CN108291271A - The zinc abstraction method of environmental protection - Google Patents
The zinc abstraction method of environmental protection Download PDFInfo
- Publication number
- CN108291271A CN108291271A CN201580084777.3A CN201580084777A CN108291271A CN 108291271 A CN108291271 A CN 108291271A CN 201580084777 A CN201580084777 A CN 201580084777A CN 108291271 A CN108291271 A CN 108291271A
- Authority
- CN
- China
- Prior art keywords
- metal
- ferrite
- sulfur dioxide
- zinc
- processing method
- 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.)
- Pending
Links
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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/32—Refining zinc
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
Abstract
The present invention relates to a kind of zinc abstraction methods of environmental protection, provide a kind of processing method of Zn ferrite, include the following steps：The Zn ferrite (Zinc Ferrite) generated in zinc wet type smelting procedure is set to generate evaporated metal oxide, form waste gas of sulfur dioxide and environment protection clean clinker by evaporation (Fuming) process；By making the evaporated metal oxide and the form waste gas of sulfur dioxide generated in described evaporation (Fuming) step be reacted, to be converted to the metal sulfate compound and/or metal hydrosulfide (Metal Sulfate or Sulfite) of solids；It is metal sulfate compound and concentration sulfur dioxide gas to decompose (Decomposition) and by making the metal hydrosulfide (Metal Sulfite) be reacted with sulfuric acid.
Description
Technical field
The present invention relates to a kind of environment-friendly treatment methods of the Zn ferrite generated in the smelting procedure of zinc.
Background technology
The method for extracting zinc from zinc concentrate has dry type smelting process and wet type smelting process.Dual wet type smelting process exists
Roasting (Roasting) zinc concentrate is simultaneously allowed to after dissolving (Leaching), is finally led to after purified (Purification) process
Cross electrolysis (Electrolysis) extraction high-purity Zn.
Zn ferrite (Zinc ferrite) is generated in the calcining process of this wet type smelting process, the substance is in conduct
The neutral dissolution (Neutral Leaching) and/or weak acid of two traditional step dissolution mechanisms dissolve (Weak Acidic
Leaching it) will not be dissolved well in process.
Therefore, in order to further dissolve the zinc in Zn ferrite (Zinc ferrite), lead in most of zinc abstraction factory
Following strong acid dissolution (Strong Acidic Leaching) process is crossed to increase the rate of recovery of zinc.
ZnOFe2O3+4H2SO4- ＞ ZnSO4+Fe2(SO4)3+4H2O
At this point, the Tie Tong dissolved together with zinc is crossed is converted to goethite (Goethite), autunezite in other processes
(Jarosite) or the form of bloodstone (Hematite) etc. and detach/be discharged to except process.
But since this substance as zinc abstraction waste material contains heavy metal and sulfidic material, in most of smelting
In factory by the permanently keeping of this substance in for antipollution special accumulation field.In this case, the valuable gold in part
Category is permanently accumulated without being recovered together with zinc abstraction waste material.
In addition, the permanent keeping of environmentally harmful zinc abstraction waste material is in because society's worry in area and various countries are progressive
Environmental legislation is strengthened and is difficult to ensure the additional situation for accumulating factory.
This additional accumulation factory ensures that the going concern to zinc abstraction cause from now on becomes powerful barrier factors.
Invention content
The project of the present invention is that zinc abstraction waste material is technically converted to environmentally friendly substance and solves accumulation and ask by exploitation one kind
Topic, and the method for the most of valuable metal and oxysulfide matter such as recycle the zinc in Zn scrap returns.
In the one of the present invention realizes example, a kind of processing method of Zn ferrite is provided comprising following steps：Pass through steaming
Hair (Fuming) process makes the Zn ferrite (Zinc Ferrite) generated in zinc wet type smelting procedure generate evaporated metal oxygen
Compound, form waste gas of sulfur dioxide and environmentally friendly clinker；And by making the evaporated metal oxide and in the evaporation (Fuming)
The form waste gas of sulfur dioxide generated in step reacts to each other, to be converted to the metal sulfate compound and/or gold of solids
Belong to hydrosulfide (Metal-Sulfate or Sulfite).
An example as the metal sulfate compound has zinc sulfate.In addition, as the metal hydrosulfide
An example has zinc sulfite.It as with next example, is illustrated by taking zinc as an example, but other gold included in zinc abstraction process
Category can also apply the process.
