud or high-calcium red mud after desalination; The additive is one or more of SiO ₂ , MgO, FeO, Fe ₂ O ₃ , MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O.

In the described step 1, the following two parameters (a) and (b) are ensured at the same time through regulation and control, while ensuring that copper oxides, nickel oxides, cobalt oxides and iron oxides in the slag are reduced to metal copper and metal oxides respectively. Nickel, metal cobalt and FeO, metal iron content in slag <3%. It can be controlled by adding one or both of reducing agent and carbon-containing iron-containing material, wherein the amount of the reducing agent is the reduction of copper oxide, nickel oxide, cobalt oxide and iron oxide in the slag. The theoretical amount of metallic copper, metallic nickel, metallic cobalt and FeO is 110-140%; the carbon-containing iron-containing materials are steel dust and soot, iron concentrate carbon-containing pre-reduced pellets, iron concentrate carbon-containing metal Pelletization, zinc hydrometallurgy volatilization kiln slag, coke furnace dust sludge and soot.

In the steps 1 and 2, the fuel and the reducing agent are one or more of solid, liquid or gaseous fuels, which are injected in the form of injection or feeding, and the loading gas is preheated oxidizing One or more of gas, nitrogen or argon, the preheating temperature is 0-1200°C; the solid fuel and reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite The shape is granular or powdery, the particle size of the granular material is 5-25mm, the particle size of the powdery material is ≤150μm, the liquid fuel and reducing agent are heavy oil, and the gaseous fuel and reducing agent are coal gas and/or natural gas;

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

The iron-containing materials mentioned in 1 and 2 are ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sinter, ordinary iron concentrate pellets, ordinary iron concentrate metallized pellets, ordinary iron concentrate Concentrate carbon-containing pre-reduction pellets, steel slag, zinc smelting slag, coke smelting dust and sludge, steel soot and dust sludge, nickel-containing smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud , one or more of high-calcium red mud after desodiumization, coal fly ash, and sulfuric acid slag; the steel soot and dust sludge include blast furnace gas sludge, converter dust sludge, electric furnace dust sludge, hot (cold) rolling dirt Mud, sintering dust, pellet dust, cast iron dust, blast furnace gas ash, electric furnace dust, steel rolling oxide scale.

The copper-containing material and the iron-containing material are in a hot or cold state, wherein the hot material is directly obtained from a metallurgical furnace outlet or a slag outlet.

The zinc hydrometallurgy slag and dust sludge need to be dehydrated and dried.

Among the above raw materials, zinc smelting slag and soot, lead smelting slag and soot contain indium and bismuth, lead, silver, zinc, and bismuth; red mud contains sodium and potassium, and steel soot and dust sludge contain indium, bismuth, silver, Sodium and potassium, the above materials all have iron, lead smelting slag and zinc smelting slag all contain copper, copper soot and dust sludge contain indium and bismuth, so in the method of invention, indium, bismuth, sodium, potassium, zinc, lead will be Into the fume in the form of oxides for recycling.

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

In steps 1 and 2, the copper-containing material, iron-containing material and fluorine-containing material are all pelletized or powdered materials or granulated; wherein, the particle size of the powdered material is ≤150 μm, and the particle size of the granular material is 5-25 mm. The powdery material is injected by blowing, and the granular material is added by blowing or feeding. The loading gas is preheated argon, nitrogen, reducing gas (coal gas and/or natural gas), and oxidizing gas. One or more, the preheating temperature is 0～1200℃;

In the above steps 1 and 2, the injection method is used for feeding, and specifically, one or more of the refractory spray guns are used to insert the slag or place the reaction slag on the top, side or bottom.

In the above steps 1 and 2, during the slag reaction process, the copper components, nickel components, cobalt components, and gold and silver components in the slag are enriched in the copper-rich nickel phase, and realize aggregation, growth and settlement , the iron component is enriched in the iron-rich phase to achieve aggregation, growth and settlement, and the zinc, lead, indium and bismuth components in the slag enter the dust recovery respectively. In the method for setting the temperature range of the temperature of the described control mixed slag:

When the temperature of the mixed slag is higher than the upper limit of the set temperature, one or more of nickel smelting slag, copper-containing materials, metallurgical flux, iron-containing materials or fluorine-containing materials is added to avoid excessive temperature and protect refractory materials Another function of adding fluorine-containing materials is to reduce the viscosity and accelerate the aggregation, growth and settlement of the copper-nickel-rich phase and iron-rich phase in the slag.

In the steps 1 and 2, when adjusting the alkalinity, the alkaline material is one or more of lime powder, red mud, red mud after desodination, carbide slag, dolomite powder or quicklime powder; The basic iron-containing material is an iron-containing material with CaO/SiO ₂ ≥ 1, and the basic iron-containing material is basic sintered ore, basic iron concentrate, basic pre-reduced pellets, basic metallized balls One or more of lumps, steel slag or blast furnace slag.

In the steps 1 and 2, when adjusting the alkalinity, the acidic material is one or more of silica, fly ash, and coal gangue; the acidic iron-containing material is an iron-containing material with CaO/SiO ₂ ≤ 1, and the acidic iron-containing material is Iron materials are acid sinter, acid iron concentrate, acid pre-reduced pellets, acid metallized pellets, copper slag, lead smelting slag, zinc smelting slag, nickel smelting slag, tin smelting slag, ferroalloy slag, blast furnace slag one or several;

In step 1, while ensuring the two parameters (a) and (b), the slag should be fully mixed, the mixing method is natural mixing or stirring mixing, and the stirring method is one of the following methods: argon stirring, nitrogen stirring One or more of stirring, nitrogen-argon mixed gas stirring, reducing gas stirring, oxidizing gas, electromagnetic stirring, mechanical stirring, the gas preheating temperature is 0-1200°C;

In steps 1 and 2, the copper-nickel-rich phase and iron-rich phase in the slag gather, grow and settle, which is conducive to the floating of silicate. Among them, the copper-rich nickel phase includes copper, white matte, copper matte, and copper-rich nickel phase. Nickel-cobalt phase, multiple types of iron-containing components, or part of the copper-nickel-cobalt component enters the iron-rich phase, and the iron-rich phase includes multiple types of metallic iron, FeO phase, and fayalite phase;

