CN1093418A - Complex compound electrolysis system zinc - Google Patents
Complex compound electrolysis system zinc Download PDFInfo
- Publication number
- CN1093418A CN1093418A CN93104303A CN93104303A CN1093418A CN 1093418 A CN1093418 A CN 1093418A CN 93104303 A CN93104303 A CN 93104303A CN 93104303 A CN93104303 A CN 93104303A CN 1093418 A CN1093418 A CN 1093418A
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- zinc
- electrolysis
- solution
- leaching
- temperature
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- 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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- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention is mineral or the useless by product of industry that contains zinc oxide, zinc hydroxide, zinc carbonate and metallic zinc with the leaching of ammonium chloride hot solution, makes zinc generate zinc ammonia complex Zn (NH
3)
2Cl
2Solution, gained solution zinc dust precipitation deleading, behind the impurity such as copper, cadmium, nickel, can be without deironing at NH
4Cl-NH
4Electrolysis makes metallic zinc in the OH system.
Description
The present invention relates to a kind of novel method of zinc hydrometallurgy, promptly is to make the method that zinc ammonia complex carries out electrolysis system zinc again with containing the zinc raw material.
The zinc hydrometallurgy of countries in the world all is the zinc salt electrolytic process at present, and promptly the solution with vitriol, muriate or zincate carries out electrolysis.Industrial production all adopts the zinc sulfate electrolysis, and the zinc chloride electrolysis still is in conceptual phase, and the zincate electrolysis is owing to be to carry out under strong alkaline condition, can only obtain spongy zinc powder and can not get cathode zinc.One of present inventor once studied the novel process of successfully carrying out electrolysis system zinc with zinc ammonia complex in 1989, and had obtained Chinese invention patent, and the patent No. is CN89102917.6.Along with the deep development of research work, existing proposition is wider than above-mentioned patent subject range, technology is simpler, yield is higher, more helps the novel process of suitability for industrialized production.
The present invention is mineral or the useless by product of industry that contains zinc oxide, zinc hydroxide, zinc carbonate and metallic zinc with the leaching of ammonium chloride hot solution, make zinc become zinc ammonia complex solution, to impurity such as institute's iron content, copper, chromium, cadmium, nickel in the solution, without deironing, only need with behind zinc dust precipitation copper, lead, cadmium, the nickel, at NH
4Cl-NH
4Electrolysis in the OH system just can obtain high-quality cathode zinc.
The ammonium chloride solution concentration that the present invention uses is 20～40% weight parts, and temperature of reaction is 55～125 ℃, and the removal of impurity purifies the back and add ammoniacal liquor in electrolytic solution, makes it at NH
4Cl-NH
4Carry out electrolysis in the OH system, control pH value 4-7, temperature 40-85 ℃, current density 200-800A/m
2, bath voltage 2.6-3.1V.
Below at length set forth the present invention and above-mentioned patent (CN89102917.6) difference:
1, raw material is extensive, and the present invention not only is applicable to the raw material that contains zinc oxide, zinc hydroxide and zinc carbonate, and is applicable to the raw material of containing metal zinc.The reaction formula of various raw materials and ammonium chloride is as follows:
The zinc that is these forms all generates Zn(NH when reacting with ammonium chloride
3)
2Cl
2Complex compound.
2, leaching ammonium chloride solution concentration range, range of reaction temperature and zinc leaching rate are significantly improved.The ammonium chloride solution concentration that the present invention proposes is 20-40%, and temperature of reaction is 55-125 ℃, and zinc leaching rate reaches more than 90%.Can do different selections for different raw material reaction temperature, to oxide compound or oxyhydroxide, temperature of reaction can be controlled in below 100 ℃, and for zinc carbonate mineral or metal cadmia, and temperature of reaction should be more than 100 ℃, otherwise long reaction time, the zinc yield is low.
