CN1227379C - Technqiue for soaking copper pyrites - Google Patents
Technqiue for soaking copper pyrites Download PDFInfo
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- CN1227379C CN1227379C CNB031352103A CN03135210A CN1227379C CN 1227379 C CN1227379 C CN 1227379C CN B031352103 A CNB031352103 A CN B031352103A CN 03135210 A CN03135210 A CN 03135210A CN 1227379 C CN1227379 C CN 1227379C
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- CN
- China
- Prior art keywords
- chalcopyrite
- leaching
- ammonium persulfate
- weight percentage
- acid
- 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.)
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- 239000010949 copper Substances 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002791 soaking Methods 0.000 title 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052951 chalcopyrite Inorganic materials 0.000 claims abstract description 43
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 238000002386 leaching Methods 0.000 claims description 47
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 6
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical group [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a technology for extracting chalcopyrite, which is characterized in that under the conditions of low temperature and normal pressure, silver salt is used as a catalyst, and ammonium persulfate is used as an oxidizing agent; the chalcopyrite is oxidized and extracted, the temperature is controlled from 70 to 95 DEG C, and the chalcopyrite is extracted for five to ten hours; thus, a copper sulfate solution can be obtained, wherein the extraction rate of the copper sulfate solution can reach more than 96%, and the recovery rate of copper can reach more than 97%. Because high temperature and high pressure are not needed, when the chalcopyrite is extracted, equipment can not be corroded, the requirement for the pressure is low, environment can not be damaged, the silver salt which is used in the process can not be consumed, the ammonium persulfate can be circularly used after regenerated, and the production cost can be reduced. Thus, the present invention provides a method for extracting chalcopyrite, which has the advantages of simple technological processes, short production period, low production cost and high production efficiency.
Description
The technical field is as follows: the field of hydrometallurgy
(II) technical background: the known wet leaching of chalcopyrite adopts methods such as acid leaching, ammonia leaching, chloride or ferric sulfate leaching and the like. The sulfuric acid leaching is carried out at the temperature of 493-503K, the chalcopyrite is roasted with acid to be converted into sulfate, and gases such as hydrogen sulfide and sulfur dioxide are generated by the method, so that equipment is corroded, and the working environment is polluted; chloride leaching is the electrochemical dissolution of chalcopyrite in the presence of ferric chloride, and the method generates acid, seriously corrodes equipment and needs high-performance anticorrosive material preparation equipment; ammonia leaching is carried out under high pressure, when oxygen exists, leaching is carried out by stirring, the method needs high-pressure conditions, and the requirement on the tightness of equipment is high; the bacterial leaching is widely applied to theleaching of low-grade copper ores, but the leaching period is long.
In addition, direct sulfation of chalcopyrite with steam and oxygen at 773K has the reaction equation:
the method also produces gases such as hydrogen sulfide, sulfur dioxide and the like, pollutes the environment and requires high-temperature conditions.
Because the method needs high temperature and high pressure conditions, and has high process energy consumption, long leaching period, complex operation and high equipment requirement, the production cost of the product is very high, and the wide application of copper products is limited, the research on the chalcopyrite leaching process which has high efficiency, energy saving, high comprehensive utilization and environmental friendliness is very important.
A process for preparing copper sulfate directly from copper ore powder is disclosed in a patent entitled "method for preparing copper sulfate directly from chalcopyrite" (publication No. 1094014) filed by southern Kao university at 22.3.1994. Roasting the brass ore powder at the temperature of 350-400 ℃, leaching with water, introducing air into filtrate, adding calcium carbonate serving as a neutralizing agent to maintain the pH value to be about 3.5 for deironing, concentrating the filtrate, and cooling to obtain pure copper sulfate.
Whereas in patent application No. 97182088.0 entitled "method for leaching chalcopyrite" a method for leaching copper from chalcopyrite using ferric sulphate is provided in which an acceptable leaching rate is achieved by controlling the surface potential of the chalcopyrite to an empirically determined "window" in the broadrange of 350 to 450 mV. The most effective process conditions include the selection of the surface potential, the leaching temperature, the PH of the leaching solution, and the grinding fineness of the chalcopyrite.