It can be executed in Drechsel system by making the evaporated metal oxide and in described evaporation (Fuming) step
The form waste gas of sulfur dioxide generated in rapid is reacted, to be converted to the metal sulfate compound and/or metal sulfurous of solids
The step of acid compound (Metal-Sulfate or Sulfite).
The processing method of the Zn ferrite can further comprise：(Decomposition) process is decomposed, by making acquisition
The metal hydrosulfide (Metal Sulfite) reacted with sulfuric acid and be allowed to decompose (Decomposition),
Metal sulfate compound and concentration sulfur dioxide gas (SO are recycled by the decomposition process2)。
It can recycle and pass through back in neutral and/or weak acid dissolution process (Neutral＆Weak Acidic Leaching)
The metal sulfate compound received.
It can be by being sent into the recovered concentration sulfur dioxide gas to sulfuric acid preparation section, in sulfuric acid preparation
Utilize the concentration sulfur dioxide gas.
By the processing method of the Zn ferrite ironworker can be removed in the strong acid dissolution process not added and in additional
Zinc wet type smelting procedure is executed in the case of the iron-containing waste generated in sequence.
The processing method of the Zn ferrite further comprises the steps：Pass through the metal sulfate chemical combination that will be obtained
Object (Metal Sulfate) or the metal hydrosulfide (Metal Sulfite) be added to closed blast furnace (ISF,
Imperial Smelting Furnace), to recycle valuable metal, and the sulfur dioxide gas generated at this time is sent into
Sulfuric acid preparation section and sulfuric acid preparation in utilize the sulfur dioxide gas.
It, can be in zinc abstraction process in the case where realizing the processing method of Zn ferrite of example using the one of the present invention
Dissolution equipment and process are improved to be easy, and can also reduce process running expense.
Furthermore it is possible to solve to need to precipitate dissolved iron and the waste material that generates permanently accumulates the environmental problem of keeping,
And the addition valuable metal other than zinc can be obtained.
Furthermore it is possible to reduce the generation of other waste materials or waste water for being generated in the waste gas treatment process being discharged.
More specifically, while insurmountable environmental problem in existing zinc abstraction method can be eliminated, can make
The rate of recovery of zinc and other valuable metals included in zinc concentrate maximizes.
Description of the drawings
Fig. 1 be indicate include the present invention one realize example Zn ferrite processing method zinc metallurgical process process
Figure.
Fig. 2 is the work of the process for the method for indicating to handle the zinc oxide obtained by described evaporation (Fuming) step
Sequence figure.
Specific implementation mode
With reference to the embodiment that describes in detailed below while with reference to attached drawing, it will clear advantages and features of the invention and
The method for realizing these.But the present invention is not limited to embodiments as disclosed below, but can be with different from each other more
Kind mode realizes that the present embodiment only makes disclosure of the invention comprehensive, and for the technology to the technical field of the invention
Personnel inform the scope of the present invention and provide that the present invention is only defined by the scope of the claims.It is identical in the specification
Reference numeral refers to identical structural element.
Therefore, in several embodiments, in order to avoid faintly explaining the present invention, to known technology without specifically
It is bright.If without other definition, all term (including technical terms and scientific terms) energy used in the present specification
Enough meanings being commonly understood by with those skilled in the art use.In addition, in the specification, when mentioning
When certain part " comprising " structural element, without especially opposite record, other structures are not precluded in this expression
Element can further comprise other structures element.In addition, singulative includes plural shape as long as not specifically mentioned in sentence
Formula.
Fig. 1 is the process chart of the process for the zinc abstraction method for indicating one embodiment of the invention.
The zinc abstraction method of one embodiment of the invention is illustrated referring to Fig.1.First, following reaction is executed：It is logical
It crosses and is roasted by (roasting) and produces the roasting for including zinc oxide (ZnO) and Zn ferrite (Zinc ferrite) for zinc concentrate
Sand, and the sulphur in concentrate is converted into sulfur dioxide (SO in roasting process2)。
The main component of zinc concentrate includes Zn, Fe and S, and includes Pb, Cu, Cd, Co, Ag, Au as other metals
Deng.
Calcining process is that the zinc concentrate of the difficult oxide morphology for being dissolved in sulfuric acid is made to be oxidized to soluble Zn calcining
(calcine) process.