In the above steps 1 and 2, the oxidizing gas is one of preheated air, oxygen or oxygen-enriched air, and the injection method is to use a refractory spray gun to insert the slag or place it on the top or side or bottom of the reaction slag to blow One or more of them, the preheating temperature is 0～1200℃;

In step 2, the direct reduction process uses a rotary hearth furnace, a tunnel kiln, a car bottom road, a shaft furnace, a rotary kiln or an induction furnace as the reduction equipment, and uses gas-based or coal-based reduction technology, and the gas-based reduction is natural gas and/or Or coal gas, the coal base is reduced to one or more of anthracite, bituminous coal, lignite, coking coal, coke powder or coke, the reduction temperature is 900-1400°C, and the alkalinity CaO/SiO ₂ ratio = 0.8-1.5;

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

In step 2, when cooling and sedimentation are required, the cooling method is natural cooling or rotary cooling or centrifugal cooling, and the sedimentation method is natural sedimentation or rotary sedimentation or centrifugal sedimentation;

Further, the specific operation of rotation and centrifugation is as follows: the device containing the slag after the reaction is placed on the rotating platform, and rotates at a certain speed. The rotation speed depends on the quality of the slag and the height or depth of the heat preservation device. The rotation time It depends on the quality of the slag and the solidification of the slag; the device containing the slag after the reaction is placed on a rotating platform to rotate, the purpose is to accelerate the aggregation, growth and settlement of the copper-rich nickel phase and iron-rich phase, which is beneficial to Silicate floats up, shortens the settling time, improves the settling effect, and increases production efficiency;

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

In step 2, the copper component, nickel component, cobalt component, and gold-silver component in the molten slag after the reaction continue to be enriched in the copper-nickel-rich phase to achieve growth and settlement, or partially enrich in the Iron-rich phase: The iron component in the mixed slag continues to enrich in the iron-rich phase, and realizes growth and settlement.

In the described step 2, during separation, the gravity separation method can be adopted to be shaker separation, chute separation or a combination of the two.

If the method of the present invention is adopted, the slag of the iron-rich phase and iron-containing silicate phase obtained at last contains copper≤0.1%, and the recovery rate of the final iron is ≥91%, the recovery rate of zinc is ≥92%, and the recovery rate of lead is ≥92%. The recovery rate is ≥92%, the enrichment rate of nickel is ≥91%, the enrichment rate of cobalt is ≥91%, the enrichment rate of gold is ≥90%, and the enrichment rate of silver is ≥90%.

In order to better explain the present invention and facilitate understanding, the present invention is described in detail through specific embodiments. Wherein, if the detection methods and raw materials used in the following examples are not clearly indicated, conventional techniques in the art can be used. Unless otherwise specified, the percentages used in the present invention are all percentages by weight.

When the step (1) slag in the following examples 1-10 is mixed, the two parameters (a) and (b) guaranteed by regulation and control are specifically:

(a) The temperature of the reaction slag containing copper and iron is 1100～1500°C;

(b) The basicity of the reaction slag containing copper and iron is CaO/SiO ₂ ratio=0.15～1.5.

Example 1

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing:

The molten nickel smelting slag obtained from the slag outlet of the smelting furnace in the "matte-making process" process is added to the DC electric arc furnace, and lime, SiO ₂ , MgO, and Al ₂ O ₃ are added at the same time to form a mixed slag; the mixed slag is heated to melt state, forming the reaction slag, and allowing the reaction slag to achieve natural mixing; real-time monitoring of the reaction slag, and ensuring the two parameters (a) and (b) at the same time through regulation, to obtain the slag after the reaction is completed; corresponding to (a): The temperature of the reaction slag is 1660°C, and a refractory spray gun is inserted into the reaction slag, and nitrogen is used as the loading gas to spray copper slag, copper-containing soot, miscellaneous copper, copper-containing waste and copper-containing waste with a particle size of ≤150 μm at room temperature. Circuit board, add blast furnace gas sludge, electric furnace dust sludge, converter dust sludge, ordinary iron concentrate direct reduced iron and blast furnace gas ash at the same time, so that the temperature drops to 1490 ° C; (b): the alkalinity of copper-containing reaction slag CaO/ SiO ₂ ratio=2.6, add silica, fly ash and coal gangue mixture to the reaction slag, make the copper-containing reaction slag alkalinity ratio drop to 0.28; Metal iron content in the slag is 1.1%;

Step 2, separation and recovery using method one:

Keep warm for 45 minutes. After the reaction is completed, the molten slag will settle by itself, and the slag-gold will be separated to obtain a molten copper-nickel-rich layer, an iron-rich layer, and an iron-containing silicate mineral phase. The steps are as follows: (1) The iron-containing silicate mineral phase in the molten state is treated with slag outside the furnace, and method F is adopted. After the silicate slag is air-cooled, it is used as a raw material for direct reduction of ironmaking. During the direct reduction process, rotary The kiln is used as reduction equipment, using gas-based reduction technology, the gas-based reducing agent is natural gas and coal gas, the reduction temperature is 950 ° C, the alkalinity CaO/SiO ₂ ratio is 0.8, and the electric furnace melting temperature is 1550 ° C after reduction, and the product is metal Molten iron and slag; (2) The molten copper-nickel-rich phase is sent to the converter; (3) The iron-rich phase layer is poured into the heat preservation device, and it is used as the raw material for blast furnace ironmaking after air cooling; (4) Zinc component, indium component, The lead component, bismuth component, potassium component, and sodium component volatilize and enter the dust recovery in the form of oxides; the slag contains less than 0.1% copper, the recovery rate of zinc is 92%, the recovery rate of lead is 93%, and the recovery rate of indium is 92%, bismuth recovery rate 94%, sodium recovery rate 95%, potassium recovery rate 96%, iron recovery rate 96%, nickel enrichment rate 93%, cobalt enrichment rate 95%, gold The enrichment rate of silver is 93%, and the enrichment rate of silver is 94%. Wherein, in all embodiments of the present invention, copper-containing slag refers to the slag phase after the copper-rich nickel phase is separated, specifically the copper content in the iron-rich phase and silicate mineral phase, the enrichment rate of nickel and cobalt It refers to the percentage of the content of nickel and cobalt in the copper-rich nickel phase to the total amount of nickel and cobalt in the raw material. percentage of the total.

