US20100263490A1 - Methods and systems for recovering rhenium from a copper leach - Google Patents
Methods and systems for recovering rhenium from a copper leach Download PDFInfo
- Publication number
- US20100263490A1 US20100263490A1 US12/424,863 US42486309A US2010263490A1 US 20100263490 A1 US20100263490 A1 US 20100263490A1 US 42486309 A US42486309 A US 42486309A US 2010263490 A1 US2010263490 A1 US 2010263490A1
- Authority
- US
- United States
- Prior art keywords
- metal
- rhenium
- solution
- bearing
- activated carbon
- 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.)
- Abandoned
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G47/00—Compounds of rhenium
-
- 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
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B15/0086—Treating solutions by physical methods
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
- C22B5/00—General methods of reducing to metals
-
- 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
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- 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 present invention relates generally to the recovery of rhenium and relates more specifically to the recovery of rhenium from a copper leach.
- Rhenium was the last naturally occurring element to be discovered and the last element discovered having a stable isotope. Rhenium is typically recovered as a byproduct of molybdenum refinement. Since recovery of rhenium from molybdenite is difficult and the concentrations of rhenium in molybdenite are very low, typically from about 0.002% to about 0.02%, rhenium is one of the most expensive metals available in commodity markets. Rhenium has several characteristics that make it unique, such as, for example, the second highest melting point amongst metals, amongst the densest metals, a super conductor, and the greatest number of oxidation states of any element. Industrial applications include the use of rhenium in catalysts, electronics, thermocouples, high temperature turbine blades, and photoflash devices.
- Rhenium may be extracted from ores that contain copper and molybdenum. Common practice for leaching copper from low-grade copper ore is to place the ore in a heap leach pad and leach the ore with dilute sulfuric acid solution. The resulting copper-bearing solution is typically concentrated via solvent extraction and/or electrowon to produce pure copper cathode. Typically, the copper-bearing solution has less than one part per million of dissolved rhenium and may contain significant amounts of other metals in the copper-bearing solution. Recovery of rhenium from the copper-bearing solution is not economically feasible and hence rhenium is, along with other metal values, typically not recovered from the copper-bearing solution before the electrowinning stage.
- rhenium is recovered as a result of the molybdenite roasting to produce molybdenum.
- the acid blow-down from the molybdenite roasting off-gas contains concentrations of rhenium which are much higher than the concentrations of rhenium in the copper-bearing solution.
- the acid blow-down stream does not contain the metal values such as copper or molybdenum since they have already been recovered upstream, and this allows rhenium to be recovered from the acid blow-down stream by ion exchange, solvent extraction and/or crystallization.
- the present invention provides new methods of rhenium recovery.
- the methods can include subjecting a copper-bearing solution to an activated carbon bed, and adsorbing rhenium onto the activated carbon.
- the methods can also include heating a basic aqueous elution solution and eluting the rhenium from the activated carbon with the heated elution solution.
- various embodiments of the present invention provide systems for the recovery of rhenium from copper leach heap.
- Systems can include an effluent entry in communication with at least one activated carbon bed and an effluent exit in communication with the activated carbon bed and distal to the effluent entry.
- effluent entry can feed a copper-bearing solution comprising a rhenium metal value through the activated carbon bed while the effluent exit allows the remainder of the copper-bearing solution to exit the activated carbon bed after allowing the rhenium to adsorb onto the activated carbon.
- the at least one activated carbon bed can be a plurality of activated carbon beds connected to each other in series.
- Various embodiments of the systems can include an elution stream controllably in communication with the at least one bed of activated carbon.
- the systems can include an eluate port controllably in communication with the bed of activated carbon and the eluate exit can be operable to remove a rhenium stream.
- FIG. 1 is a block diagram illustrating a rhenium recovery process, according to various embodiments of the present invention
- FIG. 2 is a block diagram illustrating a rhenium recovery system, according to various embodiments of the present invention
- FIG. 3 is a block diagram illustrating a first exemplary process for recovering rhenium and a second metal value from a metal-bearing material, according to various embodiments of the present invention
- FIG. 4 is a block diagram illustrating a second exemplary process for recovering rhenium and a second metal value from a metal-bearing material, according to various embodiments of the present invention
- FIG. 5 is a block diagram illustrating a third exemplary process for recovering rhenium and a second metal value from a metal-bearing material, according to various embodiments of the present invention
- FIG. 6 is a block diagram illustrating a method for recovering rhenium according to various embodiments of the present invention.
- FIG. 7 is a flow diagram further illustrating a plant scale process for recovering rhenium, according to various embodiments of the present invention.
- Various embodiments of the present invention are an improvement to the recovery of rhenium from ore bodies comprising copper and molybdenum.
- rhenium can be recovered from a copper-bearing stream produced from copper leaching. Since the world demand for rhenium continues to increase, improvements are needed to recover rhenium from new sources. Since copper leach solutions can comprise dissolved rhenium, the present invention provides methods and systems for the recovery of rhenium from such solutions.
- Rhenium recovery process 10 can comprise metal-bearing stream 22 , stationary phase 23 , elution solution 25 , and remainder solution 24 .
- Metal-bearing stream 22 can comprise one or more metal values.
- metal-bearing stream 22 comprises rhenium.
- metal-bearing stream 22 can be a product resulting from a metal leaching process, such as, for example, a pregnant leach solution.
- metal-bearing stream 22 can be acidic, and may comprise sulfuric acid.
- metal-bearing stream 22 can be a product of a solvent extraction process following a metal leaching process, such as, for example, a raffinate solution.
- the metal-bearing stream 22 can be the product of leaching prior to solvent extraction, such as, for example, a pregnant leach solution.
- metal-bearing solution can be a solution exiting from an electrowinning apparatus, such as, for example, lean electrolyte.
- stationary phase 23 can be any material, which can operably adsorb rhenium. In general, any porous material exhibiting adsorption properties due to high surface area is suitable.
- stationary phase 23 can comprise carbon, such as, for example, activated carbon, activated charcoal, and/or activated coal.
- carbon useful for stationary phase 23 includes a coconut shell activated carbon having a U.S. sieve mesh size of 6 ⁇ 12. Any type or size of activated carbon, such as powder, particle, or granular sizes may be used in the present invention.