The key reaction of calcining process is as described below.
ZnS+3/2O2—>ZnO+SO2
ZnS+2FeS+5O2—>ZnOFe2O3+3SO2
The SO generated in calcining process2It is utilized when can prepare sulfuric acid in sulfuric acid plant.
The zinc oxide and Zn ferrite (Zinc ferrite) generated in calcining process can imported into calcining dissolution process.
Neutral and weak acid dissolving (Neutral＆Weak Acid Leaching) process is to make to generate as in calcining process
Calcining main component zinc oxide (ZnO) dissolving (leaching) in the process of sulfuric acid solvent.
Zn ferrite (Zinc ferrite) difficult soluble substance in the calcining generated in calcining process, neutral and weak
It will not be dissolved in sour dissolution process.
Key reaction in neutral and weak acid dissolution process is as described below.
ZnO+H2SO4—>ZnSO4+H2O
For neutral dissolution process, when reacting beginning, pH ranges can be 2.0 to 2.5, pH at the end of reaction
Range can be 3.5 to 5.0.
Weak acid dissolution process makes the undissolved residue zinc oxide (ZnO) in neutral dissolution process dissolve and convert.
It has been observed that implementing strong acid dissolution process (strong in the past in order to handle Zn ferrite (Zinc ferrite)
Acid leaching) and process that dissolved iron is removed with residual iron (goethite, Hematite, Jarosite) form
(iron precipitation, the precipitation of iron), but the present invention one realize example in using evaporation (Fuming) step without
It can implement strong acid dissolution process (strong acid leaching) and iron removal step (iron precipitation).
For the weak acid dissolution process, when reacting beginning, pH ranges can be 1.5 to 2.0, terminate in reaction
When pH ranges can be 2.5 to 3.0.
The Zn ferrite (Zinc ferrite) not leached in the dissolution process can imported into evaporation (Fuming)
Process.
Evaporation (Fuming) process is following process：By that will include Zn ferrite (Zinc ferrite), coal
(coal) and the air of oxygen is injected into vapourizing furnace (fuming furnace) and is heated, to generate zinc oxide (ZnO) and
Form waste gas of sulfur dioxide.
The execution step of described evaporation (Fuming) process can execute at 1250 DEG C to 1350 DEG C of temperature range.
Zinc oxide (ZnO) and sulfur dioxide are discharged by the reaction process in described evaporation (Fuming) process
(SO2) exhaust gas.
It not only may include zinc oxide in the effluent using evaporation (Fuming) process discharge, but also can be further
Include the compound of the metals such as Pb, Cu, Cd, Co, Ag, Au included in zinc concentrate.
In addition, in the one of the present invention realizes example, in order to improve yield and prepare environmentally friendly clinker, the evaporation (Fuming)
Process may include melting step (Smelting) and reduction step (Reduction).
Injection it can include Zn ferrite (Zinc ferrite), coal (coal) in the fusing step (Smelting)
And oxygen air and heated, to generate zinc oxide (ZnO), form waste gas of sulfur dioxide and clinker.
It can be by being further injected into the clinker generated in the fusing step (Smelting) comprising coal (coal)
And oxygen air and execute reduction step (Reduction), and the clinker by making to remain in fusing step (Smelting)
In zinc and other volatile metals be evaporated (Fuming) oxidation and recycle zinc oxide (ZnO), lead oxide (PbO), oxidation
Indium (Indium Oxide), silver-colored (Ag) etc. simultaneously generate form waste gas of sulfur dioxide.
It can be with copper speiss (Copper as the copper (Cu) of nonvolatile matter, a part silver-colored (Ag) and gold (Au)
Speiss) together to melt metal form recycling.The realization example of the present invention may include in the form of environmentally stable clinker
The step of substance in addition to this is discharged.
Fig. 2 is the work of the process for the method for indicating to handle the zinc oxide obtained by described evaporation (Fuming) step
Sequence figure.
As can be seen from Figure 2, the sulfur dioxide gas (SO generated in evaporation step2) washing methods may include：First reaction,
By will by it is described evaporation (Fuming) step obtain zinc oxide be added in Drechsel system and make its in evaporation step
Sulfur dioxide gas (the SO of middle generation2) reacted and generate zinc sulfite (ZnSO3)；And second reaction, pass through the Asia
Zinc sulfate (ZnSO3) and sulfuric acid (H2SO4) dissolving reaction, so that it is converted to zinc sulfate (ZnSO4) and concentration sulfur dioxide gas
(SO2)。
The key reaction of first reaction and the second reaction is as described below.
