WO2019071789A1

WO2019071789A1 - Method for recovering valuable components from zinc smelting slag

Info

Publication number: WO2019071789A1
Application number: PCT/CN2017/115644
Authority: WO
Inventors: 张力; 张武
Original assignee: 东北大学
Priority date: 2017-10-10
Filing date: 2017-12-12
Publication date: 2019-04-18
Also published as: CN107674985A

Abstract

A method for recovering valuable components from zinc smelting slag. The method comprises the following steps: S1, adding zinc smelting slag to a heat insulating device or a smelting reaction device from which slag may flow out, and adding calcium-based minerals and additives to form mixed slag, heating the mixed slag to a molten state so as to form reaction slag, monitoring the reaction slag in real time, and obtaining a slag after a reaction is complete by means of regulating and controlling the temperature of the reaction slag and the specific value of alkalinity Cao/SiO2; and S2, performing sedimentation separation on the obtained slag to obtain smoke dust containing a ferrous silicate mineral phase, a copper-rich phase and an iron-rich phase and smoke dust containing zinc, lead, bismuth and indium, and migrating and enriching gold and silver components to enter the copper-rich phase; and recovering all the phases. The copper-containing slag (copper-containing slag smaller than 0. 1 wt%) may be lowered. Furthermore, components such as copper, iron, gold, silver, lead, zinc, indium, bismuth, sodium and potassium may be recovered efficiently, and low-copper materials containing iron are obtained. The metal recovery rate is high, the production cost is low, environmental friendliness is achieved, and the economic gains are high.

Description

Method for recovering valuable components from zinc smelting slag

Technical field

The invention belongs to the technical field of comprehensive utilization of resources and slag metallurgy, and particularly relates to a method for recovering valuable components from zinc smelting slag.

Background technique

The zinc smelting process includes two processes of wet zinc smelting and vertical tank zinc smelting. The two processes produce a large amount of zinc smelting slag, wherein the wet zinc smelting produces zinc leaching slag, iron slag residue, pickled iron slag, goethite Slag, hematite slag, etc., vertical tank zinc smelting produces vertical tank zinc slag. The zinc smelting slag contains secondary resources such as copper, iron, zinc, lead, indium, gold and silver, of which the iron content is as high as 50%, far exceeding the recoverable grade of iron ore (recoverable grade, iron content >26wt%). The copper content is as high as 2%, far exceeding the recoverable grade of copper ore (recoverable grade, copper content >0.2wt%), and the zinc content is as high as 25%. At present, zinc smelting slag is treated and recycled by a volatile kiln, a fumigating furnace, a blast furnace, a vortex smelting process, etc., and only some components such as lead, zinc, and silver 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 clean and efficiently use zinc smelting slag to recover valuable components is an urgent problem to be solved.

Summary of the invention

(1) Technical problems to be solved

In order to solve the above problems of the prior art, the present invention provides a method for recovering valuable components from zinc smelting slag, which not only can reduce slag containing copper (slag containing copper <0.1 wt%), but also can realize copper, High-efficiency recovery of iron, gold, silver, lead, zinc, indium, antimony, sodium, potassium and other components, obtaining low-copper iron-containing materials (iron concentrate and pig iron), high metal recovery rate, low production cost and environmental friendliness. High economic returns.

(2) Technical plan

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

A method for recovering valuable components from zinc smelting slag includes the following steps:

S1, slag mixing: adding zinc smelting slag to the smelting reaction device through which the heat preservation device or slag can flow out, and adding calcium minerals and additives to form mixed slag;

The mixed slag is heated to a molten state to form a reaction slag, uniformly mixed, and the reaction slag is monitored in real time, and the reaction slag is simultaneously adjusted to satisfy both conditions a and b, and the slag after completion of the reaction is obtained, or the reaction is completed. The molten slag is poured into the heat preservation device;

Wherein, a: the temperature of the reaction slag is controlled to be 1100 to 1450 ° C;

b: adjusting the alkalinity of the reaction slag CaO / SiO ₂ ratio = 0.15 ~ 1.8;

S2, separation and recovery: the slag obtained in step S1 is kept for 5 to 50 minutes, and the upper and lower iron-containing silicate mineral phases, the bottom copper-rich phase, the middle and lower iron-rich phase, and the zinc-containing component and lead-containing group are obtained by sedimentation and separation. The dust containing the bismuth component and the indium-containing component, the gold and silver components migrate and enrich and enter the copper-rich phase; the phases are recovered;

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

When the temperature of the reaction slag is <1100 ° C, the heating function of the reaction device itself is added, or the fuel and the preheated oxidizing gas are added to the slag to make the temperature of the reaction slag reach the range of 1100 to 1450 ° C;

When the temperature of the reaction slag is >1450 ° C, one or more of the copper-containing material, the zinc smelting slag, the metallurgical flux, the iron-containing material and the fluorine-containing material are added to the reaction slag, so that the temperature of the mixed slag reaches In the range of 1100 to 1450 ° C;

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

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

When the alkalinity CaO/SiO ₂ ratio of the reaction slag is >1.8, an acidic material and/or an acidic iron-containing material is added to the reaction slag.

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

The smelting reaction device through which the slag can flow is a rotatable smelting reaction device or a smelting reaction device with a slag port or an iron port;

The rotatable smelting reaction device is one or two of a converter and a smelting reaction slag pot;

The smelting reaction device with a slag port or an iron port is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola furnace, a side blowing molten pool melting furnace, and a bottom blowing pool. One of a smelting furnace, a top-blowing bath smelting furnace, a reverberatory furnace, an Osmite furnace, an Isa furnace, a Waukekov molten pool smelting furnace, a side blowing rotary kiln, a bottom blowing rotary kiln, and a top blowing rotary kiln 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 simultaneously reduced to metallic copper and FeO, and the metallic iron content in the slag is <3%. . By adding one or both of a reducing agent and a solid carbon-containing iron-containing material, the amount of the reducing agent and/or the solid carbon-containing iron-containing material in the slag is reduced to copper and iron oxide in the slag to metallic copper and The theoretical amount of FeO is 110-140%; the carbon-containing iron-containing materials are steel dust and soot, iron concentrate carbon-containing pre-reduction pellets, iron concentrate carbon-containing metallized pellets, and wet zinc smelting kiln Slag, coke oven dust and soot.

According to the present invention, the zinc smelting slag is one or two of slag produced by wet zinc smelting and slag produced by pyrometallurgical slag; zinc smelting slag is in a molten state or a hot or cold state, and the molten smelting method The zinc slag is obtained from a vortex melting furnace, a blast furnace, a smelting furnace, an electric furnace slag outlet, and the hot zinc smelting slag is obtained from a kiln discharge port of the volatilization kiln, a slag outlet of the vertical tank, or the zinc smelting slag is heated to a molten state;

Wherein, the slag produced by the wet zinc smelting is one or more of zinc leaching slag, volatile kiln residue, copper cadmium slag, iron slag residue, pickled iron slag, goethite slag, and hematite slag. The slag produced by the pyrometallurgical smelting is one or more of a vertical tank zinc slag, a vortex smelting slag, a blast furnace slag, a smelting furnace slag, and an electric furnace slag; and the slag produced by the wet zinc smelting It needs to be dried and dehydrated; vortex smelting furnace slag, blast furnace slag, smelting furnace slag, electric furnace slag are obtained from the smelting furnace slag outlet, the volatile kiln slag is obtained from the volatilization kiln outlet, and the vertical tank smelting slag is from the vertical tank Obtaining the material;

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

The additive is one or more of SiO ₂ , MgO, FeO, Fe ₂ O ₃ , MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O.

According to the present invention, the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead and zinc tailings, lead smelting slag, lead copper, arsenic Bronze, crude lead fire refining slag, lead smelting soot and dust, lead acid battery, copper smelting soot and dust, copper, copper-containing garbage, copper-containing circuit board, tin smelting slag, nickel smelting slag, tin tail One or several of the mines;

The copper slag is one or more of slag produced by smelting and slag, slag generated by "copper smelting", slag depleted by fire, copper slag flotation tail slag, and wet copper slag;

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

The iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon-bearing pre- Reducing pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag, copper slag, lead smelting slag, zinc One or more of smelting slag, tin smelting slag, red mud, high-calcium red mud after de-sodium removal, coal dust ash, sulfuric acid slag;

The nickel smelting slag is one or more of nickel smelting slag produced by the “smelting smelting” process, depleted slag after being blown by the “copper ice nickel blowing” process, and nickel slag slag generated by top blowing smelting;

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

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

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

The copper-containing material, the iron-containing material and the fluorine-containing material are all pellets or powdery materials or granulation; wherein, the granular material has a particle size of ≤150 μm, the granular material has a particle size of 5-25 mm, and the powdery material is sprayed. The method is sprayed into, the granular material is added by spraying or feeding, and the loading gas is one or more of preheated argon gas, nitrogen gas, 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 desodiumification, calcium carbide slag, dolomite powder or quicklime powder; the basic iron-containing material is CaO/SiO ₂ >1 one or more of alkaline sintered ore, steel slag, iron alloy slag, alkaline iron concentrate, alkaline pre-reduction pellet, alkaline metallized pellet, and alkaline blast furnace slag;

