CN104404251A - Method for leaching ore concentrate from copper oxide ores based on complexing reaction, and its leaching agent - Google Patents
Method for leaching ore concentrate from copper oxide ores based on complexing reaction, and its leaching agent Download PDFInfo
- Publication number
- CN104404251A CN104404251A CN201410592307.5A CN201410592307A CN104404251A CN 104404251 A CN104404251 A CN 104404251A CN 201410592307 A CN201410592307 A CN 201410592307A CN 104404251 A CN104404251 A CN 104404251A
- Authority
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- China
- Prior art keywords
- leaching
- copper
- copper oxide
- leaching agent
- ore concentrate
- 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
- 238000002386 leaching Methods 0.000 title claims abstract description 71
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 34
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 34
- 239000012141 concentrate Substances 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000000536 complexating effect Effects 0.000 title abstract 2
- 239000010949 copper Substances 0.000 claims abstract description 61
- 229910052802 copper Inorganic materials 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 47
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000605 extraction Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims abstract description 7
- 229960004643 cupric oxide Drugs 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 7
- 239000011707 mineral Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 241000907663 Siproeta stelenes Species 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052569 sulfide mineral Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BUGICWZUDIWQRQ-UHFFFAOYSA-N copper iron sulfane Chemical compound S.[Fe].[Cu] BUGICWZUDIWQRQ-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- -1 exist Chemical class 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052592 oxide mineral Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of mineral metallurgy, and concretely discloses a method for leaching ore concentrate from copper oxide ores based on a complexing reaction, and its leaching agent. The method is characterized in that 5-sulfosalicylic acid is used as a leaching agent to leach copper from the copper oxide ores with the copper level of above 15%, the leaching temperature is 20-60DEG C, copper oxide ores with the granularity of below 74[mu]m account for 75-95% of the weight of the copper oxide ores, the concentration of 5-sulfosalicylic acid is 0.05-0.25mol/L, the 5-sulfosalicylic acid leaching agent is mixed with copper oxide ore powder according to a liquid/solid mass ratio of 5-20:1, and the obtained mixture is fully stirred for 25-50min to obtain a copper-containing solution suitable for later lead extraction and electrodeposition treatment. The leaching agent and the leaching method have the advantages of high leaching rate and short leaching time; and the leaching method guarantees the high copper leaching rate without high temperature or a pressurizing device, and also has the advantages of simple operation and low process cost.
Description
Technical field
The invention belongs to mineral metallurgical technology field, be specifically related to a kind of copper oxide ore concentrate leaching method based on complex reaction and leaching agent thereof.
Background technology
Copper is the most general and one of the metal of most worthy, is living and industrial circle is all widely used.Occurring in nature, can be used for reclaiming the mineral mainly sulfide mineral of copper and the oxide mineral of copper.Copper sulfide mineral mainly contains chalcopyrite (CuFeS
2), purple copper (Cu
5feS
4), covellite (CuS), copper glance (Cu
2s) etc.Copper oxide mineral mainly contains malachite (Cu
2(OH)
2cO
3), chrysocolla ((Cu, Al)
2h
2si
2o
5(OH)
4nH
2and copper lazur (Cu O)
3(OH)
2(CO
3)
2) etc., wherein malachite is the most common.Copper sulfide mineral has good flotability, and application flotation easily can obtain copper ore concentrates, but at present because higher-grade copper-sulphide ores resource reduces day by day, so copper oxide ore becomes the valuable source reclaiming copper.In addition copper oxide ore worldwide has distribution, and a lot of copper deposit has a large amount of based on the cupric oxide ore of malachite mineral.From copper oxide ore, reclaim copper just become study hotspot.For copper-sulphide ores, copper oxide mineral solubleness is comparatively large, and therefore hydrometallurgy just becomes a kind of approach well reclaiming copper from copper oxide ore and concentrate.
By adding some reagent in ore pulp solution, cupric oxide thing is dissolved, thus obtain copper-containing solution, then carry out extraction and electrodeposition obtains copper metal.At present these reagent mainly inorganic acids reagent such as sulfuric acid.Recently, also result in the interest of investigator as leaching agent with organic acid.
