CN111676374B - Clean production method of copper smelting smoke dust and lead-containing secondary material - Google Patents

Clean production method of copper smelting smoke dust and lead-containing secondary material Download PDF

Info

Publication number
CN111676374B
CN111676374B CN202010426754.9A CN202010426754A CN111676374B CN 111676374 B CN111676374 B CN 111676374B CN 202010426754 A CN202010426754 A CN 202010426754A CN 111676374 B CN111676374 B CN 111676374B
Authority
CN
China
Prior art keywords
smelting
lead
copper
slag
materials
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN202010426754.9A
Other languages
Chinese (zh)
Other versions
CN111676374A (en
Inventor
方喜
张跃萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202010426754.9A priority Critical patent/CN111676374B/en
Publication of CN111676374A publication Critical patent/CN111676374A/en
Application granted granted Critical
Publication of CN111676374B publication Critical patent/CN111676374B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working 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
    • C22B7/02—Working-up flue dust
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0056—Scrap treating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working 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
    • C22B7/001—Dry processes
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

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

Abstract

The invention discloses a clean production method of copper smelting smoke dust and a lead-containing secondary material, and aims to provide a method for smelting lead by using the copper smelting smoke dust and the lead-containing secondary material. Adding an oxide material containing silicon and calcium, an oxide containing iron and a binder into copper smelting smoke dust and/or a secondary material containing lead, batching according to batches, adding water, mixing, pressing into a shaped material, stacking, solidifying and hardening, matching with coke, and completing preheating, reduction, smelting separation and layered recovery of each metal in a blast smelting furnace. The method utilizes the principle that sulfur and copper preferentially form copper matte and SiO under the conditions of not adopting sintering desulfurization and bath smelting 2 The reaction characteristics with slag, copper matte and ferric oxide in the smelting process overcome the harmful influence of copper, sulfur and arsenic on the production process in the traditional lead smelting process by adjusting the slag shape, the aim of effectively separating and recovering metals such as copper, lead, arsenic and sulfur is fulfilled, the environmental protection problem in the lead smelting process is solved, and the comprehensive economic benefit of production is improved.

