WO2006060305A2 - Processes for recovering metals from ores using organic solvent extraction and aqueous stripping at selected temperature differentials - Google Patents
Processes for recovering metals from ores using organic solvent extraction and aqueous stripping at selected temperature differentials Download PDFInfo
- Publication number
- WO2006060305A2 WO2006060305A2 PCT/US2005/042875 US2005042875W WO2006060305A2 WO 2006060305 A2 WO2006060305 A2 WO 2006060305A2 US 2005042875 W US2005042875 W US 2005042875W WO 2006060305 A2 WO2006060305 A2 WO 2006060305A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper
- temperature
- recovery process
- stripping
- process according
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
-
- 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
Definitions
- the first step in the leaching process is to contact the mined ore with an aqueous solution containing a leaching agent.
- a leaching agent For example, in copper leaching operations, sulfuric acid in an aqueous solution is contacted with the copper-containing ore. During this leaching process, acid in the leach solution is consumed and copper is dissolved, thereby increasing the copper content of the aqueous solution.
- the aqueous solution then contains the leached metal in a dilute form together with other impurities, for example iron.
- This aqueous solution (also known as the Pregnant Leach Solution - PLS) can then be treated via a process referred to as solvent extraction in which the leach solution is contacted with a non-aqueous solution containing a metal extraction reagent.
- the metal extraction reagent extracts the metal from the aqueous phase into the non-aqueous phase.
- copper in a dilute aqueous sulfuric acid solution is commonly extracted in a solvent extraction process by an oxime based extractant in an organic medium according to the chemical reaction;
- the copper loaded onto the oxime reagent in the organic medium can then be re-extracted into another aqueous medium, provided there is sufficient acid in this aqueous medium to drive the reverse chemical reaction.
- This is accomplished in a stage in the overall process known as stripping.
- the stripping process involves contacting the organic phase with an aqueous solution (also referred to as the Lean Electrolyte - LE) having a high sulfuric acid concentration with some copper. Copper is then re-extracted from the organic phase into the aqueous solution (also referred to as Rich Electrolyte - RE) which then has a relatively high concentration of copper and a lower level of sulfuric acid.
- the Rich Electrolyte solution is then subjected to a process referred to as electrowinning, which takes place in what is called a tankhouse.
- electrowinning the Rich Electrolyte solution is passed through an electrolytic cell between an anode and a cathode.
- the electrical potential placed between the two electrodes causes copper to be deposited on the surface of the cathode as copper metal.
- Sulfuric acid is generated in this process.
- the aqueous solution (now available for recycling as the Lean Electrolyte), somewhat depleted in copper and somewhat enriched in sulfuric acid, can be returned to the solvent extraction strip stage to again strip more copper off the organic medium.
- the leaching, solvent extraction/stripping and electrowinning of copper is a common, continuous practice as a method to recovery copper from ores.
- the solvent extraction process effectively concentrates the leached copper species into an aqueous solution (electrolyte) that is relatively high in copper and relatively low in other impurities, for example iron. This allows the electrowinning process to produce high quality copper metal at a high electrical current efficiency.
- Leaching of low grade copper ores is typically carried out in heap or dump leaching operations. In dump leaching operations, the ore is typically placed in a natural geological feature such as a canyon. The depth of the ore in the dump can range from relatively shallow to a few hundred meters in thickness. Heap leaching is carried out on permanent pads or on on-off pads. In the case of permanent pads, the depth of the ore can be similar to that in a dump.
- On-Off pads are designed so that the ore is placed on the prepared pad in a layer several meters thick, leached, allowed to drain and then removed from the pad.
- fresh aqueous leaching agent and/or recycled acidic raffinate solution is applied to the tops of the heaps or dump and allowed to drain down through the ore. It is then collected at the bottom of the heap or dump and fed as PLS to the solvent extraction operation.
- the temperature of the PLS exiting the copper leaching system will be dependent on the heat build up in the dump or heap. This in turn is dependent on the size of the dump or heap. The larger and deeper the size of the leaching system the less heat that will be lost by radiation to the environment. Heat loss will also be dependent on the local climatic conditions. If sulfide ores are present, bioleaching of these sulfide minerals will contribute significant amounts of heat to the dump or heap. In general, the temperature of the PLS exiting the leaching system will typically vary from about 8 0 C to about 3O 0 C.
