Patent US3880732A successfully refreshed from Google Patents.
US3880732A
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Hydrometallurgical process for the production of copper
Assignee: Pennzoil Quaker State Co
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Filing: 1974-05-23
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Granted: 1975-04-29
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Expires: 1994-05-23
Abstract
Abstract An improved process is described for the recovery of metallic copper from sulfur treated copper iron sulfide ore concentrates. X-bornite may be prepared from the chalcopyrite content of such ore concentrates by reacting said concentrates with sulfur vapor for at least about 6 minutes at 460*-500*C and 200 mm to 750 mm of Hg. By recycling the reaction product through the sulfur vapor reactor, residual chalcopyrite can be reduced but the main product of such recycling is idaite instead of x-bornite. In this improvement the sulfur treated ore concentrate is leached with cupric chloride. The pregnant liquor may be diluted with as much as about one part of water to one part of liquor and/or it may be cooled to precipitate cuprous chloride and silver chloride from the liquor. Metallic copper may then be produced from the precipitated cuprous chloride. In a preferred method, the cuprous chloride is reacted with sulfuric acid and O2 at 0-50 psig and 110*-115*C to produce cupric sulfate and hydrogen chloride. This cupric sulfate may be electrolyzed in a conventional cell to produce copper metal at the cathode and sulfuric acid and silver compounds at the anode. In one mode of practicing the invention, silver is removed from copper chloride liquor which is separated from the precipitated cuprous chloride. In the latter embodiment the liquor is first treated with oxygen to remove iron from the system and to convert the cuprous chloride to cupric chloride. Silver is removed from the resulting solution by anionic ion exchange.
Inventors
- 👤 John B Sardisco
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 13:44
CPC Classifications
C; C22; C22B; C22B1/00; C22B15/00; C22B15/0063; Y; Y02; Y02P; Y02P10/00; Y02P10/20
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
147 words
IN A PROCESS FOR THE PRODUCTION OF METALLIC COPPER FROM COPPER IRON SULFIDE ORE CONCENTRATES CONTAINING CHALCOPYRITE IN WHICH THE ORE CONCENTRATES ARE FIRST REACTED WITH SULFUR VAPOR TO FORM A SULFUR-TREATED CONCENTRATE CONTAINING A MEMBER FROM THE CLASS CONSISTING OF X-BORNITE, IDAITE AND MIXTURES THEREOF, THE IMPROVED HUDROMETALLURGICAL PROCESS COMPRISING: A. LEACHING SAID SULFUR TREATED CONCENTRATE WITH CUPRIC CHLORIDE TO ACHIEVE SUBSTANTIALLY SOLUBILIZATION OF THE COPPER CONTENT OF THE ORE CONCENTRATE, THEREBY FORMING A LEACHED SOLUTION CONTAINING CUPROUS CHLORIDE; B. CRYSTALLIZING CUPROUS CHLORIDE FROM SAID LEACH SOLUTION AND SEPARATING THE CUPROUS CLORIDE CRYSTALS THEREFROM; C. REACTING SAID CUPROUS CHLORIDE CRYSTALS WITH SULFURIC ACID AND OXYGEN TO PRODUCE COPPER SULFATE CRYSTALS; D. SEPARATING SAID CRYSTALS FROM THE COPPER SULFATE LIQUOR: E. DISSOLVING THE SEPARATED COPPER SULFATE CRYSTALS IN A SULFURIC ACID MEDIA; AND F. ELECTROLYZING THE RESULTING COPPER SULFATE SOLUTION TO PRODUCE METALLIC COPPER AT THE CATHODE.