Further, an improved method for heap leaching of chalcopyrite-containing ores as taught in the patent application entitled "an improved method for heap leaching of chalcopyrite" by Baker, Locker, Australia limited, application number 00807725.8. An acidic liquid containing iron and sulphur oxidising bacteria is added to a heap containing chalcopyrite to contact the ore, such contact releasing copper from the ore. In the process, an oxygen-containing gas is introduced into the heap as a source of oxygen for the bacteria, and the saturation level and temperature of the oxygen-containing gas introduced into the heap is controlled so as to maintain the bulk of the heap at a temperature at which thermophilic bacteria leach chalcopyrite at an economically acceptable rate.
The leaching method needs high temperature and high pressure, corrosion and harm are caused in some cases, the requirement on equipment is high, and the leaching efficiency is influenced in some cases due to long time consumption.
Disclosure of the invention
1. The invention aims to provide a method for leaching chalcopyrite by oxidizing ammonium persulfate, which is used for leaching the chalcopyrite at low temperature and normal pressure in the presence of a catalyst and an oxidant, wherein the copper leaching rate is over 96 percent.
2. Technical scheme
Uniformly stirring and mixing the chalcopyrite, the water and the acid, heating, adding a catalyst and an oxidant for oxidation leaching, and filtering to obtain a copper-containing leaching solution. The chemical reaction equation related to the invention is as follows:
setting process conditions:
1) the catalyst is silver salt, and the oxidant is ammonium persulfate;
2) mixing the chalcopyrite, water and acid in a liquid-solid ratio of 4: 1-8: 1;
3) controlling the temperature to be 70-95 ℃ during the oxidation leaching, and controlling the oxidation leaching time to be 5-10 h;
4) the dosage of the silver salt is that the weight ratio of the chalcopyrite to the silver salt is 100: 0.06-0.12;
5) the dosage of the ammonium persulfate is 20-40% to 60-80% (weight percentage) of the chalcopyrite and the ammonium persulfate;
6) the concentration of the silver salt is 0.01-0.038% (weight percentage concentration), and the concentration of the ammonium persulfate is 15-20% (weight percentage concentration).
The silver salt is not consumed in the process and can be recycled, and the ammonium persulfate can be recycled after being regenerated.
The technical and economic indexes achieved are as follows:
① the leaching rate of copper is more than 96%;
② the recovery rate of copper is above 97%.
3. Compared with the prior art, the method has the advantages that:
compared with the known wet leaching method, the method for leaching the chalcopyrite by oxidizing the ammonium persulfate can reduce the equipment requirement, can leach the chalcopyrite only under the conditions of normal pressure and low temperature, and has high leaching rate and short leaching time, thereby improving the production efficiency. The process for leaching the chalcopyrite can be completed by only heating to 70-95 ℃ and oxidizing for 5-10 hours, and the process is simple, low in equipment requirement, high in production efficiency and environment-friendly, so that the process has a good application prospect and important practical significance in leaching the chalcopyrite.
(IV) description of the drawings
FIG. 1 is a process flow diagram of the present invention
(V) detailed description of the preferred embodiments
The first embodiment is as follows:
1. chemical components of raw materials and weight percentage of each component
The raw materials are taken from a copper industry stockings company and comprise the following chemical components: 30.6-32% of S, 28-31% of Fe, 0.02-0.019% of Ni, 21-23% of Cu, 2.0-2.6% of Zn, 0.61-0.72% of Pb, 0.09-1.1% of Bi, and Al2O30.62～0.67％，CaO 0.31～0.43％，MgO 0.21～0.37％，SiO24.5～5.0％，As0.44～0.51％。
2. Thermal oxidative leaching
(1) Mixing chalcopyrite, water and sulfuric acid, wherein the liquid-solid ratio is 6: 1, and the concentration of the sulfuric acid is 4-6% (weight percentage concentration);
(2) controlling the heating oxidation process: 30 percent of chalcopyrite and 70 percent of ammonium persulfate (weight percentage), 100 percent of chalcopyrite and 0.09 percent of silver sulfate (weight ratio), 400 r/min of stirring speed and the concentration of catalyst silver sulfate: 0.01-0.018% (weight percentage concentration), 15-18% (weight percentage concentration) of ammonium persulfate, the oxidation temperature of 85-90 ℃, the oxidation time: and 7 h. The leaching rate of copper was 97.16%.
