CN107699699A - The method of zinc abstraction clinker melting and reducing production - Google Patents

Abstract

The invention discloses a production method of zinc smelting slag fusion reduction. It includes the following steps: S1, adding zinc smelting slag into a heat preservation device or a smelting reaction device where slag can flow out, adding calcium-based minerals and additives, heating to a molten state, and simultaneously adding copper oxide minerals and copper sulfide minerals , one or more of the copper-containing materials, real-time monitoring of the reaction slag, by adjusting the temperature of the reaction slag and the ratio of basicity CaO/SiO ₂ to obtain the slag; S2, the obtained slag, sedimentation and separation to obtain iron-containing Silicate mineral phase, copper-rich phase and iron-rich phase, zinc, lead, bismuth and indium-containing soot, gold and silver components migrate and enrich into the copper-rich phase, and separate the phases. The invention can not only reduce the copper content in slag (copper content in slag<0.1wt%), but also realize efficient recovery of components such as copper, iron, gold, silver, lead, zinc, indium, bismuth, sodium, potassium, etc., and obtain low-copper Iron-containing materials, high metal recovery rate, low production cost, environmental friendliness and high economic returns.

Description

Zinc smelting slag smelting reduction production method

technical field

The invention belongs to the technical field of resource comprehensive utilization and slag metallurgy, and in particular relates to a production method of zinc smelting slag fusion reduction.

Background technique

The zinc smelting process includes two processes of hydrometallurgy and vertical tank zinc smelting. The two processes produce a large amount of zinc smelting slag, among which zinc leaching slag, jarosite slag, pickling jarosite slag, goethite Slag, hematite slag, etc., vertical tank zinc smelting produces vertical tank zinc smelting furnace slag. Zinc smelting slag contains secondary resources such as copper, iron, zinc, lead, indium, gold, and silver, among which the iron content is as high as 50%, far exceeding the mineable grade of iron ore (minable grade, iron content>26wt%), The copper content is as high as 2%, far exceeding the mineable grade of copper ore (minable grade, copper content>0.2wt%), and the zinc content is as high as 25%. At present, zinc smelting slag is processed and recovered by volatilization kiln, fuming furnace, blast furnace, vortex smelting and other processes. Only part of the lead, zinc, silver and other components are recovered, and the recovery of valuable components such as copper, iron and gold is not considered. Moreover, the energy consumption is high and the pollution is large.

At present, a large amount of zinc smelting slag is accumulated, and the zinc smelting slag contains a large amount of heavy metal ions, which not only brings serious environmental pollution, but also causes waste of resources. Therefore, how to cleanly and efficiently utilize zinc smelting slag to recover valuable components is an urgent problem to be solved.

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 smelting and reducing production of zinc smelting slag, which can make full use of the physical heat resources of molten slag and thermal metallurgical flux, by processing zinc smelting slag and copper oxide minerals, Realize slag metallurgy, pyromethod copper smelting and iron smelting, can reduce slag copper content (slag copper content <0.1wt%), and simultaneously realize copper, iron, lead, zinc, gold, silver, indium, bismuth, sodium, potassium, etc. Efficient recovery of components, high metal recovery rate, low production cost, environmental friendliness and high economic returns.

(2) Technical solution

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

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

S1. Slag mixing: add zinc smelting slag to the thermal insulation device or smelting reaction device where the slag can flow out, and add calcium-based minerals and additives to heat the slag to a molten state to form a reaction slag containing copper and iron. At the same time, one or more of copper oxide minerals, copper sulfide minerals, and copper-containing materials are added, mixed evenly, and the reaction slag is monitored in real time, and the reaction slag meets the two conditions of a and b at the same time through adjustment and control to obtain the reaction finished slag;

Among them, a: adjust the temperature of the reaction slag to be 1100-1450°C;

b: control the basicity of reaction slag CaO/SiO ₂ ratio=0.2～2.0;

S2. Separation and recovery: The molten slag obtained in step S1 is kept for 5 to 50 minutes, settled and separated to obtain the middle and upper iron-containing silicate mineral phase, the bottom copper-rich phase and the middle and lower iron-rich phase, and simultaneously produce zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components, the gold and silver components migrate and enrich into the copper-rich phase; each phase is recycled.

According to the present invention, in step S1, the control method of condition a is:

When the temperature of the reaction slag is less than 1100°C, the temperature of the reaction slag reaches the range of 1100-1450°C through the heating function of the reaction device itself, or by adding fuel or molten zinc smelting slag to the slag;

When the temperature of the reaction slag is >1450°C, add one or more of copper-containing materials, zinc smelting slag, metallurgical flux, iron-containing materials, copper oxide minerals, and fluorine-containing materials to the reaction slag to make the reaction The temperature of the slag reaches the range of 1100-1450 °C;

In step S1, the regulation method of condition b is:

When the basicity CaO/ _SiO2 ratio of the reaction slag is less than 0.2, add one of alkaline materials, basic copper oxide minerals, copper sulfide minerals, copper-containing materials, and basic iron-containing materials to the reaction slag. species or several;

When the basicity CaO/ _SiO2 ratio of the reaction slag is greater than 2.0, add one of acidic materials, acidic copper oxide minerals, acidic copper sulfide minerals, acidic iron-containing materials, and acidic gold-silver-containing materials to the reaction slag. species or several.

According to the present invention, the heat preservation device is one or both of pourable smelting reaction slag tank and heat preservation pit;

The smelting reaction device from which the slag can flow out is a pourable smelting reaction device or a fixed smelting reaction device with a slag port or an iron port at the bottom;

The pourable smelting reaction device is one or both of a converter and a smelting reaction slag tank;

The fixed smelting reaction device with a slag port or an iron port is a plasma furnace, DC electric arc furnace, AC electric arc furnace, submerged arc furnace, blast furnace, blast furnace, induction furnace, cupola, side-blown molten pool smelting furnace, bottom-blown Melting pool melting furnace, top blowing melting pool melting furnace, reverberatory furnace, Osmelt furnace, Isa furnace, Vanukov melting pool melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing rotary furnace one or several.

According to the present invention, in the step S1, while satisfying the conditions a and b, the copper and iron oxides in the slag should be reduced to metallic copper and FeO, and the metallic iron content in the slag should be <3% .

By adding one or both of the reducing agent and the iron-containing material containing solid carbon, the amount of the reducing agent in the slag is 110-140% of the theoretical amount that copper and iron oxides in the slag are reduced to metallic copper and FeO; The carbon-containing iron-containing materials are iron and steel dust and soot, carbon-containing pre-reduced pellets of iron concentrate, carbon-containing metallized pellets of iron concentrate, volatile kiln slag of zinc hydrometallurgy, coke furnace dust and soot.

According to the present invention, the zinc smelting slag is one or both of the slag produced by hydrometallurgy and the slag produced by pyrometallurgy; Zinc slag is obtained from slag outlets of vortex smelting furnaces, blast furnaces, fuming furnaces, and electric furnaces, and hot zinc smelting slag is obtained from the outlets of volatilization kilns and vertical tanks, or heated to a molten state;

Wherein, the slag produced by the hydrometallurgy is one or more of zinc leaching slag, volatilized kiln slag, copper cadmium slag, ferrite slag, pickling slag, goethite slag, and hematite slag. The slag produced by the zinc pyrometallurgy is one or more of the slags of the vertical tank zinc smelting, vortex smelting, blast furnace slag, fuming furnace slag, and electric furnace slag; After drying and dehydration treatment, vortex smelting slag, blast furnace slag, fuming furnace slag and electric furnace slag are obtained from the slag outlet of the smelting furnace; The material port is obtained;

The calcium-based minerals are one or more of lime, limestone, dolomite, carbide slag, red mud, and 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 , P ₂ O ₅ , Fe, Na ₂ O;

The copper oxide minerals include one or more of cuprite, cupolite, malachite, azurite, chrysocolla, gallinite; the copper sulfide minerals include chalcocite, copper blue, One or more of chalcopyrite, bornite, chalcopyrite and tetrahedrite.

According to the present invention, the copper-containing material is copper slag, copper beneficiation tailings, crude copper pyro-refining slag, zinc smelting slag, zinc smelting soot and dust, lead-zinc tailings, lead smelting slag, lead matte, arsenic Matte copper, crude lead pyro-refining slag, lead smelting soot and sludge, lead-acid battery, copper smelting soot and sludge, miscellaneous copper, copper-containing waste, copper-containing circuit board, tin smelting slag, nickel smelting slag, tin tail One or more of the mines;

The copper slag is one or more of slag produced by matte smelting, slag produced by copper smelting, pyrotechnically depleted slag, copper slag flotation tailings, and wet copper smelting slag;

The metallurgical flux is CaO or _SiO2 -containing minerals and slag, preferably one or more of quartz sand, gold and silver-containing quartz sand, red mud, high-calcium red mud after desodiumization, calcium carbide slag, dolomite or limestone. kind;

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 sludge, nickel smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high calcium after desodiumization One or more of red mud, coal fly ash, and sulfuric acid cinder;

The nickel smelting slag is one or more of the nickel smelting slag produced by the "matte smelting" process, the depleted slag after blowing by the "copper matte blowing" process, and the nickel sedimentation slag produced by top blowing smelting;

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

The steel soot and sludge include blast furnace gas sludge, converter dust sludge, electric furnace sludge, hot/cold rolling sludge, sintering dust, pellet dust, ironworks dust collection, blast furnace gas ash, electric furnace dust, rolling steel oxidation Iron sheet;

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

The copper-containing materials, iron-containing materials and fluorine-containing materials are all pelletized or powdered materials or granulated;

Among them, the particle size of the powdery material is ≤150μm, the particle size of the granular material is 5-25mm, the powdery material is injected in the way of blowing, the granular material is added in the way of blowing or feeding, and the loading gas is preheated argon, One or more of nitrogen, reducing gas, and oxidizing gas, and the preheating temperature is 0-1200°C.

According to the present invention, the alkaline material is one or more of lime powder, red mud, high-calcium red mud after desodiumization, carbide slag, dolomite powder or quicklime powder; the alkaline iron-containing material is alkaline One or more of sinter, steel slag, ferroalloy slag, basic iron concentrate, basic pre-reduced pellets, basic metallized pellets, basic blast furnace slag;

The acidic material is one or more of silica, fly ash, and coal gangue; the acidic iron-containing material is acidic sintered ore, acidic iron concentrate, acidic pre-reduced pellets, acidic metallized pellets , copper slag, lead smelting slag, zinc smelting slag, nickel smelting slag, tin smelting slag, ferroalloy slag and acidic blast furnace slag.