3, scavenging process need not deironing.In traditional solution of zinc sulfate electrolysis process, deironing is very necessary.Because the ferric ion that exists in solution can be reduced into divalent iron ion and metallic iron on negative electrode, and two valency iron can be oxidized to ferric ion in anode, so the existence of iron can influence the quality of cathode zinc, wastes electric energy simultaneously.And the present invention is with the ammonium chloride solution leaching, and it is neutral that solution is, and ferric iron can not enter solution, has only a small amount of two valency iron to enter solution, and when electrolysis, divalent iron ion is hydrolyzed into Fe(OH immediately after being oxidized to ferric iron on the anode)
3Precipitation is separated out, thereby can to the not obviously influence of electrolytic zinc quality, also not waste electric energy again by cathodic reduction.
4, electrolysis is at NH
4Cl-NH
4Carry out in the OH system.If electrolysis is at NH
4Carry out in the Cl system, we find, electrolysis under such condition, and the time that can keep is not long, and the zinc that goes out when electrolysis is that solution PH descends when leaching half left and right sides of zinc, just there is chlorine to produce as continuing electrolysis, current efficiency decline.The electrolysis of this moment has not been that complex compound becomes the zinc chloride electrolysis in electrolysis, because during the complex compound electrolysis be following reaction takes place:
This reaction does not have chlorine to produce, and PH can not descend yet, and following reaction then takes place during the zinc chloride electrolysis:
This reaction has chlorine to produce and causes that thus solution PH reduces, and also a series of side reactions can take place, and current efficiency is descended down down to not continuing electrolysis.The reason that zinc chloride produces is because the zinc ammonia complex thermostability is relatively poor, and event can take place when being heated to decompose:
Because leaching and electrolysis are all carried out under comparatively high temps, the part complex compound is decomposed, ammonia is overflowed, thereby just formed ZnCl in the solution
2
For electrolysis can be gone on for a long time, make the zinc of leaching all become cathode zinc, must allow electrolysis be undertaken by complex compound electrolysis form all the time.Only when electrolysis, add ammoniacal liquor, make electrolysis at NH
4Cl-NH
4Carry out in the OH system.At this moment the ammoniacal liquor of adding can be offset because of complex compound decomposes the ammonia that loses, and makes zinc chloride become Zn(NH again
3)
2Cl
2:
The amount that adds ammoniacal liquor is controlled by PH.Be advisable with control PH4-7 during electrolysis.
Electrolytic condition of the present invention is: with titanium plate or aluminium sheet is negative electrode, and graphite cake is an anode; Temperature 40-85 ℃; PH4-7; Current density 200-800A/m
2, bath voltage 2.6-3.1V.Electrolysis under such condition, current efficiency can reach more than 95%, cathode zinc consumption direct current 2300-2900KWh per ton, zinc product purity reaches more than 99.9%.
The present invention uses NH
4Cl hot solution leaching contains the mineral or the useless by product of industry of zinc oxide, zinc hydroxide, zinc carbonate and metallic zinc, can electrolysis after zinc dust precipitation purifies, and purification process is simple, at NH
4Cl-NH
4Electrolysis in the OH system, favourable conduction, bath voltage is low, electrolysis does not simultaneously have zinc to redissolve phenomenon, even a couple of days that midway has a power failure do not have influence yet, so current efficiency height, power consumption is low.Adaptability to raw material of the present invention is strong, and is many with the out of use inferior raw material of traditional technology, all can obtain purity in the metallic zinc more than 99.9% with the present invention.
Embodiment 1:
Zinc gray slag 80 gram that will contain zinc oxide and metallic zinc, total zinc content are 62 grams, and contain Zn24.2g/l, contain NH
4Cl300g/l, d(proportion)=1.12 electrolysis waste solution 1000ml reaction, temperature of reaction 100-105 ℃, react 3 hours, must contain Zn81.0g/l, contain the leach liquor 1050ml of Fe1.06g/l, leach zinc 60.9 and restrain, zinc leaching rate is 98.2%.This solution is added 1 gram carry out electrolysis behind the zinc dust precipitation, add 80 milliliters of 25% ammoniacal liquor during electrolysis, control PH6.5-7.0,65 ℃ of temperature, cathode current density 400A/m
2, bath voltage 3.1V, electrolysis gets zinc 65 grams after 16 hours, and 1000 milliliters of electrolysis waste solutions contain Zn20.6g/l, contain NH
4Cl297g/l.Illustrate that the zinc that leaches can all be electrolyzed to produce cathode zinc.Current efficiency 96%, consumption direct current 2720KWh, cathode zinc contains Fe0.001%, contains Zn99.95%.