Claim 2
Dependent Claim
147 words
IN A PROCESS FOR THE PRODUCTION OF METALLIC COPPER FROM COPPER IRON SULFIDE ORE CONCENTRATES CONTAINING CHALCOPYRITE IN WHICH THE ORE CONCENTRATES ARE FIRST REACTED WITH SULFUR VAPOR TO FORM A SULFUR-TREATED CONCENTRATE CONTAINING A MEMBER FROM THE CLASS CONSISTING OF X-BORNITE, IDAITE AND MIXTURES THEREOF, THE IMPROVED HUDROMETALLURGICAL PROCESS COMPRISING: A. LEACHING SAID SULFUR TREATED CONCENTRATE WITH CUPRIC CHLORIDE TO ACHIEVE SUBSTANTIALLY SOLUBILIZATION OF THE COPPER CONTENT OF THE ORE CONCENTRATE, THEREBY FORMING A LEACHED SOLUTION CONTAINING CUPROUS CHLORIDE; B. CRYSTALLIZING CUPROUS CHLORIDE FROM SAID LEACH SOLUTION AND SEPARATING THE CUPROUS CLORIDE CRYSTALS THEREFROM; C. REACTING SAID CUPROUS CHLORIDE CRYSTALS WITH SULFURIC ACID AND OXYGEN TO PRODUCE COPPER SULFATE CRYSTALS; D. SEPARATING SAID CRYSTALS FROM THE COPPER SULFATE LIQUOR: E. DISSOLVING THE SEPARATED COPPER SULFATE CRYSTALS IN A SULFURIC ACID MEDIA; AND F. ELECTROLYZING THE RESULTING COPPER SULFATE SOLUTION TO PRODUCE METALLIC COPPER AT THE CATHODE.
Claim 3
Dependent Claim
16 words
The method according to claim 1 wherein said sulfur treated ore concentrate consists primarily of x-bornite.
Claim 4
Dependent Claim
16 words
The method according to claim 1 wherein said sulfur treated ore concentrate consists primarily of idaite.
Claim 5
Dependent Claim
43 words
The method according to claim 1 wherein said sulfur treated concentrate is leached at a temperature in the range from about 100*C to about 110*C for such period of time as to achieve substantial solubilization of the copper content of the ore concentrates.
Claim 6
Dependent Claim
47 words
The method according to claim 1 wherein a saline metal chloride selected from the group consisting of sodium chloride, potassium chloride, magnesium chloride and mixtures thereof is maintained present during the leaching step at a concentration sufficient to avoid precipitation of cuprous chloride during said leaching step.
Claim 7
Dependent Claim
86 words
The process of claim 1 wherein the lean leach solution filtrate remaining after separation of crystals of cuprous chloride is reacted with oxygen to precipitate the iron content as insoluble basic ferric salt; said basic ferric salt is separated from the filtrate; and the resulting iron free filtrate is contacted with an ion exchange resin containing a styrene-divinyl benzene matrix having functional sites provided by chemical groups selected from the groups consisting of tertiary amines and quaternary ammonium groups to remove silver ions from said filtrate.
Claim 8
Dependent Claim
32 words
The process of claim 1 wherein the amount of copper in the cuprous chloride crystallized out of the leach solution is equal to the copper content of the solubilized sulfur-treated ore concentrate.
Claim 9
Dependent Claim
105 words
The process of claim 1 wherein the leach solution is reacted with oxygen to regenerate cupric chloride and to precipitate iron as basic iron salts; absorbing silver chloride salts from the resulting substantially iron free solution by contact with a basic synthetic resin having a styrene-divinyl benzene matrix and further having functional sites provided by functionally active ion exchange groups selected from chemical groups consisting of tertiary amines and quaternary ammonium groups; recovering the silver content therefrom by regenerating the ion exchange material with a basic solution to produce a solution containing silver ions; and recycling the regenerated cupric chloride solution to the leaching step.
Claim 10
Dependent Claim
33 words
The process of claim 1 wherein the cuprous chloride in step (b) is crystallized from the leach solution at 18*-35*C and 0-1.0 part of water is added for one part of leach solution.
Claim 11
Dependent Claim
44 words
The process of claim 1 wherein the reaction of step (c) is conducted at a ratio of 1 mole CuCl with 1 mole of H2SO4 at about 95*-130*C for about 30 minutes to 2 hours to produce a solution containing solid copper sulfate crystals.
