CN105734290A - Arsenic removing technology for zinc hydrometallurgy - Google Patents
Arsenic removing technology for zinc hydrometallurgy Download PDFInfo
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- CN105734290A CN105734290A CN201610188983.5A CN201610188983A CN105734290A CN 105734290 A CN105734290 A CN 105734290A CN 201610188983 A CN201610188983 A CN 201610188983A CN 105734290 A CN105734290 A CN 105734290A
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- arsenic
- zinc
- leachate
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- 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
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
- 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
- C22B7/006—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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses an arsenic removing technology for zinc hydrometallurgy. The arsenic removing technology includes the following steps that under the normal-temperature condition, a neutralizing agent is added into a leaching agent in the metallurgical process to adjust the pH value of the leaching agent to be the constant value; and then an oxidizing agent is added to remove iron ions in the solution, the pH value of the leaching agent is kept at the constant value by adjusting the adding amount of the neutralizing agent, sediment is filtered out and removed, and filtrate generated after iron removing and arsenic removing is obtained. By means of the method, the neutralizing agent of lead-zinc oxide ore is used for replacing a neutralizing agent of calcium carbonate or whitewash used traditionally, generation of arsenic and iron slag is eliminated, zinc in lead zinc ore can be recycled through the wet process, zinc sulfate products are produced, produced lead, arsenic and iron ore sediment is rich in valuable metal such as lead and iron, lead bullion and arsenic products can be produced through a pyrogenic process, the production cost is reduced, and the phenomenon that a pipeline is blocked due to agglomeration of whitewash in the using process is avoided.
Description
Technical field
The invention belongs to metallurgical technology field, relate to the arsenic removal process of a kind of zinc hydrometallurgy.
Background technology
In hydrometallurgy industry, usually containing more foreign metal ion in the leachate of Ore, leachate then must be carried out deep impurity-removing by the metal product qualified to output.Usually containing a number of arsenic impurities in the leachate of Copper smelting dust, arsenic often exists with the form of arsenate and arsenite, and arsenic removal is the important one procedure of purification of leaching liquor.
At present, the domestic method adopting removal arsenic mainly has Calx neutralization precipitation method, calcium carbonate neutralization precipitation method, ferrum arsenic coprecipitation and the sodium sulfide sedimentation method.Calx neutralization precipitation method is to regulate about pH value of solution=5.0 with Calx, makes most arsenic and calcium in solution generate Tricalcium arsenate and calcium arsenite precipitation, produces substantial amounts of calcium sulfate precipitation simultaneously, and (Asia) zinc arsenate precipitates.This method advantage is that cost is low, and shortcoming is as follows: the quantity of slag is big and be difficult to process, zinc loss is big and arsenic removal not exclusively, Calx add fashionable need to sizing mixing thus reducing the slag dense, that produce of zinc in solution very easily block in pipeline, solution oversaturated calcium sulfate Crystallization Plugging pipeline gradually etc. with water.Calcium carbonate neutralization precipitation method arsenic removal principle is identical with Calx neutralization precipitation method arsenic removal principle, has the advantage that as follows: zinc loss is less slightly, need to not size mixing with water, be not easily blocked pipeline etc.；Shortcoming is as follows: the quantity of slag is big and is difficult to process, incomplete, zinc loss relatively big, the line clogging of arsenic removal etc..The sodium sulfide sedimentation method are mainly used in waste water to remove heavy metal, and that can cause zinc in solution of zinc sulfate precipitates loss in a large number, fail to apply in Purification of zinc sulfate solution.
