CN1408902A - Process for directly producing metal zinc by suspension electrolysing high-iron sphalerite - Google Patents
Process for directly producing metal zinc by suspension electrolysing high-iron sphalerite Download PDFInfo
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- CN1408902A CN1408902A CN02113849A CN02113849A CN1408902A CN 1408902 A CN1408902 A CN 1408902A CN 02113849 A CN02113849 A CN 02113849A CN 02113849 A CN02113849 A CN 02113849A CN 1408902 A CN1408902 A CN 1408902A
- Authority
- CN
- China
- Prior art keywords
- suspension
- zinc
- electrolysis
- oxidation
- suspension electrolysis
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- 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.)
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011701 zinc Substances 0.000 title claims abstract description 52
- 239000000725 suspension Substances 0.000 title claims abstract description 48
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052950 sphalerite Inorganic materials 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 108010010803 Gelatin Proteins 0.000 claims abstract description 4
- 229920000159 gelatin Polymers 0.000 claims abstract description 4
- 239000008273 gelatin Substances 0.000 claims abstract description 4
- 235000019322 gelatine Nutrition 0.000 claims abstract description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 32
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 238000009854 hydrometallurgy Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000010802 sludge Substances 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 239000002893 slag Substances 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- -1 electric furnace Chemical compound 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Electrolytic Production Of Metals (AREA)
Abstract
The direct metal zinc producing process includes preparing suspension ore slurry of high-iron sphalerite with suspension electrolyte compirsing sulfate and small amount of sulfuric acid, oxidizing high-rion sphalerite in the anode area of form zinc ion and element sulfur, taking out the zinc ion diffused from the anode area to the mid area togeether with the electrolyte, purifying to obtain qualified electrolyte, adding gelatin to the electrolyte, adding the electrolyte to the cathode area of suspension electrolytic bath and electrolysis to obtain metal zinc in the cathode. The suspension electrolytic bath has voltage of 1.0-1.2 V, anode current density of 100-300 A/sq m, cathode current density of 150-300 A/sq m and temperature of 30-80 deg.c.
Description
Affiliated field: the present invention relates to the chemical metallurgy technical field, is that raw material adopts suspension electrolysis direct production metallic zinc technology with the high-iron sphalerite concentrate especially.
Background technology: though the high-iron sphalerite concentrate can be used pyrometallurgy of zinc method process for producing metallic zinc such as electric furnace, ISP, the energy consumption height limited the application of this method when the electric furnace method was handled.When existing Zinc hydrometallurgy process is handled, easily generate zinc ferrite when fluidized bed roasting is handled, the leaching yield of zinc was low when calcining leached, deferrization process complexity during the peracid leaching, so during wet processing cost also than higher.
Traditional suspension electrolysis technology promptly adopts the suspension electrolysis liquid system of muriate and hydrochloric acid mixed solution can't effectively realize the direct production metallic zinc, mainly is that cathode zinc is not fine and close, causes the founding direct yield low, and practical value is little.
Summary of the invention: at the deficiency of above-mentioned prior art existence, the present invention proposes a kind of brand-new process for directly producing metal zinc by suspension electrolysing high-iron sphalerite, eliminating on the one hand traditional pyrogenic process, wet method can not be effectively, the shortcoming of low-cost processes zinc, change existing suspension electrolysis liquid simultaneously, make the galvanic deposit of metallic zinc become fine and close, improve the founding direct yield.
The present invention reaches by following technical measures:
A, employing is by the positive column, three district's suspension electrolysis grooves that intermediate zone and cathodic area are formed carry out electrolysis, the positive column that directly adds the suspension electrolysis groove through industrial ore dressing to the high-iron sphalerite concentrate below-120 orders, the positive column that after stirring the ore pulp become suspension under the agitator effect or it is formed ore pulp, adds the suspension electrolysis groove, the ore pulp liquid-solid ratio is 3～6: 1, the suspension electrolysis process is under galvanic effect, in stannous sulphate electrolyte with the high-iron sphalerite oxidation, zinc enters solution with the zine ion form, sulphur is present in the oxidation residua with the form of elementary sulfur, and oxidation sludge sends back to the positive column through sulphur removal with the zinc ore concentrate that obtains after ore dressing separates;
B, contain zine ion solution from positive column diffusion or move to the intermediate zone, emit or take out from the intermediate zone, through obtaining qualified electrolytic solution after traditional, close with the zinc hydrometallurgy leach liquor purification process processing;
Send into the cathodic area of suspension electrolysis groove behind c, the additives such as electrolytic solution adding gelatin with step b generation, cathode zinc is produced in electrolysis, and cathode zinc obtains qualified industrial zinc ingot metal through founding.
Electrolytic solution in the described suspension electrolysis groove is vitriol and a spot of sulfuric acid system, vitriol is the solution that zinc sulfate, ammonium sulfate, sodium sulfate are formed, zine ion 50～150g/l in the solution, ammonium sulfate 10～60g/l, sodium sulfate 10～60g/l, sulfuric acid 10～50g/l.