Example 2

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing:

The molten nickel smelting slag obtained from the slag outlet of the blowing furnace in the "copper matte converting" process is added to a pourable smelting reaction slag tank, and limestone, dolomite, red mud, FeO and Fe ₂ O ₃ are added at the same time to form a mixed molten slag. slag; use oxygen-enriched air with a preheating temperature of 600°C to anthracite and coke particles with a particle size of 20 mm, and inject natural gas to heat the mixed slag to a molten state to form a copper-containing reaction slag; real-time monitoring of the reaction slag, through regulation At the same time, the two parameters (a) and (b) are guaranteed to obtain the slag after the reaction is completed;

Corresponding to (a) the temperature of copper-containing reaction slag is 1660°C, insert a refractory spray gun into the reaction slag, use argon as the carrier gas, and spray copper slag, nickel smelting slag, copper-containing soot, miscellaneous Copper and iron and steel sinter dust, sinter pellet dust, cast iron dust, ordinary iron concentrate direct reduction of iron, so that the temperature drops to 1480 ° C; (b) copper-containing reaction slag alkalinity CaO/SiO ₂ ratio is 2.4, A mixture of acidic iron concentrate, acidic pre-reduced pellets, lead-containing smelting slag, and lead-containing fuming slag is added to the reaction slag to reduce the alkalinity ratio of the copper-containing reaction slag to 1.2; the metallic iron content in the slag is 3%;

Step 2, separation and recovery adopts method two:

Keep warm for 50 minutes. After the reaction is completed, the molten slag will settle naturally, and the slag-gold will be separated to obtain a molten copper-nickel-rich phase layer, iron-rich phase layer and silicate mineral phase, and simultaneously generate zinc components, lead components and indium components. , into the soot and recovered in the form of oxides, the following steps are carried out:

(1) Melt iron-containing silicate mineral phase and iron-rich phase, adopt method G to carry out slag treatment outside the furnace, and slag melting reduction ironmaking, the specific steps are as follows:

(1-1) Pour the molten slag into a pourable converter, add anthracite and bituminous coal with a particle size of 20 mm to the molten slag, carry out smelting reduction, monitor the reaction slag in real time, and ensure the temperature of the following (a) reaction slag at the same time through regulation It is 1350～1670 ℃, and (b) the alkalinity CaO/ _SiO2 ratio=0.6～2.4 two parameters of reaction slag, obtain the slag after reaction;

Corresponding to (a): the temperature of the reaction slag is 1460°C, within the temperature range;

Corresponding to (b): when the ratio of alkalinity CaO/ _SiO2 in the reaction slag is 0.8, it is within the range of alkalinity;

(1-2) Inject preheated 200°C oxidizing gas (oxygen-enriched air) into the slag for smelting reduction to form reduced mixed slag, and during the injection process, ensure (a) at the same time through regulation The temperature of reaction slag is 1350～1670 ℃, and the alkalinity CaO/SiO of (b) reaction slag Ratio=0.6～2.4 _two parameters,

(1-3) Separation and recovery:

(a) The reduced mixed slag is naturally settled to obtain molten iron and reduced slag;

(b) The slag after reduction is processed by method A in method one of step 2 to make high value-added cement raw material;

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

(d) Zinc-containing components, lead-containing components, bismuth components and indium components volatilize and enter the dust recovery in the form of oxides;

(e) Natrium-containing components and potassium-containing components volatilize and enter the dust recovery;

(2) The copper-nickel-rich phase in the molten state is sent to the converter.

(3) The zinc and lead components volatilize and enter the dust recovery in the form of oxides.

The recovery rate of zinc is 95%, the recovery rate of lead is 93%, the recovery rate of indium is 96%, the recovery rate of bismuth is 96%, the recovery rate of sodium is 97%, the recovery rate of potassium is 98%, and the slag contains copper <0.1%, iron The recovery rate is 97%; the enrichment rate of nickel is 92%, the enrichment rate of cobalt is 96%, the enrichment rate of gold is 90%, and the enrichment rate of silver is 90%.

Example 3

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing: the molten nickel smelting slag obtained from the blowing slag of the "copper matte nickel blowing" process through the slag outlet of the depletion furnace is added to the reverberatory furnace, and limestone and high-calcium red mud after desodiumization are added at the same time to form a mixture Slag: use oxygen with a preheating temperature of 900°C, inject anthracite, coke particles and coal powder with a particle size of 20mm, heat the mixed slag to a molten state, form a copper-containing reaction slag, and mix it mechanically; monitor the reaction melting in real time Slag, through the regulation and control to ensure the two parameters (a) and (b) at the same time, to obtain the slag after the reaction is completed;

Corresponding to (a): the temperature of copper-containing reaction slag is 1685°C, acid metallized pellets and copper slag are added to the reaction slag, and copper-containing soot, lead-containing slag, ordinary iron concentrate pellets, rolled steel are added at the same time Iron oxide scale and ordinary iron concentrate carbon-containing pre-reduction pellets, so that the temperature is reduced to 1420 ° C; (b): the basicity CaO/SiO ₂ ratio of copper-containing reaction slag = 2.3, adding quartz sand to the reaction slag , red mud, zinc smelting slag mixture, so that the basicity ratio of the copper-containing reaction slag is reduced to 1.2; the metallic iron content in the slag is 1.8%;

Step 2, separation and recovery adopts method two:

Keep warm for 35 minutes. After the reaction is completed, the molten slag will settle naturally, and the slag-gold will be separated to obtain molten copper-nickel-rich phase, iron-rich phase layer and silicate mineral phase. , recovered in the form of oxides, the following steps are carried out:

(1) The molten copper-nickel phase is sent to the converter;

(2) The molten iron-rich phase layer and the silicate mineral phase are used as raw materials for direct reduction of ferronickel; during the reduction process, the zinc component, lead component, bismuth component and indium component volatilize and enter the smoke; the direct reduction process In the process, a rotary hearth furnace is used, the reduction temperature is 1200°C, the alkalinity CaO/SiO ₂ ratio = 1.0, and anthracite and coal powder with a particle size of ≤150 μm;

(3) Zinc-containing components, indium components, bismuth components and lead-containing components volatilize and enter the dust recovery, the slag contains copper <0.1%, the recovery rate of iron is 96%, the recovery rate of zinc is 93%, and the recovery rate of lead is 96%. The recovery rate of indium is 92%, the recovery rate of indium is 93%, the recovery rate of bismuth is 94%; the enrichment rate of nickel is 93%, that of cobalt is 97%, that of gold is 91%, and that of silver The enrichment rate was 92%.