Usually, when adopting ferrum arsenic coprecipitation deironing arsenic, first the pH of solution is transferred to 3.0, temperature rises to 70～100 DEG C, passes into air or oxygen in leachate, and ventilation limit, limit adds lime water or calcium carbonate to neutralize the acid produced in course of reaction, iron ion is allowed to precipitate with goethitum form, arsenic generates (Asia) ferric arsenate and (Asia) Tricalcium arsenate etc. with ferrum, calcium, and the basis of its arsenic removal is that Calx neutralizes (or calcium carbonate neutralization), provides Fe simultaneously3+With the absorption property that (Asia) arsenate forms more stable salt and hydrated ferric oxide., it is achieved the efficient removal of arsenic.Traditional ferrum arsenic coprecipitation has the advantage that ferrum arsenic co-precipitation flow process is short, arsenic removal totally can reach below 1mg/L, zinc loses less than calcium carbonate neutralisation etc..Shortcoming is as follows: the arsenic scum amount of generation is big and be difficult to process, blocking pipeline, solution need to be raised to higher temperature, energy resource consumption is higher, operating procedure condition require strict, when adopting air or oxygen as oxidant reaction and sedimentation time longer, in order to increase response speed, improve efficiency and then need cost huge fund to put into and build multiple continuous print reactive tanks.This several method of Integrated comparative, ferrum arsenic coprecipitation is the dearsenicating method being most frequently with.
Summary of the invention
Defect for prior art, it is an object of the invention to provide the arsenic removal process of a kind of zinc hydrometallurgy, without heating in arsenic removal iron removal, and having that the response time is short, arsenic removal de-ironing efficiency high, the plumbous symplesite precipitate strainability of generation is good and can the advantage of comprehensively recovering valuable metal.
To achieve these goals, technical scheme is as follows:
The arsenic removal process of a kind of zinc hydrometallurgy, comprises the following steps:
Under normal temperature condition, the pH value adding nertralizer adjustment leachate in metallurgical process in leachate is steady state value, it is subsequently adding oxidant and removes the iron ion in solution, and make the pH value of leachate be maintained at steady state value by regulating the addition of nertralizer, it is filtered to remove precipitate, it is thus achieved that the filtrate after deironing arsenic removal.
Described nertralizer is lead-zinc.
Described pH value is 4.5～5.
Described oxidant is hydrogen peroxide.
Total addition of described oxidant is in metallurgical process in leachate 2～3 times of ferrous ion gross mass.
Total addition of described oxidant is in metallurgical process in leachate 2.2 times of ferrous ion gross mass.
The interpolation speed of described oxidant is as the criterion less than 1g/L keeping the content of the ferric ion in solution.
Control iron concentration < 20mg/L in filtrate.
Control arsenic ion concentration < 1mg/L in filtrate.
In described metallurgical process, leachate is at least one in zinc metallurgy leachate, Copper smelting dust leachate.
Owing to adopting technique scheme, the present invention has the following advantages and beneficial effect:
The method of the present invention adopts nertralizer lead-zinc to replace nertralizer calcium carbonate or the lime water of tradition use, eliminate the generation of arsenic scum, can zinc in hydrometallurgic recovery Pb-Zn deposits, output zinc sulfate product, the plumbous symplesite precipitate of output is rich in valuable metals such as galvanized irons, pyrogenic attack output lead bullion and arsenic product can be passed through, reduce production cost, it is to avoid lime water in use lumps the phenomenon of blocking pipeline.
Oxidant hydrogen peroxide higher for oxidation effectiveness and nertralizer lead-zinc are combined use by the method for the present invention, and strictly control in course of reaction the pH value of leachate all the time in 4.5～5 scopes, adopt hydrogen peroxide as the ferrous iron in oxidizing leachate, goethite precipitation response speed is fast, and leachate need not be carried out extra heating and thermal insulation in actual mechanical process, the rapid subsidence to arsenic ferrum can be completed and remove.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
The arsenic removal process of a kind of zinc hydrometallurgy, comprises the following steps:
nullUnder normal temperature condition，The pH value adding nertralizer lead-zinc adjustment leachate in zinc metallurgy leachate is 4.5～5，It is subsequently adding oxidant hydrogen peroxide and removes the iron ion in solution，Ferrous ion major part is made to remove with the form of goethitum，Remove as ferric hydroxide on a small quantity，The interpolation speed of hydrogen peroxide is as the criterion less than 1g/L keeping the content of the ferric ion in solution，Total addition is 2.2 times of ferrous ion gross mass in zinc metallurgy leachate，And make the pH value of leachate be maintained at 4.5～5 by regulating the addition of nertralizer lead-zinc，It is filtered to remove plumbous symplesite precipitate，Complete the arsenic removal deironing cleaning procedure to zinc metallurgy leachate，Iron content arsenic content in detection filtrate，When the concentration of iron ion is less than 20mg/L，During arsenic ion concentration < 1mg/L，Show that the iron-holder containing arsenic is qualified and can enter next process.