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

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

Containing the copper-rich phase in a hot or cold state, sent to a converter or a smelting furnace for copper smelting, or slow cooling and magnetic separation to separate the metal iron, and then sent to a converter or a smelting furnace for copper smelting, or magnetic separation to separate metal iron Or after the separation of the metal iron without magnetic separation, the direct reduction, the reduction product is separated by magnetic separation, and then sent to the converter or the converter to smelt copper;

The zinc-containing component, the lead-containing component, the cerium-containing component and the indium-containing component are volatilized, and are collected into the dust as an oxide;

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

Method A: After water quenching or air cooling, directly used in cement raw materials:

Method B: Return to the reaction mixture slag as a hot metallurgical flux:

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

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

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

E-1, retaining the iron-containing silicate mineral phase and/or the iron-rich phase of the iron-containing slag in the smelting reaction device or pouring the slag into the heat preservation device, and adding the molten steel slag to the slag One or more of lime, limestone, ferroalloy slag, fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, high-calcium red mud or calcium carbide slag after de-sodium, fully mixed, Obtaining a slag mixture;

E-2, blowing an oxidizing gas having a preheating temperature of 0 to 1200 ° C into the slag mixture, and ensuring slag mixing The temperature of the combined material is >1460 ° C; when the content of ferrous oxide is <1%, the slag after oxidation is obtained;

E-3, performing air cooling or water quenching on the oxidized slag to obtain a high value-added cement clinker;

Method F: the iron-containing silicate mineral phase and/or the iron-rich phase iron-containing slag as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: the iron-containing silicate mineral phase and/or After the iron-rich slag of the iron-rich phase is air-cooled, water-quenched or slow-cooled, it is used as a blast furnace ironmaking or direct reduction ironmaking raw material, and after direct reduction, magnetic separation or electric furnace melting is used, and the magnetic separation product is metal iron. With tailings, electric furnace melting, the product is molten iron and slag;

Or, after the iron-containing silicate mineral phase and/or the iron-rich phase iron-containing slag is poured into the heat preservation device, the separation is performed by the following method: magnetic separation after slag modification: into the heat preservation device The slag is blown into an oxidizing gas having a preheating temperature of 0 to 1200 ° C, and the slag temperature is ensured to be >1250 ° C to complete the transformation of the magnetite in the slag; the oxidized slag is slowly cooled to room temperature and broken. , magnetic separation, the product is magnetite concentrate and tailings, tailings as building materials;

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

G-1, retaining the iron-containing silicate mineral phase and/or the iron-rich phase of the iron-containing slag in the smelting reaction device or pouring the slag into the heat preservation device, and adding the iron slag to the slag The iron material and the reducing agent are subjected to smelting reduction, and the reaction slag is monitored in real time, and the following conditions are satisfied by the regulation: the temperature of the reaction slag is 1350 to 1670 ° C, and the alkalinity of the reaction slag is CaO / SiO ₂ ratio = 0.6 to 2.4. Obtaining slag after completion of the reaction;

G-2, smelting and reducing the oxidizing gas after preheating into the slag to form a reduced slag, wherein: the preheating temperature of the oxidizing gas is 0 to 1200 ° C, and during the blowing process, Through regulation, the following conditions are satisfied: the temperature of the slag after the completion of the reaction is 1350 to 1670 ° C, and the alkalinity CaO / SiO ₂ ratio of the slag after the completion of the reaction = 0.6 to 2.4;

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

Method I: pouring the reduced mixed slag into the slag pot, slowly cooling to room temperature to obtain slow cooling slag; metal iron is settled to the bottom of the reaction device to form iron slag; the remaining slow slag contains metal iron layer, Broken to a particle size of 20 to 400 μm, grinding, magnetic separation to separate the remaining metal iron and tailings;

Method II: mixed slag after reduction, sedimentation, slag-gold separation, obtaining molten iron and reduced slag; reducing slag, according to one or several of A to E, slag treatment; molten iron Send to converter or electric furnace steelmaking;

Or, containing the iron-rich phase water quenching or air cooling or pouring into a heat preservation device to slow cooling or by manual sorting and re-election, as a blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material or flotation Copper extraction raw materials or magnetic separation of metal iron for use as raw materials for copper smelting or direct reduction of iron; during flotation, the flotation products are copper-bearing concentrates and iron concentrates, copper concentrates are returned to copper smelting systems, iron concentrates As a blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, the reduction product is magnetically separated and separated, the metal iron and tailings are obtained, and the tailings are returned to the copper smelting system;

The direct reduction process uses any one of a rotary hearth furnace, a tunnel kiln, a car bottom furnace, a shaft furnace, a rotary kiln, and an induction furnace as a reduction device, using a gas-based or coal-based reduction technology, the gas base is natural gas and/or Gas, coal-based is one or several of anthracite, bituminous coal, lignite, coking coal, coke powder, coke, reduction temperature is 900-1400 ° C, alkalinity CaO / SiO ₂ ratio = 0.8 ~ 1.5; The secondary combustion of the slag surface provides heat, and the gas flowing out of the furnace can be used as a heat source for the drying furnace material and the heat preservation device;

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

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

The mixing is uniform for natural mixing or stirring, and the stirring is mixed with argon stirring, nitrogen stirring, nitrogen- One or more of argon gas mixture agitation, reducing gas agitation, oxidizing gas agitation, electromagnetic agitation, and mechanical agitation.

According to the present invention, the fuel and the reducing agent are one or more of a solid, liquid or gaseous fuel, which is injected by spraying or feeding, and the blowing and charging gas is a preheated oxidizing gas, One or more of nitrogen or argon, the preheating temperature is 0 to 1200 ° C;

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

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

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

(1) The method for recovering valuable components from zinc smelting slag of the present invention can treat hot slag, fully utilize physical heat resources of molten zinc smelting slag and hot metallurgical flux, and can treat cold slag. By adjusting the physical and chemical properties of the slag and utilizing the physical and chemical properties of the copper-containing slag, the slag metallurgy process is realized; and the current slag accumulation, environmental pollution problems, and heavy metal element pollution problems are solved.

(2) Metallurgical reaction of slag in slag, adding calcium-based minerals to fully release iron oxides, forming free iron oxides, achieving growth and sedimentation of iron-rich phase, and iron-containing components in slag Aggregation, growth and sedimentation, the iron-rich phase includes a variety of metal iron, FeO phase, and fayalite phase, as a raw material for blast furnace ironmaking or direct reduction or smelting reduction ironmaking; at the same time, calcium minerals effectively modify viscosity and lower viscosity It helps to settle the copper-containing component.

(3) The copper component and the gold and silver components in the mixed slag migrate and concentrate in the copper-rich phase, and the copper-rich phase contains copper, white copper, matte phase, and iron-containing components, and realizes Grow and settle, or part of the copper component enters the iron-rich phase.

(4) The zinc-containing component, the lead-containing component, the cerium-containing component and the indium-containing component in the mixed slag are separately transported, enriched in the soot, and recovered; part of the sodium-containing component and the potassium-containing component Volatilizes into the soot.

(5) Separating and accumulating copper-rich phase and iron-rich phase in different parts to achieve high-efficiency recovery of copper and iron components in slag. The slag contains copper <0.1wt%, which can process solid copper-containing materials and achieve high resource efficiency. Comprehensive utilization.

(6) The slag can be tempered and used as a cement raw material or building material or as a substitute for crushed stone as aggregate and road material.

(7) The method of the invention adds an additive, on the one hand, the viscosity can be lowered, on the other hand, the melting point can be lowered, and at a certain temperature (1100-1450 ° C), the copper-rich phase is precipitated, and the iron-rich obtained after sedimentation and separation is obtained. The phase is a low copper iron-rich phase and an iron-containing silicate phase, wherein the iron-rich phase and the iron-containing silicate phase have a copper content of less than 0.1%, and the iron concentrate can be obtained by direct reduction or smelting reduction of iron. iron.

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

(3) Beneficial effects

Advantageous effects of the invention:

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

(2) The raw material of the present invention may be liquid molten zinc smelting slag (≥1100 ° C) flowing out from the slag outlet, which contains abundant thermal energy resources, has the characteristics of high temperature and high heat, and fully utilizes the slag physical heat resource. Efficient energy conservation; 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 adjusts the physicochemical properties of the slag, injects a gas, controls the oxygen potential, and causes the copper component in the slag, The gold and silver components migrate and enrich to the copper-rich phase to achieve aggregation, growth and sedimentation.

(4) In the method of the invention, adding cold material and molten zinc smelting slag avoids excessive slag temperature and improves the life of the heat preservation device; adding cold material and molten zinc smelting slag improves the processing amount of the raw material, and can not only process the liquid state Slag, and can handle a small amount of cold materials, the material adaptability is strong; the addition of cold materials to achieve the chemical heat released by the reaction and the efficient use of slag physical heat.

(5) The invention adjusts the physicochemical properties of the slag, controls the oxygen potential, and simultaneously adds the calcium-based minerals, and the iron component is enriched in the iron-rich phase to achieve aggregation, growth and sedimentation; zinc component and lead group in the slag The fraction, the bismuth component, the sodium component, the potassium component and the indium component are volatilized, and are taken into the soot as an oxide for recovery.