- the size of the activated carbon typically measured in mesh size, can be determined by such factors as metal-bearing stream flow rate, activated carbon bed volume, adsorption capacity, and the like.
- stationary phase 23 can be static or fluidized.
- stationary phase 23 can be fluidized in the flow of metal-bearing stream 22 .
- the fluidized stationary phase 23 can be collected in a down stream process, such as, for example, use of a screen or a sieve.
- the collected stationary phase 23 can then be subjected to elution solution 25 for recovery of metal value 28 .
- stationary phase 23 can be static in a column with a mobile phase, such as metal-bearing stream 22 , passing over stationary phase 23 and adsorbing metal value 28 onto stationary phase 23 .
- Stationary phase 23 containing adsorbed metal value 28 can be subjected to elution solution 25 for recovery of metal value 28 .
- remainder solution 24 can comprise metal-bearing stream 22 less material adsorbed on stationary phase 23 .
- remainder solution 24 comprises at least 80% less rhenium than metal-bearing stream 22 , and preferably at least 90% less rhenium, and more preferably at least 95% less rhenium.
- remainder solution 24 can be further processed to recover at least one metal value.
- the at least one metal value is at least one of copper and molybdenum.
- remainder solution 24 can be cycled for its acid content to any other process in a metal recovery system, such as, for example, a leaching process, a conditioning process, and/or a solvent extraction process.
- elution solution 25 can comprise any eluate, which can extract metal value 28 off of stationary phase 23 .
- elution solution 25 can be an aqueous solution having a pH greater than about 7.
- elution solution 25 can comprise a hydroxide salt in an aqueous solution.
- a hydroxide salt can be at least one of sodium hydroxide, ammonium hydroxide, lithium hydroxide, and potassium hydroxide.
- elution solution 25 can be an aqueous solution comprising sodium hydroxide in an amount from about 0.1% to about 10% or preferably an amount from about 0.2% to about 5%, or more preferably an amount from about 0.5% to about 2.5%.
- elution solution 25 can be an aqueous solution comprising ammonium hydroxide in an amount from about 0.1% to about 10% or preferably an amount from about 0.2% to about 5%, or more preferably an amount from about 0.5% to about 2.5%.
- elution solution 25 can be heated to a temperature greater than or equal to 80° C.
- elution solution 25 can be heated to a temperature from about 80° C. to about 130° C., and preferably to a temperature from about 90° C. to about 120° C., and more preferably to a temperature from about 105° C. to about 115° C., and even more preferably to a temperature from about 108° C. to about 110° C.
- the amount of the hydroxide salt in the aqueous solution can be decreased.
- the temperature of elution efficiency increases.
- the costs of elution solution 25 decrease.
- a method for recovering rhenium can comprise passing metal-bearing stream 22 through stationary phase 23 and adsorbing a metal value on stationary phase 23 .
- the method can comprise removing remainder solution 24 from stationary phase 23 .
- the method can further comprise recovering a second metal value from remainder solution 24 .
- the method can comprise stopping the metal-bearing stream 22 and eluting metal value 28 from stationary phase 23 .
- the method can further comprise heating elution solution 25 then eluting metal value 28 from stationary phase 23 .
- metal value 28 is rhenium.
- Metal-bearing material 212 may be an ore, a concentrate, or any other material from which metal values may be recovered.
- Metal values such as, for example, copper, gold, silver, zinc, platinum group metals, nickel, cobalt, molybdenum, rhenium, uranium, rare earth metals, and the like may be recovered from metal-bearing material 212 in accordance with various embodiments of the present invention.
- metal-bearing material 212 is a copper ore or concentrate, and in an exemplary embodiment, metal-bearing material 212 is a copper sulfide ore or concentrate.
- processed metal-bearing material 213 may comprise metal-bearing material 212 prepared for metal recovery process 20 in any manner that enables the conditions of processed metal-bearing material 213 to be suitable for a chosen processing method, as such conditions may affect the overall effectiveness and efficiency of processing operations. Desired composition and component concentration parameters may be achieved through a variety of chemical and/or physical processing stages, the choice of which will depend upon the operating parameters of the chosen processing scheme, equipment cost and material specifications. For example, metal-bearing material 212 may undergo comminution, flotation, blending, and/or slurry formation, as well as chemical and/or physical conditioning to produce processed metal-bearing material 213 . In an exemplary embodiment, processed metal-bearing material 213 is a concentrate.
- processed metal-bearing material 213 is subjected to reactive processing 214 to put a metal value or metal values in processed metal-bearing material 213 in a condition for later metal recovery steps, namely metal recovery 218 .
- exemplary suitable processes include reactive processes that tend to liberate the desired metal value or metal values from the metal-bearing material 212 .
- reactive processing 214 may comprise leaching. Leaching can be any method, process, or system that enables a metal value to be leached from processed metal-bearing material 213 .
- leaching utilizes acid to leach a metal value from processed metal-bearing material 213 .
- leaching can employ a leaching apparatus, such as, for example, a heap leach, a vat leach, a tank leach, a pad leach, a leach vessel or any other leaching technology useful for leaching a metal value from processed metal-bearing material 213 .
- leaching may be conducted at any suitable pressure, temperature, and/or oxygen content.
- Leaching can employ one of a high temperature, a medium temperature, or a low temperature, combined with one of high pressure, or atmospheric pressure.
- Leaching may utilize conventional atmospheric or pressure leaching, for example, but not limited to, low, medium or high temperature pressure leaching.
- pressure leaching refers to a metal recovery process in which material is contacted with an acidic solution and oxygen under conditions of elevated temperature and pressure.
- Medium or high temperature pressure leaching processes for chalcopyrite are generally thought of as those processes operating at temperatures from about 120° C. to about 190° C. or up to about 250° C.
- reactive processing 214 may comprise any type of reactive process to put a metal value or values in processed metal-bearing material 213 in a condition to be subjected to later metal recovery steps.
- reactive processing 214 provides a metal-bearing slurry 215 for conditioning 216 .
- conditioning 216 can be, for example, but is not limited to, a solid liquid phase separation step, an additional leach step, a pH adjustment step, a dilution step, a concentration step, a metal precipitation step, a filtering step, a settling step, and the like, as well as combinations thereof.
