CN110373552A - A kind of harmless treatment process using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting - Google Patents

A kind of harmless treatment process using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting Download PDF

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Publication number
CN110373552A
CN110373552A CN201910669595.2A CN201910669595A CN110373552A CN 110373552 A CN110373552 A CN 110373552A CN 201910669595 A CN201910669595 A CN 201910669595A CN 110373552 A CN110373552 A CN 110373552A
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oxygen
furnace
blowing
lead
zinc
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赖春波
蔺淼
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Tongling Minrui Oxygen Enriched Sideblowing Technology Co Ltd
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Tongling Minrui Oxygen Enriched Sideblowing Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/69Sulfur trioxide; Sulfuric acid
    • C01B17/74Preparation
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/02Obtaining lead by dry processes
    • C22B13/025Recovery from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/30Obtaining zinc or zinc oxide from metallic residues or scraps
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04Working-up slag
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a kind of harmless treatment process using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting, include the following steps: step 1, and melting is melted in desulfurization;Step 2 melts rapidly, sulfate fast decoupled;Step 3 is collected;Step 4, reduction volatilization melting;Step 5, the metals such as lead zinc-silver in waste residue are reduced into metal phase and volatilize with flue gas, and the clinker after dilution is discharged from outlet;Step 6, the metallic vapours such as lead zinc-silver are oxidized to metal oxide by Secondary Air, and the metal oxide recycles metal oxide by bag collection, and the flue gas of sulfur-bearing enters sulfate system, passes through standard relieving haperacidity method extracting sulfuric acid.The present invention is suitable for large-scale industrialization industrial production, has the characteristics that applicable slag type is more, invests small, high-efficient, energy-saving and environmental protection.