The main technical details of described suspension electrolysis suspension electrolysis: bath voltage 1.0～1.2V, anode material are graphite, anodic current density 100～300A/m
2, cathode current density 150～300A/m
2, 30～80 ℃ of temperature, ore pulp liquid-solid ratio 3～6: 1, anodic oxidation current potential 0.5～0.8V, oxidization time 3～6 days, anodic current efficiency＞95%.Ton zinc direct current consumption＜1500 degree.Additive adopts gelatin.
Adopt ion-exchange membrane or industrial filter cloth to make barrier film between the intermediate zone of described suspension electrolysis groove and positive column and the cathodic area, the liquid level in cathodic area is higher than the intermediate zone, to prevent in the intermediate zone that the solution that does not purify enters the cathodic area, zinc metal sheet quality when influencing the electrolysis in cathodic area.
The process for directly producing metal zinc by suspension electrolysing high-iron sphalerite schema that description of drawings: Fig. 1 proposes for the present invention.
Embodiment:
Embodiment one: with the positive column of 200g high-iron sphalerite (containing zinc 41.37%, sulphur 31.87%) by liquid-solid ratio adding in 3: 1 suspension electrolysis groove, feed direct current and carry out oxidation, electric current 1.0A, oxidation 96h, anodic oxidation current potential 0.7V, 50 ℃ of suspension electrolysis temperature.Suspension electrolysis liquid composition: Zn
2+80g/l, NH
4 +10g/l, sulfuric acid 10g/l.Oxidation residua 118g, slag contain zinc 9.24%, sulphur 53.56%.The suspension electrolysis oxidation leaching yield of zinc reaches 86.37%, and the XRD of slag and sem analysis result show the elementary sulfur of sulphur based on the oxidation output, is to be present in the unoxidized zink sulphide on a small quantity, and the zinc metal sheet of negative electrode output meets the standard of No. 2 zinc.
Embodiment two: with the positive column of 150g high-iron sphalerite (containing zinc 41.37%, sulphur 31.87%) by liquid-solid ratio adding in 4: 1 suspension electrolysis groove, feed direct current and carry out oxidation, electric current 0.5A, oxidation 72h, anodic oxidation current potential 0.6V, 50 ℃ of suspension electrolysis temperature.Suspension electrolysis liquid composition: Zn
2+80g/l, NH
4 +10g/l, sulfuric acid 10g/l.Oxidation residua 138g, slag contain zinc 28.04%, sulphur 45.94%.The suspension electrolysis oxidation leaching yield of zinc reaches 37.64%, and the XRD of slag and sem analysis result show the elementary sulfur of sulphur based on the oxidation output, is to be present in the unoxidized zink sulphide on a small quantity, and the zinc metal sheet of negative electrode output meets the standard of No. 1 zinc.
Embodiment three: with the positive column of 100g high-iron sphalerite (containing zinc 41.37%, sulphur 31.87%) by liquid-solid ratio adding in 6: 1 suspension electrolysis groove, feed direct current and carry out oxidation, electric current 0.5A, oxidation 96h, anodic oxidation current potential 0.6V, 60 ℃ of suspension electrolysis temperature.Suspension electrolysis liquid composition: Zn
2+100g/l, NH
4 +10g/l, sulfuric acid 15g/l.Oxidation residua 57g, slag contain zinc 8.61%, sulphur 55.54%.The suspension electrolysis oxidation leaching yield of zinc reaches 88.14%, and the XRD of slag and sem analysis result show the elementary sulfur of sulphur based on the oxidation output, is to be present in the unoxidized zink sulphide on a small quantity, and the zinc metal sheet of negative electrode output meets the standard of No. 2 zinc.Embodiment four adds 500g high-iron sphalerite (contain zinc 41.37%, sulphur 31.87%) by liquid-solid ratio the positive column of suspension electrolysis groove at 3: 1, feed direct current and carry out oxidation, electric current 2.0A, oxidation 120h, anodic oxidation current potential 0.7V, 60 ℃ of suspension electrolysis temperature.Suspension electrolysis liquid composition: Zn
2+120g/l, NH
4 +10g/l, sulfuric acid 20g/l.Oxidation residua 308g, slag contain zinc 6.76%, sulphur 52.67%.The suspension electrolysis oxidation leaching yield of zinc reaches 90.02%, and the XRD of slag and sem analysis result show the elementary sulfur of sulphur based on the oxidation output, is to be present in the unoxidized zink sulphide on a small quantity, and the zinc metal sheet of negative electrode output meets the standard of No. 1 zinc.