(6) In the natural cooling process of the method of the invention, the addition of the additive, the copper component and the gold and silver component in the slag are enriched in the copper-rich phase, and the aggregation, growth and sedimentation are realized, and the iron component in the slag is enriched in Iron-rich phase, and achieve aggregation, growth and settlement, the slag-containing insulation device is placed on a rotating or centrifugal platform to accelerate the accumulation, growth and settlement of the copper-rich phase and the iron-rich phase; Accelerate the growth and settlement of the copper-rich phase and the iron-rich phase, and shorten the settling time.

(7) The method of the invention adopts the methods of manual sorting, magnetic separation, re-election or slag-gold separation to respectively perform the silicate mineral phase, the iron-rich phase and the copper-rich phase distributed in the middle upper part, the middle lower part and the bottom part. Separation, high efficiency recovery of copper component, gold and silver component, iron component, indium component, antimony component, sodium component, potassium component, etc. in slag, copper content of slag <0.1wt%; The phase and iron-rich phase settle in the middle and lower parts. Therefore, the amount of slag to be sorted is small, the slag is quenched and tempered, the mineral grindability is increased, and the cost of grinding, magnetic separation and re-election is low; the subsequent separation process uses physical beneficiation. (Magnetic separation or re-election), the separated medium is water, and there is no environmental pollution during the separation process. The slag treatment process has the characteristics of short process, simple operation, high recovery rate, high efficiency, cleanliness and environmental protection; tailings as Cement raw materials, building materials, instead of crushed stone as aggregates, road materials.

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

(10) The method of the invention has short process flow, strong operability and low production cost.

(11) The invention fully utilizes the slag physical heat resource and the hot metallurgical flux, and can also treat the cold slag, realizes slag metallurgy, and the copper component and the gold and silver component in the slag are concentrated in the copper-rich phase. And to achieve aggregation, growth and sedimentation, iron components are enriched in the iron-rich phase, to achieve aggregation, growth and sedimentation, separation of copper-rich phase and iron-rich phase in different parts, copper-rich phase and iron-rich phase sedimentation Middle and lower portions, wherein the copper-rich phase comprises a plurality of copper phases, white ice copper, amber phase, and iron-containing components, and the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phases to realize slag High-efficiency recovery of copper component, iron component, gold and silver component; can process solid copper-containing materials, this method has short process flow, high metal recovery rate, low production cost, strong material adaptability, large processing capacity and environmental friendliness High economic returns can solve the problem of efficient recycling of metallurgical resources and thermal energy.

Detailed ways

The present invention provides a method for recovering valuable components from zinc smelting slag, which comprises the following steps:

Step S1, slag mixing:

The zinc smelting slag is added to the smelting reaction device through which the heat preservation device or the slag can flow out, and the calcium-based mineral and the additive are added to form a mixed slag;

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

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

(b) the alkalinity of the reaction slag CaO / SiO ₂ ratio = 0.15 ~ 1.8;

The control method is:

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

When the temperature of the reaction slag < lower limit of the set temperature range is 1100 ° C, the heating function of the reaction device itself is added, or the fuel and the preheated oxidizing gas are added to the slag, and when the fuel is injected, the preheating is simultaneously injected. An oxidizing gas such that the temperature of the reaction slag reaches a set temperature range;

When the temperature of the reaction slag containing copper and iron > the upper limit of the set temperature range is 1450 ° C, one of the copper-containing material, the zinc smelting slag, the metallurgical flux, the iron-containing material or the fluorine-containing material is added to the copper-containing reaction slag. Kind or several, so that the temperature of the mixed slag reaches a set temperature range;

Corresponding to (b):

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

When the ratio of alkalinity CaO/SiO ₂ in the reaction slag containing copper and iron is >1.8, an acidic material and/or an acidic iron-containing material is added to the reaction slag;

Step S2, separation and recovery:

After the reaction is completed, the slag is kept for 5 to 50 minutes, settled, and slag-gold is separated to obtain a molten state in the bottom molten state, a molten iron phase in the middle and lower portions, and a molten iron-containing silicate mineral phase in the upper middle portion, and simultaneously The zinc-containing component, the lead-containing component, the indium-containing component and the cerium-containing component enter 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 completion of the reaction is subjected to the following steps:

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

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

(3) The zinc-containing component, the lead-containing component, the indium-containing component, the cerium-containing component, the sodium-containing component, and the potassium-containing component are volatilized, and are collected into the dust as an oxide;

(4) The iron-rich phase is obtained by water quenching or air cooling or pouring into a heat preservation device, or by manual sorting and re-election, as a raw material for blast furnace ironmaking or direct reduction of ironmaking raw materials or smelting reduction of ironmaking raw materials or flotation Copper raw material or magnetic separation to separate metal iron as raw material for copper smelting or direct reduction ironmaking; flotation products are copper-containing concentrates and iron concentrates, copper concentrates are returned to copper smelting system, iron concentrates are used as blast furnace ironmaking materials or Directly reducing ironmaking raw materials or smelting reduction ironmaking raw materials; wherein, in the direct reduction process, after reduction and magnetic separation of the reduction products, metal iron and tailings are obtained, and the tailings are returned to the copper smelting system;

The direct reduction process uses a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary kiln or an induction furnace as a reduction device. The gas-based or coal-based reduction technology is used to reduce the gas base to natural gas and/or gas, and the coal base is reduced to One or more of anthracite, bituminous coal, lignite, coking coal, coke breeze or coke, the reduction temperature is 900-1400 ° C, and the alkalinity CaO/SiO ₂ ratio is 0.8-1.5.

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

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

The iron-containing silicate mineral phase is directly quenched or air-cooled as a cement raw material or further processed into a high value-added cement raw material;

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

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

Method C: pouring a glass ceramic with a silicate mineral phase or as a slag wool;

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

(1) The iron-containing silicate slag remains in the smelting reaction device or the slag is poured into the heat-preserving device, and the pre-heated oxidizing gas is blown into the slag, and when the slag oxidized ferrous content is <1%, Complete oxidation of the slag to obtain oxidized slag, wherein the preheating temperature of the oxidizing gas is 0 to 1200 ° C; and throughout the process, ensure (c) silicate slag temperature > 1460 ° C;

Corresponding to (c) the control method adopted:

When the temperature of the iron-containing silicate slag is <1460 ° C, the preheated fuel and the preheated oxidizing gas are injected, the heat is burned, the heat is supplemented, or the device is heated by itself, so that the temperature of the silicate slag is >1460 ° C;

(2) The slag after oxidation is directly air-cooled or water-quenched, used as slag cement, cement conditioner, additive in cement production or cement clinker;

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

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

(2) blowing a preheated oxidizing gas into the slag mixture, and when the ferrous oxide content is less than 1%, the oxidation of the slag is completed to obtain the oxidized slag, wherein the preheating temperature of the oxidizing gas is 0 ~ 1200 ° C; and throughout the process, to ensure (d) slag mixture temperature > 1460 ° C; temperature control method and method D step (1) silicate slag temperature control method;

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

Method F: slag containing iron silicate mineral phase as blast furnace ironmaking raw material or direct reduction ironmaking raw material: slag containing iron silicate mineral phase is air-cooled, water quenched or slowly cooled, and used as blast furnace ironmaking Or directly reduce the ironmaking raw material, after direct reduction, using magnetic separation or electric furnace melting, the magnetic separation product is metal iron and tailings, electric furnace melting, the product is molten iron and molten slag;

Or, after pouring the slag containing the iron silicate mineral phase into the heat preservation device, the separation is performed by the following method: magnetic separation after the slag modification: the slag in the heat preservation device is blown into the preheating of 0 to 1200 ° C Hot oxidizing gas, and ensure that its slag temperature is >1250 °C, complete the transformation of magnetite in the slag; slowly cool the slag after oxidation to room temperature, crush and magnetic separation, the product is magnetite concentrate With tailings, tailings as building materials.

Method G: Slag smelting reduction ironmaking of iron-containing silicate mineral phase:

G-1. Retaining the slag containing the iron silicate mineral phase in the smelting reaction device or pouring the slag into the heat preservation device, or adding the iron-containing material, adding a reducing agent to the slag, performing smelting reduction, and monitoring the reaction in real time. The slag is obtained by controlling and simultaneously ensuring the following two parameters (a1) and (b1), and obtaining the slag after completion of the reaction;

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

(b1) The alkalinity of the reaction slag CaO / SiO ₂ ratio = 0.6 ~ 2.4;

The control method is:

Correspondence (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 heating function of the reaction device itself is added, or the fuel and the preheated oxidizing gas are added to the slag to make the temperature of the reaction slag reach the set temperature range;

When the temperature of the reaction slag is lower than the upper limit of the set temperature range, one or more of a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag to bring the temperature of the reaction slag to a set temperature range. ;

Corresponding (b1):

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

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

G-2, smelting and reducing the oxidizing gas after preheating into the slag to form a reduced slag, wherein: the preheating temperature of the oxidizing gas is 0 to 1200 ° C, and during the blowing process, Two parameters (a2) and (b2) are guaranteed by regulation:

(a2) the temperature of the slag after the completion of the reaction is 1350 ~ 1670 ° C;

(b2) the alkalinity CaO / SiO ₂ ratio of the slag after the completion of the reaction = 0.6 ~ 2.4;

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

G-3, separation and recovery:

Use one of the following methods:

Method I: Perform the following steps:

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

(b) Separation: metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the metal ferrous layer in the remaining slow slag is crushed to a particle size of 20 to 400 μm, and the remaining metal is separated by magnetic separation. Iron and tailings;

(c) recycling of tailings, used as cement raw materials, building materials, instead of crushed stone as aggregate, road material or phosphate fertilizer;

Method II: Perform the following steps:

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

(b) the slag after the reduction, and the slag treatment outside the furnace is specifically carried out by using one or more of the methods A to E in the separation and recovery method 1 of the step S2 to carry out the slag treatment outside the furnace;

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

(d) Part of the zinc-containing component, the lead-containing component and the indium-containing component volatilize, and enter the soot recovery in the form of an oxide.

