US4230487A
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US
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Method of selectively bringing into solution the non-ferrous metals contained in sulphurized ores and concentrates
Assignee: Societe Miniere et Metallurgique de Penarroya
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Filing: 1979-09-07
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Granted: 1980-10-28
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Expires: 1999-09-07
Abstract
Abstract The invention provides a method for selectively solubilizing the non-ferrous metals contained in sulphurized ores and concentrates, with regard to the iron and sulphur therein, by subjecting the ore or concentrate to lixiviation with an aqueous solution of cupric chloride at a temperature above 50 DEG C., preferably at a temperature between 70 DEG C. and 105 DEG C., and then regenerating said aqueous solution in situ at atmospheric pressure by means of air and a regeneration agent selected from the group consisting of hydrochloric acid and ferrous chloride. The invention also contemplates the preferable inclusion in the aqueous cupric chloride solution of an agent for solubilizing cuprous chloride selected from the group consisting of an alkali metal chloride, an alkaline earth metal chloride, ammonium chloride, and ferrous chloride. When the regeneration agent is hydrochloric acid, the pH of the aqueous cupric chloride solution is at most 1 in the presence of ferrous chloride and at most 3 in the absence of ferrous chloride. When the regeneration agent is ferrous chloride, the pH of the aqueous cupric chloride solution ranges between 1 and 3, the temperature of the solution exceeds 50 DEG C., and the solution contains at least 1g/l of cuprous ions and at least 2g/l of ferrous ions, with the result that geothite is precipitated and may be separated, and the non-ferrous metals isolated as the aqueous solutions of the metal chlorides.
Inventors
- 👤 Jean-Michel Demarthe
- 👤 Louis Gandon
- 👤 Andre Georgeaux
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 09:27
CPC Classifications
C; C22; C22B; C22B3/00; C22B3/04; C22B3/06; C22B3/10; Y; Y02; Y02P; Y02P10/00; Y02P10/20
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
208 words
A method for selectively solubilizing at least one non-ferrous metal selected from the group consisting of lead, zinc, copper, silver, cadmium, nickel, and cobalt, and contained, in the form of its sulphide, in an initial product selected from the group consisting of sulphurized ores and concentrates, comprising subjecting said initial product to lixiviation at a temperature above 50° C. with an aqueous solution containing cupric chloride and an agent for solubilizing cuprous chloride, the aqueous solution having an oxido-reduction potential of between 400 and 800 millivolts in relation to a hydrogen electrode potential throughout the operation, whereby the metal sulphides are converted to the respective soluble metal chlorides, the cupric chloride is reduced to cuprous chloride which remains in solution due to said solubilizing agent, and elemental sulfur is produced, and regenerating the resulting reaction mixture in situ at atmospheric pressure and at a temperature above 50° C. with air and hydrochloric acid while maintaining the pH of the solution at a value of at most 1 when the solution contains ferrous chloride and at a value of at most 3 when ferrous chloride is absent, whereby the cuprous chloride is oxidized to cupric chloride, and isolating an aqueous solution containing said at least one non-ferrous metal chloride.
Claim 2
Independent Claim
208 words
A method for selectively solubilizing at least one non-ferrous metal selected from the group consisting of lead, zinc, copper, silver, cadmium, nickel, and cobalt, and contained, in the form of its sulphide, in an initial product selected from the group consisting of sulphurized ores and concentrates, comprising subjecting said initial product to lixiviation at a temperature above 50° C. with an aqueous solution containing cupric chloride and an agent for solubilizing cuprous chloride, the aqueous solution having an oxido-reduction potential of between 400 and 800 millivolts in relation to a hydrogen electrode potential throughout the operation, whereby the metal sulphides are converted to the respective soluble metal chlorides, the cupric chloride is reduced to cuprous chloride which remains in solution due to said solubilizing agent, and elemental sulfur is produced, and regenerating the resulting reaction mixture in situ at atmospheric pressure and at a temperature above 50° C. with air and hydrochloric acid while maintaining the pH of the solution at a value of at most 1 when the solution contains ferrous chloride and at a value of at most 3 when ferrous chloride is absent, whereby the cuprous chloride is oxidized to cupric chloride, and isolating an aqueous solution containing said at least one non-ferrous metal chloride.
Claim 3
Dependent Claim
20 words
The method of claim 1 wherein the lixiviation is carried out at a temperature between 70° C. and 105° C.
Claim 4
Dependent Claim
24 words
The method of claim 1 wherein the elemental sulfur and any unreacted residue are separated from the reaction mixture before regenerating the resulting solution.
Claim 5
Dependent Claim
20 words
The method of claim 1 wherein the pH is maintained by controlling the rate of addition of the hydrochloric acid.
Claim 6
Dependent Claim
20 words
The method of claim 1 wherein the oxido-reduction potential is maintained by controlling the rate of delivery of the air.
Claim 7
Dependent Claim
16 words
The method of claim 1 wherein the agent for solubilizing cuprous chloride comprises a chloride ion.
Claim 8
Dependent Claim
33 words
The method of claim 1 wherein the agent for solubilizing cuprous chloride is selected from the group consisting of an alkali metal chloride, an alkaline earth metal chloride, ammonium chloride, and ferrous chloride.