Description

Clean production method of copper smelting smoke dust and lead-containing secondary material
Technical Field
The invention belongs to the technical field of heavy metal recovery and pollution prevention, and particularly relates to a simple, reliable and convenient-to-implement method for main harmful impurities copper, sulfur and arsenic remained in the traditional lead smelting process.
Background
The copper smelting smoke dust generally contains 3-15% of copper, 10-30% of lead, 1-6% of bismuth, 1-3% of tin, 5-20% of zinc, 3-15% of arsenic and a small amount of rare metals such as indium, germanium, gold, silver and the like, and the common recovery process is to firstly recover zinc, copper, bismuth and arsenic by a wet method and then recover lead and other metals by a pyrogenic process. The method has the following defects that firstly, 20-50% of copper in the copper dust exists in a form insoluble in acid, the recovery rate is not high generally, and if the recovery rate is increased, the copper dust needs to be subjected to sintering or a strong oxidant is used in the leaching process, so that the cost is greatly increased; secondly, because the lead slag contains certain copper, lead oxides can be converted into lead sulfate and other substances in the acid leaching process, the burden of lead recovery by a post-process pyrogenic process can be increased, and because copper matte formed by sulfur and copper forms a distillation product and a copper matte mixture in the smelting process, the normal operation of lead smelting is hindered, the crude lead slag and the copper matte in the furnace are not separated clearly, so that the entrainment of each metal is serious, the recovery rate of each metal is not high, the recovery rate of lead smelting is low due to the double influence of copper and sulfur, the smelting process is difficult, normal production cannot be realized, even the furnace is dead, and a large amount of low-grade copper matte is generated in the smelting process. In addition, arsenic is accumulated in smoke dust in the smelting process, and normal production is influenced by serious entrainment in slag and products, so that the research and development of the clean production method of copper smelting smoke dust and lead-containing secondary materials is of great significance.
Disclosure of Invention
The invention aims to provide a clean smelting method of copper smelting smoke dust, which has a simple process. The method utilizes copper smelting smoke dust and lead-containing secondary materials, overcomes the influence of copper, sulfur and arsenic on the production process in the traditional lead smelting by adopting a blast smelting furnace and utilizing the reaction mechanism between silicon dioxide and slag, copper matte and ferric oxide and the influence of the silicon dioxide on the slag temperature under the condition of not adopting sintering desulfurization or molten pool smelting process, and achieves the aim of effectively separating and recovering copper, lead, sulfur, arsenic, gold and silver and other multiple metals.
The object of the invention is achieved by the following steps comprising the following step a): raw material preparation and solidification, B) high-temperature smelting and separation,
A: preparation and curing of raw materials
Adding auxiliary materials of iron, silicon and calcium into copper smelting smoke dust and/or secondary lead materials, supplementing according to batches, adding a bonding agent, mixing into a 5-13% aqueous mixture, crushing, uniformly mixing, pressing into a brick-shaped block material in a brick making machine under the pressure of 20-100 mpa, stacking and curing for 3-5 days to naturally cure and harden the block material and meet the smelting requirement;
b: high temperature smelting separation
B, feeding the shaped bricks cured and hardened in the step A and coke into a blast furnace according to a certain proportion, preparing auxiliary materials containing silicon and calcium and return materials, adding the auxiliary materials and the return materials into a smelting furnace in batches, adding the materials from the side of the top of the furnace, entering a preheating zone, passing through an upper reduction zone and a lower reduction zone, entering a smelting zone, and forming strong oxygen in the smelting zone by using a coke layer and blowing airReducing reaction environment, the reaction temperature is 900-1300 ℃, and SiO is finished in a smelting zone 2 FeO, CaO slag and dissolve AL 2 O 3 The PbO in the lead silicate is replaced by MgO, ZnO, CaO and FeO, the replaced lead oxide is reduced to metallic lead, redundant sulfur, copper and iron form copper matte, and after the furnace burden is completely melted, the formed liquid flows downwards and is overheated by a high-heat coke layer to complete most of reduction reaction; carrying out oxidation reduction reaction smelting in a smelting furnace, enabling molten liquid formed by smelting to flow into a hearth for continuous reaction to finish the unfinished chemical reaction, layering according to density difference, discharging crude lead at the lowest layer through a siphon port of the smelting furnace, discharging the crude lead at the lowest layer, slag at the uppermost layer, copper matte and yellow slag at the middle layer, continuously reacting and separating under the condition of high-temperature slag, finally discharging the crude lead and the slag together through a slag discharge port to a front bed or a precipitation pot, separating out water quenching slag, copper matte and ferric arsenite, continuously carrying out cyclic collection treatment on generated smoke dust, finishing the whole smelting process, and smelting to form SiO in the slag 2 The content of SiO is more than 28 percent 2 The content is larger than the content of FeO, and the temperature range of the smelting slag is 1200-1350 ℃.