(e) part of the indium component, the strontium component, the sodium component, and the potassium component are volatilized into the dust to be recovered;

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

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

(1) obtaining the molten iron-rich phase and the iron-containing silicate mineral phase, and performing slag treatment by one or more of the methods A to G described in the first method;

(2) molten copper-rich phase, sent to converter copper or bake furnace copper or as a raw material for copper, cobalt and nickel separation, or crushed magnetic separation of metal iron and then sent to converter or blowing furnace copper, or Magnetic separation of metal iron or separation of metal iron without magnetic separation, direct reduction, reduction products after magnetic separation of metal iron, and then sent to converter or blowing furnace copper;

(3) part of the zinc-containing component, the lead-containing component, the indium-containing component and the cerium-containing component are volatilized, and the oxide is recycled into the dust;

(4) Part of the sodium component and potassium component volatilize into the soot.

Method 3: When the slag rotatable converter and the reaction slag tank are used, the slag after the reaction is completed is carried out as follows:

(1) obtaining a molten iron-containing silicate mineral phase, which is subjected to slag treatment by one or more of the methods A to G described in the first method;

(2) The iron-rich phase treatment method is the same as step (4) in the first method;

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

(4) part of the zinc-containing component, the lead-containing component, the indium-containing component and the cerium-containing component are volatilized, and the oxide is recycled into the dust;

(5) Part of the sodium component and potassium component volatilize into the soot.

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

(1) obtaining a molten iron-containing silicate mineral phase and an iron-rich phase, and performing slag treatment by one or more of the methods A to G described in the first method;

(2) molten copper-rich phase, sent to converter or blowing furnace for copper smelting, or slow cooling, crushed magnetic separation of metal iron and then sent to converter or blowing furnace for copper smelting, or magnetic separation of metal iron or not After separation of the metal iron by magnetic separation, the reduction product is directly separated by magnetic separation, and then sent to a converter or a blowing furnace for copper smelting;

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

(1) Settlement cooling: the slag after the completion of the reaction is slowly cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to the bottom of the reaction device to form a copper-rich bismuth; the iron-containing silicate mineral phase floats; the copper-rich phase metal The slow cooling slag between the strontium and the iron-containing silicate mineral is an iron-rich phase, and simultaneously forms a zinc-containing component and a lead-containing component; the gold-silver component migrates to the copper-rich phase;

(2) Separation: manually take out the copper-rich bismuth deposited at the bottom, magnetically separate the metal iron and then send it to the converter or the smelting furnace for copper smelting, or separate the metal iron by crushing and then send it to the converter or the smelting furnace for copper smelting. , or magnetic separation of metal iron or magnetic separation without magnetic separation, direct reduction, reduction products after magnetic separation of metal iron, and then sent to the converter or blowing furnace copper; the middle and lower iron-rich phase layer as The blast furnace ironmaking raw material or the direct reduction ironmaking raw material or the smelting reduction ironmaking raw material or the flotation copper extraction raw material or the magnetic separation and separation of the metal iron is used as a raw material for copper smelting or direct reduction; in the flotation process, the flotation product is copper-containing Concentrate and iron concentrate, copper concentrate returned to copper smelting system, iron concentrate as blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, the reduction product is magnetically separated after separation , obtaining metal iron and tailings, and tailings returning to the copper smelting system;

The direct reduction process uses a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary kiln or an induction furnace as a reduction device. The gas-based or coal-based reduction technology is used to reduce the gas base to natural gas and/or gas, and the coal base is reduced to One or more of anthracite, bituminous coal, lignite, coking coal, coke breeze or coke, the reduction temperature is 900-1400 ° C, the alkalinity CaO / SiO ₂ ratio = 0.8 ~ 1.5;

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

In the steps S1 and S2, the zinc smelting slag is one or two of slag produced by wet zinc smelting and slag produced by pyrometallurgical slag, wherein the slag produced by the wet zinc smelting is zinc leaching residue and volatilized One or more of kiln residue, iron slag residue, pickled iron slag, goethite slag, hematite slag, slag produced by pyrometallurgical smelting is vertical tank zinc slag, vortex smelting slag, blast furnace One or more of slag, smelting furnace slag, and electric furnace slag.

The zinc smelting slag is in a molten state, a hot state or a cold state, wherein: the wet zinc slag is subjected to drying and dehydration treatment, and the vortex melting furnace slag, the blast furnace slag, the fuming furnace slag, and the electric furnace slag are obtained from the smelting furnace slag opening. The volatile kiln slag is obtained from the outlet of the volatilization kiln, and the zinc slag of the vertical tank is obtained from the slag outlet of the vertical tank, or the zinc smelting slag is heated to the molten state. state.

In the steps S1 and S2, the smelting reaction device through which the slag can flow out is a rotatable smelting reaction device or a smelting reaction device with a slag port or an iron port. among them:

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

The rotatable smelting reaction device is a converter and a smelting reaction slag pot.

The smelting reaction device with the slag port or the iron slag flowing out is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola, and a side blowing molten pool melting furnace. Bottom blowing pool melting furnace, top blowing molten pool melting furnace, reverberatory furnace, Osmet furnace, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing back Converter.

In the step S1, the calcium-based mineral is specifically one or more of lime, limestone, dolomite, calcium carbide slag, red mud or high-calcium red mud after de-sodium removal.

In the step S1, when the two parameters (a) and (b) are ensured by the regulation, the metal iron content in the slag is determined by ensuring that the copper and iron oxides in the slag are reduced to metallic copper and FeO. 3%. By adding one or both of a reducing agent and a solid carbon-containing iron-containing material, the amount of the reducing agent and/or the solid carbon-containing iron-containing material in the slag is reduced to copper and iron oxide in the slag to metallic copper and The theoretical amount of FeO is 110-140%; the carbon-containing iron-containing materials are steel dust and soot, iron concentrate carbon-containing pre-reduction pellets, iron concentrate carbon-containing metallized pellets, and wet zinc smelting kiln Slag, coke oven dust and soot.

In the steps S1 and S2, the fuel and the reducing agent are one or more of a solid, a liquid or a gas, which are injected by spraying or feeding, and the loading gas is a preheated oxidizing gas. One or more of nitrogen, argon, preheating temperature is 0-1200 ° C, solid fuel and reducing agent is one or more of coal powder, fly ash, coke powder, coke, bituminous coal or anthracite The shape is granular or powdery, the granular material has a particle size of 5 to 25 μm, the powdery material has a particle size of ≤150 μm, the liquid fuel is heavy oil, and the gaseous fuel is one or both of gas and/or natural gas.

In the steps S1 and S2, the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead and zinc tailings, lead smelting slag, lead ice Copper, arsenic matte, crude lead fire refining slag, lead smelting soot and dust, lead acid battery, copper smelting soot and dust, copper, copper-containing garbage, copper-containing circuit board, tin smelting slag, nickel smelting slag One or several of tin tailings.

Zinc smelting slag is zinc smelting slag produced by wet zinc smelting and pyrometallurgical smelting, including leaching slag, iron slag, copper cadmium slag, goethite slag, hematite slag, volatile kiln slag, vertical tank smelting slag , smelting furnace slag, electric furnace zinc slag.

The copper slag is one or more of slag produced by "smelting smelting", slag generated by "copper blasting", igniting furnace slag, copper slag flotation tailings, and wet copper slag.

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

The nickel smelting slag is one or more of the nickel smelting slag produced by the “smelting smelting” process, the depleted slag after the “copper ice nickel blowing” process, and the nickel slag slag produced by the top blowing smelting.

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

The iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon pre-reduction ball Group, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, sodium removal after high-calcium red mud One or several of coal powder ash and sulfuric acid slag.

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

The wet zinc slag and dust must be dehydrated and dried.

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

Among the above raw materials, zinc smelting slag and soot, lead smelting slag and soot contain indium, antimony, lead, silver and zinc; red mud contains sodium and potassium, and steel soot and dust contain indium, antimony, silver and sodium. Potassium, the above materials all have iron; lead smelting slag and zinc smelting slag contain copper, copper soot and dust contain indium and antimony, in the method of the invention, indium, antimony, sodium, potassium, zinc, lead will be oxide The form enters the soot and is 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 material, the iron-containing material and the fluorine-containing material are pellets or powdery materials or granulation; wherein the granular material has a particle size of 5 to 25 μm, and the granular material has a particle size of ≤ 150μm, the granular material is sprayed by injection, and the loading gas is one or more of preheated argon gas, nitrogen gas, reducing gas (gas and/or natural gas), and oxidizing gas, and the preheating temperature is 0 to 1200 ° C, the blowing method is one or several types in which a refractory spray gun is inserted into the slag or placed in the upper portion or the side or bottom of the reaction slag.