According to the present invention, the separation and recovery in step S2 is processed as follows:

Contains the copper-rich phase in the hot or cold state, sent to the converter or blowing furnace for copper smelting, or slowly cooled, broken, and magnetically separated to separate metallic iron and then sent to the converter or blowing furnace for copper smelting, or magnetically separated to separate metallic iron Or directly reduce the metal iron without magnetic separation, and then send the reduced product to the converter or blowing furnace for copper smelting after magnetic separation and separation of the metal iron;

The zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components volatilize and enter the dust recovery in the form of oxides;

Containing the iron-containing silicate mineral phase and/or the iron-rich phase, the slag treatment is carried out by any one of the following methods A-G:

Method A: After water quenching or air cooling, it can be directly used as cement raw material:

Method B: Return to reactive mixed slag as hot metallurgical flux:

Method C: for pouring glass-ceramics or as slag wool;

Method D: keeping the iron-containing silicate mineral phase and/or the iron-containing slag of the iron-rich phase in the smelting reaction device or pouring the slag into the heat preservation device, blowing into the iron-containing slag Preheating oxidizing gas at a temperature of 0-1200°C, and ensuring that the temperature of the silicate slag is >1460°C; when the content of ferrous oxide in the slag is less than 1%, the oxidized slag is obtained; the oxidized slag Direct air cooling or water quenching, used as slag cement, cement regulator, additive in cement production or cement clinker;

Method E: For the production of high value-added cement clinker, the method is as follows:

E-1. Retain the iron-containing 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 molten steel slag to the slag , lime, limestone, ferroalloy slag, fly ash, alkaline lean iron ore, bauxite, molten blast furnace slag, red mud, high calcium red mud after desodiumization or calcium carbide slag, fully mixed, Obtain slag mixture material;

E-2. Blow an oxidizing gas with a preheating temperature of 0 to 1200°C into the slag mixture material, and ensure that the temperature of the slag mixture material is >1460°C; when the content 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-containing slag of the iron-rich phase are used as blast furnace ironmaking raw materials or direct reduction ironmaking raw materials: the iron-containing silicate mineral phase and/or The iron-containing slag of the iron-rich phase is air-cooled, water-quenched or slowly cooled, and 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, and the product of magnetic separation is metallic iron Melting with tailings and electric furnace, the products are molten iron and slag;

Or, after pouring the iron-containing silicate mineral phase and/or the iron-rich slag of the iron-rich phase into the heat preservation device, the following method is used for separation: magnetic separation after modification of the slag: into the heat preservation device The slag is blown into the oxidizing gas with a preheating temperature of 0-1200°C, and the slag temperature is guaranteed to be >1250°C to complete the transformation of magnetite in the slag; the oxidized slag is slowly cooled to room temperature and crushed , Magnetic separation, the products are magnetite concentrate and tailings, and the tailings are used as building materials;

Method G: ironmaking by smelting reduction of iron-containing slag of the iron-containing silicate mineral phase and/or the iron-rich phase includes the following steps:

G-1. Keep the iron-containing 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 the iron-containing slag to the iron-containing slag Iron materials and reducing agents are smelted and reduced, and the reaction slag is monitored in real time, and the following conditions are met at the same time through regulation and control: the temperature of the reaction slag is 1350-1670 °C and the alkalinity CaO/SiO ₂ ratio of the reaction slag=0.6-2.4, Obtain the slag after the reaction is completed;

G-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, The following conditions are met at the same time through regulation and control: the temperature of the molten slag after the reaction is 1350-1670°C and the basicity CaO/ _SiO2 ratio of the molten slag after the reaction is 0.6-2.4;

G-3. Use one of the following two methods to separate and recover:

Method Ⅰ: Pour the reduced mixed slag into the thermal insulation slag tank, slowly cool to room temperature to obtain slow cooling slag; metal iron settles to the bottom of the reaction device to form iron lumps; the metal iron layer in the remaining slow cooling slag, Crushing to a particle size of 20-400 μm, 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 subjected to slag treatment according to one or more of A to E; The molten iron is sent to the converter or electric furnace for steelmaking;

Or, the iron-rich phase containing said iron-rich phase can be quenched in water or air-cooled or poured into a heat preservation device for slow cooling or combined with manual sorting and re-selection to obtain it as raw material for blast furnace ironmaking or direct reduction ironmaking raw material or smelting reduction ironmaking raw material or flotation Extract copper raw materials or separate metallic iron by magnetic separation as raw materials for copper smelting or direct reduction iron smelting; during the flotation process, the flotation products are copper-containing concentrates and iron concentrates, and the copper concentrates are returned to the copper smelting system, and the iron concentrates are As a raw material for blast furnace ironmaking or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, after the reduction product is separated by magnetic separation, metallic iron and tailings are obtained, and the tailings are returned to the copper smelting system;

The direct reduction process adopts any one of rotary hearth furnace, tunnel kiln, car bottom furnace, shaft furnace, rotary kiln, and induction furnace as reduction equipment, and utilizes gas-based or coal-based reduction technology, and the gas-based is natural gas and/or Coal gas, the coal base is one or more of anthracite, bituminous coal, lignite, coking coal, coke powder, coke, the reduction temperature is 900-1400 ℃, the alkalinity CaO/SiO ₂ ratio = 0.8-1.5; the gas produced by reduction is in The secondary combustion on the surface of the slag 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 silver, when adding these raw materials, some indium components, bismuth components, potassium-containing components, and sodium-containing components Parts are volatilized and enter the smoke in the form of oxides.

According to the present invention, in the step S2, the cooling method is natural cooling, rotary cooling or centrifugal cooling, and the sedimentation method is natural sedimentation, rotary sedimentation or centrifugal sedimentation;

The uniform mixing is natural mixing or stirring mixing, stirring and mixing is one or more of argon stirring, nitrogen stirring, nitrogen-argon mixed gas stirring, reducing gas stirring, oxidizing gas stirring, electromagnetic stirring, mechanical stirring kind.

According to the present invention, the fuel and reducing agent are one or more of solid, liquid or gaseous fuels, which are injected in the form of injection or feeding, and the injection loading gas is preheated oxidizing gas, One or more of nitrogen or argon, the preheating temperature is 0-1200°C;

The solid fuel and the reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite, and the shape is granular or powdery. The particle size of the granular material is 5-25mm. 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;

The oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, and nitrogen-oxygen.

The method for smelting reduction production of zinc smelting slag in the present invention makes full use of the physical heat resources of molten slag and hot metallurgical flux, and realizes slag metallurgy, pyrometallurgy and iron smelting by processing zinc smelting slag and copper oxide minerals: ① The hot flux in the slag reacts, and through the slag metallurgical reaction of the mature slag system, the iron oxide is fully released to form an iron-rich phase, which realizes growth and settlement. The iron-rich phase includes metallic iron, FeO phase, and fayalite phase As a raw material for blast furnace ironmaking or direct reduction or smelting reduction ironmaking; ②Through the slag metallurgical reaction, the copper oxide ore phase is fully released, controlling the oxygen position of the slag, and the copper components and gold in the slag The silver components migrate and enrich in the copper-rich phase respectively, and the copper-rich phase includes copper, white matte, matte phase, and iron-containing components, and realize growth and precipitation, or part of the copper components enter the iron-rich phase ③ the zinc components in the slag are enriched in the dust for recycling; ④ the lead, indium and bismuth components in the slag are enriched in the dust for recycling; ⑤ realize the recovery of sulfur dioxide; Separation, magnetic separation, re-election or slag-gold sedimentation methods to separate the copper-rich phase, iron-rich phase and iron-containing silicate phase that have settled in different parts. After the copper-rich phase is separated, the iron-rich phase and iron-containing silicate phase The copper content in the phase is <0.1%; ⑦The low-copper iron-rich phase and the iron-containing silicate phase are directly reduced or smelted to obtain metallic iron and molten iron; it can handle solid and hot copper-containing slag, copper oxide minerals, Gold and silver minerals to achieve the purpose of efficient and comprehensive utilization of resources.

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

(1) The method for producing by zinc smelting slag of the present invention can handle both hot state slag and cold state slag, make full use of molten slag physical heat resources and hot state metallurgical flux, process copper oxide minerals, and realize It can not only process zinc smelting slag, but also process copper oxide minerals. It is a new copper smelting process to realize the production of copper and iron; and solve the current problems of massive accumulation of slag, environmental pollution, and heavy metal element pollution.

(2) The slag metallurgical reaction in the slag, adding calcium-based minerals, fully releases the iron oxides, forms free iron oxides, and realizes the growth and settlement of the iron-rich phase. The iron-containing components in the slag Aggregation, growth and sedimentation; at the same time, calcium-based minerals reduce the viscosity and help the copper-containing and iron-containing components to settle. The iron-rich phase includes a variety of metallic iron, FeO phase, and fayalite phase.

(3) The copper components and gold and silver components in the slag migrate and enrich respectively in the copper-rich phase. The copper-rich phase contains copper, white matte, matte phase, and iron-containing components, and realizes growth And sedimentation, or part of the copper component into the iron-rich phase.

(4) Zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components in the slag migrate respectively, enrich in the soot, and realize recovery; some sodium-containing components and potassium-containing components volatilize into the fumes, and be recycled.

(5) Separation of copper-rich phase iron oxides settled in different parts to realize efficient recovery of copper components and iron components in slag. The slag contains copper <0.1wt%. Solid copper-containing materials can be processed to achieve efficient resource synthesis use.

(6) The slag can be quenched and tempered, and can be used as cement raw material or building material, or as aggregate and road material instead of crushed stone. The tailing slag has high utilization value, and no solid waste is generated in the whole process.

(7) Adding additives in the method of the present invention can reduce the viscosity on the one hand, and reduce the melting point on the other hand, and help the copper-rich phase to settle at a certain temperature (1100-1450 ° C), and the iron-rich phase obtained after sedimentation and separation It is a 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 metallic iron can be obtained by direct reduction or smelting reduction ironmaking .

(8) The method of the present invention can be carried out continuously or discontinuously, the process flow is short, clean and environment-friendly, and the metal recovery rate is high.