- conditioning 216 can be a solid liquid phase separation step configured to yield a metal-bearing solution 217 and a metal-bearing solid.
- conditioning 216 may be one or more leaching steps.
- conditioning 216 may be any method, process, or system that further prepares metal-bearing material 212 for recovery.
- conditioning 216 utilizes acid to leach a metal value from a metal-bearing material.
- conditioning 216 may employ a leaching apparatus such as, for example, a heap leach, a vat leach, a tank leach, a pad leach, a leach vessel or any other leaching technology useful for leaching a metal value from a metal-bearing material.
- conditioning 216 may be a leach process conducted at any suitable pressure, temperature, and/or oxygen content.
- conditioning 216 may employ one of a high temperature, a medium temperature, or a low temperature, combined with one of high pressure, or atmospheric pressure.
- Conditioning 216 may utilize conventional atmospheric or pressure leaching, for example, but not limited to, low, medium or high temperature pressure leaching.
- Medium or high temperature pressure leaching processes for chalcopyrite are generally thought of as those processes operating at temperatures from about 120° to about 190° C. or up to about 250° C.
- conditioning 216 may comprise dilution, settling, filtration, solution/solvent extraction, ion exchange, pH adjustment, chemical adjustment, purification, concentration, screening, and size separation.
- conditioning 216 is a high temperature, high pressure leach. In other embodiments, conditioning 216 is an atmospheric leach. In further embodiments, conditioning 216 is a solid liquid phase separation. In still further embodiments, conditioning 216 is a settling/filtration step. In various embodiments, conditioning 216 produces metal-bearing solution 217 .
- metal-bearing solution 217 may be passed through stationary phase 23 .
- metal value 28 can be adsorbed onto stationary phase 23 .
- a remainder solution 24 can be removed from stationary phase 23 .
- Metal value 28 can be eluted off stationary phase 23 with elution solution 25 .
- Elution solution 25 can be heated as described herein.
- metal value 28 is rhenium.
- stationary phase 23 can be combined with metal-bearing solution 217 to create a slurry.
- stationary phase 23 is fluidized in the slurry.
- a course carbon powder can be advantageous for use as stationary phase 23 .
- Metal value 28 can be adsorbed on to stationary phase 23 .
- Fluidized stationary phase 23 can be collected by use of a screen or a sieve.
- Metal value 28 can be eluted off stationary phase 23 with elution solution 25 as described herein.
- remainder solution 24 may be subjected to metal recovery 218 to yield metal value 220 .
- metal recovery 218 can comprise electrowinning remainder solution 24 to yield recovered metal value 220 as a cathode.
- metal recovery 218 may be configured to employ conventional electrowinning processes and include a solvent extraction step, an ion exchange step, an ion selective membrane, a solution recirculation step, and/or a concentration step.
- metal recovery 218 may be configured to subject remainder solution 24 to a solvent extraction step to yield a rich electrolyte solution, which may be subject to an electrowinning circuit to recover a desired metal value 220 .
- metal recovery 218 may be configured to employ direct electrowinning processes without the use of a solvent extraction step, an ion exchange step, an ion selective membrane, a solution recirculation step, and/or a concentration step.
- metal recovery 218 may be configured to feed remainder solution 24 directly into an electrowinning circuit to recover a desired metal value 220 .
- metal value 220 is copper.
- a first exemplary process 30 for recovering rhenium and a second metal value from a metal-bearing material 212 is illustrated according to various embodiments of the present invention.
- processed metal-bearing material 213 is subjected to reactive processing 214 to put a metal value or metal values in processed metal-bearing material 213 in a condition for later metal recovery steps, namely first metal recovery 225 and second metal recovery 218 .
- reactive processing 214 comprises a leaching process.
- reactive processing 214 provides metal-bearing slurry 215 for conditioning 216 .
- conditioning 216 can be a solid liquid phase separation step configured to yield metal-bearing solution 217 and a metal-bearing solid.
- metal-bearing solution 217 is subjected to first metal recovery 225 to recover first metal value 28 .
- First metal recovery 225 comprises valve 222 in communication with conditioning 216 , and first stationary phase 23 A and second stationary phase 23 B connected in parallel with valve 222 .
- Valve 222 can control flow of metal-bearing solution 217 to either first stationary phase 23 A or second stationary phase 23 B.
- metal-bearing solution 217 passes through a first stationary phase 23 A until first stationary phase 23 A is loaded with metal value 28 to near capacity. Then valve 222 switches the flow of metal-bearing solution 217 to pass through second stationary phase 23 B. After valve 222 switches, elution solution 25 A can be passed through stationary phase 23 A to elute metal value 28 . When second stationary phase 23 B is loaded with metal value 28 to near capacity, valve 222 switches flow of metal-bearing solution 217 back to stationary phase 23 A. After valve 222 switches the second time, elution solution 25 B can be passed through stationary phase 23 B to elute metal value 28 .
- remainder solution 24 may be subjected to metal recovery 218 to yield metal value 220 .
- metal recovery 218 can comprise electrowinning remainder solution 24 to yield recovered metal value 220 as a cathode.
- metal recovery 218 may be configured to feed remainder solution 24 directly into an electrowinning circuit to recover a desired metal value 220 .
- metal value 220 is copper.
- a second exemplary process 40 for recovering rhenium and a second metal value from a metal-bearing material 212 is illustrated according to various embodiments of the present invention.
- processed metal-bearing material 213 is subjected to reactive processing 214 to put a metal value or metal values in processed metal-bearing material 213 in a condition for later metal recovery steps, namely first metal recovery 225 and second metal recovery 218 .
- reactive processing 214 comprises a leaching process.
- reactive processing 214 provides metal-bearing slurry 215 for conditioning 216 .
- conditioning 216 can be a solid liquid phase separation step configured to yield metal-bearing solution 217 and a metal-bearing solid.
- metal-bearing solution 217 is subjected to first metal recovery 225 to recover first metal value 28 .
- First metal recovery 225 comprises valve 222 in communication with conditioning 216 , and first stationary phase 23 A and second stationary phase 23 B connected in parallel with valve 222 .
- Valve 222 can control flow of metal-bearing solution 217 to either first stationary phase 23 A or second stationary phase 23 B.