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

In the steps S1 and S2, during the slag reaction, the copper component and the gold and silver components in the slag are enriched in the copper-rich phase, and aggregation, growth and sedimentation are achieved, and the iron component is enriched in iron-rich. The phase, the aggregation, the growth and the sedimentation are realized, and the zinc component, the lead component, the indium component and the strontium component in the slag respectively enter the soot and are recovered in the form of oxide;

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

When the temperature of the mixed slag is > the upper limit of the set temperature, one or more of zinc smelting slag, copper-containing material, iron-containing material, metallurgical flux or fluorine-containing material are added, in order to avoid excessive temperature and protect the refractory material. Another effect of adding fluorine-containing materials is to lower the viscosity, accelerate the copper-rich phase in the slag, and accumulate, grow and settle the iron-rich phase, which is beneficial to the silicate floating.

In the steps S1 and S2, when the alkalinity is adjusted, the alkaline material is one or more of lime powder, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite powder or quicklime powder; The alkaline iron-containing material is a CaO/SiO ₂ >1 iron-containing material. The alkaline iron-containing material is one or more of an alkaline sintered ore, a steel slag, an iron alloy slag, an alkaline iron concentrate, an alkaline pre-reduction pellet or an alkali metallized pellet, and an alkaline blast furnace slag.

In the steps S1 and S2, when the alkalinity is adjusted, the acidic material is one or more of silica, fly ash and coal gangue; the acidic iron-containing material is CaO/SiO ₂ ≤1. Iron-containing material. The acidic iron-containing material is acid sinter, acid iron concentrate, acid pre-reduction pellet, acid metallized pellet, copper slag, lead smelting slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag One or several of acidic blast furnace slag.

In the step S1, the two parameters of (a) and (b) are ensured, and the slag is thoroughly mixed, and the mixing mode is natural mixing or stirring mixing, and the stirring mode is one of the following modes: argon stirring, One or more of nitrogen agitation, nitrogen-argon mixed gas agitation, reducing gas agitation, oxidizing gas, electromagnetic stirring, and mechanical agitation.

In the steps S1 and S2, the copper-rich phase and the iron-rich phase in the slag are aggregated, grown and settled, which is favorable for the silicate to float, wherein the copper-rich phase includes copper, white ice copper, matte phase, and A plurality of iron components, or a part of the copper component, enters the iron-rich phase, and the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phase, and is used as a raw material for blast furnace ironmaking or direct reduction or smelting reduction ironmaking.

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 several of the slag inserted into the slag by the refractory spray gun or placed in the upper part or the side or bottom of the reaction slag.

In the step S2, the direct reduction process uses a rotary hearth furnace, a tunnel kiln, a car bottom furnace, a shaft furnace, a rotary kiln, an induction furnace as a reduction device, and uses a gas-based or coal-based reduction technology, and the gas base is natural gas and/or The gas and coal are reduced 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 is 0.8-1.5.

In the step S2, the cooling mode is natural cooling or rotary cooling or centrifugal cooling, and the sedimentation mode is natural sedimentation or rotary sedimentation or centrifugal sedimentation.

In the step S2, the specific operation of the rotation and the centrifugal cooling is: the device containing the slag after the reaction is completed is placed on the rotating platform, and is rotated according to a certain speed, and the rotation speed depends on the quality of the slag and the height or depth of the heat preservation device. The rotation time depends on the slag quality and the slag solidification condition; the device containing the slag after the completion of the reaction is placed on the rotating platform for the purpose of accelerating the copper-rich phase, the iron-rich phase gathering, growing up and Settling is beneficial to the silicate (phosphorus-rich phase) floating, shortening the settling time, improving the sedimentation effect and improving production efficiency.

In the step S2, in the slag cooling process after the completion of the reaction, most of the copper-rich phase settles in the middle and lower portions due to the difference in density and the mineral size, and the iron-rich phase settles in the middle and upper portions.

In the step S2, the copper component and the gold and silver component in the slag after the reaction is completed to migrate and enrich in the copper-rich phase, and the growth and sedimentation are realized; the iron components in the mixed slag continue to migrate and become rich respectively. It is concentrated in the iron-rich phase and achieves growth and settlement.

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

By using the method of the invention, in the finally obtained iron-rich phase and slag containing iron silicate mineral phase, the slag contains copper ≤ 0.1%, the iron recovery rate is ≥ 95%, and the zinc recovery rate is ≥ 96%, lead The recovery rate is ≥96%, the recovery rate of indium is ≥92%, the gold enrichment rate is ≥90%, the silver enrichment rate is ≥90%, the nickel enrichment rate is ≥93%, and the cobalt is rich. The collection rate is ≥95%, the recovery rate of strontium is ≥92%, the recovery rate of sodium is ≥95%, and the recovery rate of potassium is ≥95%.

The copper content of the slag refers to the slag phase after the copper-rich phase separation, specifically the copper content in the iron-rich phase and the iron-containing silicate mineral phase, and the nickel and cobalt enrichment ratio refers to the 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. The enrichment ratio of gold and silver refers to the percentage of gold and silver in the copper-rich phase as a percentage of the total amount of gold and silver in the raw material.

For a better explanation of the present invention, the present invention will be described in detail by the following examples. Wherein, the treatment methods and raw materials used in the following examples are not specifically indicated, and the conventional techniques in the art can be employed. Unless otherwise stated, the percentages used in the present invention are all by weight.

Example 1

Step 1, slag mixing:

The cold zinc smelting slag (zinc leaching slag and volatile kiln slag) is added to the DC arc furnace, and lime, and SiO ₂ , MgO, and Al ₂ O _{3 are added} to form a mixed slag; the mixed slag is heated to a molten state to form The copper-containing reaction slag is used to realize the natural mixing of the reaction slag; the reaction slag is monitored in real time, and the two parameters of (a) and (b) are simultaneously controlled to obtain the slag after the completion of the reaction;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1660 ° C, and the refractory spray gun is inserted into the reaction slag, and the nitrogen gas is used as the loading gas, and the copper slag, the copper-containing soot and the copper mixed with the powdery particle size ≤150 μm are sprayed at normal temperature. And copper-containing garbage and copper-containing circuit boards, at the same time adding blast furnace gas mud, electric furnace dust, converter dust, ordinary iron concentrate, ordinary iron concentrate direct reduced iron and blast furnace gas ash, so that the temperature is reduced to 1350 ° C;

(b): the alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 1.8, and a mixture of silica, fly ash and coal gangue is added to the reaction slag to reduce the alkalinity ratio of the copper-containing reaction slag to 1.7; The metal iron content in the slag is 0.7%.

Step 2, separation and recovery method 1:

After 10 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and at the same time, a zinc-containing component, a lead-containing component, and a cerium-containing component are formed. The component and the indium-containing component enter the soot recovery, and the following steps are performed:

(1) molten iron-containing silicate mineral phase, subjected to slag treatment outside the furnace, using the above method F, after the iron-containing silicate slag is air-cooled, used as a direct reduction ironmaking raw material, in the direct reduction process, using a slewing As a reduction equipment, the kiln uses gas-based reduction technology. The gas-based reducing agent is natural gas and gas. The reduction temperature is 900 ° C, the alkalinity CaO / SiO ₂ ratio is 0.8, and the electric furnace melting temperature is 1550 ° C after reduction. The product is metal. Hot metal and slag;

(2) molten copper-rich phase, sent to converter 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) The zinc-containing component, the lead-containing component, the cerium-containing component, the indium-containing component, the sodium-containing component and the potassium-containing component are volatilized into the dust to be recovered.

The finally obtained slag contains copper <0.1%, zinc recovery rate is 96%, lead recovery rate is 97%, iron recovery rate is 98%, indium recovery rate is 92%, hydrazine recovery rate is 92%, gold rich The set rate was 91%, the silver enrichment rate was 92%, the sodium recovery rate was 96%, and the potassium recovery rate was 95%.

Example 2

Step 1, slag mixing:

The cold zinc smelting slag (zinc leaching slag) is added to the pourable smelting reaction slag, and limestone, dolomite, red mud and FeO and Fe ₂ O _{3 are added} to form mixed slag; the preheating temperature is 800 ° C Oxygen-enriched air, natural gas, 20mm anthracite and coke particles are sprayed, and the mixed slag is heated to a molten state to form a copper-containing reaction slag; the reaction slag is monitored in real time, and both (a) and (b) are ensured through regulation. Parameters to obtain the slag after the completion of the reaction;

Corresponding to (a) copper-containing reaction slag temperature is 1520 °C, using refractory spray gun to insert into the reaction slag, using argon as carrier gas, spraying normal temperature powder particle size ≤150μm copper slag, copper-containing soot, copper, steel sintering Dust, sintered pellet dust, iron plant dust, ordinary iron concentrate direct reduced iron, so that the temperature is reduced to 1440 ° C;

(b) copper-containing reaction slag basicity CaO / SiO ₂ ratio of 2.4, adding acidic iron concentrate, acidic pre-reduction pellets, lead-containing smelting slag, lead-containing smelting furnace slag mixture to the reaction slag, including The copper reaction slag basicity ratio decreased to 1.6; the slag has a metallic iron content of 2.7%.

