CN1252292C - Arsonium-containing cupric sulfide concentrate smelting process by wet method - Google Patents
Arsonium-containing cupric sulfide concentrate smelting process by wet method Download PDFInfo
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- CN1252292C CN1252292C CNB031171966A CN03117196A CN1252292C CN 1252292 C CN1252292 C CN 1252292C CN B031171966 A CNB031171966 A CN B031171966A CN 03117196 A CN03117196 A CN 03117196A CN 1252292 C CN1252292 C CN 1252292C
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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
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Abstract
The present invention relates to an arsenic-containing cupric sulfide concentrate smelting process by a wet method. The present invention takes a sodium chloride or calcium chloride solution containing bivalent copper ions as a leaching agent, and copper concentrate is leached via pressurization oxygen so as to obtain copper ion extract and sulfur and arsenic containing leaching slag. Copper concentrate and carbonate are added in reducing environment so as to reduce bivalent copper ions into univalent copper ions, copper metals via electro deposit after filtration and purification, and elemental sulfur products are prepared via slag leaching and flotation. Therefore, the arsenic is piled up as tailings, and copper powder is used for replacement and recycling when gold and silver are dissolved in purified liquid. The present invention is a simple process for pressurization oxygen leaching-no extractive purification-Cu+ electro deposit, and a leaching agent has the advantages of high leaching efficiency and strong adaptability. The process can effectively process the copper concentrate containing arsenic and noble metals via comprehensive recovery without extra-fine grinding, and the process can save a large number of energy and reduce cost and has the advantages of high cation film electro deposit performance, high current efficiency and good initiativeness.
Description
Technical field the invention belongs to a kind of wet method smelting process that contains the pozzuolite copper ore concentrates.
Pyrometallurgical smelting is adopted in the smelting of background technology copper sulfide concentrate more, because it can comprehensively reclaim sulphur and precious metal wherein, slag also can be used for producing building materials.But, will cause serious environmental to pollute when copper ore concentrates contains arsenic when heavier.Since the seventies in last century, each state wishes to find the way of avoiding the arsenic evil all at the wet method smelting process of this type of copper ore concentrates of exploitation.Wherein more influential achievement in research has following several:
First kind is in-pulp electrolysis direct production copper sponge.This method is because technical difficulty is big, and the production cost height is early than having stopped research around the nineteen ninety.
Second kind is the direct sulfuric acid leaching of the ultra-fine mill-logical oxygen of heating.The deadly defect of this method is that power consume is too high, adds that leaching reaction is difficult to thoroughly, continuous mutually stopping in the period of 1988-1990.
The third is a CESL pressurization leaching-out technique, leaches copper exactly under the pressure condition of 150-160 ℃ temperature and 0.8-1.5MPa.This technology is that Engineering Service company of Canadian bright section proposed in 1992, requires ore grinding to account for 95% to-40 μ m on the technology, and extraction temperature is 150 ℃, and pressure is 1.38MPa, and floatation recovery is soaked sulphur and the precious metal in the slag, and the direct electrodeposition of leach liquor is produced cathode copper.Though there is the total yield of reporting its copper to reach more than 90%, because of grinding fineness requires height, the production poplar is originally still too big, does not obtain popularization so far.
The 4th kind of INTEC technology, i.e. chloride system blowing air or the electrolysis of oxygen leaching-cuprous chloride.This technology is that Australia proposed in 1992, way is copper ore concentrates to be carried out the ventilation of heating of four sections adverse current normal pressures leach, enter diaphragm electrodeposition groove output copper powder in the solution and after purifying, electrolysis waste solution returns leaching, because leaching process complexity, new progress never again just after finishing 1 ton test of daily output in 1998 is in halted state.
The 5th kind is the airtight leaching-extraction of fine grinding-oxygen-electrodeposition technology.This technology also is to be proposed by Australia, promotes in western mining industry technology company.Gordian technique is fine grinding, requires-10 μ m to account for 80%, leaches under 1000 ℃ and 1MPa condition then, and the shortcoming of this method is to handle chalcopyrite, and grinding fineness is higher, and energy consumption is bigger.
Therefore, have now and can realize that substantially the method for wet processing purpose all be unable to do without the problem of fine grinding or ultra-fine mill and High Temperature High Pressure, adaptability is relatively poor besides.