Example two:
1. raw materials
The raw materials are taken from a copper industry stockings company and comprise the following chemical components:
S 30～31％，Fe 29～32％，Ni 0.01～0.012％，Cu 20～22％，Zn 2.5～3.0％，Pb0.64～0.70％，Bi 0.08～1.0％，Al2O30.67～0.70％，CaO 0.3～0.40％，MgO0.25～0.40％，SiO24.9～5.1％，As 0.50～0.54％。
2. thermal oxidative leaching
(1) Mixing chalcopyrite, water and nitric acid, wherein the liquid-solid ratio is as follows: 5: 1, the concentration of nitric acid is 5-10% (weight percentage);
(2) controlling the heating oxidation process: chalcopyrite to ammonium persulfate: 35 percent to 65 percent (weight percentage), 100 percent to 0.1 percent (weight ratio) of copper ore to silver nitrate, 600 revolutions per minute of stirring speed, 0.022 to 0.025 percent (weight percentage concentration) of catalyst silver nitrate, 18 to 20 percent (weight percentage concentration) of ammonium persulfate, oxidation temperature: and (3) oxidizing at 90-95 ℃ for: 7-8 h. The leaching rate of copper is 99.27-99.47%.
Claims (2)
1. A chalcopyrite leaching process is characterized in that chalcopyrite, water and acid are stirred and mixed evenly, heating is carried out, a catalyst and an oxidant are added, oxidation leaching is carried out, and then a leaching solution containing copper is obtained by filtering, wherein the leaching solution contains the following components:
1) the catalyst is silver sulfate or silver nitrate, and the oxidant is ammonium persulfate;
2) the liquid-solid ratio of the chalcopyrite, the water and the acid is 4: 1-8: 1, the acid is sulfuric acid or nitric acid, the weight percentage concentration of the sulfuric acid is 4-6%, and the weight percentage concentration of the nitric acid is 5-10%;
3) controlling the temperature to be 70-95 ℃ during oxidation leaching;
4) the weight ratio of the added silver sulfate or silver nitrate is that chalcopyrite to silver salt is 100: 0.06-0.12;
5) the weight percentage of the added amount of the ammonium persulfate is 20-40% of the chalcopyrite and 60-80% of the ammonium persulfate;
6) the weight percentage concentration of silver sulfate or silver nitrate is 0.01-0.038%, and the weight percentage concentration of ammonium persulfate is 15-20%.
2. The chalcopyrite leaching process according to claim 1, characterized by: the weight ratio of the chalcopyrite to the silver sulfate is 100: 0.09, and the weight ratio of the chalcopyrite to the silver nitrate is 100: 0.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031352103A CN1227379C (en) | 2003-06-12 | 2003-06-12 | Technqiue for soaking copper pyrites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031352103A CN1227379C (en) | 2003-06-12 | 2003-06-12 | Technqiue for soaking copper pyrites |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1462812A CN1462812A (en) | 2003-12-24 |
| CN1227379C true CN1227379C (en) | 2005-11-16 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031352103A Expired - Fee Related CN1227379C (en) | 2003-06-12 | 2003-06-12 | Technqiue for soaking copper pyrites |
Country Status (1)
| Country | Link |
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| CN (1) | CN1227379C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336924C (en) * | 2005-06-16 | 2007-09-12 | 昆明理工大学 | Method for preparing primary titanium-rich material from high calcium-magnesium-titanium headings |
| RS63140B1 (en) * | 2015-10-30 | 2022-05-31 | Tech Resources Pty Ltd | Heap leaching |
| CN105316490A (en) * | 2015-11-13 | 2016-02-10 | 武汉工程大学 | Technique for recycling ammonium sulfate to extract copper from copper sulphide minerals through wet process |
| CN114231739A (en) * | 2021-12-22 | 2022-03-25 | 中国地质科学院 | Method for leaching chalcopyrite |
| CN115404352A (en) * | 2022-09-21 | 2022-11-29 | 中南大学 | Copper sulfide ore leaching method |
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2003
- 2003-06-12 CN CNB031352103A patent/CN1227379C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1462812A (en) | 2003-12-24 |
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