Except Ore Leaching, at present, ammonia leaching achieves good effect and applies widely, and the principle of ammonia leaching is cupric ion and ammonia generation complex reaction, forms complex compound, can be expressed as (1) and (2) by reaction equation below:
The ammonia of cupric oxide leaches the technology having become the extraction copper that one grows up.But the report extracting copper about application complex reaction is only limitted to ammonium salt or the ammoniacal liquor such as ammonium chloride, ammonium sulfate, ammonium nitrate, also find no the technical scheme of the complex reaction object height effect leaching copper based on other so far.
Summary of the invention
For the limitation that prior art exists, the object of the invention be to provide high and other the reagent except ammonium salt or ammoniacal liquor of a kind of leaching efficiency can to the new copper oxide ore concentrate leaching method of cupric ion generation complex reaction and corresponding leaching agent thereof, the waste material that the copper leaching efficiency of this leaching agent is high, making is simple, pharmacy and chemical industry can be utilized to produce, the method is conducive to reclaiming copper better.
To achieve these goals, technical scheme of the present invention is specific as follows:
With a leaching agent for copper oxide ore concentrate complex reaction, described leaching agent is that 5 – sulphosalicylic acids and water Homogeneous phase mixing form.
In an embodiment of the present invention, described leaching agent contains the strength of solution of 5 – sulphosalicylic acids between 0.05mol/L ~ 0.25mol/L.
The know-why of technical solution of the present invention: described 5-sulphosalicylic acid comprises 3 Gong Neng Tuan – OH ， – COOH ， – SO
3h, 5 – sulphosalicylic acids can partly or entirely dehydrogenation, and 5 – sulphosalicylic acids mainly exist, shown in specific as follows with five kinds of structure types.
If 5 – sulphosalicylic acids ionize in aqueous completely, then undertaken by following reaction equation (3) and (4):
C
7H
6O
6S
(s)→C
7H
3O
6S
3– (aq)+3H
+ (aq)(3)
Or C
7h
6o
6s
(s)+ 3H
2o
(aq)→ C
7h
3o
6s
3 – (aq)+ 3H
3o
+ (aq)(4)
Because the essential mineral in copper oxide ore concentrate is malachite, can distribute and following reaction equation (5) and (6) occurs:
CuCO
3.Cu(OH)
2(s)+2H
3O
+ (aq)→Cu
2+ (aq)+CO
2(g)+3H
2O
(aq)+Cu(OH)
2(s)(5)
Cu(OH)
2(s)+2H
3O
+ (aq)→Cu
2+ (aq)+4H
2O
(aq)(6)
(5) and the equation of (6) can represent with combined reaction equation below:
CuCO
3.Cu(OH)
2(s)+4H
+ (aq)→2Cu
2+ (aq)+3H
2O
(aq)+CO
2(g)(7)
Therefore, the reaction equation that leaching process is total can be expressed as following formula:
3CuCO
3.Cu(OH)
2(s)+4C
7H
6O
6S
(s)→6Cu
2+ (aq)+4C
7H
3O
6S
3– (aq)+9H
2O
(aq)+3CO
2(g)(8)
The ionization in aqueous of 5 – sulphosalicylic acids produces hydrogen ion, and impel copper oxide mineral to dissolve, this is the effect of the acidleach that 5 – sulphosalicylic acids have.In addition, research discovery 5 – sulphosalicylic acid can form stable coordinating with cupric ion, therefore, 5 – sulphosalicylic acids (abbreviation: SSA) following reaction can be there is in the aqueous solution:
Cu
2+ (aq)+2SSA
(s)→Cu(SSA)
2 2+ (aq)(9)
Cu (SSA)
2 2+be the intermediate product of complex reaction, the reaction equation in the aqueous solution can have multiple.
Therefore, not only 5 – sulphosalicylic acids can provide sour environment dissolved oxygen copper thing but also there is above-mentioned complex reaction, that is to say that 5 – sulphosalicylic acids have ionization and complex reaction characteristic.
To achieve these goals, another technical scheme of the present invention is specific as follows:
Use leaching agent described above to a leaching method for copper oxide ore concentrate, the method is specially: carry out muck, ore grinding to the copper oxide ore concentrate that copper grade is more than 15%, and the weight that in ore, granularity is less than 74 μm accounts for 75% ~ 95%; At control extraction temperature is 20 DEG C ~ 60 DEG C, 5 – sulphosalicylic acid leaching agent solution and cupric oxide concentrate powder is mixed by quality liquid-solid ratio 5 ~ 20:1, fully stirs 25min ~ 50min, be obtained by reacting next step extraction applicable, electrodeposition copper-containing solution.