- metal-bearing solution 217 passes through a first stationary phase 23 A until first stationary phase 23 A is loaded with metal value 28 to near capacity. Then valve 222 switches the flow of metal-bearing solution 217 to pass through second stationary phase 23 B. After valve 222 switches, elution solution 25 A can be passed through stationary phase 23 A to elute metal value 28 . When second stationary phase 23 B is loaded with metal value 28 to near capacity, valve 222 switches flow of metal-bearing solution 217 back to stationary phase 23 A. After the valve 222 switches the second time, elution solution 25 B can be passed through stationary phase 23 B to elute metal value 28 .
- solvent extraction 230 can be configured to selectively extract a metal value, such as, for example copper.
- a metal value such as, for example copper
- an organic chelating agent for example, an aldoxime/ketoxime blend
- the metal value containing organic stream may comprise a copper compound.
- Solvent extraction 230 can be configured to select for a metal value, such as copper by the selection of an appropriate mixture of ketoximes and/or aldoximes.
- Solvent extraction 230 can produce a raffinate solution and a rich electrolyte 32 .
- solvent extraction 230 can yield a rich electrolyte 32 comprising a metal value.
- Raffinate from solvent extraction 230 advantageously may be used in a number of ways. For example, all or a portion of raffinate may be recycled to reactive processing 214 , such as, for example to aid with temperature control or solution balancing, or it may be used in other leaching operations, or it may be used for any combination thereof.
- the use of raffinate in reactive processing 214 may be beneficial because the acid values contained in raffinate may act to optimize the potential for leaching oxide and/or sulfide ores that commonly dominate heap leaching operations. It should be appreciated that the properties of raffinate, such as component concentrations, may be adjusted in accordance with the desired use of raffinate.
- rich electrolyte 32 may be subjected to metal recovery 218 to yield metal value 220 .
- metal recovery 218 can comprise electrowinning rich electrolyte 32 to yield recovered metal value 220 as a cathode.
- metal recovery 218 may be configured to feed rich electrolyte 32 directly into an electrowinning circuit to recover a desired metal value 220 .
- metal value 220 is copper.
- a third exemplary process 50 for recovering rhenium and a second metal value from a metal-bearing material 212 is illustrated according to various embodiments of the present invention.
- processed metal-bearing material 213 is subjected to reactive processing 214 to put a metal value or metal values in processed metal-bearing material 213 in a condition for later metal recovery 218 .
- reactive processing 214 comprises a leaching process.
- reactive processing 214 provides metal-bearing slurry 215 for conditioning 216 .
- metal-raffinate 36 may be passed through stationary phase 23 .
- metal value 28 can be adsorbed onto stationary phase 23 .
- a remainder solution 24 can be removed from stationary phase 23 .
- Metal value 28 can be eluted off stationary phase 23 with elution solution 25 .
- Elution solution 25 can be heated as described above.
- metal value 28 is rhenium.
- a column comprising a stationary phase, such as activated carbon 302 can be placed in communication with a rhenium-rich pregnant leach solution 304 (“Re-rich PLS 304 ”).
- Re-rich PLS 304 can comprise rhenium and copper.
- Re-rich PLS 304 can originate from an active copper leach or a stockpile copper leach, for example, residing in a pond or a pit.
- Re-rich PLS 304 can be an acid blow-down stream or leach of molybdenite roaster flue fumes and dusts.
- Re-rich PLS 304 can be a raffinate stream.
- any solution comprising rhenium, in any concentration is suitable for use herewith, For example, solutions containing more or less than 1 mg/L rhenium, even in the presence of iron, copper, molybdenum, vanadium and other metals, are suitable for use herewith.
- flow through a plurality of columns, in series, in parallel, or in any other arrangement is within the scope of this disclosure.
- Rhenium can be adsorbed 306 onto activated carbon 302 of the column and a rhenium-lean pregnant leach solution 308 can exit from the column.
- the rhenium-loaded column 310 can be placed in communication with elution solution 312 .
- Elution solution 312 can be heated 314 to a temperature.
- elution solution 312 can comprise any eluate, which can extract rhenium off of the loaded column 310 .
- elution solution 312 can be an aqueous solution having a pH greater than about 7.
- elution solution 312 can comprise a hydroxide salt in an aqueous solution.
- a hydroxide salt can be at least one of sodium hydroxide, ammonium hydroxide, lithium hydroxide, and potassium hydroxide.
- elution solution 312 can be an aqueous solution comprising sodium hydroxide in an amount from about 0.1% to about 10% or preferably an amount from about 0.2% to about 5%, or more preferably an amount from about 0.5% to about 2.5%.
- elution solution 312 can be an aqueous solution comprising ammonium hydroxide in an amount from about 0.1% to about 10% or preferably an amount from about 0.2% to about 5%, or more preferably an amount from about 0.5% to about 2.5%.
- elution solution 312 can be heated 314 to a temperature greater than or equal to 80° C.
- elution solution 312 can be heated 314 to a temperature from about 80° C. to about 130° C., and preferably to a temperature from about 90° C. to about 120° C., and more preferably to a temperature from about 105° C. to about 115° C., and even more preferably to a temperature from about 108° C. to about 110° C.
- the amount of the hydroxide salt in the aqueous solution can be decreased.
- the elution efficiency increases.
- the costs of the elution solution 312 decrease.
- rhenium can be eluted 316 from rhenium-loaded column 310 to produce Re-rich aqueous eluate 318 .
- the stationary phase of the column can be regenerated 320 and recycled as activated carbon 302 .
- Re-rich eluate 318 can be subjected to a rhenium recovery 322 to produce pure rhenium 326 and Re-lean aqueous eluate 324 .
- Re-lean eluate 324 can be recycled 328 to elution solution 312 .
- plant scale process 70 for recovering rhenium is illustrated according to various embodiments of the present invention.
- rhenium rich PLS 704 flows into a first adsorption column 728 containing first partially loaded carbon 730 from second adsorption column 732 .
- Any suitable adsorption column may be used with the present invention, for example, a twelve-foot diameter by twelve-foot high adsorption column.
- First partially adsorbed rhenium PLS 734 flows from first adsorption column 728 into second adsorption column 732 containing second partially loaded carbon 736 from third adsorption column 738 .
- the amount of rhenium adsorbed onto second partially loaded carbon 736 can be less than that adsorbed onto first partially loaded carbon 730 .