Step 2, separation and recovery method 2:

After 50 minutes of heat preservation, the slag after the reaction is completed and rotated, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and at the same time, a zinc-containing component, a lead-containing component, and a cerium-containing component are formed. The component and the indium-containing component enter the soot recovery, and the following steps are performed:

(1) Melting the iron-containing silicate mineral phase and the iron-rich phase, using the method G to carry out the slag treatment, and the iron-silicate slag smelting and reducing the iron-making, the specific steps are as follows:

(1-1) The above iron-containing slag is poured into a pourable converter, and an anthracite coal and bituminous coal having a particle size of 20 mm are added to the slag for smelting reduction, and the reaction slag is monitored in real time, and the following (a) reaction melting is ensured by regulation. The temperature of the slag is 1350 to 1670 ° C, and (b) the ratio of the alkalinity CaO / SiO _{2 of the} reaction slag = 0.6 to 2.4, and the slag after the completion of the reaction is obtained;

Corresponding to (a): the temperature of the reaction slag is 1400 ° C, in the temperature range;

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

(1-2) Spraying an oxidizing gas (oxygen-enriched air) preheated at 200 ° C into the slag to perform smelting reduction to form a mixed slag after reduction, and ensuring (a) during the blowing process The reaction slag has a temperature of 1350 to 1670 ° C, and (b) the reaction slag has a basicity CaO/SiO ₂ ratio of 0.6 to 2.4;

(1-3) Separation and recovery:

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

(b) the slag after reduction is processed into a high value-added cement raw material by the method A in the method of the step S2;

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

(d) the strontium-containing component, the sodium-containing component, and the potassium-containing component are recycled into the soot;

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

(3) The zinc-containing component, the lead-containing component, the cerium-containing component, the indium-containing component, the sodium-containing component and the potassium-containing component are volatilized into the dust to be recovered.

The final copper content is <0.1%, the zinc recovery rate is 99%, the lead recovery rate is 97%, the iron recovery rate is 98%, the indium recovery rate is 95%, the ruthenium recovery rate is 96%, and the gold is enriched. The rate was 91%, the silver enrichment rate was 93%, the sodium recovery rate was 96%, and the potassium recovery rate was 96%.

Example 3

Step 1, slag mixing:

The zinc smelting slag (the volatile kiln residue obtained from the outlet of the volatilization kiln) is added to the DC arc furnace, and the limestone and the decalcified high calcium red mud are added to form a mixed slag; the oxygen is sprayed at a preheating temperature of 900 ° C. Blowing particle size of 20mm anthracite, coke and pulverized coal, heating the mixed slag to a molten state, forming a copper-containing reaction slag, mechanically stirring and mixing; monitoring the reaction slag in real time, and ensuring both (a) and (b) through regulation Parameters to obtain the slag after the completion of the reaction;

Corresponding to (a): the temperature of the copper-containing reaction slag is 1685 ° C, adding acid metallized pellets, copper smelting slag and copper-containing blowing slag to the reaction slag, and adding copper-containing soot, lead-containing slag, ordinary iron Concentrate pellets, rolled iron oxide phosphorus and ordinary iron concentrates containing carbon pre-reduction pellets, reducing the temperature to 1420 ° C;

(b): the alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 2.3, and a mixture of quartz sand, red mud, and wet zinc smelting kiln slag is added to the reaction slag to make the alkali of the copper-containing reaction slag The ratio is reduced to 1.6; the metal iron content in the slag is 2.2%.

Step 2, separation and recovery method 2:

After heat preservation for 35 min, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and a silicate mineral phase, and at the same time, a zinc-containing component, a lead-containing component, and a cerium-containing component are formed. With the indium-containing component, enter the soot to be recovered, and perform the following steps:

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

(2) The molten iron-rich phase and the iron-containing silicate mineral phase are used as direct reduction ironmaking raw materials. During the reduction process, some zinc components, lead components, indium components and strontium components are volatilized into the soot; direct reduction process In the middle, the rotary hearth furnace is used, the reduction temperature is 1200 ° C, the alkalinity CaO / SiO ₂ ratio = 1.0, and the reducing agent is anthracite and pulverized coal having a particle size of ≤ 150 μm;

(3) The zinc-containing component, the lead-containing component, the cerium-containing component and the indium-containing component are volatilized into the dust to be recovered.

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

Example 4

Step 1, slag mixing:

Cold smelting slag (iron slag) is added to the plasma furnace, and dolomite, MgO, Al ₂ O ₃ , and Fe are added to form mixed slag; the mixed slag is heated to a molten state to form a copper-containing reaction slag And the reaction slag is electromagnetically stirred to achieve mixing; the reaction slag is monitored in real time, and two parameters of (a) and (b) are simultaneously controlled to obtain the slag after completion of the reaction;

Corresponding to (a) copper-containing reaction slag temperature is 1670 ° C, adding red mud, sulfuric acid slag, fluorite, lead ice copper, lead-containing soot, zinc-containing soot, arsenic matte and wet method to the reaction slag Zinc slag, reducing the temperature to 1450 ° C;

(b) The alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 2.0, and the copper-containing blowing slag is added to the reaction slag to reduce the alkalinity ratio of the copper-containing reaction slag to 1.7; the preheating temperature is 600 The air of °C is sprayed with natural gas, coke particles with a particle size of 20 mm, and the metal iron content in the slag is 1.7%.

Step 2, separation and recovery method 2:

After 32 min of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and an iron-containing silicate mineral phase, and at the same time, a zinc-containing component, a lead-containing component, and a bismuth-containing component are formed. The component and the indium-containing component are introduced into the soot and recovered as an oxide, and the following steps are performed:

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

(2) molten iron-rich phase and iron-containing silicate mineral phase step S2 separation and recovery method 1 method F, oxidation modified magnetic separation: 1 pour slag into the thermal insulation slag tank, spray into the slag The oxygen-enriched air with a heat temperature of 900 ° C realizes the transformation of magnetite; 2 slowly cools to room temperature, magnetic separation and separation, and obtains iron concentrate and tailings;

The finally obtained slag contains copper <0.1%, the recovery of iron is 96%, the recovery of zinc is 98%, the recovery of lead is 96%, the recovery of indium is 95%, and the recovery of hydrazine is 94%. The gold enrichment rate is 91%, and the silver enrichment rate is 91%.

Example 5

Step 1, slag mixing: adding zinc smelting slag (hot state vertical tank zinc slag, molten vortex smelting slag obtained by slag outlet, molten blast furnace slag and molten electric furnace slag) to the thermal insulation slag tank, adding limestone and Fe to form a mixture Slag; using oxygen-enriched air with a preheating temperature of 600 ° C, blowing bituminous coal with a particle size of ≤150 μm, heating the mixed slag to a molten state, forming a copper-containing reaction slag, and mixing the reaction slag; real-time monitoring of the reaction melting The slag, through the regulation and the two parameters (a) and (b), obtain the slag after the completion of the reaction;

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

(b): The alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 1.5, both within the required range; the metal iron content in the slag is 1.2%.

Step 2, separation and recovery method 5:

After the heat preservation for 30 min, the molten slag after the completion of the reaction is poured into the heat preservation slag tank, and the slag treatment outside the furnace is performed, and the following steps are performed:

(1) Settlement cooling: the slag after the completion of the reaction is naturally cooled to room temperature to obtain slow cooling slag; the copper-rich white ice phase precipitates to the bottom of the reaction device to form a copper-rich strontium; the iron-containing silicate mineral phase floats; The copper-rich strontium and silicate mineral intermediate slow-cooling slag is an iron-rich phase, and at the same time, a zinc-containing component, an indium-containing component, a cerium-containing component and a lead-containing component are formed;

(2) Separation: manually extracting the copper-rich strontium deposited at the bottom, directly reducing, magnetically separating the iron, and then sending the product to the converter;

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

(4) The zinc-containing component, the indium-containing component, the cerium-containing component and the lead-containing component are volatilized, and are collected into the soot.

The finally obtained slag contains copper <0.15%, iron recovery rate is 96%, zinc recovery rate is 98%, lead recovery rate is 97%, indium recovery rate is 93%, and ruthenium recovery rate is 94%. The gold enrichment rate is 93%, and the silver enrichment rate is 94%.

Example 6

Step 1, slag mixing: adding cold zinc smelting slag (salted iron slag, goethite slag, hematite slag) to an AC arc furnace, while adding lime, MgO, Al ₂ O ₃ , Fe ₂ O ₃ Forming mixed slag; heating the mixed slag to a molten state, forming a copper-containing reaction slag, spraying argon gas having a preheating temperature of 200 ° C, and mixing the reaction slag; monitoring the reaction slag in real time, and regulating At the same time, the two parameters (a) and (b) are guaranteed, and the slag after the completion of the reaction is obtained;

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

(b): The alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 0.1, and the basic iron concentrate, the converter sludge, the alkaline pre-reduction pellet, and the high-calcium red mud after sodium removal are added to the reaction slag. The alkalinity ratio of the copper-containing reaction slag is raised to 0.15; the gas is injected into the gas, and the metal iron content in the slag is 2.6%.