Summary of the invention the objective of the invention is to propose a kind of wet method smelting process that contains the pozzuolite copper ore concentrates, and this technology does not need the fine grinding copper ore concentrates, and energy consumption is little, cost is low, adaptability is strong, overcomes the deficiencies in the prior art with this.
This pozzuolite copper ore concentrates wet method smelting process that contains that the present invention proposes is characterized in that:
(1) with containing the sodium-chlor of bivalent cupric ion or calcium chloride solution as leaching agent, pressurised oxygen leaches copper ore concentrates, allows the copper metal enter solution with the form of cupric ion, allows sulphur, arsenic and most of iron stay with solid form and soaks in the slag;
(2) leach (1) step gained leach liquor, in reducing environment, add copper ore concentrates, bivalent cupric ion is reduced into univalent copper ion, filter, purify;
(3) electrodeposition (2) step gained scavenging solution gets electro deposited copper.
Leaching agent contains Cu
2+The 30-60 grams per liter, NaCl 200-280 grams per liter, perhaps CaCl
2The 200-300 grams per liter.
The liquid-solid ratio that leaches is 5: 1-10: 1, and temperature 110-130 ℃, oxygen is pressed 0.5-1MPa, carries out in high-pressure reactor.
Add carbonate in the reduction scavenging process, the pH value that controls environment is 4-5.0, stirs 2-3 hour, after clarification separates, purifies slag and returns the leaching operation.
Leach liquor contains Cu
2+The 15-30 grams per liter, the Fe1-5 grams per liter, the leach liquor after the purification contains Cu
2+≤ 1 grams per liter, Fe≤1 grams per liter, Zn
2+≤ 5 grams per liters.
Electrodeposition adopts the cationic membrane Winning cell, cathode current density be the 1000-6000 peace/square metre.
Negative electrode is separated out shot copper or copper powder, and anode output electrodeposition raffinate contains Cu
2+The 30-60 grams per liter returns the high-pressure reactor operation.
Leached mud carries out filtration washing one time, and filtrate is participated in reduction and purified, and filter residue adopts method for floating to reclaim elementary sulfur, output higher-grade sulphur concentrate.
When containing precious metal such as gold and silver in the scavenging solution, adopt the copper powder displacement to reclaim.
Operational path of the present invention can be described as simply: pressurised oxygen leaching-no extracting and purifying-Cu
+Electrodeposition.Because the leaching efficiency of leaching agent is high and be easy to get, be suitable for handling all types of copper ore concentratess, particularly to handle and contain the many copper ore concentratess of precious metals such as arsenic and gold and silver big superiority is arranged, no extracting and purifying makes technical process succinct, scale is changeable, and is versatile and flexible; Copper ore concentrates need not ultra-fine mill, can save energy consumption in a large number, reduces cost; Adopt high-performance cationic membrane electrodeposition current efficiency height, power consumption low, add the copper ore concentrates reduction and purify the cost that can reduce purification significantly, have initiative.
Appended drawings is a process flow sheet of the present invention.
Embodiment
Example 1
In the high-pressure reactor of 100 liters of titanium lined materials, the input composition is Cu
2+32 grams per liters, the Fe0.2 grams per liter, Zn 2.1 grams per liters, 14 kilograms of 70 liters of leaching agents of NaCl 250 grams per liters and copper concentrate powders (dry weight), the main component of copper ore concentrates is: Cu 16.5%, Fe 41%, S 36%, As 1.5%, Ag 750g/t, Zn 1.2%.Feed industrial oxygen, control oxygen is pressed 0.5-0.6MPa, and temperature 110-125 ℃, agitation leach is after 4 hours, clarification, filter, washing 75 liters of leach liquors of output (containing wash water), its composition is: Cu 59.4 grams per liters (Cu wherein
2+30 grams per liters), Fe 2.5 grams per liters, As＜0.01 grams per liter, SO
4 2-＜0.1 grams per liter, Zn 4 grams per liters, Ag 0.135 grams per liter.Output is soaked 13 kilograms of slags (containing Cu 0.71%).This leach liquor adds 14 kilograms of copper concentrate powders in 100 liters of steel basins, be heated to 85-90 ℃ under the normal pressure, and adds the technical grade Paris white, and process control pH value 4.0-5.0 stirred after 2 hours, and clarification separates the output scavenging solution and (contains Cu for 63 liters
2+0.5 grams per liter, Fe 0.2 grams per liter, Zn 2.8 grams per liters), but in 100 liters displacement slot, add 30 gram electrolytic copper powders and stir 1 hour after-filtration washing output sponge silver 25 gram, filtrate enters the electrodeposition system, control cathode current density 4500 peaces/square metre, cathode compartment can be separated out the shot copper product continuously, and anolyte compartment's regenerated leach liquor (contains Cu
2+31 grams per liters, Cu
+Trace), returns the leaching operation, so circulation.Flotation of leached residue can get the elementary sulfur product, and arsenic promptly stays in flotation tailings with harmless ferric arsenate form to be stored up.