Compared with the prior art, aiming at copper-lead-containing smelting smoke dust and lead-containing secondary materials, the invention utilizes SiO under the conditions of not adopting sintering desulfurization and molten pool smelting 2 The reaction characteristics with slag, copper matte and ferric oxide in the smelting process are adjusted through special high-temperature slag shapes, so that the harmful influence of copper, sulfur and arsenic on the production process in the traditional lead smelting is overcome, and the aim of effectively separating and recovering copper, lead, arsenic, sulfur and other metals is finally fulfilled. Through the optimized adjustment of the special high-temperature slag type, the problem that the traditional lead smelting blast furnace is easy to be distilled in a hearth to cause a groove diaphragm in the smelting production process is thoroughly eliminated, so that the reaction is not thorough, and the metal is seriously entrained with an avoiding end with low metal recovery rate, thereby achieving the purposes of thorough and effective reaction, stable production, effective separation and recovery of the metals and improving the comprehensive economic benefit.
Drawings
FIG. 1 is a schematic view of the process of the present invention.
Detailed Description
The invention is further described with reference to the accompanying drawings, but the invention is not limited in any way, and any variations or modifications based on the teachings of the invention are within the scope of the invention.
As shown in fig. 1, the present invention comprises the following step a): mixing and solidifying treatment, B) melting and smelting, B): stripping and collecting;
a: mixing and curing process
Adding auxiliary materials of iron, silicon and calcium into copper smelting smoke dust and/or secondary lead materials, supplementing according to batches, adding a bonding agent, mixing into a 5-13% aqueous mixture, crushing, uniformly mixing, pressing into a brick-shaped block material in a brick making machine under the pressure of 20-100 mpa, stacking and curing for 3-5 days to naturally cure and harden the block material and meet the smelting requirement;
b: melting and smelting
B, feeding the shaped bricks cured and hardened in the step A and coke into a blast furnace together according to a certain ratio, preparing auxiliary materials containing silicon and calcium and return materials, adding the auxiliary materials and the return materials into a smelting furnace in batches, adding the materials from the side of the top of the furnace, entering a preheating zone, passing through an upper reduction zone and a lower reduction zone, entering a smelting zone, forming a strong oxidation-reduction reaction environment by adopting a coke layer and blowing in the smelting zone, wherein the reaction temperature is 900-1300 ℃, and the SiO is completed in the smelting zone 2 FeO, CaO slag and dissolve AL 2 O 3 The method comprises the following steps that (1) PbO in lead silicate is replaced by MgO, ZnO, CaO and FeO, the replaced lead oxide is reduced to metallic lead, redundant sulfur copper and iron form copper matte, and after furnace burden is completely melted, the formed liquid flows downwards and is overheated by a high-heat coke layer to complete most of reduction reaction; carrying out redox reaction smelting in a smelting furnace, allowing the molten liquid formed by smelting to flow into a hearth for continuous reaction to complete the unfinished chemical reaction, layering according to density difference, discharging crude lead at the lowest layer through a siphon port of the smelting furnace, discharging molten slag at the uppermost layer, allowing copper matte and yellow slag at the middle layer, continuously reacting and separating under the condition of high-temperature molten slag, discharging the molten slag together through a slag discharge port to a front bed or a precipitation pot, separating out water quenching slag, copper matte and ferric arsenite, and continuously carrying out circulating collection treatment on the generated smoke dust to complete the whole smelting process, wherein the smelting formsSiO in slag 2 SiO content greater than 28% 2 The content is larger than the FeO content, and the temperature range of the smelting slag is 1200-1350 ℃.
Wherein the exothermic reaction is:
C+O 2 =CO 2 +O 1
C+O 2 =CO 2 +O 2
C+CO 2 = CO+O 3
the reduction reaction is as follows:
PbO+CO=Pb+CO 2
PbO+C=Pb+CO
the sulfonium making reaction is as follows:
Cu 2 O+FeS= Cu 2 S+FeO
the invention has the beneficial effects that:
in the method, oxides containing iron, silicon and calcium are added into copper smelting smoke dust and secondary lead materials, wherein the oxides of the calcium convert lead sulfate in lead sulfate slag into lead oxide and lead hydroxide with better smelting adaptability, and simultaneously, the materials are cured by a large amount of heat generated by the reaction of the oxides of the calcium and water in the raw materials, so that the viscosity of the materials is changed and the materials are easy to mix, and calcium sulfate is generated in the process as a binder of the materials; the addition of calcium oxide is to add calcium element which must be added in the smelting process and to serve as a curing agent and a binder of the material; the iron oxide is added with an iron element which is necessary to be added in the smelting process, is used as a sulfur-fixing agent for sulfur-fixing smelting in the smelting process, is unoxidized iron powder which can be used as a reducing agent in the smelting process, is ferrous oxide with a grid structure generated in the oxidation process, becomes a binder, a curing agent and a hardening agent of the shaped brick, and is used as a curing agent of the shaped brick by utilizing heat generated in the oxidation process;
by utilizing the principle of sulfur production and the principle of preferential combination of copper and sulfur in the pyrometallurgical oxidation-reduction reaction process, the copper, the sulfur and the iron are preferentially combined to generate liquid copper matte, the copper and the sulfur are separated from crude lead and molten slag, and the purpose of reducing low-concentration SO in the lead smelting process is achieved 2 The sulfur, copper and iron are simultaneously discharged by utilizing the sulfur selection principleSolidified in copper matte to achieve the purpose of sulfur fixation and smelting.
The oxide of silicon is added by using SiO 2 The sulfur-fixing smelting is realized in the lead smelting process, so that the effective separation of the crude lead, copper matte and slag is realized.
One is to require SiO in the slag 2 ≥28%， SiO 2 The content is more than FeO content, and the basic slag form is characterized in that: SiO 2 2 The content is 28-45%, the FeO content is 20-28%, the CaO content is 5-15%, the melting point of the slag must be larger than 1200 ℃, and the melting point is obviously different from the melting point of 1050-1200 ℃ of the traditional lead smelting slag. Secondly, a large amount of SiO is added 2 Make excessive SiO 2 Form FeO.SiO together with FeO in copper matte 2 Slag, FeO + SiO 2 =FeO. SiO 2 Thus reducing the copper matte generation amount and improving the matte grade. The problem that copper matte formed in the sulfur making process is easy to form a eutectic with FeO is avoided, and more copper matte bodies are formed at the same time, so that the matte grade in the copper matte is reduced.
Thirdly, Fe is easily formed in the lead smelting process 3 O 4， Fe is easier to form under the condition of peroxide and oxygen enrichment 3 O 4 And is of Fe 3 O 4 The formation of a distillation product is easier, and an interlayer is formed to prevent the normal operation of lead smelting.
Reaction: 9FeO +5O 2 =3Fe 3 O 4
Fe 3 O 4 Ten FeS = FeO ten SO 2 ↑
The above reaction must be carried out at a temperature of 1400 ℃ or higher, if SiO is added 2 Rear Fe 3 O 4 The conversion becomes easy and the slag reaction can be carried out at 1100 ℃:
Fe 3 O 4 decaFeS Ten 5SiO 2 =5(FeO.SiO 2 ) Ten S0 2 ↑
And fourthly, the slag melting point is improved to activate the reaction activity of the unreacted lead-containing material lead sulfide (the melting point of the lead sulfide is 1114 ℃) and lead sulfate (the melting point of the lead sulfate is 1070 ℃), so that the lead sulfide in the matte concretion, the lead sulfate and the lead oxide form an interactive reaction, the lead content in the copper matte is reduced, the copper content in the matte is improved, the recovery rate of lead and silver is improved, and the reaction and melting process can be smoothly carried out.
The main reaction: 3PbSO4 ten PbS =4PbO ten 4SO2 ↓ ≠ 4
PbSO4 ten PbS =2Pb ten 2SO2 ↓
PbS ten 2PbO =3Pb decaso 2 ≠ ≈ c
Fifthly, the lead smelting process is carried out under the high-temperature strong reduction condition, at the moment, under the condition of a certain temperature (700-1000 ℃), iron oxide and arsenic oxide preferentially form iron arsenide to enter molten slag in a large amount of CO reduction atmosphere, and finally the iron arsenide and the arsenic oxide are layered in a hearth, discharged together with the matte slag, and precipitated, layered and recovered in a front bed or a slag settling pot.
The main reaction: 4FeO decas 2 O 3 Ten 7CO =2AsFe ten 7CO 2 ↑
In the treatment and smelting process of copper smelting smoke dust and secondary lead materials, a copper sulfonium principle is formed by sulfur and copper, the smelting process is optimized under the condition of high-silicon high-temperature slag, the furnace condition is stabilized, copper is effectively recovered, most of sulfur is fixed, the influence and harm of sulfur and copper to the lead smelting process are thoroughly solved, valuable metals (copper, lead, zinc, silver and the like) are effectively separated, and the comprehensive economic benefit is improved and the environmental protection problem is solved.
In the high-temperature smelting blast process, a 23-25% oxygen-enriched air condition can be adopted as a blast operation process condition, under the same equipment and process conditions, the lump material processing capacity is improved by 15-25%, the coke is saved by 15-30%, and the furnace-shaped production control is more stable.
The adhesive in the step A is iron powder, clay or polyurethane adhesive.
The silicon-containing auxiliary materials added in the step A are silica and cullet, the calcium-containing auxiliary materials are limestone, and the iron-containing auxiliary materials are iron ore or iron powder.