Every technic index of the method for the present invention is good, obtains good economic benefit, simple to operate, produces without intractable arsenic scum, and the strainability of arsenic deposition of iron thing is good, recyclable valuable metal, has promotional value in the hydrometallurgy industry of the whole nation.
Embodiment 2
The arsenic removal process of a kind of zinc hydrometallurgy, comprises the following steps:
nullUnder normal temperature condition，It is 3～10g/L to iron-holder、Arsenic concentration be about in the Copper smelting dust leachate of 20～40g/L add nertralizer lead-zinc regulate leachate pH value be 4.5～5，It is subsequently adding oxidant hydrogen peroxide and removes the iron ion in solution，Ferrous ion major part is made to remove with the form of goethitum，Remove as ferric hydroxide on a small quantity，The interpolation speed of hydrogen peroxide is as the criterion less than 1g/L keeping the content of the ferric ion in solution，Total addition is 2.2 times of ferrous ion gross mass in Copper smelting dust leachate，And make the pH value of leachate be maintained at 4.5～5 by regulating the addition of nertralizer lead-zinc，It is filtered to remove plumbous symplesite precipitate，Complete the arsenic removal deironing cleaning procedure to Copper smelting dust leachate，Iron content arsenic content in detection filtrate，When the concentration of iron ion is less than 20mg/L，During arsenic ion concentration < 1mg/L，Show that the iron-holder containing arsenic is qualified and can enter next process.
The method of the present invention adopts nertralizer lead-zinc to replace nertralizer calcium carbonate or the lime water of tradition use, eliminate the generation of arsenic scum, can zinc in hydrometallurgic recovery Pb-Zn deposits, output zinc sulfate product, the plumbous symplesite precipitate of output is rich in valuable metals such as galvanized irons, pyrogenic attack output lead bullion and arsenic product can be passed through, reduce production cost, it is to avoid lime water in use lumps the phenomenon of blocking pipeline.
Oxidant hydrogen peroxide higher for oxidation effectiveness and nertralizer lead-zinc are combined use by the method for the present invention, and strictly control in course of reaction the pH value of leachate all the time in 4.5～5 scopes, adopt hydrogen peroxide as the ferrous iron in oxidizing leachate, goethite precipitation response speed is fast, and leachate need not be carried out extra heating and thermal insulation in actual mechanical process, the rapid subsidence to arsenic ferrum can be completed and remove.
Embodiment 3
The arsenic removal process of a kind of zinc hydrometallurgy, comprises the following steps:
nullUnder normal temperature condition，The pH value adding nertralizer lead-zinc adjustment leachate in zinc metallurgy leachate is 4.5～5，It is subsequently adding oxidant hydrogen peroxide and removes the iron ion in solution，Ferrous ion major part is made to remove with the form of goethitum，Remove as ferric hydroxide on a small quantity，The interpolation speed of hydrogen peroxide is as the criterion less than 1g/L keeping the content of the ferric ion in solution，Total addition is 2 times of ferrous ion gross mass in zinc metallurgy leachate，And make the pH value of leachate be maintained at 4.5～5 by regulating the addition of nertralizer lead-zinc，It is filtered to remove plumbous symplesite precipitate，Complete the arsenic removal deironing cleaning procedure to zinc metallurgy leachate，Iron content arsenic content in detection filtrate，When the concentration of iron ion is less than 20mg/L，During arsenic ion concentration < 1mg/L，Show that the iron-holder containing arsenic is qualified and can enter next process.