(3) Beneficial effects

Beneficial effects of the invention:

(1) The present invention can realize valuable components such as copper components, gold and silver, iron components, zinc components, lead components, indium components, bismuth components, sodium components, and potassium components in slag through slag metallurgy. The comprehensive utilization of components solves the problem of massive accumulation of slag, can process copper oxide minerals on a large scale, realizes the simultaneous production of copper and iron, and solves the two worldwide problems of refractory copper oxide minerals and recovery of iron-containing components.

(2) The zinc smelting slag of the present invention can be liquid zinc smelting slag (vortex smelting slag or blast furnace slag) (≥1100°C) flowing out of the slag outlet, which has the characteristics of high temperature and high heat, and fully utilizes the physical heat of slag Resources; liquid molten zinc smelting 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 uses slag metallurgy and adds calcium-based minerals at the same time to release iron oxides in the fayalite phase and enrich them in the iron-rich phase to achieve aggregation, growth and settlement. The iron-rich phase includes metallic iron and FeO Various phases and fayalite phases are used as raw materials for blast furnace ironmaking or direct reduction or smelting reduction ironmaking; copper components and gold and silver components in slag migrate to copper-rich phases to achieve aggregation, growth and settlement, rich The copper phase includes copper, white matte, matte phase, iron-containing components, or some copper components enter the iron-rich phase; lead components, zinc components, bismuth components, indium components, sodium components, Potassium components volatilize and enter the dust in the form of oxides for recovery.

(4) in the inventive method, add cold state material and liquid state zinc smelting slag, have avoided slag temperature too high, improve the life-span of heat preservation device; Add cold state material and liquid state zinc smelting slag, have improved raw material handling capacity, not only can It can process liquid 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 chemical heat and physical heat of slag.

(5) In the natural cooling process of the method of the present invention, with the addition of additives, the copper components, gold, and silver components in the slag migrate and enrich respectively in the copper-rich phase, and realize aggregation, growth and settlement; Separation migrates and enriches in the iron-rich phase, and realizes aggregation, growth and settlement; the heat preservation device equipped with slag is placed on a rotating platform to rotate, and accelerates the aggregation, growth and settlement of copper-rich and iron-rich phases; The addition of fluorine materials accelerates the aggregation, growth and settlement of copper-rich and iron-rich phases.

(6) The method of the present invention adopts the method of artificial sorting, magnetic separation, re-election or slag-gold separation, respectively to the iron-containing silicate mineral phase, iron-rich phase and copper-rich phase distributed in the upper part, middle part and bottom Separation to achieve efficient recovery of valuable components in the slag, the slag contains copper <0.1wt%; since the copper-rich phase and iron-rich phase settle in the middle and lower parts, the amount of slag in the sorting furnace is small, the slag is quenched and tempered, and the minerals can be The abrasiveness is increased, and the separation cost is low; magnetic separation or gravity separation is adopted, and the separation medium is water, which will not cause environmental pollution; the tailings are used as cement raw materials, building materials, instead of crushed stones as aggregates, and road materials.

(8) The low-copper iron-rich phase and iron-containing silicate phase can be used as raw materials for blast furnace ironmaking or direct reduction or smelting reduction ironmaking to obtain metallic iron and molten iron.

(9) The present invention utilizes slag metallurgy to not only achieve efficient recovery of valuable components in slag, but also realize large-scale production of copper oxide minerals and simultaneously produce copper and iron, which is a new copper smelting process. 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 effectively solve the problem of efficient recycling of metallurgical resources and thermal energy.

detailed description

The present invention proposes a method for producing by smelting reduction of zinc smelting slag, which comprises the following steps:

Step S1, slag mixing:

Put the zinc smelting slag into the thermal insulation device or the smelting reaction device where the slag can flow out, and add calcium-based minerals and additives, heat the slag to a molten state to form a reaction slag containing copper and iron, and add copper oxide ore at the same time One or more of copper sulfide minerals, copper-containing materials, mixed evenly, and real-time monitoring of the reaction slag, by controlling and ensuring the following two parameters (a) and (b) at the same time, the molten slag after the reaction is completed slag;

(a) The temperature of reaction slag is 1100～1450 ℃;

(b) basicity CaO/SiO of reaction slag Ratio=0.2～ _2.0 ;

The control method is:

Corresponding to (a): The method of controlling the temperature of the reaction slag within the set temperature range is:

When the temperature of the copper-containing reaction slag is lower than the lower limit of the set temperature range of 1100°C, through the heating function of the reaction device itself, or by adding fuel or molten zinc smelting slag (vortex smelting slag and/or blast furnace smelting) to the copper-containing reaction slag slag), so that the temperature of the reaction slag reaches the set temperature range, and when the fuel is added, the preheating oxidizing gas is injected at the same time;

When the temperature of the copper-containing reaction slag is greater than the upper limit of the set temperature range of 1450°C, add one or more of copper-containing materials, zinc smelting slag, metallurgical flux, iron-containing materials or fluorine-containing materials to the copper-containing reaction slag , so that the temperature of the mixed slag reaches the set temperature range;

Corresponding to (b):

When the ratio of basicity CaO/SiO ₂ in the reaction slag containing copper and iron is <0.2, add alkaline materials, basic copper oxide minerals, copper sulfide minerals, copper-containing materials, alkaline One or several kinds of iron materials;

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag containing copper and iron is >2.0, add acidic materials, acidic copper oxide minerals, acidic copper sulfide minerals, acidic iron-containing materials, acidic gold-containing materials to the reaction slag One or more of silver materials.

Step S2, separation and recovery:

After the reaction is completed, the molten slag is kept for 5-50 minutes, settles, and the slag-gold is separated to obtain the molten copper-rich phase at the bottom, the molten iron-rich phase at the middle and lower parts, and the molten iron-containing silicate mineral phase at the upper and middle parts. Part of the zinc-containing component, lead-containing component and indium-containing component enters the soot, wherein the gold and silver components migrate to the copper-rich phase; one of the following methods is used:

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) Molten copper-rich phase, sent to converter or blowing furnace for copper smelting or as raw material for separation of copper, cobalt and nickel or crushed magnetic separation to separate metal iron and then sent to converter or blowing furnace for copper smelting, or separated by magnetic separation Metal iron or metal iron is not separated by magnetic separation, and then directly reduced, and the reduction product is separated by magnetic separation, and then sent to the converter or blowing furnace for copper smelting;

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

(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 blast furnace ironmaking raw materials or direct reduction ironmaking raw materials or smelting reduction ironmaking raw materials or flotation extraction Copper raw materials or metallic iron separated by magnetic separation are used as raw materials for copper smelting or direct reduction iron smelting; flotation products are copper-containing concentrates and iron concentrates, copper concentrates are returned to the copper smelting system, and iron concentrates are used as raw materials for blast furnace ironmaking or Direct reduction of ironmaking raw materials or smelting reduction of ironmaking raw materials; wherein, in the direct reduction process, the reduction products are separated by magnetic separation to obtain metallic iron and tailings, and the tailings are returned to the copper smelting system;

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 technology. Gas-based reduction is natural gas and/or coal gas, and coal-based reduction is 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 is 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:

Water quenching or air cooling of iron-containing silicate mineral phase can be directly used as cement raw material or further processed into high value-added cement raw material;

Method B: Part or all of the iron-bearing silicate mineral phase is returned to the copper-bearing 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: pouring glass-ceramic with iron-containing silicate mineral phase or as slag wool;

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

(1) The iron-containing silicate slag is kept in the smelting reaction device or poured into the heat preservation device, and blown into the slag with preheated oxidizing gas. When the content of ferrous oxide in the slag is less than 1%, Complete the oxidation of the slag to obtain the oxidized slag, wherein the preheating temperature of the oxidizing gas is 0-1200°C; and during the whole process, ensure that (c) the temperature of the silicate slag is >1460°C;

Corresponding to the control method adopted in (c):

When the temperature of iron-containing silicate slag is less than 1460°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 1460°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) Iron-containing silicate slag is kept in the smelting reaction device or poured into the heat preservation device, and molten steel slag, lime, limestone, ferroalloy slag, fly ash, and basic iron lean ore are added to the slag , bauxite, molten blast furnace slag, red mud, high-calcium red mud after desodination or one or more of calcium carbide slag, fully mixed to obtain slag mixture material;

(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 to 1200°C; and throughout the process, ensure that (d) the temperature of the slag mixture material is >1460°C; the temperature control method is the same as the temperature control method for silicate slag in step (1) of method D;

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

Method F: The slag of iron-containing silicate mineral phase is used as blast furnace ironmaking raw material or direct reduction ironmaking raw material: the slag of iron-containing silicate mineral phase is air-cooled, water quenched or slowly cooled, and used as 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 containing iron silicate mineral phase into the heat preservation device, the following method is used for separation: magnetic separation after slag modification: blowing into the slag in the heat preservation device Hot 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 oxidized slag to room temperature, crush and magnetically separate, and the product is magnetite concentrate As with tailings, tailings are used as construction materials.