The invention has the beneficial effects as follows: the present invention is by adopting certain density 5 – sulphosalicylic acids as leaching agent, from copper oxide ore concentrate, metallurgical extraction obtains copper-containing solution, by controlling different extraction temperature, granularity, liquid-solid ratio and leaching agent concentration in reaction vessel, copper leaching rate in copper oxide ore can be made close to 98%; And this leaching method does not need high temperature, pressure exerting device, and simple to operate, process costs is low, thus can provide the excellent copper-containing solution of next step copper applicable extraction and electrodeposition process, to reach the effect of reclaiming copper.
Embodiment
Following content is the detailed description of carrying out the present invention.
Embodiment 1:
Embodiments providing a kind of is the leaching agent of the copper oxide ore concentrate complex reaction of 25% with copper grade, and this leaching agent is that 5 – sulphosalicylic acids and water Homogeneous phase mixing form.Described leaching agent is 0.05mol/L containing the strength of solution of 5 – sulphosalicylic acids.Under the weight being less than 74 μm at temperature 30 DEG C, ore grain size accounts for 80%, leaching agent solution and cupric oxide concentrate powder quality liquid-solid ratio be the condition of 20:1, the leaching yield of copper is about 85.5%.
Embodiment 2:
Embodiments providing a kind of is the leaching agent of the copper oxide ore concentrate complex reaction of 25% with copper grade, and this leaching agent is mainly 5 – sulphosalicylic acids and water Homogeneous phase mixing forms.Described leaching agent is 0.10mol/L containing the strength of solution of 5 – sulphosalicylic acids.Under the weight being less than 74 μm at temperature 30 DEG C, ore grain size accounts for 80%, leaching agent solution and cupric oxide concentrate powder quality liquid-solid ratio be the condition of 20:1, the leaching yield of copper is about 94.2%.
Embodiment 3:
Embodiments providing a kind of is the leaching agent of the copper oxide ore concentrate complex reaction of 25% with copper grade, and this leaching agent is mainly 5 – sulphosalicylic acids and water Homogeneous phase mixing forms.Described leaching agent is 0.20mol/L containing the strength of solution of 5 – sulphosalicylic acids.Under the weight being less than 74 μm at temperature 30 DEG C, ore grain size accounts for 80%, leaching agent solution and cupric oxide concentrate powder quality liquid-solid ratio be the condition of 20:1, the leaching yield of copper is about 96.8%.
Embodiment 4:
Embodiments providing a kind of is the leaching agent of the copper oxide ore concentrate complex reaction of 25% with copper grade, and this leaching agent is mainly 5 – sulphosalicylic acids and water Homogeneous phase mixing forms.Described leaching agent is 0.25mol/L containing the strength of solution of 5 – sulphosalicylic acids.Under the weight being less than 74 μm at temperature 30 DEG C, ore grain size accounts for 80%, leaching agent solution and cupric oxide concentrate powder quality liquid-solid ratio be the condition of 20:1, the leaching yield of copper is about 98.0%.
Embodiment 5:
The embodiment of the present invention proposes the leaching method of copper in a kind of copper oxide ore concentrate.The method comprises: carry out muck, ore grinding to the copper oxide ore concentrate that copper grade is 30%, and the weight that in ore, granularity is less than 74 μm accounts for 75%; Control extraction temperature be 25 DEG C, be that 5 – sulphosalicylic acid leaching agents and the cupric oxide powder of 0.15mol/L mix according to quality liquid-solid ratio 15:1 by concentration, fully stir 25min, obtain applicable next step extract, electrodeposition copper-containing solution.The leaching yield of described copper is 90.2%.
Embodiment 6:
The embodiment of the present invention proposes the leaching method of copper in a kind of copper oxide ore concentrate.The method comprises: carry out muck, ore grinding to the copper oxide ore concentrate that copper grade is 35%, and the weight that in ore, granularity is less than 74 μm accounts for 85%; Control extraction temperature be 35 DEG C, be that 5 – sulphosalicylic acid leaching agents and the cupric oxide powder of 0.20mol/L mixes according to 15:1 by concentration, fully stir 25min, obtain applicable next step extraction, electrodeposition copper-containing solution.The leaching yield of described copper is 97.9%.