Description

A kind of harmless treatment using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting Technique
Technical field
The present invention relates to lead-zinc residue process field more particularly to a kind of utilization oxygen-enriched side-blowing furnace bath smelting low-grade leads The harmless treatment process of zinc waste residue.
Background technique
Lead is smelted, no matter zinc abstraction and Copper making use that technique, finally all can output it is a considerable amount of low-grade Lead-zinc residue and flue dust.These waste particles are tiny and contain the valuable members of associations such as a certain amount of zinc, lead, copper, indium and gold, silver Element, if this part waste residue cannot efficiently use, it will cause serious environmental pollution and the wasting of resources.In order to comprehensively utilize These slags reduce environmental pollution while making effective use of secondary resource, obtain the double benefit of economy and environment, realize ring Border, the sustainable development of resource and society, domestic and foreign scholars have done a large amount of research, have proposed a series of method.These sides Method is summed up on technology type can be divided into wet processing and thermal process.But all there is generate secondary pollution for two kinds of techniques With costly problem.
With the development of the society, the demand to resource is also increasing, and Global Mineral is increasingly exhausted, improves again The recycling in production-goods source, it appears it is particularly important, and equipment is continuously improved, using advanced reclaiming technology, It is only the key of development.
Currently also there is polytechnic trial, for example Publication No. CN102776376B discloses a kind of wet process-pyrogenic process connection It closes technique and recycles the method containing valuable metal in lead-zinc residue, it is characterised in that: producing including elementary lead, the leaching of secondary zinc oxide Out, elemental copper, indium and tin are produced and producing for zinc;Using above-mentioned technique recycling metal, the rate of recovery of lead and zinc is high, Copper, indium and tin leach separator well, and waste residue recycles, is both the further recycling to existing resource, in turn avoids valuable metal Pollution to environment, safer environmental protection;Meanwhile this method principle is simple, process is reasonable, yield and product sample higher, cost It is cheap.Above scheme to the utilization rate of waste residue or relatively low, if while misoperation, will lead to liquid air blowing, to generate Secondary pollution.
Summary of the invention
Oxygen-enriched side-blowing bath melting low-grade lead is utilized present invention aims to solve the deficiencies of the prior art, and provides a kind of a kind of The harmless treatment process of zinc waste residue, the waste residue for solving lead smelting, zinc abstraction and Copper making are largely stored up and can not be handled, and ring is caused The problem of border is seriously polluted.
The technical solution adopted by the present invention is that: it is a kind of to utilize the harmless of the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting Change treatment process, include the following steps: step 1, melting is melted in desulfurization: waste residue, solvent and beans are continuously added to side-blowing bath In smelting furnace, oxygen-enriched air is blasted to slag layer by the side air port of side-blowing bath smelting furnace;Step 2, side-blowing bath melting Waste residue melt in furnace is blasted the strong stirring of oxygen-enriched air, so that furnace charge particle is uniform rapidly in side-blowing bath smelting furnace Distribution is melted rapidly, sulfate fast decoupled;Step 3, copper and lead in waste residue form lead copper matte, are deposited on the bottom of furnace, It is collected;Lead zinc flue gas rich in sulfide passes through electric dust-collecting and dust-removing, integrates back wherein leaded flue dust enters lead Zn system It receives, the flue gas of sulfur-bearing enters sulfate system, passes through standard relieving haperacidity method extracting sulfuric acid;Step 4, reduction volatilization melting: through step 3 Reduction coal and solvent is added in treated waste residue, while being blasted to slag layer by the side air port of side-blowing bath smelting furnace oxygen-enriched Air;Step 5, the metals such as lead zinc-silver in waste residue are reduced into metal phase and volatilize with flue gas, and the clinker after dilution is arranged from outlet Out;Step 6, the metallic vapours such as lead zinc-silver are oxidized to metal oxide, the metal oxide passes through cloth bag by Secondary Air It gathers dust and recycles metal oxide, the flue gas of sulfur-bearing enters sulfate system, passes through standard relieving haperacidity method extracting sulfuric acid.
As a further improvement of the present invention, the step 1, the side leading wind open height of side-blowing bath smelting furnace be lower than 0.4~0.8 meter of static weld pool surface.