Step 2, separation and recovery method 1:

After holding for 28 minutes, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and an iron-containing silicate mineral phase, and at the same time, a zinc-containing component, an indium-containing component, and a The bismuth component and the lead-containing component are volatilized into the dust to be recovered, and the following steps are performed:

(1) The molten iron-containing silicate mineral phase is separated and recovered in the first method A in step S2, and water quenched as a cement raw material;

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

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

(4) The zinc-containing component, the indium-containing component, the cerium-containing component, the lead-containing component, the sodium-containing component and the potassium-containing component are volatilized, and are collected into the soot.

The finally obtained slag contains copper <0.1%, the iron recovery rate is 97%, the zinc recovery rate is 97%, the lead recovery rate is 96%, the indium recovery rate is 92%, and the ruthenium recovery rate is 92%. The gold enrichment rate is 91%, the silver enrichment rate is 93%, the sodium recovery rate is 97%, and the potassium recovery rate is 95%.

Example 7

Step 1, slag mixing: adding zinc smelting slag (hot vertical tank zinc slag obtained from the slag outlet) to the submerged arc furnace, adding limestone, SiO ₂ , FeO and MgO to form mixed slag; heating the mixed slag In the molten state, a copper-containing reaction slag is formed, an argon-nitrogen gas mixture having a preheating temperature of 400 ° C is sprayed, and the reaction slag is mixed; the reaction slag is monitored in real time, and (a) and ( b) two parameters, obtaining the slag after the completion of the reaction;

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

(b): The alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 0.8, both within the required range; the air is sprayed with a particle size of ≤150 μm using 200 ° C air, and injected into natural gas, and the metal iron content in the slag It is 2.6%.

Step 2, separation and recovery method 4:

After 14 min of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and at the same time, a zinc-containing component, a lead-containing component, and a The bismuth component and the indium-containing component are recycled into the soot to be recovered as follows:

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

(2) The molten iron-rich phase and the iron-containing silicate mineral are specifically subjected to the method F in the separation and recovery method of the step S2, and after water quenching, as a raw material for direct reduction ironmaking;

The finally obtained zinc slag contains copper <0.1%, iron recovery rate is 95%, zinc recovery rate is 96%, lead recovery rate is 97%, indium recovery rate is 92%, and ruthenium recovery rate is 93%. The gold enrichment rate is 91%, and the silver enrichment rate is 94%.

Example 8

Step 1, slag mixing: adding zinc smelting slag (melting vortex melting furnace slag obtained at the discharge port) to the blast furnace, adding dolomite, red mud, MgO, spraying 600 g of oxygen into the coke powder with particle size ≤ 150 μm, and spraying Into the gas, the mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is mixed; the reaction slag is monitored in real time, and two parameters (a) and (b) are simultaneously controlled to obtain a reaction. Finished slag;

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

(b): The alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 1.0, both within the required range; the metal iron content in the slag is 2.9%.

Step 2, separation and recovery method 3:

After 37 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a copper-rich phase, a ferrosilicate-containing mineral phase and an iron-rich phase in the middle and upper portions, and a zinc-containing component and a lead-containing component are simultaneously formed. The bismuth-containing component and the indium-containing component are collected into the soot to be recovered, and the following steps are performed:

(1) molten iron-containing silicate mineral phase slag, poured into a smelting device, and subjected to slag treatment outside the furnace, specifically adopting method B in the separation and recovery method 1 of step S2, and returning the middle and upper slag all to the slag Copper reaction slag, as a hot metallurgical flux, adjusting the composition of the copper-containing reaction slag to control the temperature of the copper-containing reaction slag;

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

(3) The zinc-containing component, the lead-containing component, the cerium-containing component and the indium-containing component are volatilized into the dust recovery;

(4) After the iron-rich phase is subjected to water quenching or air cooling or pouring into a heat preservation device for slow cooling, it is used as a blast furnace ironmaking raw material or directly reduces ironmaking.

The finally obtained slag contains copper <0.1%, iron recovery rate is 96%, zinc recovery rate is 96%, lead recovery rate is 97%, indium recovery rate is 94%, and strontium recovery rate is 93%. The gold enrichment rate is 90%, and the silver enrichment rate is 91%.

Example 9

Step 1, slag mixing: adding zinc smelting slag (melting blast furnace slag obtained at the discharge port) to the side blowing furnace, adding limestone at the same time to form mixed slag; spraying ≤150 μm coke powder with preheated air at a temperature of 900 ° C, The mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is mixed; the reaction slag is monitored in real time, and two parameters (a) and (b) are simultaneously controlled to obtain the reaction. slag;

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

(b): The alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 1.2, both within the required range; the metal iron content in the slag is 1.4%.

Step 2, separation and recovery method 2:

After heat preservation for 46 min, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated, and the iron-rich slag containing the iron-containing silicate mineral phase and the iron-rich phase in the middle and upper portions is obtained, and the zinc-containing component is formed at the same time. The lead-containing component, the bismuth-containing component and the indium-containing component are recycled into the soot, and the following steps are performed:

(1) The upper middle iron-containing slag is poured into the smelting device, and the middle and upper slag is poured into the glass ceramics by the method C in the separation and recovery method 1 of the step S2;

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

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

Example 10

Step 1, slag mixing: adding zinc smelting slag (melted electric furnace slag obtained at the discharge port) to the thermal insulation pit, adding limestone and Fe to form mixed slag; using oxygen-enriched air with a preheating temperature of 800 ° C, blowing Particle size ≤150μm bituminous coal, the mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is mixed; the reaction slag is monitored in real time, and two parameters (a) and (b) are ensured through regulation. Obtaining slag after completion of the reaction;

(b): The alkalinity CaO/SiO ₂ ratio of the copper-containing reaction slag is 0.5, both within the required range; the metal iron content in the slag is 2.2%.

Step 2, separation and recovery method 5:

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

(1) Settling cooling: heat preservation for 45 min, the slag after the reaction is completed and slowly cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to the bottom of the reaction device to form copper-rich strontium; the iron-containing silicate mineral phase floats; The intermediate phase of the copper phase metal lanthanum and the silicate mineral is an iron-rich phase, and at the same time, a zinc-containing component and a lead-containing component are formed;

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

(4) The zinc-containing component, the lead-containing component, the cerium-containing component and the indium-containing component are recovered into the soot.

The finally obtained slag contains copper <0.1%, the iron recovery rate is 98%, the zinc recovery rate is 97%, the lead recovery rate is 96%, the indium recovery rate is 92%, and the ruthenium recovery rate is 92%. The gold enrichment rate is 91%, and the silver enrichment rate is 92%.

The above description of the specific embodiments of the present invention is intended to be illustrative only, and the invention is intended to be understood by those skilled in the art It is not limited to the specific embodiments described above. Various changes or modifications may be made without departing from the scope of the invention.

Claims

A method for recovering valuable components from zinc smelting slag, comprising the steps of:

S1, slag mixing: the zinc smelting slag is added to the smelting reaction device through which the heat preservation device or the slag can flow out, and the calcium-based mineral and the additive are added, and the mixture is stirred and mixed to form a mixed slag;

The mixed slag is heated to a molten state to form a reaction slag, uniformly mixed, and the reaction slag is monitored in real time, and the reaction slag is simultaneously adjusted to satisfy both conditions a and b, and the slag after completion of the reaction is obtained, or the reaction is completed. The molten slag is poured into the heat preservation device;

Wherein, a: the temperature of the reaction slag is controlled to be 1100 to 1450 ° C;

b: adjusting the alkalinity of the reaction slag CaO / SiO 2 ratio = 0.15 ~ 1.8;

S2, separation and recovery: the slag obtained in step S1 is kept for 5 to 50 minutes, and the upper and lower iron-containing silicate mineral phases, the bottom copper-rich phase, the middle and lower iron-rich phase, and the zinc-containing component and lead-containing group are obtained by sedimentation and separation. The dust containing the bismuth component and the indium-containing component, the gold and silver components migrate and enrich and enter the copper-rich phase; the phases are recovered;
The method for recovering valuable components from zinc smelting slag according to claim 1, wherein in step S1, the regulating method of condition a is:

When the temperature of the reaction slag is <1100 ° C, the heating function of the reaction device itself is added, or the fuel and the preheated oxidizing gas are added to the slag to make the temperature of the reaction slag reach the range of 1100 to 1450 ° C;

When the temperature of the reaction slag is >1450 ° C, one or more of the copper-containing material, the zinc smelting slag, the metallurgical flux, the iron-containing material and the fluorine-containing material are added to the reaction slag, so that the temperature of the mixed slag reaches In the range of 1100 to 1450 ° C;

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

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

When the alkalinity CaO/SiO 2 ratio of the reaction slag is >1.8, an acidic material and/or an acidic iron-containing material is added to the reaction slag.
The method for recovering valuable components from zinc smelting slag according to claim 1, wherein the heat insulating device is one or two of a pourable smelting reaction slag irrigation and a heat preservation pit;

The smelting reaction device through which the slag can flow is a rotatable smelting reaction device or a smelting reaction device with a slag port or an iron port;

The rotatable smelting reaction device is one or two of a converter and a smelting reaction slag pot;