Method G: Smelting reduction ironmaking of slag containing iron silicate mineral phase:

G-1. Keep the slag of the iron-silicate mineral phase in the smelting reaction device or pour the slag into the heat preservation device, add iron-containing materials, add a reducing agent to the slag, and carry out melting reduction. Real-time monitoring of reaction melting Slag, by controlling and ensuring the following two parameters (a1) and (b1) at the same time, the slag after the reaction is completed;

(a1) The temperature of the reaction slag is 1350～1670°C;

(b1 ₎ basicity CaO/SiO of reaction slag Ratio=0.6～2.4;

The control method is:

Corresponding to (a1):

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 gas to the slag;

When the temperature of the reaction slag is higher than the upper limit of the set temperature range, one or more of metallurgical flux, iron-containing material or fluorine-containing material is added to the reaction slag to make the temperature of the reaction slag reach the set temperature range ;

Corresponding to (b1):

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. 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, The two parameters (a2) and (b2) are guaranteed at the same time through regulation:

(a2) the temperature of the molten slag after the reaction is completed is 1350～1670 ℃;

(b2 ₎ the basicity CaO/SiO of the molten slag after the reaction is completed Ratio=0.6～2.4;

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

G-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, and slowly cool to room temperature to 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) The reduced slag is treated with slag outside the furnace, and the specific method is: using one or more of the methods A to E in the separation and recovery method 1 of step S2 to treat slag outside the furnace;

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

(d) Part of the zinc-containing components, lead-containing components and indium-containing components volatilize, and enter the dust recovery as ZnO, _PbO and _Ln2O3 ;

(e) Part of the indium component, bismuth component, sodium component, and potassium component volatilize into the smoke and dust for recovery;

(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 obtained molten iron-rich phase and iron-containing silicate mineral phase are treated with slag by one or more of the methods A to G described in method one;

(2) The copper-rich phase in the molten state is sent to converter copper smelting or blowing furnace for copper smelting or as a raw material for the separation of copper, cobalt and nickel, or is sent to converter or blowing furnace for copper smelting after crushing magnetic separation to separate metal iron, or Separation of metallic iron by magnetic separation or separation of metallic iron without magnetic separation, direct reduction, the reduction product is separated by magnetic separation of metallic iron, and then sent to converter or blowing furnace for copper smelting;

(3) Part of the zinc-containing components, lead-containing components and indium-containing components volatilize, and enter the dust recovery as oxides;

(4) Part of the sodium 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:

(1) The molten iron-containing silicate mineral phase obtained is treated with slag by one or more of methods A to G described in method one;

(2) After the iron-rich phase is water-quenched or air-cooled or poured into a heat preservation device for slow cooling, it is used as a raw material for blast furnace ironmaking or direct reduction ironmaking;

(3) The copper-rich phase in the molten state or poured into the heat preservation device for slow cooling, then sent to the converter or blowing furnace for copper smelting, or crushed magnetic separation to separate metal iron and then sent to the converter or blowing furnace for copper smelting, or through magnetic separation After separating metallic iron or separating metallic iron without magnetic separation, it is directly reduced, and the reduction product is separated from metallic iron by magnetic separation, and then sent to the converter or blowing furnace for copper smelting;

(4) Part of the zinc-containing components, lead-containing components, indium-containing components and bismuth-containing components are volatilized, and enter the dust recovery as oxides;

(5) Part of the sodium 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 obtained molten iron-containing silicate mineral phase and the iron-rich phase are treated with slag by one or more of the methods A to G described in method one;

(2) The copper-rich phase in the molten state is sent to the converter or blowing furnace for copper smelting, or after slow cooling, it is crushed and separated by magnetic separation to separate the metallic iron and then sent to the converter or blowing furnace for copper smelting, or the metallic iron or non-metallic iron is separated by magnetic separation After the metal iron is separated by magnetic separation, it is directly reduced, and the reduced product is sent to the converter or blowing furnace for copper smelting after the metal iron is separated by magnetic separation;

(3) Part of the zinc-containing components, lead-containing components, indium-containing components and bismuth-containing components volatilize, and enter the dust recovery as oxides;

(4) Part of the sodium and potassium components volatilize into the smoke.

Method 5: Use a heat preservation device or a smelting reaction device where slag can flow out. When the slag is poured 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 slowly cooled to room temperature to obtain slowly cooled slag; the copper-rich phase settles to the bottom of the reaction device to form a copper-rich lump; the iron-containing silicate mineral phase floats; the copper-rich phase metal The slow cooling slag between lump and iron-containing silicate minerals is an iron-rich phase, and simultaneously generates zinc-containing components and lead-containing components; gold and silver components migrate to copper-rich phases;

(2) Separation: Manually remove the copper-rich lump that settled at the bottom, and then send it to the converter or blowing furnace for copper smelting after magnetic separation and separation of metal iron, or send it to converter or blowing furnace for copper smelting after magnetic separation and separation of metal iron , or after separating metallic iron by magnetic separation or without separating metallic iron by magnetic separation, it is directly reduced, and the reduced product is sent to converter or blowing furnace for copper smelting after magnetic separation and separation of metallic iron; the iron-rich phase layer in the middle is used as a blast furnace Ironmaking raw materials or direct reduction ironmaking raw materials or smelting reduction ironmaking raw materials or flotation copper extraction raw materials or magnetic separation to separate metallic iron as raw materials for copper smelting or direct reduction; in the flotation process, the flotation product is copper-containing concentrate Ores and iron concentrates, copper concentrates are returned to the copper smelting system, and iron concentrates are used as blast furnace ironmaking raw materials or direct reduction ironmaking raw materials or smelting reduction ironmaking raw materials; wherein, in the direct reduction process, after the reduction product is separated by magnetic separation, Obtain metallic iron and tailings, and return the tailings to the copper smelting system;

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 technology. Gas-based reduction is natural gas and/or coal gas, and coal-based reduction is One or more of anthracite, bituminous coal, lignite, coking coal, coke powder or coke, the reduction temperature is 900-1400°C, the alkalinity CaO/ _SiO2 ratio = 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: as cement raw material, building material, instead of gravel as aggregate, and road material ;

(4) Part of the zinc-containing components, lead-containing components, indium-containing components and bismuth-containing components volatilize, and enter the dust recovery as oxides;

(5) Part of the sodium and potassium components volatilize into the smoke.

In the steps S1 and S2, the zinc smelting slag is one or both of the slag produced by the hydrometallurgy and the slag produced by the pyrometallurgy, wherein the slag produced by the hydrometallurgy is zinc leaching slag, volatile One or more of kiln slag, jarosite slag, pickled jarosite slag, goethite slag, hematite slag, and the slag produced by pyrometallurgy is the vertical tank zinc smelting slag, vortex smelting slag, blast furnace slag One or more of slag, fuming furnace slag, and electric furnace slag.

Zinc smelting slag is in molten state, hot state or cold state, among which: zinc smelting slag from hydrometallurgy needs to be dried and dehydrated; The volatilized kiln slag is obtained from the outlet of the volatilization kiln, and the zinc smelting slag is obtained from the slag outlet of the vertical tank, or the zinc smelting slag is heated to a molten state.

In the steps S1 and S2, the smelting reaction device from which slag can flow out is a pourable smelting reaction device or a fixed smelting reaction device with a slag port or an iron port at the bottom; wherein:

The heat preservation device is a pourable smelting reaction slag tank and a heat preservation pit.

The pourable smelting reaction device is a converter and a smelting reaction slag tank.

The fixed smelting reaction device with a slag port or an iron port 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, a bottom Blowing bath melting furnace, top blowing melting bath melting furnace, reverberatory furnace, Osmet furnace, Isa furnace, Vanukov bath melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing rotary furnace.

In the step S1, the calcium-based minerals are specifically 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 , P ₂ O ₅ , Fe or Na ₂ O.

In the step S1, the copper oxide minerals include one or more of cuprite, cupolite, malachite, azurite, chrysocolla, and gallinite.

Copper sulfide minerals include one or more of chalcocite, copper blue, chalcopyrite, bornite, chalcocite, and tetrahedrite.

In the step S1, the following two parameters (a) and (b) are ensured at the same time through regulation and control, and the reduction of copper and iron oxides in the slag to metallic copper and FeO is satisfied at the same time, and the metallic iron content in the slag is <3 %. By adding one or both of the reducing agent and the iron-containing material containing solid carbon, the amount of the reducing agent in the slag is 110-140% of the theoretical amount that copper and iron oxides in the slag are reduced to metallic copper and FeO; The carbon-containing iron-containing materials are iron and steel dust and soot, carbon-containing pre-reduced pellets of iron concentrate, carbon-containing metallized pellets of iron concentrate, volatile kiln slag of zinc hydrometallurgy, coke furnace dust and soot.

In the steps S1 and S2, the fuel and the reducing agent are one or more of solid, liquid or gas, which are injected in the form of blowing or feeding, and the loading gas is preheated oxidizing gas , nitrogen, argon, the preheating temperature is 0-1200°C, the solid fuel and reducing agent are one or more of coal powder, fly ash, coke powder, coke, 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 is heavy oil, and the gaseous fuel is one or both of coal gas and/or natural gas.

In the steps S1 and S2, the copper-containing materials are copper slag, copper beneficiation tailings, crude copper pyro-refining slag, zinc smelting slag, zinc smelting soot and sludge, lead-zinc tailings, lead smelting slag, lead ice Copper, 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, nickel smelting slag , one or more of tin tailings.

Zinc smelting slag is the zinc smelting slag produced by hydrometallurgy and pyrometallurgy, including leaching slag, alumite slag, copper cadmium slag, goethite slag, hematite slag, volatilization kiln slag, vertical tank zinc smelting slag , Fuming furnace slag, electric furnace zinc smelting slag.

Copper slag is one or more of the slags produced by "matte smelting", slags produced by "copper smelting", pyro-process depleted slags, copper slag flotation tailings, and hydrometallurgical copper smelting slags.

Lead smelting slag is one or both of 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" The "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.

Nickel smelting slag is one or more of the nickel smelting slag produced by the "matte smelting" process, the depleted slag after blowing by the "copper matte blowing" process, and the nickel sedimentation slag produced by top blowing smelting.

The metallurgical flux is a mineral containing CaO or SiO ₂ , 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.

Iron-containing materials 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 carbon-containing pre-reduced balls Smelting powder, steel slag, zinc smelting slag, coke smelting dust and sludge, steel soot and sludge, nickel smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high calcium red mud after desodiumization One or more of coal powder ash and sulfuric acid cinder.

Copper-containing materials and iron-containing materials are hot or cold, and the hot materials are directly obtained from the discharge port or slag discharge port of the metallurgical furnace.

Zinc slag and dust sludge from hydrometallurgy need to be dehydrated and dried.

Steel soot and sludge include blast furnace gas sludge, converter dust sludge, electric furnace sludge, hot/cold rolling sludge, sintering dust, pellet dust, ironworks dust collection, blast furnace gas ash, electric furnace dust, steel rolling oxide scale.

Among the above raw materials, zinc smelting slag and soot, lead smelting slag and soot contain indium, bismuth, lead, silver and zinc; red mud contains sodium and potassium, and iron 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, in the method of invention, indium, bismuth, sodium, potassium, zinc, lead will be with oxide In the form of dust, it can be recycled.

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

In the steps S1 and S2, the copper-containing materials, iron-containing materials and fluorine-containing materials are all pelletized or powdered materials or granulated; wherein, the particle size of the granular materials is 5-25 mm, and the particle size of the powdered materials is ≤ 150μm, the granular material is injected by blowing, the loading gas is one or more of preheated argon, nitrogen, reducing gas (coal gas and/or natural gas), and oxidizing gas, and the preheating temperature is 0-1200°C, the blowing method is one or more of inserting the slag with a refractory lance or blowing into the top, side or bottom of the reaction slag.