As a further improvement of the present invention, step 1, control furnace charge it is aqueous≤12%, 10~50 ton/hours of feeding quantity, 5~20mm of coal particle size, oxygen-rich concentration 60%~80%, 1050~1250oC of smelting temperature.
As a further improvement of the present invention, the melting of the step 1 and step 4 uses the same side-blowing bath melting Furnace.
As a further improvement of the present invention, by control oxygen coal than realizing that the melting of step 1 and step 4 is converted.
As a further improvement of the present invention, the melting of the step 1 and step 4 uses different side-blowing baths respectively Smelting furnace.
As a further improvement of the present invention, the side-blowing bath melting furnace high-temperature waste residue of step 1 is put into step by chute In rapid four side-blowing bath smelting furnace, to realize continuous production.
As a further improvement of the present invention, step 4,5~20 mm of reduction coal (coke) granularity, oxygen-rich concentration 30~70%, 1100~1300 oC of smelting temperature.
The beneficial effect that the present invention uses is: the present invention uses the low-grade lead-zinc residue of oxygen-enriched side-blowing technical treatment, effectively It solves the problem of that current a large amount of stockpilings can not be handled and causes severe environmental pollution.It is raw that the present invention is suitable for large-scale industry chemical industry It produces, has the characteristics that applicable slag type is more, invests small, high-efficient, energy-saving and environmental protection.After output of the present invention is containing Pb-Zn dust recycling Lead Zn system remanufacture can be returned, circular economy is formed;Standard relieving haperacidity process production sulphur can be used in output high-concentration sulfur dioxide Acid can effectively solve environmental pollution caused by low-concentration sulfur dioxide;Output clinker forms vitreum, and without water-soluble influence The composition of environment becomes general solid waste, and waste residue can comprehensively utilize, and becomes product.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Below with reference to Fig. 1 and embodiment, the present invention is described further.
The present invention completes in two stages, the first stage be fusing, the desulfurization slag making stage, by dispensing requirements into furnace continuously Waste residue, flux, the coal grain prepared is added, blasts oxygen-enriched air from furnace lower part air port, furnace charge melts in furnace and oxidation reaction, Output high temperature sludge contains sulfur dioxide flue gas.Second stage is the reduction melting stage, is applied alone coal and oxygen-enriched air to react, restores The lead and zinc in high temperature sludge that first segment produces.Become metal vapors, is oxidized to metal oxide in Secondary Air, passes through waste heat boiler After recycling thermal energy, metal oxide is recycled by bag collection.The present invention can single furnace production or twin furnace production, when single furnace produces First segment and second segment can realize conversion by control oxygen coal ratio.The high temperature sludge that twin furnace can produce the first stage when producing It is put into second furnace and is restored, it can be achieved that continuous production, output lead zinc oxide flue dust, clinker obtains poor by chute Change.
Embodiment 1, desulfurization slag making melting, waste residue are defeated by belt by waste residue, flux, beans through drying and dehydrating to 12% or so Machine conveying is sent to be continuously added to side-blowing bath smelting furnace.Wherein solvent uses lime stone, and side-blowing bath smelting furnace is using in Xinxiang City Join the side-blown converter of oxygen-enriched side-blowing technological development Co., Ltd production.It is being lower than at static weld pool surface 0.5m through side simultaneously The oxygen-enriched air that air port is blasted to slag layer.Guarantee stirring strongly, keeping furnace charge particle in the melt rapidly and equal for slag melt Even distribution, waste residue melt rapidly, sulfate fast decoupled, complete chemical reaction process and control corresponding conditions, make lacking in waste residue Part copper and lead form lead copper matte, sink collection in the timing releasing of the bottom of furnace, while can be enriched with a certain amount of noble metal;High-temperature slag It is then continuously released out of side-blown converter through siphon, into another furnace, sulfide passes through the high sulfur dioxide concentration of pyrolytic output Flue gas, after waste heat boiler recovery waste heat, electric dust-collecting and dust-removing, using standard relieving haperacidity method, extracting sulfuric acid, tail gas qualified discharge. Desulfurization melting condition: control furnace charge it is aqueous≤12%, 10-50 tons of feeding quantity (determines additional amount according to the size of stove), coal particle size 10mm, the industrial pure oxygen of oxygen-rich concentration 60%, 1200 °C of smelting temperature.