In the step A, the auxiliary materials containing silicon and calcium are powder materials.
And C, crushing in the step A by adopting a double-roller crushing mode or other crushing modes.
In the step B, the size and the length of the prepared brick-shaped material block are in the range of 150-300, the width of the brick-shaped material block is in the range of 80-150, and the thickness of the brick-shaped material block is in the range of 40-80.
And step B, proportioning coke which accounts for 10-18% of the weight of the brick block materials and the auxiliary materials in the smelting furnace, and adding the coke into the blast smelting furnace in batches.
In step B, SiO in the slag formed by smelting 2 The content is 28% -45%, the content of FeO is 20% -28%, and the content of CaO is 5% -15%.
In the step B, the auxiliary materials containing silicon and calcium are powder or lump materials.
In the step B, the temperature of the molten slag is 1250-1300 ℃.
And controlling the temperature of the molten slag in the step B to be higher than 1200 ℃. If the temperature of the molten slag is lower than 1200 ℃, the copper matte and the yellow slag are easy to form a distillation structure, and stay in the hearth to cause an environment hindering the smelting process, and finally the hearth stacking and dead furnace phenomenon is formed.
The working principle and the working process of the invention are as follows:
the method is characterized in that copper smelting smoke dust and secondary lead-containing materials (which can be used independently or in a mixed manner as main raw materials) are subjected to process calculation according to batches, auxiliary materials containing silicon, calcium and iron are added according to required slag types, silicon is silica, cullet, silicon-containing waste materials and the like, calcium is limestone, lime calcium-containing waste residues and the like, iron is iron ore, rotary kiln slag magnetic separation iron powder, iron-containing waste residue and the like are added, wherein the auxiliary materials are fine powder materials and can be added in a first-time preparation manner, if the auxiliary materials are lump materials, iron is iron powder obtained by magnetic separation of rotary kiln slag, the iron in the iron powder is mainly iron powder existing in a metal iron form and mixed with the materials for making bricks, the metal iron powder is easy to generate oxidation under the condition of certain moisture and air to form a net-shaped stable structure of iron oxide, meanwhile, moisture in the bricks is evaporated due to the heating effect of the oxidation reaction, so that the bricks are hardened and solidified, the smelting requirement can be met, the purpose of curing and hardening can be achieved, if other iron-containing auxiliary materials are adopted, a good adhesive is selected certainly to meet the requirements of curing, hardening and smelting, the batch mixture needs to contain 5-13% of water, the roughly mixed materials are crushed uniformly and secondarily mixed, a crusher adopts double-roller crushing, the materials enter a brick making machine and are pressed into standard brick-shaped blocks under the pressure of 20-100 MPa, and the blocks are naturally stacked and solidified for 3-5 days to be cured and hardened to meet the requirements of smelting in a furnace.
The method comprises the steps of proportioning 10-18% by weight of secondary blocky auxiliary materials required by solid brick proportioning, adding coke into a blast smelting furnace in batches, adding materials from the side of the top of the furnace, feeding the materials into a preheating zone, passing through an upper reduction zone and a lower reduction zone, reducing most of lead oxide into elemental lead by the carbon monoxide, completing partial interaction reaction between lead sulfate, lead oxide and lead sulfide to form metallic lead, generating the temperature of 900-1350 ℃ in the smelting zone and a coke layer rich in deposited carbon under the condition of blast air to form a strong oxidation-reduction reaction environment, completing slagging reaction of SO2, FeO and CaO in the smelting zone, dissolving AI2O3, MgO, ZnO, CaO and FeO, performing replacement reaction on the lead oxide in lead silicate, reducing the replaced lead oxide into the metallic lead, forming redundant sulfur, copper and iron into copper sulfonium, and forming carbon monoxide formed by air and carbon and the iron and arsenic in the bricks under the condition of 700-1100 ℃, and (2) forming a strong reduction reaction to generate iron arsenide, wherein the slag, copper matte, iron arsenide reduced lead and complete reaction materials are subjected to the strong reduction reaction through a high-temperature carbon layer and enter a hearth, the incomplete chemical reaction is continuously completed, the materials are layered according to density, the bottom layer is crude lead and is discharged through an siphon suction port of a smelting furnace hearth, the top layer is molten slag, the middle layer is copper matte, iron arsenide and yellow slag, the materials are continuously subjected to reaction separation under the condition of high-silicon high-temperature molten slag, and are finally discharged together with slag through a slag discharge port to a front bed or a precipitation pot, water quenching slag, copper matte, iron arsenide and iron arsenide are separated, and the generated smoke dust can be subjected to wet recovery of multiple metals or continuous cyclic collection treatment to complete the whole smelting process.