The copper-containing material and the iron-containing material are in a hot or cold state. The hot material is directly obtained from the metallurgical furnace outlet or slag outlet, and the temperature of the hot material is 200-1750°C.

In the steps S1 and S2, during the slag reaction process, the copper components and gold and silver components in the slag are enriched in the copper-rich phase, and realize aggregation, growth and settlement, and the iron components are enriched in the iron-rich phase. Phase, to achieve aggregation, growth and sedimentation, the zinc component, lead component, bismuth component and indium component in the slag enter the fume respectively, and are recovered in the form of oxides. Among them, the copper-rich phase includes copper, white matte , matte phase, multiple types of iron-containing components, or part of the copper component enters the iron-rich phase, and the iron-rich phase includes multiple types of metallic iron, FeO phase, and fayalite phase, used as blast furnace ironmaking or direct reduction or melting Reduction of raw materials for ironmaking.

In the step S1, in the method of controlling the temperature of the mixed slag in the set temperature range:

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

In the steps S1 and S2, when adjusting the alkalinity, the alkaline material is one or more of lime powder, red mud, high-calcium red mud after desodiumization, carbide slag, dolomite powder or quicklime powder; The basic iron-containing material is CaO/SiO ₂ ≥ 1 iron-containing material; the basic iron-containing material is alkaline sintered ore, steel slag, ferroalloy slag, alkaline iron concentrate, alkaline pre-reduced pellets or alkali One or more of permanent metallized pellets and basic blast furnace slag.

In the steps S1 and S2, when adjusting the alkalinity, the acidic material is one or more of silica, fly ash, and coal gangue; the acidic iron-containing material is CaO/SiO ₂ ≤ 1 Iron-containing materials; the acidic iron-containing materials are acidic sintered ore, acidic iron concentrate, acidic pre-reduced pellets, acidic metallized pellets, copper slag, lead smelting slag, zinc smelting slag, nickel smelting slag, tin smelting One or more of slag, ferroalloy slag, acidic blast furnace slag.

In the step S1, while ensuring the two parameters (a) and (b), the slag is fully mixed, the mixing method is natural mixing or stirring mixing, and the stirring method is one of the following methods: argon stirring, One or more of nitrogen stirring, nitrogen-argon mixed gas stirring, reducing gas stirring, oxidizing gas, electromagnetic stirring, mechanical stirring.

In the above steps S1 and S2, the copper-rich phase and the iron-rich phase in the slag gather, grow and settle, which is beneficial for the silicate to float up.

In the steps S1 and S2, the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen, and the preheating temperature is 0-1200°C, the injection method is one or more of inserting the slag with a refractory lance or blowing into the top, side or bottom of the reaction slag.

In the step S2, the direct reduction process uses rotary hearth furnaces, tunnel kilns, car bottom furnaces, shaft furnaces, rotary kilns, and induction furnaces as reduction equipment, and uses gas-based or coal-based reduction technology, and the gas-based is natural gas and/or Coal gas, coal-based reduction to one or more of anthracite, bituminous coal, lignite, coking coal, coke powder, and coke, the reduction temperature is 900-1400 ° C, and the alkalinity CaO/SiO ₂ ratio = 0.8-1.5.

In the step S2, the cooling method is natural cooling, rotary cooling or centrifugal cooling, and the settling method is natural settling, rotary settling or centrifugal settling.

In the step S2, the specific operation of rotation and centrifugal cooling 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 depends on the quality of the slag and the solidification of the slag; the device containing the slag after the reaction is placed on the rotating platform to rotate, the purpose is to accelerate the accumulation, growth and development of copper-rich and iron-rich phases. Settling is conducive to the floating of silicate (phosphorus-rich phase).

In the step S2, during the cooling process of the molten slag after the reaction, due to the difference in density and mineral size, most of the copper-rich phases settle in the middle and lower parts, and the iron-rich phases settle in the middle and upper parts.

In the step S2, the copper components and gold and silver components in the slag after the reaction continue to migrate, enrich in the copper-rich phase, and realize growth and settlement, or part of the copper components are enriched in the iron-rich phase ; The iron components in the mixed slag continue to migrate, enrich in the iron-rich phase, and realize growth and settlement.

In the step S2, the gravity separation method is shaker separation, chute separation or a combination of the two.

To sum up, in the above-mentioned step S2, in the slag of the iron-rich phase and iron-containing silicate mineral phase finally obtained, the slag contains copper ≤ 0.1%, the recovery rate of iron ≥ 95%, and the recovery rate of zinc ≥ 95%, recovery rate of lead ≥94%, recovery rate of indium ≥91%, enrichment rate of gold ≥90%, enrichment rate of silver ≥90%, enrichment rate of nickel ≥92% , the enrichment rate of cobalt is ≥92%, the recovery rate of bismuth is ≥92%, the recovery rate of sodium is ≥93%, and the recovery rate of potassium is ≥93%.

Among them, the copper content in slag refers to the slag phase after the copper-rich phase is separated, specifically the copper content in the iron-rich phase and iron-containing silicate mineral phase, and the enrichment rate of nickel and cobalt refers to the amount of nickel in the copper-rich phase. The content of cobalt accounts for the percentage of the total amount of nickel and cobalt in the raw material, and the enrichment rate of gold and silver refers to the percentage of the content of gold and silver in the copper-rich phase to the total amount of gold and silver in the raw material.

In order to better explain the present invention and facilitate understanding, the present invention is described in detail through the following examples. Wherein, the treatment methods and raw materials used in the following examples are not clearly indicated, all can adopt the conventional technology in this field, unless otherwise specified, the percentages used in the present invention are all weight percentages.

Example 1

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: Add cold zinc smelting slag (zinc leaching slag and volatilized kiln slag) into DC electric arc furnace, add lime, and SiO ₂ , MgO, Al ₂ O ₃ at the same time to form mixed slag; mix mixed slag Heating to a molten state to form a copper-containing reaction slag, adding copper oxide concentrate at the same time, and allowing the reaction slag to achieve natural 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;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1660°C, a refractory spray gun is inserted into the reaction slag, and nitrogen with a preheating temperature of 1100°C is used as the loading gas, and copper slag with a particle size of ≤150 μm at room temperature is sprayed , copper-containing soot, miscellaneous copper and copper-containing waste, and copper-containing circuit boards. At the same time, blast furnace gas sludge, electric furnace dust sludge, converter dust sludge, ordinary iron concentrate, ordinary iron concentrate direct reduced iron, and blast furnace gas ash are added to make the temperature down to 1450°C;

(b): the basicity CaO/SiO ratio of copper _- containing reaction slag=1.8, add silica, fly ash and coal gangue mixture in the reaction slag, make the copper-containing reaction slag alkalinity ratio drop to 1.7; The metallic iron content in the slag is 0.5%.

Step 2, separation and recovery using method one:

Keep warm for 45 minutes. After the reaction is completed, the molten slag will settle naturally, and the slag-gold will be separated to obtain molten copper-rich phase, iron-rich phase and iron-containing silicate mineral phase, and simultaneously generate zinc-containing components, lead-containing components, and bismuth-containing components. Components and indium-containing components enter the dust recovery, and the following steps are carried out:

(1) The iron-containing silicate mineral phase in the molten state is treated with slag outside the furnace. Method F is used. After the iron-containing silicate slag is air-cooled, it is used as a raw material for direct reduction of ironmaking. During the direct reduction process, a rotary kiln is used As reduction equipment, gas-based reduction technology is used. The gas-based reducing agent is natural gas and coal gas. The reduction temperature is 900°C, the alkalinity CaO/ _SiO2 ratio is 0.8, and the electric furnace melting temperature is 1450°C after reduction. The product is metal molten iron. with slag;

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

(3) The molten iron-rich phase is poured into the heat preservation device, and is used as a raw material for blast furnace ironmaking after air cooling;

(4) Zinc-containing components, lead-containing components, bismuth-containing components, indium-containing components, sodium-containing components and potassium-containing components volatilize and enter the dust recovery.

The finally obtained slag contains copper<0.1%, recovery rate of zinc is 96%, recovery rate of lead is 95%, recovery rate of iron is 97%, recovery rate of indium is 92%, recovery rate of bismuth is 92%, gold is rich in The collection rate is 91%, the enrichment rate of silver is 92%, the recovery rate of sodium is 95%, and the recovery rate of potassium is 95%.

Example 2

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: add cold zinc smelting slag (zinc leaching slag) into pourable smelting reaction slag pot, add limestone, dolomite, red mud, FeO and Fe ₂ O ₃ at the same time to form mixed slag, and add Copper oxide concentrate and copper sulfide concentrate; use oxygen-enriched air with a preheating temperature of 800°C to inject natural gas, anthracite and coke particles with a particle size of 20mm, and heat the mixed slag to a molten state to form a copper-containing reaction slag; Monitor the reaction slag in real time, and ensure the two parameters (a) and (b) at the same time through regulation, and obtain the slag after the reaction is completed;

Corresponding to (a) the temperature of the copper-containing reaction slag is 1520°C, use a refractory spray gun to insert into the reaction slag, use normal temperature argon as the carrier gas, spray into the normal temperature powdery copper slag, copper-containing soot, miscellaneous copper, steel Sinter dust, sinter pellet dust, cast iron dust, ordinary iron concentrate direct reduction of iron, so that the temperature drops to 1440 ℃;

(b) the copper _- containing reaction slag has a basicity CaO/SiO ratio of 2.4, and 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 make the reaction slag containing The basicity ratio of the copper reaction slag dropped to 1.6; the metallic iron content in the slag was 2.9%.