Reduction volatilization melting when using two furnaces, goes out from preceding fire grate through the slag after the completion of fusing desulphurization reaction, directly flows Enter reduction furnace, reduction coal and flux are equally continuously added into furnace, the reduction volatilization of leaded cadmia is completed in reduction furnace, through poor Clinker after change is discharged from outlet.The flue gas of output is through waste heat boiler recovery waste heat in furnace, after bag-type dusting, desulfurizing tower washing After empty, the flue dust of leaded zinc be transported to lead Zn system generation.Reduction volatilization melting condition: control reduction 10 mm of coal particle size, richness The industrial pure oxygen of oxygen concentration 50%, 1300 oC of smelting temperature, the recovery time 60 minutes.
Embodiment 2, desulfurization slag making melting, waste residue are defeated by belt by waste residue, flux, beans through drying and dehydrating to 12% or so Machine conveying is sent to be continuously added to side-blowing bath smelting furnace.Wherein solvent uses lime stone, and side-blowing bath smelting furnace is using in Xinxiang City Join the side-blown converter of oxygen-enriched side-blowing technological development Co., Ltd production.It is being lower than at static weld pool surface 0.5m through side simultaneously The oxygen-enriched air that air port is blasted to slag layer.Guarantee stirring strongly, keeping furnace charge particle in the melt rapidly and equal for slag melt Even distribution, waste residue melt rapidly, sulfate fast decoupled, complete chemical reaction process and control corresponding conditions, make lacking in waste residue Part copper and lead form lead copper matte, sink collection in the timing releasing of the bottom of furnace, while can be enriched with a certain amount of noble metal;Sulfide is logical The flue gas for crossing the high sulfur dioxide concentration of pyrolytic output, after waste heat boiler recovery waste heat, electric dust-collecting and dust-removing, using standard system Acid system, extracting sulfuric acid, tail gas qualified discharge.Desulfurization melting condition: control furnace charge it is aqueous≤12%, 10-50 tons of feeding quantity (according to The size of stove determines additional amount), coal particle size 5mm, the industrial pure oxygen of oxygen-rich concentration 60%, 1200 °C of smelting temperature.
Reduction volatilization melting, when using a furnace, after the completion of desulfurization melting, changing furnace internal oxidition atmosphere is to go back Primordial Qi Atmosphere increases air port and improves air quantity, reduction coal and flux are added into furnace, make the metals such as the lead zinc-silver in slag be reduced into metal phase with Flue gas volatilization, clinker obtain dilution.Clinker is discharged from outlet.Reduction volatilization melting condition: control reduction 5 mm of coal particle size, richness The industrial pure oxygen of oxygen concentration 40%, 1200 oC of smelting temperature, the recovery time 50 minutes.
The present invention does not have to pre- desulfurization, desulfurization while material melts in side-blown converter.One can be used when treating capacity is smaller The segmentation production of platform furnace, two furnace continuous productions are used when treating capacity is larger.
The present invention uses the low-grade lead-zinc residue of oxygen-enriched side-blowing technical treatment, and effectively solving current a large amount of stockpilings can not locate The problem of managing, causing severe environmental pollution.The present invention is suitable for large-scale industrialization industrial production, and with being applicable in, slag type is more, throws Provide the features such as small, high-efficient, energy-saving and environmental protection.Output of the present invention can return lead Zn system remanufacture, shape after recycling containing Pb-Zn dust At circular economy;Standard relieving haperacidity process production sulfuric acid can be used in output high-concentration sulfur dioxide, can effectively solve low concentration dioxy Change environmental pollution caused by sulphur;Output clinker forms vitreum, and without the water-soluble composition for influencing environment, becomes general solid Useless, waste residue can comprehensively utilize, and become product.
Those skilled in the art should know the protection scheme of the present invention is not limited only to the above embodiments, can also be Various permutation and combination and transformation are carried out on the basis of above-described embodiment, on the premise of without prejudice to spirit of the invention, to the present invention The various transformation carried out are fallen within the scope of protection of the present invention.