Above content is only preferred embodiment of the present invention, and for those of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, this description should not be construed as limitation of the present invention.
Claims (3)
1., with the leaching agent of copper oxide ore concentrate complex reaction, it is characterized in that, described leaching agent is that 5 – sulphosalicylic acids and water Homogeneous phase mixing form.
2., according to a kind of leaching agent with the complex reaction of copper oxide ore concentrate according to claim 1, it is characterized in that, described leaching agent is 0.05mol/L ~ 0.25mol/L containing the strength of solution of 5 – sulphosalicylic acids.
3. one kind uses leaching agent in claim 1 to 2 described in any one to the leaching method of copper oxide ore concentrate, the method is specially: carry out muck, ore grinding to the copper oxide ore concentrate that copper grade is more than 15%, and the weight that in ore, granularity is less than 74 μm accounts for 75% ~ 95%; At control extraction temperature is 20 DEG C ~ 60 DEG C, 5 – sulphosalicylic acid leaching agent solution and cupric oxide concentrate powder is mixed by quality liquid-solid ratio 5 ~ 20:1, fully stirs 25min ~ 50min, be obtained by reacting next step extraction applicable, electrodeposition copper-containing solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410592307.5A CN104404251A (en) | 2014-10-29 | 2014-10-29 | Method for leaching ore concentrate from copper oxide ores based on complexing reaction, and its leaching agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410592307.5A CN104404251A (en) | 2014-10-29 | 2014-10-29 | Method for leaching ore concentrate from copper oxide ores based on complexing reaction, and its leaching agent |
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| Publication Number | Publication Date |
|---|---|
| CN104404251A true CN104404251A (en) | 2015-03-11 |
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|---|---|---|---|
| CN201410592307.5A Pending CN104404251A (en) | 2014-10-29 | 2014-10-29 | Method for leaching ore concentrate from copper oxide ores based on complexing reaction, and its leaching agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116040692A (en) * | 2022-12-30 | 2023-05-02 | 中铁资源集团有限公司 | Method for improving grade of cobalt oxide for crude hydrogen production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120935A (en) * | 1976-06-04 | 1978-10-17 | Inspiration Consolidated Copper Company | Dump leaching of copper |
| CN1489161A (en) * | 2003-08-21 | 2004-04-14 | 上海交通大学 | Method for removing residual copper of aluminium corroding foil surface of negative electrode for aluminium electrolytic capacitor |
| CN102051648A (en) * | 2011-01-20 | 2011-05-11 | 广州市二轻工业科学技术研究所 | Cyanogen-free plating method of zinc alloy die casting |
| CN103801459A (en) * | 2014-01-15 | 2014-05-21 | 湖南有色金属研究院 | Method for recovering refractory copper in acid leaching system through select flotation |
-
2014
- 2014-10-29 CN CN201410592307.5A patent/CN104404251A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120935A (en) * | 1976-06-04 | 1978-10-17 | Inspiration Consolidated Copper Company | Dump leaching of copper |
| CN1489161A (en) * | 2003-08-21 | 2004-04-14 | 上海交通大学 | Method for removing residual copper of aluminium corroding foil surface of negative electrode for aluminium electrolytic capacitor |
| CN102051648A (en) * | 2011-01-20 | 2011-05-11 | 广州市二轻工业科学技术研究所 | Cyanogen-free plating method of zinc alloy die casting |
| CN103801459A (en) * | 2014-01-15 | 2014-05-21 | 湖南有色金属研究院 | Method for recovering refractory copper in acid leaching system through select flotation |
Non-Patent Citations (5)
| Title |
|---|
| SHABANI M A等: "Investigation on leaching of malachite by citric acid", 《INTERNATIONAL JOURNAL OF MINERALS, METALLURGY, AND MATERIALS》 * |
| 中山大学、辽宁大学等校: "《高等学校试用教材 无机化学实验》", 31 May 1978, 人民教育出版社 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116040692A (en) * | 2022-12-30 | 2023-05-02 | 中铁资源集团有限公司 | Method for improving grade of cobalt oxide for crude hydrogen production |
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Application publication date: 20150311 |