Example 4

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing: the molten nickel smelting slag obtained from the slag outlet of the top-blown molten pool smelting furnace is added to the plasma furnace, and dolomite, MgO, Al ₂ O ₃ , and Fe are added at the same time to form a mixed slag; the mixed slag Heating to a molten state to form a copper-containing reaction slag, and electromagnetically stirring the reaction slag to achieve mixing; real-time monitoring of the reaction slag, and ensuring the two parameters (a) and (b) through regulation at the same time to obtain the slag after the reaction is completed. slag;

Corresponding to (a) the temperature of copper-containing reaction slag is 1670°C, add red mud, sulfuric acid slag, fluorite, lead matte, lead-containing soot, zinc-containing soot, arsenic matte and wet smelting to the reaction slag Zinc slag, to reduce the temperature to 1440°C; (b) the basicity CaO/ _SiO2 ratio of copper-containing reaction slag is 2.0, add copper slag to the reaction slag, and reduce the basicity ratio of copper-containing reaction slag to 0.7 ; Use air to blow natural gas, coke particles with a particle size of 20mm, and the content of metallic iron in the slag is 0.9%;

Step 2, separation and recovery adopts method two:

Keep warm for 14 minutes. After the reaction is completed, the molten slag will settle naturally, and the slag-gold will be separated to obtain molten copper-rich nickel phase, iron-rich phase layer and iron-containing silicate mineral phase, and simultaneously generate zinc-containing components and lead-containing components. Into the soot, recovered in the form of oxides, the following steps:

(1) The molten copper-nickel phase is sent to the converter;

(2) The molten iron-rich phase layer and the iron-containing silicate mineral phase Step 2 Separation and recovery method 1 Method F, oxidation modification magnetic separation: ① Pour the molten slag into the insulation slag tank, spray into the molten slag Preheat the oxygen-enriched air with a temperature of 900°C to realize the transformation of magnetite; ② slow cooling to room temperature, magnetic separation and separation, to obtain iron concentrate and tailings;

(3) Part of the zinc-containing components, bismuth components, indium components and lead-containing components volatilizes and enters the dust in the form of oxides for recovery. The slag contains copper <0.1%, the recovery rate of iron is 95%, and the recovery of zinc The recovery rate is 92%, the recovery rate of lead is 92%, the recovery rate of indium is 93%, the recovery rate of bismuth is 94%; the enrichment rate of nickel is 93%, the enrichment rate of cobalt is 94%, and the enrichment rate of gold is 92%, and the enrichment rate of silver is 94%.

Example 5

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing: put the molten nickel smelting slag obtained from the top-blowing molten pool smelting through the slag outlet of the sinking electric furnace into the heat preservation slag tank, and add limestone and Fe at the same time to form a mixed slag; use a preheating temperature of 600 °C Oxygen-enriched air, injecting 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; real-time monitoring of the reaction slag, and simultaneously ensuring (a) and (b) two parameters, obtain the slag after the completion of the reaction;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1430°C; (b): the basicity CaO/SiO ₂ ratio of the copper-containing reaction slag is 1.5, both within the required range; the metallic iron content in the slag is 2.2 %;

Step 2, separation and recovery using method five:

Pour the slag after the reaction into the thermal insulation slag tank, keep it warm for 25 minutes, and carry out the slag treatment outside the furnace, and perform the following steps:

(1) Settling cooling: After the reaction is completed, the molten slag is cooled to room temperature by rotation to obtain slow cooling slag; the copper-rich nickel phase settles to the bottom of the reaction device to form a copper-rich nickel lump; the iron-containing silicate mineral phase floats; copper-rich The slow cooling slag between the nickel phase metal lump and the silicate mineral is an iron-rich phase, and simultaneously generates zinc-containing components and lead-containing components;

(2) Separation: Manually remove the copper-nickel lump that settled at the bottom, and the product is sent to the converter; the iron-rich phase layer in the middle is directly sent to the converter for ironmaking;

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

(4) Some zinc-containing components and lead-containing components volatilize and enter the dust recovery in the form of oxides. The slag contains less than 0.1% copper, the recovery rate of iron is 92%, the recovery rate of zinc is 94%, and the recovery rate of lead is 95%. %; the enrichment rate of nickel is 95%, the enrichment rate of cobalt is 93%, the enrichment rate of gold is 91%, and the enrichment rate of silver is 92%.

Example 6

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing: Add the molten nickel smelting slag obtained from the slag outlet of the smelting furnace in the "matte-making process" process, and the molten nickel smelting slag obtained from the slag outlet of the blowing furnace in the "copper matte blowing" process to the AC electric arc furnace , and add lime, MgO, Al ₂ O ₃ , Fe ₂ O ₃ at the same time to form mixed slag; heat the mixed slag to a molten state to form copper-containing reaction slag, spray into argon with a preheating temperature of 800°C, And the reaction slag is mixed; the reaction slag is monitored in real time, and the two parameters (a) and (b) are guaranteed at the same time through regulation to obtain the slag after the reaction is completed;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1080°C, and the electric arc furnace is heated to raise the temperature to 1330°C; (b): the basicity CaO/SiO ₂ ratio of the copper-containing reaction slag is 0.1, and the reaction slag is heated to 1330°C; Add alkaline iron concentrate, converter sludge, alkaline pre-reduced pellets, and high-calcium red mud after desodination to the slag to increase the alkalinity ratio of the copper-containing reaction slag to 0.3; inject natural gas, and the metal in the slag Iron content is 1.6%;

Step 2, separation and recovery using method one:

Keep warm for 38 minutes, the slag after the reaction is naturally settled, and the slag-gold is separated to obtain molten copper-nickel-rich phase, iron-rich phase and iron-containing silicate mineral phase, and simultaneously generate zinc-containing components and lead-containing components. Into the soot, recovered in the form of oxides, the following steps:

(1) The iron-containing silicate mineral phase adopts method A in step 2 separation and recovery method one, and water quenching is directly used as cement raw material;

(2) The copper-nickel-rich phase in the molten state is sent to the converter;

(3) The iron-rich phase layer is poured into the insulation device and cooled as the raw material for direct reduction of ferronickel;

(4) Zinc-containing components, lead-containing components, indium-containing components and bismuth-containing components volatilize and enter the smoke for recycling. The slag contains copper<0.1%, the recovery rate of iron is 91%, and the recovery rate of zinc is 92%. %, lead recovery rate is 92%, sodium recovery rate is 95%, potassium recovery rate is 96%, nickel enrichment rate is 94%, cobalt enrichment rate is 92%, gold enrichment rate is 91% , the enrichment rate of silver is 92%.

Example 7

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing: add the cold nickel smelting slag obtained from the "matte-making process" process and the cold nickel smelting slag obtained from the "copper matte blowing" process through the depletion furnace into the submerged arc furnace, and at the same time Add limestone, SiO ₂ , FeO and MgO to form a mixed slag; heat the mixed slag to a molten state to form a copper-containing reaction slag, spray argon-nitrogen mixed gas with a preheating temperature of 900°C, and make the reaction The slag is mixed; the reaction slag is monitored in real time, and the two parameters (a) and (b) are guaranteed at the same time through regulation to obtain the slag after the reaction is completed;

Corresponding to (a): the temperature of copper-containing reaction slag is 1320°C; (b): the basicity CaO/SiO ₂ ratio of copper-containing reaction slag is 0.8, all within the required range; air is used, and the injection particle size is ≤150μm Coal powder and natural gas, the content of metallic iron in the slag is 2.7%;

Step 2, separation and recovery using method four:

Keep warm for 36 minutes, the slag after the reaction is naturally settled, slag-gold is separated, and the molten copper-nickel-rich phase, iron-rich phase and iron-containing silicate mineral phase are obtained, and zinc components and lead components are formed at the same time, and enter the smoke dust , to be recovered in the form of Z oxide, the following steps are carried out:

(1) The molten copper-nickel phase is sent to the converter;

(2) The molten iron-rich phase layer and iron-containing silicate minerals specifically adopt the method F in the separation and recovery method one of step 2, after water quenching, as the raw material for direct reduction of ferronickel;

(3) Part of the zinc-containing components and lead-containing components volatilize and enter the dust recovery in the form of oxides, the slag contains less than 0.1% copper, the recovery rate of iron is 91%, the recovery rate of zinc is 93%, and the recovery rate of lead The enrichment rate of nickel is 93%, the enrichment rate of cobalt is 95%, the enrichment rate of gold is 91%, and the enrichment rate of silver is 92%.

Example 8

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing: the molten nickel smelting slag obtained from the slag outlet of the smelting furnace of the "matte-making process" process, and the molten nickel smelting slag obtained from the blowing slag of the "copper matte nickel conversion" process through the slag outlet of the depletion furnace Add the blast furnace, add dolomite, red mud, MgO at the same time, use coke powder with oxygen particle size ≤ 150μm at a preheating temperature of 800°C, and inject gas to heat the mixed slag to a molten state to form a copper-containing reaction slag. And the reaction slag is mixed; the reaction slag is monitored in real time, and the two parameters (a) and (b) are guaranteed at the same time through regulation to obtain the slag after the reaction is completed;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1330°C; (b): the basicity CaO/SiO ₂ ratio of the copper-containing reaction slag is 1.0, all within the required range; the metallic iron content in the slag is 1.9 %;

Step 2, separation and recovery using method three:

Keep warm for 19 minutes, the slag after the reaction is naturally settled, and the slag-gold is separated to obtain the copper-rich nickel phase, the iron-containing silicate mineral phase and the iron-rich phase in the upper middle part, and simultaneously generate zinc-containing components and lead-containing components , into the soot, recovered in the form of oxides, the following steps are carried out:

(1) The molten iron-containing silicate mineral phase is poured into the smelting device, and the slag is processed outside the furnace. Specifically, the method B in the separation and recovery method 1 of step 2 is used to return all the slag in the middle and upper parts to the copper-containing Reaction slag, as a hot metallurgical flux, adjusts the composition of copper-containing reaction slag and controls the temperature of copper-containing reaction slag;

(2) The molten copper-nickel phase is sent to the converter or converting furnace;

(3) Part of the zinc-containing components and lead-containing components volatilize and enter the dust recovery in the form of oxides, the slag contains less than 0.1% copper, the recovery rate of iron is 93%, the recovery rate of zinc is 92%, and the recovery rate of lead 94%, sodium recovery rate 95%, potassium recovery rate 96%, nickel enrichment rate 91%, cobalt enrichment rate 97%, gold enrichment rate 92%, silver enrichment rate 93%.

Example 9

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing: molten nickel smelting slag obtained from top-blown molten pool smelting through the slag outlet of the sinking electric furnace and molten nickel obtained from the blowing slag of the "copper matte nickel blowing" process through the slag outlet of the depletion furnace The smelting slag is added to the side-blowing furnace, and limestone is added at the same time to form a mixed slag; air with a preheating temperature of 900°C is used to spray ≤150 μm coke powder, and the mixed slag is heated to a molten state to form a copper-containing reaction slag, and make The reaction slag is mixed; the reaction slag is monitored in real time, and the two parameters (a) and (b) are guaranteed at the same time through regulation to obtain the slag after the reaction is completed;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1340°C; (b): the basicity CaO/SiO ₂ ratio of the copper-containing reaction slag is 1.2, both within the required range; the metallic iron content in the slag is 2.1 %;

Step 2, separation and recovery adopts method two:

Keep warm for 31 minutes, the slag after the reaction is naturally settled, and the slag-gold is separated to obtain a copper-rich nickel phase, an iron-rich phase and an iron-containing silicate mineral phase in the middle and upper parts, and simultaneously generate zinc-containing components and lead-containing components. , into the soot, recovered in the form of oxides, the following steps are carried out: (1) the iron-rich phase and iron-containing silicate mineral phase are poured into the smelting device, and the method C in the separation and recovery method one of step 2 is adopted to melt the upper and middle parts Slag poured glass-ceramics;

(2) The copper-nickel-rich phase in the molten state is slowly cooled and processed with the method four in the step two; (3) part of the zinc-containing component and the lead-containing component enters the soot in the form of oxides;

The finally obtained slag contains less than 0.1% copper, the recovery rate of iron is 94%, the recovery rate of zinc is 92%, the recovery rate of lead is 92%; the enrichment rate of nickel is 97%, and the enrichment rate of cobalt is 93%. %, the enrichment rate of gold is 92%, and the enrichment rate of silver is 92%.