Claims (8)

1. a kind of harmless treatment process using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting, it is characterized in that including such as Lower step:
Melting is melted in step 1, desulfurization: waste residue, solvent and beans being continuously added in side-blowing bath smelting furnace, by side-blown molten The side air port of pond smelting furnace blasts oxygen-enriched air to slag layer;
Step 2, the waste residue melt in side-blowing bath smelting furnace is blasted the strong stirring of oxygen-enriched air, so that furnace charge particle exists It is uniformly distributed rapidly, melts rapidly, sulfate fast decoupled in side-blowing bath smelting furnace;
Step 3, copper and lead in waste residue form lead copper matte, are deposited on the bottom of furnace, are collected;Lead zinc rich in sulfide Flue gas passes through electric dust-collecting and dust-removing, wherein leaded flue dust enters lead Zn system synthetical recovery, the flue gas of sulfur-bearing enters sulfate system, Pass through standard relieving haperacidity method extracting sulfuric acid;
Reduction volatilization melting: step 4 is added reduction coal and solvent through step 3 treated waste residue, while passing through side-blowing bath The side air port of smelting furnace blasts oxygen-enriched air to slag layer;
Step 5, the metals such as lead zinc-silver in waste residue are reduced into metal phase and volatilize with flue gas, and the clinker after dilution is arranged from outlet Out;
Step 6, the metallic vapours such as lead zinc-silver are oxidized to metal oxide, the metal oxide passes through cloth bag by Secondary Air It gathers dust and recycles metal oxide, the flue gas of sulfur-bearing enters sulfate system, passes through standard relieving haperacidity method extracting sulfuric acid.
2. a kind of harmless treatment work using the low-grade lead-zinc residue of oxygen-enriched side-blowing bath melting according to claim 1 Skill, it is characterized in that the step 1, the side leading wind open height of side-blowing bath smelting furnace is lower than static weld pool surface 0.4~0.8 Rice.
3. a kind of harmless treatment using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting according to claim 1 Technique, it is characterized in that step 1, control furnace charge is aqueous≤12%, 10~50 ton/hours of feeding quantity, coal particle size 5~20mm, oxygen-enriched Concentration 60%~80%, 1050~1250oC of smelting temperature.
4. a kind of harmless treatment using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting according to claim 1 Technique, it is characterized in that the melting of the step 1 and step 4 uses the same side-blowing bath smelting furnace.
5. a kind of harmless treatment using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting according to claim 4 Technique, it is characterized in that the melting conversion by control oxygen coal than realizing step 1 and step 4.
6. a kind of harmless treatment using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting according to claim 1 Technique, it is characterized in that the melting of the step 1 and step 4 uses different side-blowing bath smelting furnaces respectively.
7. a kind of harmless chemical industry using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting according to claim 6 Skill, it is characterized in that the side-blowing bath melting furnace high-temperature waste residue of step 1 is put into the side-blowing bath smelting furnace of step 4 by chute It is interior, to realize continuous production.
8. as claimed in any of claims 1 to 7 a kind of useless using oxygen-enriched side-blowing furnace bath smelting low-grade lead zinc The butanedionedioxime of slag, it is characterized in that step 4,5~20 mm of reduction coal (coke) granularity, oxygen-rich concentration 30~70%, smelting temperature 1100~1300 oC.
CN201910669595.2A 2019-07-24 2019-07-24 A kind of harmless treatment process using the low-grade lead-zinc residue of oxygen-enriched side-blowing furnace bath smelting Pending CN110373552A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111893310A (en) * 2020-09-08 2020-11-06 新乡市中联富氧侧吹技术开发有限公司 Harmless recycling treatment method for solid hazardous waste
CN113373313A (en) * 2021-06-17 2021-09-10 兰州理工大学 Method for recovering indium in lead-silver slag by melting desulfurization-fuming indium volatilization
CN113802007A (en) * 2021-09-03 2021-12-17 中国恩菲工程技术有限公司 Method and system for treating waste cathode of aluminum electrolysis cell
CN115807165A (en) * 2023-01-29 2023-03-17 中南大学 Oxidation desulfurization method and device for lead-zinc sulfide ore

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107083488A (en) * 2017-04-19 2017-08-22 安徽华铂再生资源科技有限公司 A kind of waste lead acid battery lead cream bath smelting processing method
CN110042260A (en) * 2019-05-24 2019-07-23 昆明有色冶金设计研究院股份公司 A kind of smelting process of low-grade difficult smelting charge of lead and zinc

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107083488A (en) * 2017-04-19 2017-08-22 安徽华铂再生资源科技有限公司 A kind of waste lead acid battery lead cream bath smelting processing method
CN110042260A (en) * 2019-05-24 2019-07-23 昆明有色冶金设计研究院股份公司 A kind of smelting process of low-grade difficult smelting charge of lead and zinc

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111893310A (en) * 2020-09-08 2020-11-06 新乡市中联富氧侧吹技术开发有限公司 Harmless recycling treatment method for solid hazardous waste
CN113373313A (en) * 2021-06-17 2021-09-10 兰州理工大学 Method for recovering indium in lead-silver slag by melting desulfurization-fuming indium volatilization
CN113802007A (en) * 2021-09-03 2021-12-17 中国恩菲工程技术有限公司 Method and system for treating waste cathode of aluminum electrolysis cell
CN115807165A (en) * 2023-01-29 2023-03-17 中南大学 Oxidation desulfurization method and device for lead-zinc sulfide ore
CN115807165B (en) * 2023-01-29 2023-05-26 中南大学 Oxidative desulfurization method and device for lead-zinc sulfide ore

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Application publication date: 20191025