The process of each metal oxide in the smelting separation process is as follows: zinc mainly forms compounds with iron and silicon into the slag, and the other part enters the smoke dust in the form of oxides. About 30-50% of the tin is reduced with the lead into lead bullion, another part into slag and another part into soot as oxides. Antimony is reduced and smelted into lead bullion mainly together with lead, and the rest part of the antimony enters slag and smoke dust. Most of the bismuth and lead are reduced and smelted into crude lead, and a small part of the bismuth and lead enter into slag and smoke. The gold and silver are mainly reduced and smelted with lead to crude lead, and a very small part of the gold and silver enters slag and copper matte.
Example 1
According to the implementation of the process flow of the clean smelting method of the copper smelting smoke dust, 500 tons of copper smelting smoke dust, 150 tons of other lead materials, 243 tons of iron-containing materials and 107 tons of other auxiliary materials are used for mixed brickmaking to form 1000 tons, the moisture content is 8.5 percent, and the main components are prepared: 18.31% of Pb, 6.42% of S and SiO 2 19.76%, 18.25% of Fe and 5.5% of CaO, and the total amount of 150 tons per day of the raw materials fed into a blast furnace produced 150.29 tons of crude lead, the vertical yield being 88.6%, 153.48 tons of matte, 5.26% of copper and 3.2% of lead; 112.35 tons of iron arsenide are produced, and the water granulated slag components are as follows: pb 0.86%, Cu 0.45%, CaO 8.56%, Fe 22.34%, and SiO 2 30.33 percent, the furnace condition is normal, the production is stable, and the copper and matte separation is normal under the process condition.
Example 2
According to the process flow of the clean smelting method of the copper smelting smoke dust, 500 tons of copper smelting smoke dust, 150 tons of other lead materials, 238 tons of iron-containing materials and 112 tons of other auxiliary materials are used for mixed brickmaking to form 1000 tons, the water content is 9 percent, and the main components are prepared: 22.56% of Pb, 7.26% of S, 19.11% of Fe and SiO 2 21.22 percent and 5.8 percent of CaO, the raw materials are put into a blast furnace according to the daily amount of 150 tons, the total yield of crude lead is 190.56 tons, the vertical yield is 90.45 percent, the matte is 148.28 tons, the copper content is 5.85 percent, and the lead content is 3.35 percent; 108.45 tons of iron arsenide are produced, and the water slag components are as follows: pb 0.78%, Cu 0.35%, CaO 9.23%, Fe 23.45%, SiO 2 32.23%, the process conditions are normal, the production is stable, and the copper-matte separation is normal.
Example 3
According to the process flow of the clean smelting method of the copper smelting smoke dust, 500 tons of copper smelting smoke dust, 120 tons of other lead materials, 256 tons of iron-containing materials and 74 tons of other auxiliary materials are used for mixed brickmaking to form 1000 tons, the water content is 10 percent, and the main components are prepared: 21.85% of Pb, 7.55% of S, 20.25% of Fe and SiO 2 16.35% and 8.86% CaO, were charged into a blast furnace in an amount of 150 tons per day, yielding 165.44 tons of lead bullion in total, 81.23% of the vertical yield, 198.28 tons of matte, 3.85% copper, 1.56% lead, 98.56 tons of iron arsenide, and the grain slag component: pb 2.97%, Cu 0.54%, CaO 13.03%, Fe 28.88%, SiO 2 24.04%, the process conditionsUnder the conditions of abnormal furnace conditions, unstable production, low copper content in the copper-matte separation, high lead content and low vertical yield.
Example 4
According to the implementation of the process flow of the clean smelting method of the copper smelting smoke dust, 500 tons of copper smelting smoke dust, 150 tons of other lead materials, 220 tons of iron-containing materials and 130 tons of other auxiliary materials are used for mixed brickmaking to form 1000 tons, the water content is 10 percent, and the main components are prepared: 22.88% of Pb, 6.85% of S, 21.35% of Fe and SiO 2 23.45% and 10.86% CaO, 150 tons per day, in total, 197.44 tons of lead bullion, 91.23% of lead yield, 201.28 tons of matte, 5.12% copper, 3.45% lead, 134.85 tons of iron arsenide, water granulated slag component: pb 0.56%, Cu 0.34%, CaO 16.71%, Fe 22.88%, SiO 2 34.15 percent, the furnace condition is normal, the production is stable, and the copper and matte separation is normal under the process condition.
Example 5
According to the process flow of the clean smelting method of the copper smelting dust, 650 tons of lead sulfate-containing slag and lead-containing materials thereof, 215 tons of iron-containing materials and 135 tons of other auxiliary materials are mixed and bricked to form 1000 tons, the water content is 8.8 percent, and the main components of the mixture are as follows: 28.25% of Pb, 7.85% of S, 22.85% of Fe and SiO 2 20.45 percent and 8.86 percent of CaO, and the total yield of crude lead 238.68 tons, matte 188.45 tons, copper 1.45 percent and lead 3.98 percent by putting the materials into a blast furnace according to the daily amount of 150 tons, and the yield of iron arsenide 75.32 tons and grain slag components: 1.2% of Pb, 0.34% of Cu, 14.70% of CaO, 24.55% of Fe, and SiO 2 35.18 percent, normal furnace condition, stable production and normal copper and matte separation under the process condition.