Embodiment 2:
Zinc powder method vat powder byproduct zinc hydroxide 60 grams contain zinc 40 grams, contain Zn24g/l, NH with 1000 milliliters
4The Cl350g/l electrolysis waste solution is reaction with it under 80 ℃, and 20 milliliters of 25% ammoniacal liquor are added in the direct electrolysis of gained leach liquor, and 70 ℃ of temperature, other conditions are with example 1, and electrolysis got zinc 39 grams, current efficiency 95%, zinc purity 99.9% in 9 hours.
Embodiment 3:
200 gram smithsonite (containing zinc 60 grams) are added NH
4800 milliliters in Cl450 gram and water is 115 ℃ of reactions 3 hours, must leach liquor 780 milliliters, contain Zn2.5g/l, and contain Fe0.75g/l, zinc leaching rate 94.3%.The tail gas water must reclaim 300 milliliters of ammoniacal liquor after absorbing, and contains (NH
4)
2CO
377.7g/l, contain free NH
315.6g/l.Clean leach liquor adds 2 gram zinc dust precipitations and purifies, and electrolysis then will be reclaimed ammoniacal liquor and be added and add in addition 50 milliliters of 25% ammoniacal liquor during electrolysis, control PH6.5-7.0,65 ℃ of temperature, current density 450A/m
2, bath voltage 3.0V, electrolysis gets zinc 43 grams, current efficiency 96% after 12 hours.Cathode zinc contains Fe0.003%, Cu0.0002%, Pb0.017%, Cd0.0004%, impurity summation 0.020%, zinc purity 99.98%.
Claims (1)
- A kind ofly carry out the method for electrolytic zinc hydrometallurgy, comprise the mineral or the useless by product of industry that contain zinc oxide, zinc hydroxide, zinc carbonate and metallic zinc etc. with the liquor zinci chloridi leaching, make zinc form Zn (NH with the zinc ammonia complex form 3) 2Cl 2Complex solution, behind leach liquor zinc dust precipitation deleading, copper, cadmium, the nickel, without deironing promptly can the titanium plate or a pot plate be negative electrode, graphite cake is that anode carries out electrolysis system zinc, ammonium chloride solution concentration is 20-40% (percent by weight part) when it is characterized in that leaching, temperature 60-120 ℃, add ammoniacal liquor in the electrolytic solution after purifying, at NH 4Cl-NH 4Carry out electrolysis in the OH system, control pH value 5-7, temperature 50-80 ℃, current density 200-800A/m 2, bath voltage 2.6-3.1V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93104303A CN1034231C (en) | 1993-04-09 | 1993-04-09 | Prodn. of zinc by complex compound electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93104303A CN1034231C (en) | 1993-04-09 | 1993-04-09 | Prodn. of zinc by complex compound electrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1093418A true CN1093418A (en) | 1994-10-12 |
| CN1034231C CN1034231C (en) | 1997-03-12 |
Family
ID=4985128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93104303A Expired - Fee Related CN1034231C (en) | 1993-04-09 | 1993-04-09 | Prodn. of zinc by complex compound electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1034231C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928827A (en) * | 2010-08-31 | 2010-12-29 | 湖南子廷有色金属有限公司 | Method for removing impurities and refining zinc from zinc ammine complex |
| WO2012068621A1 (en) * | 2010-11-23 | 2012-05-31 | Metallic Waste Solutions Pty Ltd | For recovering zinc and/or zinc oxide i |
| CN103710727A (en) * | 2013-12-05 | 2014-04-09 | 中南大学 | Application of soluble bromine salt |
| CN104005051A (en) * | 2014-04-29 | 2014-08-27 | 戴兴征 | Method for extracting electrodeposited zinc from zinc oxide powder in ammonium chloride solution system |