Example 10

A method for recovering valuable components from nickel-containing smelting slag, comprising the following steps:

Step 1, slag mixing: the molten nickel smelting slag obtained from the smelting of the top-blown molten pool through the slag outlet of the sinking electric furnace, and the molten nickel obtained from the slag outlet of the "copper matte nickel blowing" process through the slag outlet of the depletion furnace The smelting slag and the molten nickel smelting slag obtained from the smelting of the top blowing molten pool are added to the heat preservation pit, and limestone and Fe are added at the same time to form a mixed slag; the oxygen-enriched air is used to blow the particle size ≤ 150μm Bituminous coal, the mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is mixed; the reaction slag is monitored in real time, and the two parameters (a) and (b) are simultaneously controlled to obtain the completion of the reaction after the slag;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1430°C; (b): the basicity CaO/SiO ₂ ratio of the copper-containing reaction slag is 0.5, all within the required range; the metallic iron content in the slag is 0.8 %;

Step 2, separation and recovery using method five:

The molten slag after the reaction is completed carries out the following steps:

(1) Settling cooling: heat preservation for 48 minutes, and the slag after the reaction is cooled to room temperature to obtain slow cooling slag; the copper-rich nickel phase settles to the bottom of the reaction device to form a copper-rich lump; the iron-containing silicate mineral phase floats; The slowly cooled slag between the copper-nickel phase and the silicate mineral is an iron-rich phase, and simultaneously generates zinc-containing components and lead-containing components;

(2) Separation: Manually remove the copper-rich nickel lump that settled at the bottom; after the iron-rich phase layer in the middle is directly reduced, the metal nickel-iron is separated by magnetic separation;

(3) Manually take out the upper silicate mineral phase and use it as cement raw material;

(4) Part of the zinc and lead components volatilize and enter the dust recovery in the form of oxides. The slag contains less than 0.1% copper, the recovery rate of iron is 91%, the recovery rate of zinc is 93%, and the recovery rate of lead is 92%. %; the enrichment rate of nickel is 96%, the enrichment rate of cobalt is 97%, the enrichment rate of gold is 91%, and the enrichment rate of silver is 92%.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms. Any skilled person who is familiar with this profession may use the technical content disclosed above to change or remodel it into an equivalent change. Example. However, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (10)