- Second partially adsorbed rhenium PLS 740 flows from second adsorption column 732 into third adsorption column 738 containing a third partially loaded carbon 742 from a fourth adsorption column 744 .
- the amount of rhenium adsorbed onto third partially loaded carbon 742 is less than that adsorbed onto second partially loaded carbon 736 .
- Third partially adsorbed rhenium PLS 746 flows from third adsorption column 738 into fourth adsorption column 744 containing fourth partially loaded carbon 748 from fifth adsorption column 750 .
- the amount of rhenium adsorbed onto fourth partially loaded carbon 748 is less than that adsorbed onto third partially loaded carbon 742 .
- Fourth partially adsorbed rhenium PLS 752 flows from fourth adsorption column 744 into fifth adsorption column 750 containing stripped activated carbon 702 .
- Rhenium lean PLS 708 flows away, for example, for other metal recovery.
- Loaded activated carbon 710 from first adsorption column 728 flows to an elution vessel 754 .
- Any suitable elution vessel may be used with the present invention, for example, one or a plurality of 2600 gallon elution vessels.
- flow through any number of columns, in series, in parallel, or in any other arrangement, is within the scope of this disclosure.
- elution solution 712 comprises one or more of sodium hydroxide, ammonium hydroxide, lithium hydroxide, and potassium hydroxide.
- Boiler 762 heats water 764 recycled through a plate heat exchanger 766 .
- Plate heat exchanger 766 in turn heats elution solution 712 to yield heated elution solution 768 , which flows to elution vessel 754 .
- the temperature of elution solution 712 is increased, for example, to about 100° C. to about 140° C., or to about 100° C. to about 120° C., or to about 100° C.-110° C.
- Spent carbon 770 flows from elution vessel 754 to carbon pre-treatment tank 772 .
- New carbon 774 is washed with water 776 in wash tank 778 to yield washed carbon 780 , which also flows to carbon pre-treatment tank 772 .
- Wash 782 with reject fine carbon flows to a carbon super sack 784 .
- Carbon super sack 784 can be drained of excess water 786 .
- Carbon in carbon pre-treatment tank 772 flows through carbon rotary kiln 773 for re-activation of carbon via pumps 775 and 777 .
- carbon rotary kiln 773 is rated at 200 lb/hour. Stripped activated carbon 702 then flows into fifth adsorption column 750 via pump 779 .
- a rhenium eluate 781 flows from elution vessel 754 , via pump 783 , to eluate tank 785 , where it is mixed with aqueous solution 788 .
- Any suitable eluate tank may be used with the present invention, for example, one or a plurality of 15000 gallon eluate tanks.
- aqueous solution 788 is sulfuric acid.
- a resulting rhenium rich aqueous eluate 718 flows to a solvent extraction (SX) process tank 790 .
- Any suitable SX process tank 790 may be used with the present invention, for example, one or a plurality of 1000 gallon SX process tanks.
- Rich organic 792 flows to a solvent extraction stripper 794 , where it is stripped with a striping solution 796 .
- solvent extraction stripper 794 is rated at 20 gal/minute.
- stripping solution 796 is sodium hydroxide.
- Lean organic 798 returns to SX process tank 790 .
- a resulting rhenium lean aqueous eluate 724 flows to a raffinate pond or is recycled and reused. Concentrated rhenium 726 is available for storage and use.
- a stationary phase comprising activated carbon was loaded with rhenium.
- Three aqueous elution solutions comprised ammonium hydroxide in varying concentrations can be prepared (see Table 1). Ammonium hydroxide was formed by adding ammonia to water. Each elution solution was heated to a temperature of about 108° C. to about 110° C. and passed through the stationary phase at a rate of about 1.5 bed volumes per hour to about 2.0 bed volumes per hour. The complete elution cycle was about 4 bed volumes to about 6 bed volumes. Rhenium can be recovered through the elution and results are shown in Table 1.
- a stationary phase comprising activated carbon was loaded with rhenium.
- Eight aqueous elution solutions comprised ammonium hydroxide in varying concentrations can be prepared (see Table 2). Ammonium hydroxide was formed by adding ammonia to water. Each elution solution was heated to a temperature (see Table 2) and passed through the stationary phase at a rate of about 1.5 bed volumes per hour to about 2.0 bed volumes per hour. The complete elution cycle was an average of about 16 bed volumes. Rhenium was recovered through the elution and results are shown in Table 2.
- a stationary phase comprising activated carbon was loaded with rhenium.
- Three aqueous elution solutions comprised sodium hydroxide in varying concentrations can be prepared (see Table 3). Each elution solution was heated to a temperature of about 108° C. to about 110° C. and passed through the stationary phase at a rate of about 1.5 bed volumes per hour to about 2.0 bed volumes per hour. The complete elution cycle was about 6 bed volumes to about 8 bed volumes. Rhenium was recovered through the elution and results are shown in Table 3.
- a stationary phase comprising activated carbon was loaded with rhenium.
- a copper heap leach solution was contacted with four columns in series containing a stationary phase comprising activated carbon.
- the copper leach solution contains 0.65 mg/L of dissolved rhenium.
- Other metals such as aluminum, cadmium, calcium, cobalt, copper, iron, magnesium, manganese, sodium, nickel, silicon, vanadium, yttrium and zinc, were present in the copper leach solution at concentrations greater than the concentration of dissolved rhenium.
- the copper leach solution was contacted with the stationary phase at a rate of 0.125 bed volume per minute for a period of 3 to 4 days. Rhenium was measured in the recovered elution solution exiting each column and results are shown as in Table 5. The average rhenium recovery from the copper leach solution was 96%.
- the average rhenium loading onto the stationary phase in column 1 was greater than 2000 mg Re per kg carbon.
- the terms “comprise”, “comprises”, “comprising”, “having”, “including”, “includes”, or any variation thereof are intended to reference a non-exclusive inclusion, such that a process, method, article, composition or apparatus that comprises a list of elements does not include only those elements recited, but can also include other elements not expressly listed and equivalents inherently known or obvious to those of reasonable skill in the art.