Embodiment 4
The arsenic removal process of a kind of zinc hydrometallurgy, comprises the following steps:
nullUnder normal temperature condition，The pH value adding nertralizer lead-zinc adjustment leachate in zinc metallurgy leachate is 4.5～5，It is subsequently adding oxidant hydrogen peroxide and removes the iron ion in solution，Ferrous ion major part is made to remove with the form of goethitum，Remove as ferric hydroxide on a small quantity，The interpolation speed of hydrogen peroxide is as the criterion less than 1g/L keeping the content of the ferric ion in solution，Total addition is 3 times of ferrous ion gross mass in zinc metallurgy leachate，And make the pH value of leachate be maintained at 4.5～5 by regulating the addition of nertralizer lead-zinc，It is filtered to remove plumbous symplesite precipitate，Complete the arsenic removal deironing cleaning procedure to zinc metallurgy leachate，Iron content arsenic content in detection filtrate，When the concentration of iron ion is less than 20mg/L，During arsenic ion concentration < 1mg/L，Show that the iron-holder containing arsenic is qualified and can enter next process.
Embodiment 5
The arsenic removal process of a kind of zinc hydrometallurgy, comprises the following steps:
nullUnder normal temperature condition，The pH value adding nertralizer lead-zinc adjustment leachate in zinc metallurgy leachate is 4.5～5，It is subsequently adding oxidant hydrogen peroxide and removes the iron ion in solution，Ferrous ion major part is made to remove with the form of goethitum，Remove as ferric hydroxide on a small quantity，The interpolation speed of hydrogen peroxide is as the criterion less than 1g/L keeping the content of the ferric ion in solution，Total addition is 2.5 times of ferrous ion gross mass in zinc metallurgy leachate，And make the pH value of leachate be maintained at 4.5～5 by regulating the addition of nertralizer lead-zinc，It is filtered to remove plumbous symplesite precipitate，Complete the arsenic removal deironing cleaning procedure to zinc metallurgy leachate，Iron content arsenic content in detection filtrate，When the concentration of iron ion is less than 20mg/L，During arsenic ion concentration < 1mg/L，Show that the iron-holder containing arsenic is qualified and can enter next process.
Obviously; the above embodiment of the present invention is only for clearly demonstrating example of the present invention; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; all of embodiment cannot be given limit by the exemplified embodiment of the present invention, every belongs to apparent change that technical scheme extended out or the variation row still in protection scope of the present invention.The all documents mentioned in the present invention are incorporated as reference all in this application, as same section document is individually recited as reference such.
Claims (10)
1. the arsenic removal process of a zinc hydrometallurgy, it is characterised in that: comprise the following steps:
Under normal temperature condition, the pH value adding nertralizer adjustment leachate in metallurgical process in leachate is steady state value, it is subsequently adding oxidant and removes the iron ion in solution, and make the pH value of leachate be maintained at steady state value by regulating the addition of nertralizer, it is filtered to remove precipitate, it is thus achieved that the filtrate after deironing arsenic removal.
2. the arsenic removal process of zinc hydrometallurgy according to claim 1, it is characterised in that: described nertralizer is lead-zinc.
3. the arsenic removal process of zinc hydrometallurgy according to claim 1, it is characterised in that: described pH value is 4.5～5.
4. the arsenic removal process of zinc hydrometallurgy according to claim 1, it is characterised in that: described oxidant is hydrogen peroxide.
5. the arsenic removal process of zinc hydrometallurgy according to claim 1, it is characterised in that: total addition of described oxidant is in metallurgical process in leachate 2～3 times of ferrous ion gross mass.