Step 2, separation and recovery adopts method two:

After 50 minutes of heat preservation, the slag was rotated and settled, and the slag-gold was separated to obtain molten copper-rich phase, iron-rich phase and iron-containing silicate mineral phase, and simultaneously formed zinc-containing components, lead-containing components, bismuth-containing components, and The indium component, the sodium-containing component and the potassium-containing component, each phase enters the soot for the following steps:

(1) For molten iron-containing silicate mineral phase and iron-rich phase, method G is used for slag treatment outside the furnace, and iron-containing slag is smelted and reduced for ironmaking. The specific steps are as follows:

(1-1) The above-mentioned iron-containing slag is poured into a pourable converter, and anthracite and bituminous coal with a particle size of 20 mm are added to the slag for smelting reduction, real-time monitoring of the reaction slag, and the following (a) reaction smelting The temperature of slag is 1350～1670 ℃, and (b) basicity CaO/SiO of reaction slag Ratio=0.6～2.4 _Two parameters, obtain the slag after reaction;

Corresponding to (a): the temperature of the reaction slag is 1480°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, and the slag-gold is separated to obtain molten iron and reduced slag;

(b) The slag after reduction is processed by method A in method one of step S2 to make high value-added cement raw materials;

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

(d) Bismuth-containing components, sodium-containing components and potassium-containing components enter the soot recovery;

(2) The molten copper-rich phase is sent to the converter for copper smelting;

(3) Zinc-containing components, lead-containing components, bismuth-containing components, indium-containing components, sodium-containing components and potassium-containing components are volatilized and recovered in the form of oxides.

The finally obtained slag contains less than 0.1% copper, 97% recovery rate of zinc, 97% recovery rate of lead, 98% recovery rate of iron, 94% recovery rate of indium, 95% recovery rate of bismuth, gold rich The collection rate is 92%, the enrichment rate of silver is 93%, the recovery rate of sodium is 93%, and the recovery rate of potassium is 94%.

Example 3

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: Add zinc smelting slag (hot volatile kiln slag obtained from the discharge port of the volatilization kiln) into the DC electric arc furnace, and at the same time add limestone and high-calcium red mud after desodiumization to form a mixed slag, and add sulfurized slag at the same time Copper concentrate: 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 in real time For slag, the slag after the reaction is completed is obtained by regulating and controlling the two parameters (a) and (b) at the same time;

Corresponding to (a): The temperature of the copper-containing reaction slag is 1685°C. Add acid metallized pellets, copper smelting slag and copper-containing blowing slag to the reaction slag, and simultaneously add copper-containing soot, lead-containing slag, and ordinary iron Concentrate pellets, rolled iron and phosphorus oxide and ordinary iron concentrate carbon-containing pre-reduced pellets, reducing the temperature to 1420°C;

(b): the alkalinity CaO/ _SiO2 ratio=2.3 of copper-containing reaction slag, add the mixture of quartz sand, red mud, wet process zinc smelting kiln slag in reaction slag, make the alkali of copper-containing reaction slag The degree ratio drops to 1.6; the metallic iron content in the slag is 1.8%.

Step 2, separation and recovery adopts method two:

Keep warm for 30 minutes, the slag settles naturally, the slag-gold separates, and the molten copper-rich matte phase, iron-rich matte phase layer and copper-containing silicate mineral phase are obtained, and zinc-containing components and lead-containing components are simultaneously formed. Components, bismuth-containing components and indium-containing components volatilize and enter the smoke for recycling. The following steps are performed:

(1) The copper-rich phase in the molten state is sent to the converter for copper smelting;

(2) The molten iron-rich phase and iron-containing silicate mineral phase are used as direct reduction ironmaking raw materials. During the reduction process, part of the zinc component, lead component, indium component and bismuth component volatilize and enter the smoke; direct reduction During the process, a rotary hearth furnace is used, the reduction temperature is 1200°C, the alkalinity CaO/ _SiO2 ratio=1.0, and the reducing agent is anthracite and pulverized coal with a particle size of ≤150 μm;

(3) Zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components volatilize and enter the dust recovery.

The finally obtained slag contains copper<0.1%, the recovery rate of iron is 98%, the recovery rate of zinc is 97%, the recovery rate of lead is 96%, the recovery rate of indium is 93%, the recovery rate of bismuth is 94%, The gold enrichment rate is 92%, and the silver enrichment rate is 93%.

Example 4

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step ₁ , mixing slag: adding cold state zinc smelting slag (alumina slag) into DC electric arc furnace, adding dolomite, MgO, _Al2O3 and Fe at the same time to form mixed slag; heating the mixed slag to a molten state, Copper-containing reaction slag is formed, and copper oxide concentrate and copper-containing materials (copper slag, lead-containing fuming slag) are added at the same time and the reaction slag is electromagnetically stirred to achieve mixing; the reaction slag is monitored in real time, and the (a ) and (b) two parameters to obtain the slag after the completion of the reaction;

Corresponding to (a) the temperature of the copper-containing reaction slag is 1670°C, and red mud, coal fly ash, sulfuric acid cinder, fluorite, lead matte, lead-containing soot, zinc-containing soot, and arsenic matte are added to the reaction slag and hydrometallurgy slag to reduce the temperature to 1440°C;

(b) The basicity CaO/ _SiO2 ratio of the copper-containing reaction slag is 2.0, and the copper-containing blowing slag is added to the reaction slag to reduce the basicity ratio of the copper-containing reaction slag to 1.7; use a preheating temperature of 1100°C air, coke grains with a particle size of 20mm, natural gas injection, and a metal iron content of 1.3% in the slag.

Step 2, separation and recovery adopts method two:

After 28 minutes of heat preservation, the molten slag will settle naturally, and the slag-gold will be separated to obtain molten copper-rich phase, iron-rich phase and iron-containing silicate mineral phase, and simultaneously generate zinc-containing components, lead-containing components, bismuth-containing components and The indium component enters the soot recovery in the form of oxide, and the following steps are performed:

(1) The copper-rich phase in the molten state is sent to the converter for copper smelting;

(2) Separation and recovery of the molten iron-rich phase and iron-containing silicate mineral phase step S2 Method F, oxidation modification magnetic separation: ① pour the molten slag into the thermal insulation slag tank, spray pre-treated slag into the molten slag Oxygen-enriched air with a heating temperature of 900°C realizes the transformation of magnetite; ②slowly cools to room temperature and separates by magnetic separation to obtain iron concentrate and tailings;

(3) Zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components volatilize and enter the dust recovery.

The finally obtained slag contains copper<0.1%, the recovery rate of iron is 97%, the recovery rate of zinc is 98%, the recovery rate of lead is 95%, the recovery rate of indium is 94%, the recovery rate of bismuth is 93%, The gold enrichment rate is 91%, and the silver enrichment rate is 90%.

Example 5

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: add zinc smelting slag (hot vertical tank zinc smelting slag, molten vortex smelting slag obtained from the slag outlet, molten blast furnace slag and molten electric furnace slag) into the insulation slag tank, and add limestone and Fe at the same time to form a mixed slag, add sulfide ore concentrate and copper-containing materials (copper pyro-refining slag, copper-containing soot, miscellaneous copper and copper-containing waste); use 800°C oxygen-enriched air to inject bituminous coal with a particle size of ≤150 μm, and mix the molten The 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 guaranteed at the same time through regulation to obtain the completed slag;

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

(b): The basicity CaO/ _SiO2 ratio of the copper-containing reaction slag is 1.5, both within the required range; the metallic iron content in the slag is 1.7%.

Step 2, separation and recovery using method five:

Pour the molten slag after the reaction into the thermal insulation slag tank for slag treatment, and perform the following steps:

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

(2) Separation: Manually remove the copper-rich lumps that have settled at the bottom, directly reduce them, and after the iron is separated by magnetic separation, the product is sent to the converter;

(3) manually take out the upper silicate mineral phase, obtain silicate tailings, use as cement raw material;

(4) Zinc-containing components, indium-containing components, bismuth-containing components and lead-containing components volatilize and enter the dust recovery.

The finally obtained slag contains copper<0.1%, the recovery rate of iron is 98%, the recovery rate of zinc is 96%, the recovery rate of lead is 96%, the recovery rate of indium is 92%, the recovery rate of bismuth is 93%, The gold enrichment rate is 93%, and the silver enrichment rate is 93%.

Example 6

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: add cold zinc smelting slag (jaosite slag, goethite slag, hematite slag after pickling) into AC electric arc furnace, and add lime, MgO, Al ₂ O ₃ , Fe ₂ O ₃ at the same time , forming a mixed slag, adding copper oxide concentrate and copper-containing materials (lead-containing smelting slag, arsenic matte, lead matte and lead fire refining slag) at the same time; heating the mixed slag to a molten state to form a copper-containing reaction The slag is sprayed into the argon gas with a preheating temperature of 1100°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 by adjusting and controlling, and the molten slag after the reaction is completed slag;

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

(b): The alkalinity CaO/SiO ₂ ratio of copper-containing reaction slag is 0.1, and alkaline iron concentrate, converter sludge, alkaline pre-reduced pellets, and high-calcium red mud after desodiumization are added to the reaction slag , so that the basicity ratio of the copper-containing reaction slag rises to 0.3; the metallic iron content in the slag is 1.5%.

Step 2, separation and recovery using method one:

After 13 minutes of heat preservation, the molten slag will settle naturally, and the slag-gold will be separated to obtain molten copper-rich phase, iron-rich phase and iron-containing silicate mineral phase, and simultaneously generate zinc-containing components, indium-containing components, bismuth-containing components and The lead component volatilizes and enters the flue dust to be recovered, and the following steps are carried out:

(1) The iron-containing silicate mineral phase adopts method A in step S2 separation and recovery method one, and water quenching is directly used as cement raw material;

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

(3) The molten iron-rich phase is poured into the heat preservation device for cooling and then directly reduced for ironmaking;

(4) Zinc-containing components, indium-containing components, bismuth-containing components, lead-containing components, sodium-containing components and potassium-containing components volatilize and enter the dust recovery.

The finally obtained slag contains copper<0.1%, the recovery rate of iron is 97%, the recovery rate of zinc is 96%, the recovery rate of lead is 98%, the recovery rate of indium is 92%, the recovery rate of bismuth is 94%, The gold enrichment rate was 92%, the silver enrichment rate was 92%, the sodium recovery rate was 95%, and the potassium recovery rate was 96%.

Example 7

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: Add zinc smelting slag (hot zinc smelting slag obtained from the slag outlet) into the submerged arc furnace, add limestone, SiO ₂ , FeO and MgO at the same time to form a mixed slag, and add copper oxide concentrate at the same time Ore and copper-containing materials (nickel smelting slag "sulfur-making smelting" nickel smelting slag, "copper matte blowing" nickel blowing slag, nickel blowing slag depleted slag obtained by pyrolysis, nickel top-blown molten pool The smelting slag and the smelting slag in the melting pool are obtained by a subsidence electric furnace); the mixed slag is heated to a molten state to form a copper-containing reaction slag, and an argon-nitrogen mixed gas with a preheating temperature of 800°C is injected, and the 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 copper-containing reaction slag is 1320°C;

(b): The basicity CaO/SiO ₂ ratio of the copper-containing reaction slag is 0.8, both within the required range; adding coal powder and natural gas with a particle size of ≤150 μm, the metallic iron content in the slag is 0.8%.