- Other combinations and/or modifications of structures, arrangements, applications, proportions, elements, materials, or components used in the practice of the instant invention, in addition to those not specifically recited, can be varied or otherwise particularly adapted to specific environments, manufacturing specifications, design parameters or other operating requirements without departing from the scope of the instant invention and are intended to be included in this disclosure.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Various embodiments provide new methods of rhenium recovery. The methods can include subjecting a metal-bearing solution to an activated carbon bed, and adsorbing rhenium onto the activated carbon. The methods can also include heating a basic aqueous elution solution and eluting the rhenium from the activated carbon with the heated elution solution.
Description
- The present invention relates generally to the recovery of rhenium and relates more specifically to the recovery of rhenium from a copper leach.
- Rhenium was the last naturally occurring element to be discovered and the last element discovered having a stable isotope. Rhenium is typically recovered as a byproduct of molybdenum refinement. Since recovery of rhenium from molybdenite is difficult and the concentrations of rhenium in molybdenite are very low, typically from about 0.002% to about 0.02%, rhenium is one of the most expensive metals available in commodity markets. Rhenium has several characteristics that make it unique, such as, for example, the second highest melting point amongst metals, amongst the densest metals, a super conductor, and the greatest number of oxidation states of any element. Industrial applications include the use of rhenium in catalysts, electronics, thermocouples, high temperature turbine blades, and photoflash devices.
- Rhenium may be extracted from ores that contain copper and molybdenum. Common practice for leaching copper from low-grade copper ore is to place the ore in a heap leach pad and leach the ore with dilute sulfuric acid solution. The resulting copper-bearing solution is typically concentrated via solvent extraction and/or electrowon to produce pure copper cathode. Typically, the copper-bearing solution has less than one part per million of dissolved rhenium and may contain significant amounts of other metals in the copper-bearing solution. Recovery of rhenium from the copper-bearing solution is not economically feasible and hence rhenium is, along with other metal values, typically not recovered from the copper-bearing solution before the electrowinning stage.
- Generally, rhenium is recovered as a result of the molybdenite roasting to produce molybdenum. The acid blow-down from the molybdenite roasting off-gas contains concentrations of rhenium which are much higher than the concentrations of rhenium in the copper-bearing solution. In addition, the acid blow-down stream does not contain the metal values such as copper or molybdenum since they have already been recovered upstream, and this allows rhenium to be recovered from the acid blow-down stream by ion exchange, solvent extraction and/or crystallization.
- Since the demand for rhenium continues to increase on a year-by-year basis, new methods for rhenium recovery from sources other than molybdenum roasting processes are needed.
- In accordance with various embodiments, the present invention provides new methods of rhenium recovery. The methods can include subjecting a copper-bearing solution to an activated carbon bed, and adsorbing rhenium onto the activated carbon. The methods can also include heating a basic aqueous elution solution and eluting the rhenium from the activated carbon with the heated elution solution.
- In addition, various embodiments of the present invention provide systems for the recovery of rhenium from copper leach heap. Systems can include an effluent entry in communication with at least one activated carbon bed and an effluent exit in communication with the activated carbon bed and distal to the effluent entry. In such systems, effluent entry can feed a copper-bearing solution comprising a rhenium metal value through the activated carbon bed while the effluent exit allows the remainder of the copper-bearing solution to exit the activated carbon bed after allowing the rhenium to adsorb onto the activated carbon. In an exemplary embodiment of the present invention, the at least one activated carbon bed can be a plurality of activated carbon beds connected to each other in series. Various embodiments of the systems can include an elution stream controllably in communication with the at least one bed of activated carbon. In an exemplary embodiment, the systems can include an eluate port controllably in communication with the bed of activated carbon and the eluate exit can be operable to remove a rhenium stream.
- Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and the specific examples are intended for purposes of illustration only, and are not intended to limit the scope of the present invention.
- The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way. The present invention will become more fully understood from the detailed description and the accompanying drawings wherein:
-
FIG. 1 is a block diagram illustrating a rhenium recovery process, according to various embodiments of the present invention; -
FIG. 2 is a block diagram illustrating a rhenium recovery system, according to various embodiments of the present invention; -
FIG. 3 is a block diagram illustrating a first exemplary process for recovering rhenium and a second metal value from a metal-bearing material, according to various embodiments of the present invention; -
FIG. 4 is a block diagram illustrating a second exemplary process for recovering rhenium and a second metal value from a metal-bearing material, according to various embodiments of the present invention; -
FIG. 5 is a block diagram illustrating a third exemplary process for recovering rhenium and a second metal value from a metal-bearing material, according to various embodiments of the present invention; -
FIG. 6 is a block diagram illustrating a method for recovering rhenium according to various embodiments of the present invention; and -
FIG. 7 is a flow diagram further illustrating a plant scale process for recovering rhenium, according to various embodiments of the present invention. - The following description is merely exemplary in nature, and is not intended to limit the present invention, its applications, or its uses. It should be understood that throughout the drawings, corresponding reference numerals indicate like or corresponding parts and/or features. The descriptions' specific examples indicated in various embodiments of the present invention are intended for purposes of illustration only and are not intended to limit the scope of the invention disclosed herein. Moreover, recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features.
- Various embodiments of the present invention are an improvement to the recovery of rhenium from ore bodies comprising copper and molybdenum. In various embodiments, rhenium can be recovered from a copper-bearing stream produced from copper leaching. Since the world demand for rhenium continues to increase, improvements are needed to recover rhenium from new sources. Since copper leach solutions can comprise dissolved rhenium, the present invention provides methods and systems for the recovery of rhenium from such solutions.