Claims (8)

1. A clean production method of copper smelting smoke dust and lead-containing secondary materials is characterized by comprising the following steps: comprising the following step A): raw material preparation and solidification, B) high-temperature smelting and separation;
a: preparation and curing of raw materials
Adding auxiliary materials of iron, silicon and calcium into copper smelting smoke dust and/or secondary lead materials, supplementing according to batches, adding a bonding agent, mixing to obtain a 5-13% aqueous mixture, crushing, uniformly mixing, pressing into a brick block material in a brick making machine under the pressure of 20-100 mpa, stacking and curing for 3-5 days to naturally cure and harden the brick block material and meet the smelting requirement;
b: high temperature smelting separation
B, feeding the shaped bricks and coke cured and hardened in the step A into a blast furnace according to a certain ratio, wherein coke is mixed according to 10-18% of the weight of brick shaped blocks and auxiliary materials, preparing auxiliary materials containing silicon and calcium and return materials, adding the auxiliary materials and the return materials into a smelting furnace in batches, adding the materials from the side of the furnace top, entering a preheating zone, passing through an upper reduction zone and a lower reduction zone, entering a smelting zone, forming a strong redox reaction environment by adopting a coke layer and air blast in the smelting zone, wherein the reaction temperature is 900-1300 ℃, and SiO is completed in the smelting zone 2 FeO, CaO slag and dissolve Al 2 O 3 The method comprises the following steps that (1) PbO in lead silicate is replaced by MgO, ZnO, CaO and FeO, the replaced lead oxide is reduced to metallic lead, redundant sulfur copper and iron form copper matte, and after furnace burden is completely melted, the formed liquid flows downwards and is overheated by a high-heat coke layer to complete most of reduction reaction; carrying out oxidation reduction reaction smelting in a smelting furnace, enabling molten liquid formed by smelting to flow into a hearth for continuous reaction to finish the unfinished chemical reaction, layering according to density difference, discharging crude lead at the lowest layer through a siphon port of the smelting furnace, discharging the crude lead at the lowest layer, slag at the uppermost layer, copper matte and yellow slag at the middle layer, continuously reacting and separating under the condition of high-temperature slag, finally discharging the crude lead and the slag together through a slag discharge port to a front bed or a precipitation pot, separating out water quenching slag, copper matte and ferric arsenate, and continuously carrying out circulating collection treatment on generated smoke dust to finish the whole smelting process, wherein SiO in the slag formed by smelting, SiO, is collected in a smelting way 2 The content is more than 28 percent and less than or equal to 45 percent, and SiO 2 The content of FeO is more than that of FeO, the content of FeO is between 20 and 28 percent, the content of CaO is between 5 and 15 percent, and the temperature range of the smelting slag is 1200 to 1350 ℃.
2. The clean production method of copper smelting dust and lead-containing secondary materials according to claim 1, wherein the binder in step A is iron powder.
3. The clean production method of copper smelting dust and lead-containing secondary materials according to claim 1, wherein the silicon-containing auxiliary material added in the step A is silica or cullet, the calcium-containing auxiliary material is limestone, and the iron-containing auxiliary material is iron ore or iron powder.
4. The clean production method of copper smelting dust and lead-containing secondary material according to claim 1, wherein the auxiliary materials containing silicon and calcium in the step A are powder materials.
5. The clean production method of copper smelting dust and lead-containing secondary materials according to claim 1, characterized in that the crushing in the step A adopts a double-roller crushing mode.
6. The clean production method of copper smelting dust and lead-containing secondary materials according to claim 1, wherein in the step B, the brick-shaped material block is required to have a length range of 150-300 mm, a width range of 80-150 mm and a thickness range of 40-80 mm.
7. The clean production method of copper smelting dust and lead-containing secondary materials according to claim 1, wherein in the step B, the auxiliary materials containing silicon and calcium are powder or lump materials.
8. The clean production method of copper smelting dust and lead-containing secondary materials according to claim 1, wherein in the step B, the temperature of the molten slag is 1250-1300 ℃.
CN202010426754.9A 2020-05-19 2020-05-19 Clean production method of copper smelting smoke dust and lead-containing secondary material Expired - Fee Related CN111676374B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010426754.9A CN111676374B (en) 2020-05-19 2020-05-19 Clean production method of copper smelting smoke dust and lead-containing secondary material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010426754.9A CN111676374B (en) 2020-05-19 2020-05-19 Clean production method of copper smelting smoke dust and lead-containing secondary material