ZnO+SO2→ZnSO3
ZnSO3+H2SO4→ZnSO4+SO2+H2O
By transferring the solution of zinc sulfate obtained by the zinc sulfite dissolving step to neutral and weak acid dissolution process, and
And the silver contained in zinc sulfite residue is separated into solids with lead sulfide precipitation, to be used as lead and silver recovery process
Raw material use.
About in the Drechsel system of first reaction zinc sulfite that generates handled other are second anti-
It answers, is returned by putting into sulfuric acid process or closed blast furnace (ISF, Imperial Smelting Furnace)
Receive zinc sulfite in zinc, and in closed blast furnace (ISF, Imperial Smelting Furnace) sulfuric acid plant into
The processing of sulfur dioxide gas caused by row.
More than, the realization example of the present invention is illustrated with reference to attached drawing, but the technology people of the technical field of the invention
Member it will be understood that can implement in other specific forms in the case where not changing the technological thought or essential feature of the present invention.
It is therefore to be understood that above recorded realization example be exemplary rather than in all respects it is limited.This
The range of invention is presented by the range of the claims described after above-mentioned detailed description, should be interpreted that from claim
Form after having altered or change derived from the meaning and range of book and its impartial concept is within the scope of the present invention.
Claims (8)
1. a kind of processing method of Zn ferrite, includes the following steps：
The Zn ferrite (Zinc Ferrite) generated in zinc wet type smelting procedure is set to generate by evaporation (Fuming) process
Evaporated metal oxide and form waste gas of sulfur dioxide；And
By making the evaporated metal oxide and the form waste gas of sulfur dioxide generated in described evaporation (Fuming) step carry out
Reaction, to be converted to the metal sulfate compound and/or metal hydrosulfide (Metal-Sulfate or of solids
Sulfite)。
2. the processing method of Zn ferrite according to claim 1, wherein
According to the processing method of the Zn ferrite, in strong acid dissolution process (the Strong Acidic not added
Leaching it in the case of), is held by neutral and/or weak acid dissolution process (Neutral＆Weak Acidic Leaching)
Row zinc wet type smelting procedure.
3. the processing method of Zn ferrite according to claim 2, wherein
It is executed in Drechsel system by making the evaporated metal oxide and generating in described evaporation (Fuming) step
Form waste gas of sulfur dioxide reacted, to be converted to the metal sulfate compound and/or metal hydrosulfide of solids
The step of (Metal-Sulfate or Sulfite).
4. the processing method of Zn ferrite according to claim 3, wherein further comprise：
Decompose (Decomposition) process, by make the metal hydrosulfide (Metal Sulfite) of acquisition with
Sulfuric acid is reacted and is allowed to decompose (Decomposition),
Metal sulfate compound and concentration sulfur dioxide gas (SO are recycled by the decomposition process2)。
5. the processing method of Zn ferrite according to claim 4, wherein
It is recycled in neutral and/or weak acid dissolution process (Neutral＆Weak Acidic Leaching) recovered described
Metal sulfate compound.
6. the processing method of Zn ferrite according to claim 4, wherein
It is recycled in neutral and/or weak acid dissolution process (Neutral＆Weak Acidic Leaching) recovered described
Metal sulfate compound, and undissolved silver and lead are concentrated and are recycled with solids.
7. the processing method of Zn ferrite according to claim 4, wherein
It, should to be utilized in sulfuric acid preparation by being sent into the recovered concentration sulfur dioxide gas to sulfuric acid preparation section
Concentrate sulfur dioxide gas.