- With reference to
FIG. 1 ,rhenium recovery process 10 is illustrated according to various embodiments of the present invention.Rhenium recovery process 10 can comprise metal-bearingstream 22,stationary phase 23,elution solution 25, andremainder solution 24. Metal-bearingstream 22 can comprise one or more metal values. In an exemplary embodiment, metal-bearingstream 22 comprises rhenium. In various embodiments, metal-bearingstream 22 can be a product resulting from a metal leaching process, such as, for example, a pregnant leach solution. Generally, metal-bearingstream 22 can be acidic, and may comprise sulfuric acid. In some aspects of the present invention, metal-bearingstream 22 can be a product of a solvent extraction process following a metal leaching process, such as, for example, a raffinate solution. In other aspect the metal-bearingstream 22 can be the product of leaching prior to solvent extraction, such as, for example, a pregnant leach solution. In other aspects of the present invention, metal-bearing solution can be a solution exiting from an electrowinning apparatus, such as, for example, lean electrolyte. - In various embodiments,
stationary phase 23 can be any material, which can operably adsorb rhenium. In general, any porous material exhibiting adsorption properties due to high surface area is suitable. In an exemplary embodiment,stationary phase 23 can comprise carbon, such as, for example, activated carbon, activated charcoal, and/or activated coal. Another example of carbon useful forstationary phase 23 includes a coconut shell activated carbon having a U.S. sieve mesh size of 6×12. Any type or size of activated carbon, such as powder, particle, or granular sizes may be used in the present invention. The size of the activated carbon, typically measured in mesh size, can be determined by such factors as metal-bearing stream flow rate, activated carbon bed volume, adsorption capacity, and the like. - In various embodiments,
stationary phase 23 can be static or fluidized. In an aspect of the invention,stationary phase 23 can be fluidized in the flow of metal-bearingstream 22. The fluidizedstationary phase 23 can be collected in a down stream process, such as, for example, use of a screen or a sieve. The collectedstationary phase 23 can then be subjected toelution solution 25 for recovery ofmetal value 28. In another aspect of the invention,stationary phase 23 can be static in a column with a mobile phase, such as metal-bearingstream 22, passing overstationary phase 23 and adsorbingmetal value 28 ontostationary phase 23.Stationary phase 23 containing adsorbedmetal value 28 can be subjected toelution solution 25 for recovery ofmetal value 28. - In various embodiments,
remainder solution 24 can comprise metal-bearingstream 22 less material adsorbed onstationary phase 23. In an exemplary embodiment,remainder solution 24 comprises at least 80% less rhenium than metal-bearingstream 22, and preferably at least 90% less rhenium, and more preferably at least 95% less rhenium. In an aspect of the present invention,remainder solution 24 can be further processed to recover at least one metal value. In an exemplary embodiment, the at least one metal value is at least one of copper and molybdenum. In another aspect of the present invention,remainder solution 24 can be cycled for its acid content to any other process in a metal recovery system, such as, for example, a leaching process, a conditioning process, and/or a solvent extraction process. - In various embodiments,
elution solution 25 can comprise any eluate, which can extractmetal value 28 off ofstationary phase 23. In general,elution solution 25 can be an aqueous solution having a pH greater than about 7. In an exemplary embodiment,elution solution 25 can comprise a hydroxide salt in an aqueous solution. For example, a hydroxide salt can be at least one of sodium hydroxide, ammonium hydroxide, lithium hydroxide, and potassium hydroxide. In an exemplary embodiment,elution solution 25 can be an aqueous solution comprising sodium hydroxide in an amount from about 0.1% to about 10% or preferably an amount from about 0.2% to about 5%, or more preferably an amount from about 0.5% to about 2.5%. In another exemplary embodiment,elution solution 25 can be an aqueous solution comprising ammonium hydroxide in an amount from about 0.1% to about 10% or preferably an amount from about 0.2% to about 5%, or more preferably an amount from about 0.5% to about 2.5%. - With continued reference to
FIG. 1 , in various embodiments,elution solution 25 can be heated to a temperature greater than or equal to 80° C. In an exemplary embodiment,elution solution 25 can be heated to a temperature from about 80° C. to about 130° C., and preferably to a temperature from about 90° C. to about 120° C., and more preferably to a temperature from about 105° C. to about 115° C., and even more preferably to a temperature from about 108° C. to about 110° C. In an aspect of the invention, as the temperature ofelution solution 25 is increased, the amount of the hydroxide salt in the aqueous solution can be decreased. As the temperature ofelution solution 25 is increased, the elution efficiency increases. In addition, as the temperature ofelution solution 25 is increased, the costs ofelution solution 25 decrease. - In various embodiments, a method for recovering rhenium can comprise passing metal-bearing
stream 22 throughstationary phase 23 and adsorbing a metal value onstationary phase 23. The method can comprise removingremainder solution 24 fromstationary phase 23. The method can further comprise recovering a second metal value fromremainder solution 24. The method can comprise stopping the metal-bearingstream 22 and elutingmetal value 28 fromstationary phase 23. The method can further compriseheating elution solution 25 then elutingmetal value 28 fromstationary phase 23. In an exemplary embodiment,metal value 28 is rhenium. - Now referring to
FIG. 2 ,rhenium recovery system 20 is illustrated according to various embodiments of the present invention. Metal-bearingmaterial 212 may be an ore, a concentrate, or any other material from which metal values may be recovered. Metal values such as, for example, copper, gold, silver, zinc, platinum group metals, nickel, cobalt, molybdenum, rhenium, uranium, rare earth metals, and the like may be recovered from metal-bearingmaterial 212 in accordance with various embodiments of the present invention. Various aspects and embodiments of the present invention, however, prove especially advantageous in connection with the recovery of copper from copper sulfide concentrates and/or ores, such as, for example, chalcopyrite (CuFeS2), chalcocite (Cu2S), bornite (Cu5FeS4), covellite (CuS), enargite (Cu3AsS4), digenite (Cu9S5), and/or mixtures thereof. Thus, in various embodiments, metal-bearingmaterial 212 is a copper ore or concentrate, and in an exemplary embodiment, metal-bearingmaterial 212 is a copper sulfide ore or concentrate. - In various embodiments, processed metal-bearing
material 213 may comprise metal-bearingmaterial 212 prepared formetal recovery process 20 in any manner that enables the conditions of processed metal-bearingmaterial 213 to be suitable for a chosen processing method, as such conditions may affect the overall effectiveness and efficiency of processing operations. Desired composition and component concentration parameters may be achieved through a variety of chemical and/or physical processing stages, the choice of which will depend upon the operating parameters of the chosen processing scheme, equipment cost and material specifications. For example, metal-bearingmaterial 212 may undergo comminution, flotation, blending, and/or slurry formation, as well as chemical and/or physical conditioning to produce processed metal-bearingmaterial 213. In an exemplary embodiment, processed metal-bearingmaterial 213 is a concentrate. - With continued reference to