The smelting reaction device with a slag port or an iron port is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola furnace, a side blowing molten pool melting furnace, and a bottom blowing pool. One of a smelting furnace, a top-blowing bath smelting furnace, a reverberatory furnace, an Osmite furnace, an Isa furnace, a Waukekov molten pool smelting furnace, a side blowing rotary kiln, a bottom blowing rotary kiln, and a top blowing rotary kiln Or several.
A method for recovering valuable components from zinc smelting slag according to claim 1, wherein in said step S1, while satisfying said conditions a and b, copper in said slag should be simultaneously satisfied And the iron oxide is reduced to metallic copper and FeO, and the metal iron content in the slag is <3%.
The method for recovering valuable components from zinc smelting slag according to claim 1, wherein the zinc smelting slag is one of slag produced by wet zinc smelting and slag produced by pyrometallurgical slag or Two kinds; zinc smelting slag is molten or hot or cold, and molten smelting slag is obtained from vortex melting furnace, blast furnace, smelting furnace, electric furnace slag outlet, and hot zinc smelting slag is discharged from volatilization kiln Obtaining the slag outlet of the vertical tank or heating the zinc smelting slag to a molten state;

Wherein, the slag produced by the wet zinc smelting is one or more of zinc leaching slag, volatile kiln residue, copper cadmium slag, iron slag residue, pickled iron slag, goethite slag, and hematite slag. The slag produced by the pyrometallurgical zinc slag is one or more of a vertical tank zinc slag, a vortex smelting slag, a blast furnace slag, a smelting furnace slag, and an electric furnace slag; The slag produced by the wet zinc smelting needs to be subjected to drying and dehydration treatment; the vortex smelting furnace slag, the blast furnace slag, the smelting furnace slag, the electric furnace slag are obtained from the smelting furnace slag outlet, and the volatile kiln slag is obtained from the volatilization kiln discharge port. The vertical tank zinc slag is obtained from the vertical tank discharge port;

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

The additive is one or more of SiO 2 , MgO, FeO, Fe 2 O 3 , MnO 2 , Al 2 O 3 , TiO 2 , Fe or Na 2 O.
The method for recovering valuable components from zinc smelting slag according to claim 2, wherein the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc Smelting soot and dust, lead and zinc tailings, lead smelting slag, lead ice copper, arsenic copper, coarse lead fire refining slag, lead smelting soot and dust, lead acid battery, copper smelting soot and dust, copper One or more of 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 smelting and slag, slag generated by "copper smelting", slag depleted by fire, copper slag flotation tail slag, and wet copper slag;

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

The iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon-bearing pre- Reducing pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag, copper slag, lead smelting slag, zinc smelting slag, tin smelting slag, red mud, high calcium after sodium removal One or more of red mud, coal dust ash, and sulfuric acid slag;

The nickel smelting slag is one or more of nickel smelting slag produced by the “smelting smelting” process, depleted slag after being blown by the “copper ice nickel blowing” process, and nickel slag slag generated by top blowing smelting;

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

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

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

The copper-containing material, the iron-containing material and the fluorine-containing material are all pellets or powdery materials or granulation; wherein, the granular material has a particle size of ≤150 μm, the granular material has a particle size of 5-25 mm, and the powdery material is sprayed. The method is sprayed into, the granular material is added by spraying or feeding, and the loading gas is one or more of preheated argon gas, nitrogen gas, reducing gas and oxidizing gas, and the preheating temperature is 0-1200 ° C. .
The method for recovering valuable components from zinc smelting slag according to claim 2, wherein the alkaline material is lime powder, red mud, high-calcium red mud after desodiumification, calcium carbide slag, dolomite powder or One or more of the quicklime powder; the alkaline iron-containing material is an alkaline sintered ore having a CaO/SiO 2 >1, a steel slag, a ferroalloy slag, an alkaline iron concentrate, an alkaline pre-reduction pellet, an alkali metal One or more of a pellet or an alkaline blast furnace slag;

The acidic material is one or more of silica, fly ash and coal gangue; the acidic iron-containing material is an acid sintered ore, an acidic iron concentrate, an acidic pre-reduced pellet, CaO/SiO 2 ≤1, One or more of acid metallized pellets, copper slag, lead smelting slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, and acid blast furnace slag.
A method for recovering valuable components from zinc smelting slag according to any of claims 1-7, characterized in that:

The separation and recovery in step S2 is performed as follows:

Containing the copper-rich phase in a hot or cold state, sent to a converter or a smelting furnace for copper smelting, or slow cooling and magnetic separation to separate the metal iron, and then sent to a converter or a smelting furnace for copper smelting, or magnetic separation to separate metal iron Or after the separation of the metal iron without magnetic separation, the direct reduction, the reduction product is separated by magnetic separation, and then sent to the converter or the converter to smelt copper;

The zinc-containing component, the lead-containing component, the cerium-containing component and the indium-containing component are volatilized, and are collected into the dust as an oxide;

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

Method A: After water quenching or air cooling, directly used in cement raw materials:

Method B: Return to the reaction mixture slag as a hot metallurgical flux:

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

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

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

E-1, retaining the iron-containing silicate mineral phase and/or the iron-rich phase of the iron-containing slag in the smelting reaction device or pouring the slag into the heat preservation device, and adding the molten steel slag to the slag One or more of lime, limestone, ferroalloy slag, fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, high-calcium red mud or calcium carbide slag after de-sodium, fully mixed, Obtaining a slag mixture;

E-2, blowing an oxidizing gas having a preheating temperature of 0 to 1200 ° C into the slag mixture, and ensuring a slag mixture temperature > 1460 ° C; when the ferrous oxide content is < 1%, obtaining oxidation Slag

E-3, performing air cooling or water quenching on the oxidized slag to obtain a high value-added cement clinker;

Method F: the iron-containing silicate mineral phase and/or the iron-rich phase iron-containing slag as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: the iron-containing silicate mineral phase and/or After the iron-rich slag of the iron-rich phase is air-cooled, water-quenched or slow-cooled, it is used as a blast furnace ironmaking or direct reduction ironmaking raw material, and after direct reduction, magnetic separation or electric furnace melting is used, and the magnetic separation product is metal iron. With tailings, electric furnace melting, the product is molten iron and slag;

Or, after the iron-containing silicate mineral phase and/or the iron-rich phase iron-containing slag is poured into the heat preservation device, the separation is performed by the following method: magnetic separation after slag modification: into the heat preservation device The slag is blown into an oxidizing gas having a preheating temperature of 0 to 1200 ° C, and the slag temperature is ensured to be >1250 ° C to complete the transformation of the magnetite in the slag; the oxidized slag is slowly cooled to room temperature and broken. , magnetic separation, the product is magnetite concentrate and tailings, tailings as building materials;

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

G-1, retaining the iron-containing silicate mineral phase and/or the iron-rich phase of the iron-containing slag in the smelting reaction device or pouring the slag into the heat preservation device, and adding the iron slag to the slag The iron material and the reducing agent are subjected to smelting reduction, and the reaction slag is monitored in real time, and the following conditions are satisfied by the regulation: the temperature of the reaction slag is 1350 to 1670 ° C, and the alkalinity of the reaction slag is CaO / SiO 2 ratio = 0.6 to 2.4. Obtaining slag after completion of the reaction;

G-2, smelting and reducing the oxidizing gas after preheating into the slag to form a reduced slag, wherein: the preheating temperature of the oxidizing gas is 0 to 1200 ° C, and during the blowing process, Through regulation, the following conditions are satisfied: the temperature of the slag after the completion of the reaction is 1350 to 1670 ° C, and the alkalinity CaO / SiO 2 ratio of the slag after the completion of the reaction = 0.6 to 2.4;

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

Method I: Pour the mixed slag after reduction into a slag pot, and slowly cool to room temperature to obtain slow cooling slag; metal The iron is settled to the bottom of the reaction device to form iron slag; the remaining metal slag contained in the slow cooling slag is crushed to a particle size of 20-400 μm, and the remaining metal iron and tailings are separated by magnetic separation;

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

Or, containing the iron-rich phase water quenching or air cooling or pouring into a heat preservation device to slow cooling or by manual sorting and re-election, as a blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material or flotation Copper extraction raw materials or magnetic separation of metal iron for use as raw materials for copper smelting or direct reduction of iron; during flotation, the flotation products are copper-bearing concentrates and iron concentrates, copper concentrates are returned to copper smelting systems, iron concentrates As a blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, the reduction product is magnetically separated and separated, the metal iron and tailings are obtained, and the tailings are returned to the copper smelting system;

The direct reduction process uses any one of a rotary hearth furnace, a tunnel kiln, a car bottom furnace, a shaft furnace, a rotary kiln, and an induction furnace as a reduction device, using a gas-based or coal-based reduction technology, the gas base is natural gas and/or The gas and coal base are 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 is 0.8-1.5.
The method for recovering valuable components from zinc smelting slag according to claim 8, wherein in the step S2, the cooling mode is natural cooling or rotary cooling or centrifugal cooling, and the sedimentation mode is natural settlement or rotation. Settling or centrifugal sedimentation;

The mixing is uniformly mixed by natural mixing or stirring, and the stirring and mixing are one or several of argon stirring, nitrogen stirring, nitrogen-argon mixed gas stirring, reducing gas stirring, oxidizing gas stirring, electromagnetic stirring, mechanical stirring. Kind.
A method for recovering valuable components from zinc smelting slag according to claim 8, wherein said fuel and reducing agent are one or more of solid, liquid or gaseous fuels for injection or feeding The injection of the gas is one or more of a preheated oxidizing gas, nitrogen or argon, the preheating temperature is 0 to 1200 ° C;

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

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