- the resulting PLS can then be separated from the leached residue via a series of clarification operations and fed to solvent extraction.
- the ore grade is typically higher than in the case of ores fed to heap or dump leaching. Due to the nature of the operation, the temperature of the copper PLS will typically vary from about 15 0 C to about 3O 0 C.
- the solvent stripping step is normally carried out at temperatures above 30 deg. C. Therefore, existing solvent extraction plants generally operate with a lower temperature in the extraction stages than in the stripping stage(s).
- Electrowinning of copper is typically maintained at temperatures in the 4O 0 C to 5O 0 C range to insure the production of high grade copper cathode.
- electrowinning tankhouses are typically outfitted with boilers to allow for some heat input into the electrolyte to insure that the electrolyte temperature is maintained in the correct range.
- the Lean Electrolyte line going to stripping and the Rich Electrolyte return line from stripping are passed through interconnected heat exchangers so that the warm Lean Electrolyte is used to warm the Rich Electrolyte returning to the electrowinning tankhouse, thus minimizing energy losses from the tankhouse.
- One embodiment of the present invention includes a process comprising: (a) providing a pregnant leach solution comprising copper values; (b) contacting the pregnant leach solution with an organic phase comprising a copper extractant at an extraction temperature, T ext , to form a loaded organic phase comprising the metal values; (c) contacting the loaded organic phase with an aqueous stripping solution at a stripping temperature, T st ⁇ p , to form a copper-enriched stripping solution; wherein the difference in temperature ( ⁇ T) between the stripping temperature and the extraction temperature according to equation (I):
- ⁇ T T strip - T ext (I) is less than or equal to about 10 0 C.
- the difference in temperature ( ⁇ T) is less than or equal to about 7.5°C, less than or equal to about 5°C, less than or equal to about 2.5°C, less than or equal to about 0 0 C, less than or equal to about -2.5°C, less than or equal to about -5°C, less than or equal to about -7.5°C, and less than or equal to about -1 O 0 C.
- processes according to the present invention can be used to (1) increase overall copper production, (2) decrease overall oxime extractant concentration while maintaining copper production constant, or (3) decrease sulfuric acid concentration in the electrolyte while maintaining copper production constant or (4) some combination of two or more of these beneficial effects.
- the invention provides economic means to manipulate the extraction, strip, and electrowinning temperatures.
- the ores may be either primarily oxide type copper minerals, a mixture of oxide and sulfide type copper minerals, or sulfide type copper minerals.
- oxide type copper minerals a mixture of oxide and sulfide type copper minerals, or sulfide type copper minerals.
- the preferred copper extractants are those based on phenolic oximes (such as those disclosed in US Patent Nos. 4,978,788, 5,176,843 and 6,395,062) including ketoximes such as 2-hydroxy-5-nonylacetophenone oxime and the aldoximes such as 5- nonylsalicylaldoxime, by themselves or as mixtures with one another or with a modifier (such as those modifiers and oxime combinations disclosed in US Patent No. 6,231,784). Also preferred would be mixtures of an aldoxime with a modifier present . To illustrate some of the advantages of the present invention, as applied to copper recovery operations, one can first look at the effect of lowering the temperature during the stripping stage.
- the PLS was assumed to contain 6 gpl of copper, 70 gpl of sulfate and have a pH of 1.9.
- the organic phase was assumed to be 25% (v/v) LJX® 984N in a typical aliphatic hydrocarbon diluent.
- LIX® 984N is 0.77 M in 2-hydroxy-5- nonylacetophenone oxime and 0.88 M in 5-nonylsalicylaldoxime.
- the level of the copper on the stripped organic at a given temperature was taken from a mathematical model derived from a collection of stripping isotherms determined at different temperatures and reagent concentrations. The stripped organic value was plugged into the ISOCALC® Solvent Extraction Modeling Software and used to model the performance of a plant operating within these parameters.
- the Lean Electrolyte composition was assumed to be 170 gpl sulfuric acid and 36 gpl copper.
- the Rich Electrolyte likewise contained 45 gpl copper and the temperature in stripping was assumed to be 45 0 C.
- the targeted copper recovery was assumed to be 90% to achieve a total annual copper production of 40,000 metric tons per year.
- Table 1 illustrate the benefits in copper production afforded by the invention simply by lowering the temperature in the strip stage while keeping all the other process parameters the same.