Claim 12
Dependent Claim
168 words
In a process for the production of metallic copper from copper iron sulfide ore concentrates containing chalcopyrite in which the ore concentrates are first reacted with sulfur vapor to form a sulfur-treated concentrate containing a member from the class consisting of x-bornite, idaite and mixtures thereof, the improved hydrometallurgical process comprising: a. Leaching said sulfur treated concentrate with cupric chloride to achieve substantial solubilization of the copper content of the ore concentrate, thereby forming a leached solution containing cuprous chloride; b. Crystallizing cuprous chloride from said leach solution and separating the cuprous chloride crystals therefrom; c. Reacting said cuprous chloride crystals with sulfuric acid and oxygen to produce a copper sulfate solution; d. Crystallizing copper sulfate from said copper sulfate solution at 40*-70*C for 30 min. to 3 hours; e. Separating said copper sulfate from the resulting lean copper sulfate solution; f. Dissolving the separated copper sulfate crystals in a sulfuric acid media; and g. Electrolyzing the resulting copper solfate solution to produce metallic copper at the cathode.
Claim 13
Dependent Claim
168 words
In a process for the production of metallic copper from copper iron sulfide ore concentrates containing chalcopyrite in which the ore concentrates are first reacted with sulfur vapor to form a sulfur-treated concentrate containing a member from the class consisting of x-bornite, idaite and mixtures thereof, the improved hydrometallurgical process comprising: a. Leaching said sulfur treated concentrate with cupric chloride to achieve substantial solubilization of the copper content of the ore concentrate, thereby forming a leached solution containing cuprous chloride; b. Crystallizing cuprous chloride from said leach solution and separating the cuprous chloride crystals therefrom; c. Reacting said cuprous chloride crystals with sulfuric acid and oxygen to produce a copper sulfate solution; d. Crystallizing copper sulfate from said copper sulfate solution at 40*-70*C for 30 min. to 3 hours; e. Separating said copper sulfate from the resulting lean copper sulfate solution; f. Dissolving the separated copper sulfate crystals in a sulfuric acid media; and g. Electrolyzing the resulting copper solfate solution to produce metallic copper at the cathode.
Claim 14
Dependent Claim
37 words
The process of claim 11 wherein the reaction of step (e) is conducted with approximately 1 mole of CuCl and 4 moles of H2SO4 in a CuSO4-H2SO4-HCl media at about 95*-110*C for about 15 to 30 minutes.
Claim 15
Dependent Claim
43 words
The process of claim 11 wherein said copper sulfate solution of step (e) is distilled at a liquid temperature of about 120*-135*C for sufficient time to remove about 1 mole of HCl for each mole of cuprous chloride entering the reaction step (e).
Claim 16
Dependent Claim
133 words
In a process for the production of metallic copper from copper iron sulfide ore concentrates containing primarily chalcopyrite ore in which the ore concentrates are reacted with sulfur vapor to form a sulfur-treated concentrate containing as the principal copper-containing material therein a member from the class consisting of x-bornite, idaite and mixtures thereof, the improvement comprising: a. Leaching said sulfur treated concentrate with cupric chloride to achieve substantial solubilization of the copper content of the ore concentrate, thereby forming a leached solution containing cuprous chloride; b. Crystallizing cuprous chloride from said leach solution and separating the cuprous chloride crystals therefrom; c. Reacting said cuprous chloride crystals with sulfuric acid and oxygen to produce a cupric sulfate solution. d. Crystallizing cupric sulfate from said solution and separating the cupric sulfate crystals from said solution.