Step 2, separation and recovery using method four:

After heat preservation for 18 minutes, the molten slag will settle naturally, and the slag-gold will be separated to obtain molten copper-rich matte phase, iron-rich matte phase layer and iron-containing silicate mineral phase, and simultaneously generate zinc-containing components, lead-containing Components, bismuth-containing components and indium-containing components enter the smoke dust for recovery and recovery, and the following steps are carried out:

(1) The copper-rich phase in the molten state is sent to the converter for copper smelting;

(2) The molten iron-rich phase and iron-containing silicate minerals specifically adopt the method F in the separation and recovery method one of step S2, after water quenching, as raw materials for direct reduction ironmaking;

(3) Zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components volatilize and enter the dust recovery.

The finally obtained slag contains copper<0.1%, the recovery rate of iron is 96%, the recovery rate of zinc is 95%, the recovery rate of lead is 96%, the recovery rate of indium is 94%, the recovery rate of bismuth is 92%, The gold enrichment rate is 93%, and the silver enrichment rate is 91%.

Example 8

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: Add zinc smelting slag (melting vortex smelting slag obtained at the discharge port) into the blast furnace, add dolomite, red mud, MgO, and copper sulfide concentrate and copper oxide concentrate at the same time, using the preheating temperature Oxygen at 200°C, injecting gas and coke powder 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, through regulation and control Guarantee the two parameters (a) and (b) to obtain the slag after the reaction is completed;

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

(b): The basicity CaO/SiO ₂ ratio of the copper-containing reaction slag is 1.0, both within the required range; the metallic iron content in the slag is 2.3%.

Step 2, separation and recovery using method three:

Keep warm for 5 minutes, the slag settles naturally, and the slag-gold separates to obtain a copper-rich phase, iron-containing silicate mineral phase and iron-rich phase in the middle and upper parts, and simultaneously generates zinc-containing components, lead-containing components, and bismuth-containing components With the indium-containing components, enter the fume to be recycled, the following steps are carried out:

(1) Molten iron-containing silicate mineral phase slag is poured into the smelting device for slag treatment outside the furnace. Specifically, method B in the separation and recovery method one of step S2 is used to return all the slag in the middle and upper parts to the slag containing Copper 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 copper-rich phase in the molten state is sent to the converter or blowing furnace for copper smelting;

(3) Zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components volatilize and enter the dust recovery;

(4) After the iron-rich phase is quenched in water or air-cooled or poured into a heat preservation device for slow cooling, it can be used as raw material for blast furnace ironmaking or direct reduction ironmaking.

The finally obtained slag contains copper<0.1%, the recovery rate of iron is 97%, the recovery rate of zinc is 96%, the recovery rate of lead is 97%, the recovery rate of indium is 93%, the recovery rate of bismuth is 92%, The gold enrichment rate is 91%, and the silver enrichment rate is 90%.

Example 9

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: Add zinc smelting slag (melted blast furnace slag obtained at the discharge port) into the side blowing furnace, add limestone at the same time to form mixed slag, and add copper oxide concentrate and copper-containing materials (copper slag, copper fire Refining slag, copper-containing circuit board); use air with a preheating temperature of 900°C to spray ≤150 μm coke powder, heat the mixed slag to a molten state, form a copper-containing reaction slag, and make the reaction slag mix; Monitor the reaction slag in real time, and ensure the two parameters (a) and (b) at the same time through regulation, and obtain the slag after the reaction is completed;

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

(b): The basicity CaO/ _SiO2 ratio of the copper-containing reaction slag is 1.2, both within the required range; the metallic iron content in the slag is 1.8%.

Step 2, separation and recovery adopts method two:

Hold for 38 minutes, the slag settles naturally, and the slag-gold separates to obtain the iron-containing slag of the copper-rich phase, the iron-containing silicate mineral phase and the iron-rich phase in the middle and upper parts, and simultaneously generates zinc-containing components, lead-containing components, Bismuth-containing components and indium-containing components enter the soot recovery, and the following steps are performed:

(1) Pour the iron-containing slag in the middle and upper part into the smelting device, and use the method C in the separation and recovery method one of step S2 to pour the middle and upper part of the slag into glass ceramics;

(2) The molten copper-rich phase in the lower part is sent to the converter for copper smelting;

(3) Zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components volatilize and enter the dust recovery.

The finally obtained slag contains copper<0.1%, the recovery rate of iron is 95%, the recovery rate of zinc is 97%, the recovery rate of lead is 94%, the recovery rate of indium is 93%, the recovery rate of bismuth is 92%, The gold enrichment rate is 92%, and the silver enrichment rate is 93%.

Example 10

A method for smelting reduction production of zinc smelting slag, comprising the following steps:

Step 1, slag mixing: Add zinc smelting slag (the molten electric furnace slag obtained from the discharge port) into the heat preservation pit, add limestone and Fe at the same time to form a mixed slag, and add copper oxide concentrate at the same time; 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 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 1.4%.

Step 2, separation and recovery using method five:

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

(1) Settling cooling: keep warm for 36 minutes, cool the slag to room temperature, and obtain slow cooling slag; the copper-rich phase settles to the bottom of the reaction device to form a copper-rich lump; the iron-containing silicate mineral phase floats; the copper-rich phase metal lump The slow cooling slag between the silicate minerals is an iron-rich phase, and simultaneously generates zinc-containing components and lead-containing components;

(2) Separation: manually remove the copper-rich lump that settled at the bottom; after the iron-rich phase layer in the middle is directly reduced, magnetic separation separates metallic iron, and the tailings return to the copper system;

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

(4) Zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components enter the dust recovery.

The finally obtained slag contains copper<0.1%, the recovery rate of iron is 98%, the recovery rate of zinc is 96%, the recovery rate of lead is 95%, the recovery rate of indium is 93%, the recovery rate of bismuth is 92%, The gold enrichment rate is 92%, and the silver enrichment rate is 91%.