- NT is net transfer by the organic phase. The greater the value of NT, the more efficiently the extractant is being used and the greater the copper recovery.
- Example 1 Depending on the site specific circumstances of a copper solvent extraction plant, it may not be feasible to produce more copper as described in the above paragraph. As can be seen in Table 1 , lowering the temperature in strip results in an increase in copper NT. If it is not feasible to increase the amount of copper transferred to electrowinning, according to the invention one is alternatively able to lower the concentration of the oxime extractant in the organic phase while still maintaining the overall copper recovery at 90%. This is a significant advantage in terms of cost of the organic phase.
- Example 1 Example 1
- the organic was assayed for copper by atomic absorption spectroscopy.
- the stripped organic representing 1 stage of stripping was determined in a similar fashion by equilibrating the organic with a synthetic rich electrolyte containing 55 gpl of copper and 157 gpl of sulfuric acid. The data is summarized in Table 5.
- Case 1 represents the base case which is typical of current practice. Cooling the strip from 45 0 C to 25 0 C while maintaining the extraction temperature 25 0 C (Case 1 vs Case 2) results in an additional 2,408 tons of copper production (a 6% increase) similar to what was seen in the first example. Increasing the temperature of extraction from 25 0 C to 45 0 C while maintaining the strip temperature at 45 0 C (Case 1 vs Case 3) results in a similar increase in production as in Case 1 vs Case 2.
- manipulating the temperatures in stripping can provide the overall copper recovery operation with the flexibility to operate with lower reagent concentrations or with lower acid concentrations in the Lean Electrolyte while maintaining copper recovery/production constant.
- Increasing the temperature in extraction also provides the operation with the flexibility to operate at lower reagent concentrations. It also offers the possibility of treating a PLS with a higher acid concentration while maintaining copper recovery/production constant. It also provides the flexibility to permit treating a PLS with a higher copper content without increasing reagent concentration while maintaining copper recovery constant.
- Another aspect of the invention provides economic means to manipulate the extraction temperature (T EX O an d the strip temperature (Tst ⁇ p).
- T EX O an extraction temperature
- Tst ⁇ p the strip temperature
- Example 4 The temperature of the electrolyte can be lowered using an external cooling source.
- Current practice involves using interconnected heat exchangers to transfer heat from the Lean Electrolyte as it exits the electrowinning tank house to the incoming Rich Electrolyte coming from stripping to minimize heat loss from the electrowinning tank house. This results in cooling the Lean Electrolyte a few degrees.
- the Lean Electrolyte can be cooled more effectively by either coupling the current heat exchanger with an external cooling source such as an evaporative cooler, a compressor based refrigeration unit or using a low temperature fluid stream, for example, the PLS or makeup water.
- the temperature of the PLS can be increased by using it as the cooling fluid in a heat exchanger with the Lean Electrolyte before passing it to extraction.
- a high temperature fluid stream such as an stream from a copper concentrate leach system, for example, an autoclave or a bioreactor leach system.
- a high temperature fluid stream such as an stream from a copper concentrate leach system
- an autoclave leach system or a bioreactor leach system The advantage of using the autoclave leach system or the bioreactor leach system is that it also produces additional copper that can be recovered in addition to the heat.