1. a method for reclaiming valuable components by nickel-containing smelting slag, is characterized in that, it comprises the steps: S1. Slag mixing: Add nickel smelting slag into the reaction device, add calcium minerals and additives to form mixed slag, heat the mixed slag to a molten state as reaction slag, mix evenly, and monitor the reaction slag in real time, The mixed reaction slag satisfies condition a and condition b at the same time by adjusting and controlling to obtain the reacted slag; Wherein, the condition a is that the controlled slag temperature is between 1100 and 1500°C; The condition b is to control the basicity of the slag CaO/SiO ₂ ratio=0.15～1.5; S2. Separation and recovery: the molten slag after the reaction in step S1 is kept warm for 5-50 minutes, settled and separated to obtain the copper-nickel-rich phase at the bottom, the iron-rich phase at the middle and lower part, and the iron-containing silicate mineral phase at the middle and upper part. Generate fumes of zinc-containing components and lead-containing components, gold components and silver components migrate and enrich into copper-nickel-rich phases, nickel-containing components and cobalt-containing components migrate into copper-nickel-rich phases and iron-rich phases; The phases are recycled. 2. The method according to claim 1, characterized in that, in the step S1, the method for regulating the condition a is: When the temperature of the reaction slag is less than 1100°C, use the heating of the reaction device itself, or add fuel and preheated oxidizing air to the slag to make the temperature of the reaction slag reach the set temperature range, so that the reaction slag The temperature of slag reaches 1100～1500℃; When the temperature of the reaction slag is greater than 1500°C, one or more of nickel smelting slag, copper-containing material, blast furnace slag, steel slag, ferroalloy slag, metallurgical flux, iron-containing material or fluorine-containing material is added to the reaction slag. species, mixed evenly, so that the temperature of the mixed reaction slag reaches 1100-1500°C; The method of described condition b regulation is: When the basicity CaO/ _SiO2 ratio in the reaction slag is less than 0.15, adding alkaline materials and/or basic iron-containing materials to the reaction slag; When the basicity CaO/SiO ₂ ratio in the reaction slag is greater than 1.5, acidic materials and/or acidic iron-containing materials are added to the reaction slag. 3. The method according to claim 1, characterized in that, the reaction device is a heat preservation device or a rotatable smelting reaction device or a smelting reaction device with a slag hole or a slag hole that can flow out; wherein, the The heat preservation device is pourable smelting reaction slag tank or heat preservation pit; The rotatable smelting reaction device is a converter and a smelting reaction slag tank; The smelting reaction device with a slag port or an iron port where the slag can flow out is a plasma furnace, a DC electric arc furnace, an AC electric arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola, a side-blown molten pool melting furnace, Bottom-blown molten pool melting furnace, top-blown molten pool melting furnace, reverberatory furnace, Osmet furnace, Isa furnace, Vanukov molten pool melting furnace, side-blown rotary furnace, bottom-blown rotary furnace, top-blown rotary furnace . 4. The method according to claim 1, characterized in that, in the step S1, while satisfying the conditions a and b, they should be satisfied simultaneously, controlling the copper oxide and nickel oxide in the reaction slag , cobalt oxide and iron oxide are respectively reduced to metal copper, metal nickel, metal cobalt and FeO, and the content of metal iron in the slag is <3%. 5. The method according to claim 1, characterized in that, the nickel smelting slag is the nickel smelting slag produced by the "matte-making smelting" process, the blowing slag after the blowing of the "copper matte blowing" process, " It is one of the depleted slag produced by blowing slag after blowing in copper matte blowing process, the nickel smelting slag produced by top blowing smelting, and the sedimentation slag produced by the nickel smelting slag produced by top blowing smelting through electric furnace settlement or more; the nickel smelting slag is molten or cold, wherein: the molten nickel smelting slag is obtained from the slag outlet of the nickel smelting furnace, or the nickel smelting slag is heated to a molten state; The calcium-based minerals are one or more of lime, limestone, dolomite, carbide slag, red mud or high-calcium red mud after desodiumization; The additive is one or more of SiO ₂ , MgO, FeO, Fe ₂ O ₃ , MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O. 6. The method according to claim 2, wherein the copper-containing material is crude copper pyro-refining slag, copper beneficiation tailings, copper slag, zinc smelting slag, zinc smelting soot and dust sludge, lead-zinc tailings Mine, lead smelting slag, lead matte, arsenic matte, crude lead pyro-refining slag, lead smelting soot and dust, lead-acid batteries, copper smelting soot and dust, miscellaneous copper, copper-containing waste, copper-containing circuit boards , tin smelting slag, and tin tailings; wherein, the zinc smelting slag is the zinc smelting slag produced by hydrometallurgy and pyrometallurgy, including leaching slag, alum slag, copper cadmium slag , goethite slag, hematite slag, volatile kiln slag, blast furnace slag, fuming slag, vortex slag, vertical tank zinc smelting slag, electric furnace zinc smelting slag; lead-containing smelting slag is fuming 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 produces lead-containing smelting slag, which is produced by fuming furnace smelting Lead-containing fuming furnace slag; the copper slag is one or more of copper-containing smelting slag, copper-containing blowing slag, depleted waste slag, flotation tailings, and wet-process copper smelting slag, and the copper-containing smelting slag is produced The copper-containing smelting slag is produced in the "matte blowing" process of the copper pyro-smelting process; the depleted waste slag is copper-containing smelting slag and Copper blowing slag depleted waste slag, flotation tailings are copper-containing smelting slag and copper-containing blowing slag beneficiation tailings; 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 concentrate carbon preformed Reduction pellets, steel slag, zinc smelting slag, coke smelting dust and sludge, steel soot and dust sludge, nickel-containing smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high One or more of calcium red mud, coal powder ash, sulfuric acid slag; the iron and steel fumes and sludge include blast furnace gas sludge, converter dust sludge, electric furnace sludge, hot or cold rolling sludge, sintering dust, ball Agglomerate dust, cast iron plant dust collection, blast furnace gas ash, electric furnace dust removal ash, rolling steel oxide scale; The copper-containing material and the iron-containing material are hot or cold, wherein the hot material is directly obtained from the metallurgical furnace outlet or slag outlet; the metallurgical flux is CaO or _SiO2 -containing minerals and slag; the The fluorine-containing material is one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag; Zinc smelting slag, copper smelting slag and dust must be dehydrated and dried; The fuel is one or more of solid, liquid or gaseous fuels, and the fuel is added in the form of injection or feeding. When the injection is performed, the loading gas is preheated oxidizing gas, and the The preheating temperature is 0～1200℃; The alkaline material is one or more of lime powder, red mud, high-calcium red mud after desodiumization, calcium carbide slag, dolomite powder or quicklime powder; the alkaline iron-containing material is alkaline sintered ore, alkali One or more of alkaline iron concentrates, alkaline pre-reduced pellets, alkaline metallized pellets, steel slag or blast furnace slag; the acidic materials are silica, gold and silver-containing silica, fly ash, and coal gangue One or more of: the acidic iron-containing material is iron-containing material with CaO/SiO ₂ ≤ 1, acidic sintered ore, acidic iron concentrate, acidic pre-reduced pellets, acidic metallized pellets, copper slag, lead One or more of smelting slag, zinc smelting slag, nickel smelting slag, tin smelting slag, ferroalloy slag, blast furnace slag. 7. The method according to claim 2, wherein the copper-containing material, iron-containing material and fluorine-containing material are pellets or powdery materials or granulated; wherein the particle size of the powdery material is ≤150 μm, The particle size of the granular material is 5-25mm. The powdery material is sprayed in by blowing, and the granular material is added by blowing or feeding. The