Claims (4)
1, a kind of process for directly producing metal zinc by suspension electrolysing high-iron sphalerite is characterized in that:
A, employing is by the positive column, three district's suspension electrolysis grooves that intermediate zone and cathodic area are formed carry out electrolysis, the positive column that directly adds the suspension electrolysis groove through industrial ore dressing to the high-iron sphalerite concentrate below-120 orders, stirring the positive column that adds the suspension electrolysis groove after becoming the ore pulp of suspension or its stirring being become ore pulp under the agitator effect, the ore pulp liquid-solid ratio is 3～6: 1, the suspension electrolysis process is under galvanic effect, oxidized leaching forms solution that contains zine ion and the oxidation residua that contains elementary sulfur in stannous sulphate electrolyte, and oxidation sludge sends back to the positive column through the zinc ore concentrate that sulphur removal and ore dressing sorting obtain;
Zine ion in b, the oxidation leach liquor spreads or moves to the intermediate zone, emits or takes out from the intermediate zone then.This solution obtains qualified electrolytic solution after handling through traditional purification process close with the zinc hydrometallurgy leach liquor,
Send into the cathodic area of suspension electrolysis groove after additives such as c, electrolytic solution that step b is produced and gelatin mix, cathode zinc is produced in electrolysis, and cathode zinc is through the qualified industrial zinc ingot metal of founding acquisition.
2, technology as claimed in claim 1, it is characterized in that: the electrolytic solution in the suspension electrolysis groove is vitriol and a spot of sulfuric acid system, vitriol is the solution that zinc sulfate, ammonium sulfate, sodium sulfate are formed, zine ion 60～150g/l in the solution, ammonium sulfate 10～60g/l, sodium sulfate 10～60g/l, sulfuric acid 10～50g/l.
3, the technology described in claim 1 is characterized in that: suspension electrolysis is bath voltage 1.0～1.2V at technical parameter, and anode material is a graphite, anodic current density 100～300A/m
2, cathode current density 150～300A/m
2, 30～80 ℃ of temperature, ore pulp liquid-solid ratio (3～6): 1, anodic oxidation current potential 0.5～0.8V, oxidization time 3～6 days, anodic current efficiency＞95%.Carry out under the condition of ton zinc direct current consumption＜1500 degree.
4, technology as claimed in claim 1 is characterized in that: adopt ion-exchange membrane or industrial filter cloth to make barrier film between the intermediate zone of suspension electrolysis groove and positive column and the cathodic area, the liquid level in cathodic area is higher than the intermediate zone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021138494A CN1188548C (en) | 2002-06-07 | 2002-06-07 | Process for directly producing metal zinc by suspension electrolysing high-iron sphalerite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021138494A CN1188548C (en) | 2002-06-07 | 2002-06-07 | Process for directly producing metal zinc by suspension electrolysing high-iron sphalerite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1408902A true CN1408902A (en) | 2003-04-09 |
| CN1188548C CN1188548C (en) | 2005-02-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021138494A Expired - Fee Related CN1188548C (en) | 2002-06-07 | 2002-06-07 | Process for directly producing metal zinc by suspension electrolysing high-iron sphalerite |
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| CN (1) | CN1188548C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051490A (en) * | 2010-10-22 | 2011-05-11 | 蒙自矿冶有限责任公司 | Novel method for recovering silver in high-iron sphalerite |
| CN104131162A (en) * | 2014-06-20 | 2014-11-05 | 山东国大黄金股份有限公司 | Copper extraction raffinate comprehensive recycling and cyclic utilization method |
| CN107419111A (en) * | 2017-08-14 | 2017-12-01 | 贵州省兴安环保科技有限公司 | A kind of method that production zinc powder is leached in alloy zinc gray in-pulp electrolysis |
| CN108680790B (en) * | 2018-02-26 | 2020-10-30 | 深圳优利世科技有限公司 | Method for detecting contact resistance of polar plate for zinc electrolysis of large polar plate based on infrared thermal image |
-
2002
- 2002-06-07 CN CNB021138494A patent/CN1188548C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051490A (en) * | 2010-10-22 | 2011-05-11 | 蒙自矿冶有限责任公司 | Novel method for recovering silver in high-iron sphalerite |
| CN102051490B (en) * | 2010-10-22 | 2012-10-03 | 蒙自矿冶有限责任公司 | Novel method for recovering silver in high-iron sphalerite |
| CN104131162A (en) * | 2014-06-20 | 2014-11-05 | 山东国大黄金股份有限公司 | Copper extraction raffinate comprehensive recycling and cyclic utilization method |
| CN104131162B (en) * | 2014-06-20 | 2016-01-06 | 山东国大黄金股份有限公司 | Liquid synthetical recovery and circulation utilization method more than a kind of extraction copper |
| CN107419111A (en) * | 2017-08-14 | 2017-12-01 | 贵州省兴安环保科技有限公司 | A kind of method that production zinc powder is leached in alloy zinc gray in-pulp electrolysis |
| CN107419111B (en) * | 2017-08-14 | 2019-03-05 | 贵州省兴安环保科技有限公司 | A kind of method that production zinc powder is leached in the in-pulp electrolysis of alloy zinc gray |
| CN108680790B (en) * | 2018-02-26 | 2020-10-30 | 深圳优利世科技有限公司 | Method for detecting contact resistance of polar plate for zinc electrolysis of large polar plate based on infrared thermal image |
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| Publication number | Publication date |
|---|---|
| CN1188548C (en) | 2005-02-09 |
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