| CN106282572A (en) * | 2016-08-11 | 2017-01-04 | 李果 | A kind of method of comprehensive utilization of the complex multi-metal materials such as cupric zinc |
| CN107460500A (en) * | 2017-08-15 | 2017-12-12 | 江西金铂铼资源循环新技术有限公司 | The method that leaded secondary zinc oxide ammonium immersion liquid eddy flow electrodeposition produces electric lead |
| CN108300855A (en) * | 2018-02-05 | 2018-07-20 | 彭勃 | A kind of process of the joint of double-flow containing zinc oxide leaching and mixed liquid electrolytic zinc |
| CN108642519A (en) * | 2018-06-06 | 2018-10-12 | 潘生东 | A kind of Environment-friendlyelectrolytic electrolytic zinc technology |
| CN109095495A (en) * | 2018-09-13 | 2018-12-28 | 桐乡市思远环保科技有限公司 | The method of anhydrous zinc chloride is prepared from material containing zinc |
| CN110818434A (en) * | 2019-10-29 | 2020-02-21 | 浙江佳虹新材料科技有限公司 | Riser material and preparation method thereof |
| WO2021190025A1 (en) * | 2020-03-24 | 2021-09-30 | 鑫联环保科技股份有限公司 | Ammonium complex system-based method for separating and purifying lead, zinc, cadmium, and copper |
-
1993
- 1993-04-09 CN CN93104303A patent/CN1034231C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928827A (en) * | 2010-08-31 | 2010-12-29 | 湖南子廷有色金属有限公司 | Method for removing impurities and refining zinc from zinc ammine complex |
| WO2012068621A1 (en) * | 2010-11-23 | 2012-05-31 | Metallic Waste Solutions Pty Ltd | For recovering zinc and/or zinc oxide i |
| CN103710727A (en) * | 2013-12-05 | 2014-04-09 | 中南大学 | Application of soluble bromine salt |
| CN103710727B (en) * | 2013-12-05 | 2016-04-06 | 中南大学 | The application of soluble bromine salt |
| CN104005051A (en) * | 2014-04-29 | 2014-08-27 | 戴兴征 | Method for extracting electrodeposited zinc from zinc oxide powder in ammonium chloride solution system |
| CN106282572A (en) * | 2016-08-11 | 2017-01-04 | 李果 | A kind of method of comprehensive utilization of the complex multi-metal materials such as cupric zinc |
| CN107460500A (en) * | 2017-08-15 | 2017-12-12 | 江西金铂铼资源循环新技术有限公司 | The method that leaded secondary zinc oxide ammonium immersion liquid eddy flow electrodeposition produces electric lead |
| CN108300855A (en) * | 2018-02-05 | 2018-07-20 | 彭勃 | A kind of process of the joint of double-flow containing zinc oxide leaching and mixed liquid electrolytic zinc |
| CN108300855B (en) * | 2018-02-05 | 2019-11-15 | 彭勃 | A kind of process of the joint of double-flow containing zinc oxide leaching and mixed liquid electrolytic zinc |
| CN108642519A (en) * | 2018-06-06 | 2018-10-12 | 潘生东 | A kind of Environment-friendlyelectrolytic electrolytic zinc technology |
| CN108642519B (en) * | 2018-06-06 | 2022-09-23 | 潘生东 | Environment-friendly zinc electrolysis process |
| CN109095495A (en) * | 2018-09-13 | 2018-12-28 | 桐乡市思远环保科技有限公司 | The method of anhydrous zinc chloride is prepared from material containing zinc |
| CN110818434A (en) * | 2019-10-29 | 2020-02-21 | 浙江佳虹新材料科技有限公司 | Riser material and preparation method thereof |
| CN110818434B (en) * | 2019-10-29 | 2022-03-15 | 浙江佳虹新材料科技有限公司 | Riser material and preparation method thereof |
| WO2021190025A1 (en) * | 2020-03-24 | 2021-09-30 | 鑫联环保科技股份有限公司 | Ammonium complex system-based method for separating and purifying lead, zinc, cadmium, and copper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1034231C (en) | 1997-03-12 |
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