Claim 17
Dependent Claim
133 words
In a process for the production of metallic copper from copper iron sulfide ore concentrates containing primarily chalcopyrite ore in which the ore concentrates are reacted with sulfur vapor to form a sulfur-treated concentrate containing as the principal copper-containing material therein a member from the class consisting of x-bornite, idaite and mixtures thereof, the improvement comprising: a. Leaching said sulfur treated concentrate with cupric chloride to achieve substantial solubilization of the copper content of the ore concentrate, thereby forming a leached solution containing cuprous chloride; b. Crystallizing cuprous chloride from said leach solution and separating the cuprous chloride crystals therefrom; c. Reacting said cuprous chloride crystals with sulfuric acid and oxygen to produce a cupric sulfate solution. d. Crystallizing cupric sulfate from said solution and separating the cupric sulfate crystals from said solution.
Claim 18
Dependent Claim
72 words
A process for the production of metallic copper from cuprous chloride comprising the steps of: a. Reacting said cuprous chloride with sulfuric acid and oxygen to produce a copper sulfate solution; b. Crystallizing said copper sulfate from said solution and removing the resulting crystals therefrom; c. Dissolving the copper sulfate crystals in a water and sulfuric acid media; and d. Electrolyzing said copper sulfate solution to produce copper metal at the cathode.
Claim 19
Dependent Claim
72 words
A process for the production of metallic copper from cuprous chloride comprising the steps of: a. Reacting said cuprous chloride with sulfuric acid and oxygen to produce a copper sulfate solution; b. Crystallizing said copper sulfate from said solution and removing the resulting crystals therefrom; c. Dissolving the copper sulfate crystals in a water and sulfuric acid media; and d. Electrolyzing said copper sulfate solution to produce copper metal at the cathode.
Claim 20
Dependent Claim
28 words
The process of claim 15 wherein the crystallization of copper sulfate in step (b) is conducted at about 40*-70*C temperature, and for about 30 minutes to 3 hours.
Claim 21
Dependent Claim
84 words
A process for the production of metallic copper from cuprous chloride comprising the steps of: a. Reacting said cuprous chloride with sulfuric acid and oxygen at a ratio of about 1 mole of cuprous chloride and 1 mole of sulfuric acid in the presence of oxygen to produce copper sulfate crystals; b. Separating said copper sulfate crystals from said solution; c. Dissolving the copper sulfate crystals in a water and sulfuric acid media; and d. Electrolyzing said copper sulfate solution to produce copper metal.
Claim 22
Dependent Claim
84 words
A process for the production of metallic copper from cuprous chloride comprising the steps of: a. Reacting said cuprous chloride with sulfuric acid and oxygen at a ratio of about 1 mole of cuprous chloride and 1 mole of sulfuric acid in the presence of oxygen to produce copper sulfate crystals; b. Separating said copper sulfate crystals from said solution; c. Dissolving the copper sulfate crystals in a water and sulfuric acid media; and d. Electrolyzing said copper sulfate solution to produce copper metal.
Claim 23
Dependent Claim
28 words
The process of claim 17 wherein said crystallization of copper sulfate in step (b) is conducted at about 95* to 130*C for about 30 minutes to 2 hours.
Claim 24
Dependent Claim
73 words
The process of claim 15 wherein the solubilization of copper sulfate crystals in step (c) is conducted at about 30*-60*C for about 15 minutes to 2 hours; said water being added in an amount from 0-1.0 lb. water per pound of CuSO4 and said sulfuric acid being added as a 1-5% sulfuric acid solution in an amount ranging from about 5 to 10 lbs. of said sulfuric acid solution per pound of CuSO4.
Claim 25
Dependent Claim
76 words
The process of claim 17 wherein the solubilization of copper sulfate crystals in step (c) is conducted at about 30*-60*C for about 15 minutes to about 2 hours; said water being added in an amount from 0-1.0 lb. water per pound of CuSO4 and said sulfuric acid being added as a 1-5% sulfuric acid aqueous solution in an amount ranging from about 5 to 10 pounds of said sulfuric acid solution for 1 pound of CuSO4.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-04-28 | 1978-10-28 | 1979-04-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-04-28 | 1982-10-28 | 1983-04-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-04-28 | 1986-10-28 | 1987-04-29 | $7700.00 | Window Closed / Lapsed |