Claim 9
Dependent Claim
62 words
The method of claim 1 wherein the initial product contains lead sulphide which is converted to the soluble lead chloride by the lixiviation and is present as such in the isolated aqueous solution containing at least one non-ferrous metal chloride, crystallizing the lead chloride, separating the crystallized lead chloride from the aqueous solution, and recovering the lead from the crystallized lead chloride.
Claim 10
Dependent Claim
34 words
The method of claim 8 wherein the lead is recovered by reducing the crystallized lead chloride to obtain elemental lead and a regenerating agent as a byproduct which is recycled to the lixiviating step.
Claim 11
Dependent Claim
37 words
The method of claim 8 wherein the lead is recovered by cementing the crystallized lead chloride with metallic iron to obtain elemental lead and ferrous chloride which is recycled as a regenerating agent to the lixiviating step.
Claim 12
Dependent Claim
57 words
The method of claim 1 wherein the non-ferrous metal is selected from the group consisting of zinc, copper and lead; the lixiviation is carried out at a temperature between 85° and 103° C.; the agent for solubilizing cuprous chloride is sodium chloride; and the regeneration is carried out at a temperature of from 80° to 90° C.
Claim 13
Independent Claim
208 words
A method for selectively solubilizing at least one non-ferrous metal selected from the group consisting of lead, zinc, copper, silver, cadmium, nickel, and cobalt, and contained, in the form of its sulphide, in an initial product selected from the group consisting of sulphurized ores and concentrates, comprising subjecting said initial product to lixiviation at a temperature above 50° C. with an aqueous solution containing cupric chloride and an agent for solubilizing cuprous chloride, the aqueous solution having an oxido-reduction potential of between 400 and 800 millivolts in relation to a hydrogen electrode potential throughout the operation, whereby the metal sulphides are converted to the respective soluble metal chlorides, the cupric chloride is reduced to cuprous chloride which remains in solution due to said solubilizing agent, and elemental sulphur is produced, separating the sulphur and any unreacted residue from the reaction mixture, regenerating the resulting solution, containing at least 1 g/l of cuprous ions and at least 2 g/l of ferrous ions, in situ at atmospheric pressure and at a temperature above 50° C. with air and ferrous chloride at a pH between 1 and 3, whereby goethite is precipitated, separating the goethite from the solution, and isolating an aqueous solution containing said at least one non-ferrous metal chloride.
Claim 14
Independent Claim
208 words
A method for selectively solubilizing at least one non-ferrous metal selected from the group consisting of lead, zinc, copper, silver, cadmium, nickel, and cobalt, and contained, in the form of its sulphide, in an initial product selected from the group consisting of sulphurized ores and concentrates, comprising subjecting said initial product to lixiviation at a temperature above 50° C. with an aqueous solution containing cupric chloride and an agent for solubilizing cuprous chloride, the aqueous solution having an oxido-reduction potential of between 400 and 800 millivolts in relation to a hydrogen electrode potential throughout the operation, whereby the metal sulphides are converted to the respective soluble metal chlorides, the cupric chloride is reduced to cuprous chloride which remains in solution due to said solubilizing agent, and elemental sulphur is produced, separating the sulphur and any unreacted residue from the reaction mixture, regenerating the resulting solution, containing at least 1 g/l of cuprous ions and at least 2 g/l of ferrous ions, in situ at atmospheric pressure and at a temperature above 50° C. with air and ferrous chloride at a pH between 1 and 3, whereby goethite is precipitated, separating the goethite from the solution, and isolating an aqueous solution containing said at least one non-ferrous metal chloride.
Claim 15
Dependent Claim
36 words
The method of claim 12 wherein the non-ferrous metal is copper; the agent for solubilizing cuprous chloride is ferrous chloride; and the regeneration is conducted at a temperature of from about 93° to about 97° C.
Claim 16
Dependent Claim
20 words
The method of claim 12 wherein the lixiviation is carried out at a temperature between 70° C. and 105° C.
Claim 17
Dependent Claim
16 words
The method of claim 12 wherein the agent for solubilizing cuprous chloride comprises a chloride ion.
Claim 18
Dependent Claim
33 words
The method of claim 12 wherein the agent for solubilizing cuprous chloride is selected from the group consisting of an alkali metal chloride, an alkaline earth metal chloride, ammonium chloride, and ferrous chloride.
Claim 19
Dependent Claim
62 words
The method of claim 12 wherein the initial product contains lead sulphide which is converted to the soluble lead chloride by the lixiviation and is present as such in the isolated aqueous solution containing at least one non-ferrous metal chloride, crystallizing the lead chloride, separating the crystallized lead chloride from the aqueous solution, and recovering the lead from the crystallized lead chloride.
Claim 20
Dependent Claim
34 words
The method of claim 17 wherein the lead is recovered by reducing the crystallized lead chloride to obtain elemental lead and a regenerating agent as a by-product which is recycled to the lixiviating step.
Claim 21
Dependent Claim
37 words
The method of claim 17 wherein the lead is recovered by cementing the crystallized lead chloride with metallic iron to obtain elemental lead and ferrous chloride which is recycled as a regenerating agent to the lixiviating step.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-10-28 | 1984-04-28 | 1984-10-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-10-28 | 1988-04-28 | 1988-10-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-10-28 | 1992-04-28 | 1992-10-28 | $7700.00 | Window Closed / Lapsed |