6. the arsenic removal process of zinc hydrometallurgy according to claim 5, it is characterised in that: total addition of described oxidant is in metallurgical process in leachate 2.2 times of ferrous ion gross mass.
7. the arsenic removal process of zinc hydrometallurgy according to claim 1, it is characterised in that: the interpolation speed of described oxidant is as the criterion less than 1g/L keeping the content of the ferric ion in solution.
8. the arsenic removal process of zinc hydrometallurgy according to claim 1, it is characterised in that: control iron concentration < 20mg/L in filtrate.
9. the arsenic removal process of zinc hydrometallurgy according to claim 1, it is characterised in that: control arsenic ion concentration < 1mg/L in filtrate.
10. the arsenic removal process according to the arbitrary described zinc hydrometallurgy of claim 1 to 9, it is characterised in that: in described metallurgical process, leachate is at least one in zinc metallurgy leachate, Copper smelting dust leachate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610188983.5A CN105734290A (en) | 2016-03-29 | 2016-03-29 | Arsenic removing technology for zinc hydrometallurgy |
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| CN201610188983.5A CN105734290A (en) | 2016-03-29 | 2016-03-29 | Arsenic removing technology for zinc hydrometallurgy |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107893161A (en) * | 2017-11-21 | 2018-04-10 | 四环锌锗科技股份有限公司 | A kind of method that zinc ion is precipitated in silver-colored floatation system |
| CN110004293A (en) * | 2019-03-04 | 2019-07-12 | 中南大学 | The stanniferous processing method for decomposing slag |
| CN111874877A (en) * | 2020-08-13 | 2020-11-03 | 昆明冶金研究院有限公司 | A kind of high-efficiency method for removing arsenic from Na2SeSO3 solution |
| CN116254420A (en) * | 2023-03-10 | 2023-06-13 | 昆明理工大学 | Method for removing arsenic from solution after zinc sulfate germanium precipitation by ultrasonic assisted-dust roasting neutralization |
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| WO2004076698A1 (en) * | 2003-02-26 | 2004-09-10 | Outokumpu Technology Oy | Method for recovery of zinc by countercurrent leaching |
| CN101591733A (en) * | 2009-06-22 | 2009-12-02 | 云南永昌铅锌股份有限公司 | Precipitating alum and removing iron method in the high-iron zinc sulfide concentrate pressurized acid leaching still |
| CN103468951A (en) * | 2013-08-21 | 2013-12-25 | 黄石大江集团有限公司 | Pseudo goethite method for removing iron in zinc leaching solution |
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2016
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| WO2004076698A1 (en) * | 2003-02-26 | 2004-09-10 | Outokumpu Technology Oy | Method for recovery of zinc by countercurrent leaching |
| CN101591733A (en) * | 2009-06-22 | 2009-12-02 | 云南永昌铅锌股份有限公司 | Precipitating alum and removing iron method in the high-iron zinc sulfide concentrate pressurized acid leaching still |
| CN103468951A (en) * | 2013-08-21 | 2013-12-25 | 黄石大江集团有限公司 | Pseudo goethite method for removing iron in zinc leaching solution |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107893161A (en) * | 2017-11-21 | 2018-04-10 | 四环锌锗科技股份有限公司 | A kind of method that zinc ion is precipitated in silver-colored floatation system |
| CN110004293A (en) * | 2019-03-04 | 2019-07-12 | 中南大学 | The stanniferous processing method for decomposing slag |
| CN111874877A (en) * | 2020-08-13 | 2020-11-03 | 昆明冶金研究院有限公司 | A kind of high-efficiency method for removing arsenic from Na2SeSO3 solution |
| CN116254420A (en) * | 2023-03-10 | 2023-06-13 | 昆明理工大学 | Method for removing arsenic from solution after zinc sulfate germanium precipitation by ultrasonic assisted-dust roasting neutralization |
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