- a further extension of this invention is the concept of simply replacing the current boilers used to heat the electrolyte by use of the waste heat from copper concentrate leaching systems such as autoclave leach systems or bioreactor leach systems.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
Description
Claims
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX2007005511A MX2007005511A (en) | 2004-12-03 | 2005-11-29 | Processes for recovering metals from ores using organic solvent extraction and aqueous stripping at selected temperature differentials. |
| BRPI0518742-7A BRPI0518742A2 (en) | 2004-12-03 | 2005-11-29 | copper recovery process |
| AU2005312121A AU2005312121A1 (en) | 2004-12-03 | 2005-11-29 | Processes for recovering metals from ores using organic solvent extraction and aqueous stripping at selected temperature differentials |
| CA002587329A CA2587329A1 (en) | 2004-12-03 | 2005-11-29 | Processes for recovering metals from ores using organic solvent extraction and aqueous stripping at selected temperature differentials |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63275904P | 2004-12-03 | 2004-12-03 | |
| US60/632,759 | 2004-12-03 | ||
| US11/265,684 US20060117908A1 (en) | 2004-12-03 | 2005-11-02 | Processes for recovering metals from ores using organic solvent extraction and aqueous stripping at selected temperature differentials |
| US11/265,684 | 2005-11-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2006060305A2 true WO2006060305A2 (en) | 2006-06-08 |
| WO2006060305A3 WO2006060305A3 (en) | 2007-08-09 |
Family
ID=36565585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2005/042875 Ceased WO2006060305A2 (en) | 2004-12-03 | 2005-11-29 | Processes for recovering metals from ores using organic solvent extraction and aqueous stripping at selected temperature differentials |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20060117908A1 (en) |
| AU (1) | AU2005312121A1 (en) |
| BR (1) | BRPI0518742A2 (en) |
| CA (1) | CA2587329A1 (en) |
| MX (1) | MX2007005511A (en) |
| PE (1) | PE20060888A1 (en) |
| WO (1) | WO2006060305A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8003064B2 (en) | 2007-09-17 | 2011-08-23 | Freeport-Mcmoran Corporation | Controlled copper leach recovery circuit |
| US8070850B2 (en) * | 2008-01-11 | 2011-12-06 | E H P Technology, LLC | Process for liberating metals using direct production of leach grade acid solutions |
| US9169533B2 (en) | 2011-12-20 | 2015-10-27 | Freeport Minerals Corporation | System and method including multi-circuit solution extraction for recovery of metal values from metal-bearing materials |
| US8420048B1 (en) | 2011-12-20 | 2013-04-16 | Freeport-Mcmoran Corporation | System and method for parallel solution extraction of one or more metal values from metal-bearing materials |
| EA035483B1 (en) | 2015-12-21 | 2020-06-23 | Оутотек (Финлэнд) Ой | Removal of gypsum from leach solution |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853725A (en) * | 1972-06-28 | 1974-12-10 | Kennecott Copper Corp | Selective stripping process |
| US3917519A (en) * | 1974-02-27 | 1975-11-04 | Freeport Minerals Co | Process for the manufacture of electrolytic copper |
| SE396968B (en) * | 1975-07-01 | 1977-10-10 | Boliden Ab | PROCEDURE FOR EXTRACTING NON-IRON METALS FROM SULPHIDY MATERIALS BY ROASTING AND LACHING |
| US4594132A (en) * | 1984-06-27 | 1986-06-10 | Phelps Dodge Corporation | Chloride hydrometallurgical process for production of copper |
| EP0202833B1 (en) * | 1985-05-16 | 1991-01-23 | Imperial Chemical Industries Plc | Composition and use of the composition for the extraction of metals from aqueous solutions |
| US5176843A (en) * | 1985-05-16 | 1993-01-05 | Imperial Chemical Industries Plc | Composition and use of the composition for the extraction of metals from aqueous solution |
| US6231784B1 (en) * | 1995-02-16 | 2001-05-15 | Henkel Corporation | Water insoluble composition of an aldoxime extractant and an equilibrium modifier |
| US6319389B1 (en) * | 1999-11-24 | 2001-11-20 | Hydromet Systems, L.L.C. | Recovery of copper values from copper ores |
| US6395062B2 (en) * | 2000-02-18 | 2002-05-28 | Cognis Corporation | Process for recovery of metals from metal-containing ores |
-
2005
- 2005-11-02 US US11/265,684 patent/US20060117908A1/en not_active Abandoned
- 2005-11-17 PE PE2005001346A patent/PE20060888A1/en not_active Application Discontinuation
- 2005-11-29 AU AU2005312121A patent/AU2005312121A1/en not_active Abandoned
- 2005-11-29 BR BRPI0518742-7A patent/BRPI0518742A2/en not_active Application Discontinuation
- 2005-11-29 MX MX2007005511A patent/MX2007005511A/en unknown
- 2005-11-29 WO PCT/US2005/042875 patent/WO2006060305A2/en not_active Ceased
- 2005-11-29 CA CA002587329A patent/CA2587329A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CA2587329A1 (en) | 2006-06-08 |
| US20060117908A1 (en) | 2006-06-08 |
| PE20060888A1 (en) | 2006-10-16 |
| WO2006060305A3 (en) | 2007-08-09 |
| AU2005312121A1 (en) | 2006-06-08 |
| BRPI0518742A2 (en) | 2008-12-02 |
| MX2007005511A (en) | 2007-07-09 |
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