8. the processing method of Zn ferrite according to claim 1, wherein
Further comprise the steps：Pass through the metal sulfate compound (Metal Sulfate) that will be obtained or the gold
Belong to hydrosulfide (Metal Sulfite) and be added to closed blast furnace (ISF, Imperial Smelting Furnace),
To recycle valuable metal, and the sulfur dioxide gas generated at this time feeding sulfuric acid preparation section is sharp in sulfuric acid preparation
With the sulfur dioxide gas.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2015/012593 WO2017090784A1 (en) | 2015-11-23 | 2015-11-23 | Eco-friendly zinc smelting method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108291271A true CN108291271A (en) | 2018-07-17 |
Family
ID=58763597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580084777.3A Pending CN108291271A (en) | 2015-11-23 | 2015-11-23 | The zinc abstraction method of environmental protection |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN108291271A (en) |
| AU (1) | AU2015415628A1 (en) |
| MX (1) | MX2018006356A (en) |
| WO (1) | WO2017090784A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101889680B1 (en) | 2018-02-01 | 2018-08-17 | 고려아연 주식회사 | Method for recovering Fe from zinc sulfate solution |
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|---|---|---|---|---|
| US4619814A (en) * | 1978-05-05 | 1986-10-28 | Provincial Holdings Ltd. | Process for the recovery of non-ferrous metals from sulphide ores and concentrates |
| JPH05171310A (en) * | 1991-12-25 | 1993-07-09 | Mitsubishi Materials Corp | Zinc smelting method by reducing roasting |
| CN100392123C (en) * | 2003-07-04 | 2008-06-04 | 尤米科尔公司 | Recovery of non-ferrous metals from zinc residues |
| CN102134655A (en) * | 2010-12-29 | 2011-07-27 | 昆明理工大学 | Method for separating zinc and indium and iron from indium-enriched high-iron high-zinc calcine through reduction-magnetic separation |
| CN102912147A (en) * | 2012-11-15 | 2013-02-06 | 昆明冶金研究院 | Process for recycling lead zinc, silver and iron from tailings after carrying out sulphur flotation on zinc oxygen pressure leaching slag |
| CN103540765A (en) * | 2013-10-12 | 2014-01-29 | 中南大学 | Zinc smelting technology |
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| DE69125021T2 (en) * | 1990-11-14 | 1997-06-12 | Minproc Technology Pty Ltd | DISTILLATION BY DIRECT SULFIDISATION OF ZINC |
| KR20000052340A (en) * | 1999-01-23 | 2000-08-25 | 이호인 | Zine collecting method from steel powder containing zinc ferrite |
| EP1997919A1 (en) * | 2007-05-24 | 2008-12-03 | Paul Wurth S.A. | Method of recovering zinc- and sulphate-rich residue |
| MX349844B (en) * | 2012-07-16 | 2017-08-16 | Tam 5 S L * | Hydrometallurgical method for recovering zinc in a sulphuric medium from zinc sulphide concentrates having a high iron content. |
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2015
- 2015-11-23 WO PCT/KR2015/012593 patent/WO2017090784A1/en active Application Filing
- 2015-11-23 MX MX2018006356A patent/MX2018006356A/en unknown
- 2015-11-23 CN CN201580084777.3A patent/CN108291271A/en active Pending
- 2015-11-23 AU AU2015415628A patent/AU2015415628A1/en not_active Abandoned
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|---|---|---|---|---|
| US4619814A (en) * | 1978-05-05 | 1986-10-28 | Provincial Holdings Ltd. | Process for the recovery of non-ferrous metals from sulphide ores and concentrates |
| JPH05171310A (en) * | 1991-12-25 | 1993-07-09 | Mitsubishi Materials Corp | Zinc smelting method by reducing roasting |
| CN100392123C (en) * | 2003-07-04 | 2008-06-04 | 尤米科尔公司 | Recovery of non-ferrous metals from zinc residues |
| CN102134655A (en) * | 2010-12-29 | 2011-07-27 | 昆明理工大学 | Method for separating zinc and indium and iron from indium-enriched high-iron high-zinc calcine through reduction-magnetic separation |
| CN102912147A (en) * | 2012-11-15 | 2013-02-06 | 昆明冶金研究院 | Process for recycling lead zinc, silver and iron from tailings after carrying out sulphur flotation on zinc oxygen pressure leaching slag |
| CN103540765A (en) * | 2013-10-12 | 2014-01-29 | 中南大学 | Zinc smelting technology |
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| 黄丽美: "氧化锌脱硫技术在铅锌冶炼厂的应用与改进", 《硫酸工业》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2015415628A1 (en) | 2018-06-14 |
| WO2017090784A1 (en) | 2017-06-01 |
| MX2018006356A (en) | 2018-09-24 |
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Application publication date: 20180717 |