loading gas used for the blowing is preheated argon, nitrogen, reducing One or more of gas and oxidizing gas, the temperature of the preheating is 0-1200°C. 8. The method according to any one of claims 1-7, characterized in that, in the separation and recovery of the step S2, the following processes are carried out: Contains the copper-nickel-rich phase in hot or cold state, sent to converter or converting furnace or used as raw material for separation of copper, cobalt and nickel; The zinc-containing component and the lead-containing component volatilize and enter the soot recovery in the form of oxide; Nickel-containing components and cobalt-containing components migrate into copper-rich nickel phase and iron-rich phase; Containing the iron-containing silicate mineral phase and/or the iron-rich phase, performing any one of the following methods A-G; Method A: After water quenching or air cooling, directly use it as cement raw material; Method B: Part or all of the molten state is returned to the reaction slag as a hot metallurgical flux; Method C: for pouring glass-ceramics or as slag wool; Method D: The iron-containing silicate mineral phase and/or the iron-rich phase are retained in the smelting reaction device or poured into the heat preservation device, and blown into the molten slag with a preheating temperature of 0-1200°C Oxidizing gas, and ensure the slag temperature > 1450 °C; when the weight percentage of ferrous oxide in the slag is <1%, the oxidized slag is obtained; the oxidized slag is directly air-cooled or water-quenched and used as Slag cement, cement modifiers, additives in cement production or cement clinker; Method E: For the production of high value-added cement clinker: E-1. Keep the iron-containing silicate mineral phase and/or the iron-rich phase in the smelting reaction device or pour the slag into the heat preservation device, and add molten steel slag, lime, limestone, One or more of ferroalloy slag, fly ash, alkaline lean iron ore, bauxite, molten blast furnace slag, red mud, red mud after desodination or carbide slag are fully mixed to obtain a slag mixture material; E-2. Blow into the upward slag mixture material an oxidizing gas with a preheating temperature of 0-1190°C, and ensure that the temperature of the slag mixture material is >1450°C; when the weight percentage of ferrous oxide is less than 1%, after oxidation is obtained of slag; E-3. Perform air cooling or water quenching on the oxidized slag to obtain high value-added cement clinker; Method F: The iron-containing silicate mineral phase and/or the iron-rich phase slag are used as blast furnace ironmaking raw materials or direct reduction ironmaking raw materials: the iron-containing silicate mineral phase and/or the iron-rich phase After air cooling, water quenching or slow cooling, the slag is used as raw material for blast furnace ironmaking or direct reduction ironmaking. After direct reduction, it is separated by magnetic separation or electric furnace melting. The magnetic separation product is metallic iron and tailings, and electric furnace melting , the products are molten iron and slag; Or after pouring the slag of the iron-containing silicate mineral phase and/or the iron-rich phase into the heat preservation device, the following method is used for separation: the slag is modified and separated by magnetic separation: the slag in the heat preservation device , blowing preheated oxidizing gas at 0-1200°C, and ensuring that the slag temperature is >1250°C to complete the transformation of magnetite in the slag; slowly cool the above-mentioned oxidized slag to room temperature, crush and magnetically The products are magnetite concentrate and tailings, and the tailings are used as building materials; Method G: performing reduction ironmaking on the iron-containing slag, comprising the following steps: G-1. Keep the slag of the iron-containing silicate mineral phase and/or the iron-rich phase in the smelting reaction device or pour the slag into the heat preservation device, and add iron-containing materials into the molten slag , Reductant, smelting reduction, real-time monitoring of the reaction slag, through regulation and control to meet the conditions at the same time: the temperature of the reaction slag is 1350 ~ 1670 ° C and the basicity of the reaction slag CaO/SiO ₂ ratio = 0.6 ~ 2.4, the reaction is completed after the slag; Wherein, the method for controlling the temperature of reaction slag is: When the temperature of the reaction slag is less than 1350°C, the temperature of the reaction slag reaches 1350-1670°C by heating the reaction device itself, or adding fuel and preheated oxidizing gas to the slag; When the temperature of the reaction slag is higher than 1670°C, one or more of metallurgical flux, iron-containing material or fluorine-containing material is added to the reaction slag, so that the temperature of the reaction slag reaches 1350-1670°C; wherein, the Metallurgical fluxes are minerals containing CaO or _SiO2 ; The method of controlling the basicity of reaction slag is: When the basicity CaO/ _SiO2 ratio in the reaction slag is <0.6, add alkaline materials and/or basic iron-containing materials to the slag; When the basicity CaO/ _SiO2 ratio in the reaction slag is >2.4, add acidic materials and/or acidic iron-containing materials to the slag; G-2. During the smelting reduction in G-1, it is necessary to spray oxidizing gas preheated at 0-1200°C into the slag for smelting reduction to form reduced slag; G-3. Separation and recovery: adopt one of the following methods: Method Ⅰ: Pour the reduced mixed slag into the thermal insulation slag tank, cool to room temperature, and obtain slow cooling slag; among them, metallic iron settles to the bottom of the reaction device to form iron lumps, and the metal iron layer in the remaining slow cooling slag is , broken to a particle size of 20-400 μm, ore grinding, and magnetic separation to separate the remaining metal iron and tailings; Method II: The reduced mixed slag is cooled and settled, and the slag-gold is separated to obtain molten iron and reduced slag; the reduced slag is smelted according to one or more methods in methods A to E Slag treatment; the molten iron is sent to converter or electric furnace for steelmaking; Or contain the iron-rich phase and carry out water quenching or air cooling, or pour it into a heat preservation device for slow cooling, or combine it with manual sorting and gravity selection to obtain it as a raw material for blast furnace ferronickel smelting or direct reduction ferronickel smelting raw material or smelting reduction ferronickel smelting raw material or flotation to extract copper and nickel raw materials; flotation products are copper-containing concentrates, nickel concentrates, nickel-iron alloys and iron concentrates, and iron concentrates are used as blast furnace ironmaking raw materials or direct reduction ironmaking raw materials or smelting reduction ironmaking raw materials; The direct reduction process uses rotary hearth furnace, tunnel kiln, car bottom road, shaft furnace, rotary kiln or induction furnace as reduction equipment, and uses gas-based or coal-based reduction. Gas-based reduction uses natural gas and/or coal gas, and coal-based reduction uses One or more of anthracite, bituminous coal, lignite, coking coal, coke powder or coke, the reduction temperature is controlled to be 900-1400°C, and the alkalinity CaO/ _SiO2 ratio is controlled to be 0.8-1.5. 9. The method according to claim 8, wherein the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, nitrogen-air, argon-air, oxygen-nitrogen, and oxygen-argon The preheating temperature is 0-1200°C; the fuel and reducing agent are one or more of solid, liquid or gaseous fuels, which are injected in the form of blowing or feeding, and the blowing load The incoming gas is preheated oxidizing gas, and the preheating temperature is 0-1200°C; the solid fuel and reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite Various shapes are granular or powdery, granular materials have a particle size of 5-25 mm, and powdered materials have a particle size of ≤150 μm. The liquid fuel and reducing agent are heavy oil, and the gas fuel and reducing agent are coal gas and/or natural gas. 10. The method according to claim 1, characterized in that, in the step S1, the uniform mixing is natural mixing or stirring mixing, and the stirring method is argon stirring, nitrogen stirring, nitrogen-argon mixed gas stirring , one or more of reducing gas stirring, oxidizing gas stirring, electromagnetic stirring or mechanical stirring; In the step S2, the settling is natural settling or rotary settling or centrifugal settling; the cooling mode when carrying out cooling settling is natural cooling or rotary cooling or centrifugal cooling, and during the separation, gravity separation is shaker sorting, chute sorting or a combination of both.