It should be understood that the above description of the specific embodiments of the present invention is only to illustrate the technical route and characteristics of the present invention, and its purpose is to allow those skilled in the art to understand the content of the present invention and implement it accordingly, but the present invention It is not limited to the specific embodiments described above. All changes or modifications made within the scope of the claims of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. a method for zinc smelting slag smelting reduction production is characterized in that, comprises the following steps: S1. Slag mixing: add zinc smelting slag to the thermal insulation device or smelting reaction device where the slag can flow out, and add calcium-based minerals and additives to heat the slag to a molten state to form a reaction slag containing copper and iron. At the same time, one or more of copper oxide minerals, copper sulfide minerals, and copper-containing materials are added, mixed evenly, and the reaction slag is monitored in real time, and the reaction slag meets the two conditions of a and b at the same time through adjustment and control to obtain the reaction finished slag; Among them, a: adjust the temperature of the reaction slag to be 1100-1450°C; b: control the basicity of reaction slag CaO/SiO ₂ ratio=0.2～2.0; S2. Separation and recovery: The molten slag obtained in step S1 is kept for 5 to 50 minutes, settled and separated to obtain the middle and upper iron-containing silicate mineral phase, the bottom copper-rich phase and the middle and lower iron-rich phase, and simultaneously produce zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components, the gold and silver components migrate and enrich into the copper-rich phase; each phase is recycled. 2. The method for smelting reduction production of zinc smelting slag according to claim 1, characterized in that: in step S1, the control method of condition a is: When the temperature of the reaction slag is less than 1100°C, the temperature of the reaction slag reaches the range of 1100-1450°C through the heating function of the reaction device itself, or by adding fuel or molten zinc smelting slag to the slag; When the temperature of the reaction slag is >1450°C, add one or more of copper-containing materials, zinc smelting slag, metallurgical flux, iron-containing materials, copper oxide minerals, and fluorine-containing materials to the reaction slag to make the reaction The temperature of the slag reaches the range of 1100-1450 °C; In step S1, the regulation method of condition b is: When the basicity CaO/ _SiO2 ratio of the reaction slag is less than 0.2, add one of alkaline materials, basic copper oxide minerals, copper sulfide minerals, copper-containing materials, and basic iron-containing materials to the reaction slag. species or several; When the basicity CaO/ _SiO2 ratio of the reaction slag is greater than 2.0, add one of acidic materials, acidic copper oxide minerals, acidic copper sulfide minerals, acidic iron-containing materials, and acidic gold-silver-containing materials to the reaction slag. species or several. 3. The method for recovering valuable components from zinc smelting slag according to claim 1, characterized in that: the heat preservation device is one or both of a pourable smelting reaction slag tank and a heat preservation pit; The smelting reaction device from which the slag can flow out is a pourable smelting reaction device or a fixed smelting reaction device with a slag port or an iron port at the bottom; The pourable smelting reaction device is one or both of a converter and a smelting reaction slag tank; The fixed smelting reaction device with a slag port or an iron port is a plasma furnace, DC electric arc furnace, AC electric arc furnace, submerged arc furnace, blast furnace, blast furnace, induction furnace, cupola, side-blown molten pool smelting furnace, bottom-blown Melting pool melting furnace, top blowing melting pool melting furnace, reverberatory furnace, Osmelt furnace, Isa furnace, Vanukov melting pool melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing rotary furnace one or several. 4. The method for smelting reduction production of zinc smelting slag according to claim 1, characterized in that: in the step S1, while satisfying the conditions a and b, copper and iron in the slag should be satisfied simultaneously The oxides are reduced to metallic copper and FeO, and the metallic iron content in the slag is <3%. 5. The method for smelting reduction production of zinc smelting slag according to claim 1, characterized in that: said zinc smelting slag is one or both of slag produced by hydrometallurgy and slag produced by pyrometallurgy ; Zinc smelting slag is in a molten state or hot state or cold state. The molten zinc smelting slag is obtained from the slag outlet of the vortex smelting furnace, blast furnace, fuming furnace, and electric furnace. The hot zinc smelting slag is obtained from the outlet of the volatilization kiln, the Obtained from the slag outlet of the tank, or by heating the zinc smelting slag to a molten state; Wherein, the slag produced by the hydrometallurgy is one or more of zinc leaching slag, volatilized kiln slag, copper cadmium slag, ferrite slag, pickling slag, goethite slag, and hematite slag. The slag produced by the zinc pyrometallurgy is one or more of the slags of the vertical tank zinc smelting, vortex smelting, blast furnace slag, fuming furnace slag, and electric furnace slag; After drying and dehydration treatment, vortex smelting slag, blast furnace slag, fuming furnace slag and electric furnace slag are obtained from the slag outlet of the smelting furnace; The material port is obtained; The calcium-based minerals are one or more of lime, limestone, dolomite, carbide slag, red mud, and 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 , P ₂ O ₅ , Fe, Na ₂ O; The copper oxide minerals include one or more of cuprite, cupolite, malachite, azurite, chrysocolla, and gallinite; The copper sulfide minerals include one or more of chalcocite, copper blue, chalcopyrite, bornite, chalcocite, and tetrahedrite. 6. The method for recovering valuable components from zinc smelting slag according to claim 2, characterized in that: the copper-containing material is copper slag, copper beneficiation tailings, crude copper pyro-refining slag, zinc smelting slag , zinc smelting soot and sludge, lead-zinc tailings, lead smelting slag, lead matte, arsenic matte, crude lead pyro-refining slag, lead smelting soot and sludge, lead-acid batteries, copper smelting soot and sludge, One or more of miscellaneous copper, copper-containing garbage, copper-containing circuit boards, tin smelting slag, nickel smelting slag, and tin tailings; The copper slag is one or more of slag produced by matte smelting, slag produced by copper smelting, pyrotechnically depleted slag, copper slag flotation tailings, and wet copper smelting slag; The metallurgical flux is CaO or _SiO2 -containing minerals and slag, preferably one or more of quartz sand, gold and silver-containing quartz sand, red mud, high-calcium red mud after desodiumization, calcium carbide slag, dolomite or limestone. kind; 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 sludge, nickel smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high calcium after desodiumization One or more of red mud, coal fly ash, and sulfuric acid cinder; The nickel smelting slag is one or more of the nickel smelting slag produced by the "matte smelting" process, the depleted slag after blowing by the "copper matte blowing" process, and the nickel sedimentation slag produced by top blowing smelting; The lead smelting slag is fuming furnace slag and lead-containing smelting slag, produced by the reduction process of "ISP lead-zinc blast furnace reduction" or "sinter blast furnace reduction" or "solid high-lead slag reduction" or "liquid high-lead slag reduction process" Lead-containing smelting slag, lead-containing smelting slag is smelted through a fuming furnace to produce lead-containing fuming furnace slag; The steel soot and sludge include blast furnace gas sludge, converter dust sludge, electric furnace sludge, hot/cold rolling sludge, sintering dust, pellet dust, ironworks dust collection, blast furnace gas ash, electric furnace dust, rolling steel oxidation Iron sheet; The fluorine-containing material is one or more of fluorite, CaF ₂ , and fluorine-containing blast furnace slag; The copper-containing materials, iron-containing materials and fluorine-containing materials are all pelletized or powdered materials or granulated; Among them, the particle size of the powdery material is ≤150μm, the particle size of the granular material is 5-25mm, the powdery material is injected in the way of blowing, the granular material is added in the way of blowing or feeding, and the loading gas is preheated argon, One or more of nitrogen, reducing gas, and oxidizing gas, and the preheating temperature is 0-1200°C. 7. The method for smelting reduction production of zinc smelting slag according to claim 2, characterized in that: the alkaline material is lime powder, red mud, high-calcium red mud after desodiumization, calcium carbide slag, dolomite powder or quicklime One or several types of powder; the basic iron-containing materials are basic sintered ore, steel slag, ferroalloy slag, basic iron concentrate, basic pre-reduced pellets, basic metallized pellets, basic blast furnace slag one or more of them; The acidic material is one or more of silica, fly ash, and coal gangue; the acidic iron-containing material is acidic sintered ore, acidic iron concentrate, acidic pre-reduced pellets, acidic metallized pellets , copper slag, lead smelting slag, zinc smelting slag, nickel smelting slag, tin smelting slag, ferroalloy slag and acidic blast furnace slag. 8. according to the method for smelting reduction production of zinc smelting slag described in any one of claims 1-7, it is characterized in that: The separation and recovery in step S2 is processed as follows: Contains the copper-rich phase in the hot or cold state, sent to the converter or blowing furnace for copper smelting, or slowly cooled, broken, and magnetically separated to separate metallic iron and then sent to the converter or blowing furnace for copper smelting, or magnetically separated to separate metallic iron Or directly reduce the metal iron without magnetic separation, and then send the reduced product to the converter or blowing furnace for copper smelting after magnetic separation and separation of the metal iron; The zinc-containing components, lead-containing components, bismuth-containing components and indium-containing components volatilize and enter the dust recovery in the form of oxides; Containing the iron-containing silicate mineral phase and/or the iron-rich phase, the slag treatment is carried out by any one of the following methods A-G: Method A: After water quenching or air cooling, it can be directly used as cement raw material: Method B: Return to reactive mixed slag as hot metallurgical flux: Method C: for pouring glass-ceramics or as slag wool; Method D: keeping the iron-containing silicate mineral phase and/or the iron-containing slag of the iron-rich phase in the smelting reaction device or pouring the slag into the heat preservation device, blowing into the iron-containing slag Preheating oxidizing gas at a temperature of 0-1200°C, and ensuring that the temperature of the silicate slag is >1460°C; when the content of ferrous oxide in the slag is less than 1%, the oxidized slag is obtained; the oxidized slag Direct air cooling or water quenching, used as slag cement, cement regulator, additive in cement production or cement clinker; Method E: For the production of high value-added cement clinker, the method is as follows: E-1. Retain the iron-containing 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 molten steel slag to the slag , lime, limestone, ferroalloy slag, fly ash, alkaline lean iron ore, bauxite, molten blast furnace slag, red mud, high calcium red mud after desodiumization or calcium carbide slag, fully mixed, Obtain slag mixture material; E-2. Blow an oxidizing gas with a preheating temperature of 0 to 1200°C into the slag mixture material, and ensure that the temperature of the slag mixture material is >1460°C; when the content 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-containing slag of the iron-rich phase are used as blast furnace ironmaking raw materials or direct reduction ironmaking raw materials: the iron-containing silicate mineral phase and/or The iron-containing slag of the iron-rich phase is air-cooled, water-quenched or slowly cooled, and 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, and the product of magnetic separation is metallic iron Melting with tailings and electric furnace, the products are molten iron and slag; Or, after pouring the iron-containing silicate mineral phase and/or the iron-rich slag of the iron-rich phase into the heat preservation device, the following method is used for separation: magnetic separation after modification of the slag: into the heat preservation device The slag is blown into the oxidizing gas with a preheating temperature of 0-1200°C, and the slag temperature is guaranteed to be >1250°C to complete the transformation of magnetite in the slag; the oxidized slag is slowly cooled to room temperature and crushed , Magnetic separation, the products are magnetite concentrate and tailings, and the tailings are used as building materials; Method G: ironmaking by smelting reduction of iron-containing slag of the iron-containing silicate mineral phase and/or the iron-rich phase includes the following steps: G-1. Keep the iron-containing 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 the iron-containing slag to the iron-containing slag Iron materials and reducing agents are smelted and reduced, and the reaction slag is monitored in real time, and the following conditions are met at the same time through regulation and control: the temperature of the reaction slag is 1350-1670 °C and the alkalinity CaO/SiO ₂ ratio of the reaction slag=0.6-2.4, Obtain the slag after the reaction is completed; G-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, The following conditions are met at the same time through regulation and control: the temperature of the molten slag after the reaction is 1350-1670°C and the basicity CaO/ _SiO2 ratio of the molten slag after the reaction is 0.6-2.4; G-3. Use one of the following two methods to separate and recover: Method Ⅰ: Pour the reduced mixed slag into the thermal insulation slag tank, slowly cool to room temperature to obtain slow cooling slag; metal iron settles to the bottom of the reaction device to form iron lumps; the metal iron layer in the remaining slow cooling slag, Crushing to a particle size of 20-400 μm, 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 subjected to slag treatment according to one or more of A to E; The molten iron is sent to the converter or electric furnace for steelmaking; Or, the iron-rich phase containing said iron-rich phase can be quenched in water or air-cooled or poured into a heat preservation device for slow cooling or combined with manual sorting and re-selection to obtain it as raw material for blast furnace ironmaking or direct reduction ironmaking raw material or smelting reduction ironmaking raw material or flotation Extract copper raw materials or separate metallic iron by magnetic separation as raw materials for copper smelting or direct reduction iron smelting; during the flotation process, the flotation products are copper-containing concentrates and iron concentrates, and the copper concentrates are returned to the copper smelting system, and the iron concentrates are As a raw material for blast furnace ironmaking or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, the reduction product is separated by magnetic separation to obtain metallic iron and tailings, and the tailings are returned to the copper smelting system; The direct reduction process adopts any one of rotary hearth furnace, tunnel kiln, car bottom furnace, shaft furnace, rotary kiln, and induction furnace as reduction equipment, and utilizes gas-based or coal-based reduction technology, and the gas-based is natural gas and/or Coal gas, the coal base is one or more of anthracite, bituminous coal, lignite, coking coal, coke powder, and coke, the reduction temperature is 900-1400°C, and the alkalinity CaO/SiO ₂ ratio = 0.8-1.5. 9. The method for smelting reduction production of zinc smelting slag according to claim 8, characterized in that: in the step S2, 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; The uniform mixing is natural mixing or stirring mixing, stirring and mixing is one or more of argon stirring, nitrogen stirring, nitrogen-argon mixed gas stirring, reducing gas stirring, oxidizing gas stirring, electromagnetic stirring, mechanical stirring kind. 10. The method for smelting reduction production of zinc smelting slag according to claim 8, characterized in that: said fuel and reducing agent are one or more of solid, liquid or gaseous fuels, and are injected or fed Injection, the injection loading gas is one or more of preheated oxidizing gas, nitrogen or argon, and the preheating temperature is 0-1200°C; The solid fuel and the reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite, and the shape is granular or powdery. The particle size of the granular material is 5-25mm. 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; The oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, and nitrogen-oxygen.