Publications (2)

Publication Number Publication Date
CN111676374A CN111676374A (en) 2020-09-18
CN111676374B true CN111676374B (en) 2022-08-23

Family

ID=72452095

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010426754.9A Expired - Fee Related CN111676374B (en) 2020-05-19 2020-05-19 Clean production method of copper smelting smoke dust and lead-containing secondary material

Country Status (1)

Country Link
CN (1) CN111676374B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112981133B (en) * 2021-02-06 2023-01-03 易门铜业有限公司 Method for reducing smoke dust rate of copper smelting bottom blowing furnace
CN113564381B (en) * 2021-07-26 2022-09-23 广东飞南资源利用股份有限公司 Synergistic copper smelting method and building material
CN114890428B (en) * 2022-04-29 2023-05-09 成都理工大学 Ternary slag former for external refining of industrial silicon and impurity removing method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101871050B (en) * 2010-06-13 2011-11-16 昆明理工大学 Method for eliminating magnetic iron oxide furnace accretion produced in copper sulfide concentrate pyrometallurgical process
CN102776376B (en) * 2012-08-08 2013-10-30 汉源县广超有色金属综合回收有限责任公司 Method for recovering valuable metal from waste residue containing lead and zinc through wet-fire combination process
CN106167855B (en) * 2016-08-08 2018-03-06 方喜 A kind of cleaning method of smelting of lead containing sludge
CN107699701A (en) * 2017-10-10 2018-02-16 东北大学 By the method containing zinc and the mixing slag recovery valuable component of iron

Also Published As

Publication number Publication date
CN111676374A (en) 2020-09-18

Similar Documents

Publication Publication Date Title
CN111676374B (en) Clean production method of copper smelting smoke dust and lead-containing secondary material
CN102433448A (en) Smelting method of antimony-zinc-lead-containing concentrate
WO2019071791A1 (en) Method for smelting reduction production of zinc smelting slag
CN101157994B (en) Oxygen fused bath smelting method for lead-antimony ore
CN105671314A (en) Direct smelting method and system for producing metallic lead and zinc at the same time
CN102634653B (en) Side-blowing material-smelting production method
CN103924101A (en) Method and device for producing crude antimony trioxide by smelting of rich oxygen side-blown volatile molten pool
CN104278162A (en) Method of selectively smelting antimony-lead-containing complex materials in smelting tank
WO2019071789A1 (en) Method for recovering valuable components from zinc smelting slag
CN105950869A (en) Method for increasing matching amount of lead-silver residue of zinc hydrometallurgy in efficient resource utilization
CN106734051B (en) The processing method of CRT flint glass
CN103993164A (en) Simultaneous multi-metal smelting and separating method for mixed oxide and sulfide ore of lead and zinc
CN1323177C (en) High Iron zinc calcine process method
CN101812594B (en) Method for simultaneously smelting hydrolysis slag, pyrite and zinc kiln slag by using blast furnace
CN115341106A (en) Method and device for producing high nickel matte from low nickel matte
WO2007038840A1 (en) Method and apparatus for lead smelting
US8298316B2 (en) Method for producing pig iron
CN106086437B (en) The method and system of the direct-reduction of wet method zinc smelting dreg
CN113817924A (en) Method for producing blister copper by smelting copper dross and smelting device thereof
US3847595A (en) Lead smelting process
CN112143908B (en) Smelting process for treating complex gold ore
CN111979424A (en) Metallurgy method of high-sulfur lead slag containing zinc and tin
CN112080643B (en) Method for efficiently recovering metals in solid waste by smelting method and solid waste smelting furnace thereof
CN102864313B (en) Smelting method of natural copper mine
CN111041225B (en) Oxygen-enriched side-blown smelting method for lean high-silicon copper concentrate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20220823

CF01 Termination of patent right due to non-payment of annual fee