Example 2
To enter the electrodeposition system by the purification of last routine output and the solution after the displacement, control cathode current density 6000 peaces/square metre, can produce the electrolytic copper powder that meets GB that accounts for copper products 30%.
The technico-economical comparison that above example obtains is as follows:
Copper leaching rate 〉=95%; Ton copper products direct current consumption≤1450KWH; Whole process copper total yield 〉=94%; Ton copper workshop manufacturing cost≤3500 yuan; The leaching yield of gold and silver precious metal 〉=96%; The copper products quality meets electrolytic copper standard of country.
The non-environmental-pollution problem.
Claims (9)
1, a kind of pozzuolite copper ore concentrates wet method smelting process that contains is characterized in that:
(1) with containing the sodium-chlor of bivalent cupric ion or calcium chloride solution as leaching agent, pressurised oxygen leaches copper ore concentrates, allows the copper metal enter solution with the form of cupric ion, allows sulphur, arsenic and most of iron stay with solid form and soaks in the slag;
(2) leach (1) step gained leach liquor, in reducing environment, add copper ore concentrates, bivalent cupric ion is reduced into univalent copper ion, filter, purify;
(3) electrodeposition (2) step gained purifies leach liquor and gets electro deposited copper.
2, technology according to claim 1 is characterized in that leaching agent contains Cu
2+The 30-60 grams per liter, NaCl 200-280 grams per liter, perhaps CaCl
2The 200-300 grams per liter.
3, technology according to claim 1 is characterized in that the liquid-solid ratio that leaches is 5: 1-10: 1, and temperature 110-130 ℃, oxygen is pressed 0.5-1MPa, carries out in high-pressure reactor.
4, technology according to claim 1 is characterized in that reducing and adds carbonate in the scavenging process, and the pH value that controls environment is 4-5.0, stirs 2-3 hour, after clarification separates, purifies slag and returns the leaching operation.
5, technology according to claim 1 is characterized in that leach liquor contains Cu
2+The 15-30 grams per liter, the Fe1-5 grams per liter, the leach liquor after the purification contains Cu
2+≤ 1 grams per liter, Fe≤1 grams per liter, Zn
2+≤ 5 grams per liters.
6, technology according to claim 1 is characterized in that electrodeposition adopts the cationic membrane Winning cell, cathode current density be the 1000-6000 peace/square metre.
7, technology according to claim 1 is characterized in that negative electrode separates out shot copper or copper powder, and anode output electrodeposition raffinate contains Cu
2+The 30-60 grams per liter returns the high-pressure reactor operation.
8, technology according to claim 1 is characterized in that leached mud carries out filtration washing one time, and filtrate is participated in reduction and purified, and filter residue adopts method for floating to reclaim elementary sulfur.
9, technology according to claim 1 when it is characterized in that containing the gold and silver precious metal in the scavenging solution, adopts the copper powder displacement to reclaim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031171966A CN1252292C (en) | 2003-01-16 | 2003-01-16 | Arsonium-containing cupric sulfide concentrate smelting process by wet method |
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| CNB031171966A CN1252292C (en) | 2003-01-16 | 2003-01-16 | Arsonium-containing cupric sulfide concentrate smelting process by wet method |
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| CN1455007A CN1455007A (en) | 2003-11-12 |
| CN1252292C true CN1252292C (en) | 2006-04-19 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309849C (en) * | 2004-02-27 | 2007-04-11 | 云南铜业股份有限公司 | Method of dearsenic by parallel circulating continuous electric formation |
| CN108220618A (en) * | 2018-01-19 | 2018-06-29 | 中国地质科学院矿产综合利用研究所 | Arsenic-fixing and copper-extracting method for high-arsenic copper sulfide ore |
| CN109261345B (en) * | 2018-08-01 | 2021-10-22 | 昆明理工大学 | Copper-sulfur ore separation method |
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