FIG. 2 , after metal-bearingmaterial 212 has been suitably prepared, processed metal-bearingmaterial 213 is subjected toreactive processing 214 to put a metal value or metal values in processed metal-bearingmaterial 213 in a condition for later metal recovery steps, namelymetal recovery 218. For example, exemplary suitable processes include reactive processes that tend to liberate the desired metal value or metal values from the metal-bearingmaterial 212. In accordance with an exemplary embodiment of the present invention,reactive processing 214 may comprise leaching. Leaching can be any method, process, or system that enables a metal value to be leached from processed metal-bearingmaterial 213. Typically, leaching utilizes acid to leach a metal value from processed metal-bearingmaterial 213. For example, leaching can employ a leaching apparatus, such as, for example, a heap leach, a vat leach, a tank leach, a pad leach, a leach vessel or any other leaching technology useful for leaching a metal value from processed metal-bearingmaterial 213. - In accordance with various embodiments, leaching may be conducted at any suitable pressure, temperature, and/or oxygen content. Leaching can employ one of a high temperature, a medium temperature, or a low temperature, combined with one of high pressure, or atmospheric pressure. Leaching may utilize conventional atmospheric or pressure leaching, for example, but not limited to, low, medium or high temperature pressure leaching. As used herein, the term “pressure leaching” refers to a metal recovery process in which material is contacted with an acidic solution and oxygen under conditions of elevated temperature and pressure. Medium or high temperature pressure leaching processes for chalcopyrite are generally thought of as those processes operating at temperatures from about 120° C. to about 190° C. or up to about 250° C. In accordance with various embodiments of the present invention,
reactive processing 214 may comprise any type of reactive process to put a metal value or values in processed metal-bearingmaterial 213 in a condition to be subjected to later metal recovery steps. - In various embodiments,
reactive processing 214 provides a metal-bearingslurry 215 forconditioning 216. In various embodiments,conditioning 216 can be, for example, but is not limited to, a solid liquid phase separation step, an additional leach step, a pH adjustment step, a dilution step, a concentration step, a metal precipitation step, a filtering step, a settling step, and the like, as well as combinations thereof. In an exemplary embodiment,conditioning 216 can be a solid liquid phase separation step configured to yield a metal-bearingsolution 217 and a metal-bearing solid. - In other various embodiments,
conditioning 216 may be one or more leaching steps. For example,conditioning 216 may be any method, process, or system that further prepares metal-bearingmaterial 212 for recovery. In various embodiments,conditioning 216 utilizes acid to leach a metal value from a metal-bearing material. For example,conditioning 216 may employ a leaching apparatus such as, for example, a heap leach, a vat leach, a tank leach, a pad leach, a leach vessel or any other leaching technology useful for leaching a metal value from a metal-bearing material. - In accordance with various embodiments,
conditioning 216 may be a leach process conducted at any suitable pressure, temperature, and/or oxygen content. In such embodiments,conditioning 216 may employ one of a high temperature, a medium temperature, or a low temperature, combined with one of high pressure, or atmospheric pressure.Conditioning 216 may utilize conventional atmospheric or pressure leaching, for example, but not limited to, low, medium or high temperature pressure leaching. Medium or high temperature pressure leaching processes for chalcopyrite are generally thought of as those processes operating at temperatures from about 120° to about 190° C. or up to about 250° C. - In various embodiments,
conditioning 216 may comprise dilution, settling, filtration, solution/solvent extraction, ion exchange, pH adjustment, chemical adjustment, purification, concentration, screening, and size separation. In various embodiments,conditioning 216 is a high temperature, high pressure leach. In other embodiments,conditioning 216 is an atmospheric leach. In further embodiments,conditioning 216 is a solid liquid phase separation. In still further embodiments,conditioning 216 is a settling/filtration step. In various embodiments,conditioning 216 produces metal-bearingsolution 217. - With further reference to
FIG. 2 , in various embodiments, metal-bearingsolution 217 may be passed throughstationary phase 23. As described above,metal value 28 can be adsorbed ontostationary phase 23. Aremainder solution 24 can be removed fromstationary phase 23.Metal value 28 can be eluted offstationary phase 23 withelution solution 25.Elution solution 25 can be heated as described herein. In a preferable embodiment,metal value 28 is rhenium. - In an exemplary embodiment,
stationary phase 23 can be combined with metal-bearingsolution 217 to create a slurry. In this exemplary embodiment,stationary phase 23 is fluidized in the slurry. A course carbon powder can be advantageous for use asstationary phase 23.Metal value 28 can be adsorbed on tostationary phase 23. Fluidizedstationary phase 23 can be collected by use of a screen or a sieve.Metal value 28 can be eluted offstationary phase 23 withelution solution 25 as described herein. - In various embodiments,
remainder solution 24 may be subjected tometal recovery 218 to yieldmetal value 220. In exemplary embodiments,metal recovery 218 can compriseelectrowinning remainder solution 24 to yield recoveredmetal value 220 as a cathode. In one exemplary embodiment,metal recovery 218 may be configured to employ conventional electrowinning processes and include a solvent extraction step, an ion exchange step, an ion selective membrane, a solution recirculation step, and/or a concentration step. In one preferred embodiment,metal recovery 218 may be configured tosubject remainder solution 24 to a solvent extraction step to yield a rich electrolyte solution, which may be subject to an electrowinning circuit to recover a desiredmetal value 220. In another exemplary embodiment,metal recovery 218 may be configured to employ direct electrowinning processes without the use of a solvent extraction step, an ion exchange step, an ion selective membrane, a solution recirculation step, and/or a concentration step. In another preferred embodiment,metal recovery 218 may be configured to feedremainder solution 24 directly into an electrowinning circuit to recover a desiredmetal value 220. In an especially preferred embodiment,metal value 220 is copper. - Turning to
FIG. 3 , a firstexemplary process 30 for recovering rhenium and a second metal value from a metal-bearingmaterial 212 is illustrated according to various embodiments of the present invention. After metal-bearingmaterial 212 has been suitably prepared, processed metal-bearingmaterial 213 is subjected toreactive processing 214 to put a metal value or metal values in processed metal-bearingmaterial 213 in a condition for later metal recovery steps, namelyfirst metal recovery 225 andsecond metal recovery 218. In accordance with an exemplary embodiment of the present invention,reactive processing 214 comprises a leaching process. - In various embodiments,
reactive processing 214 provides metal-bearingslurry 215 forconditioning 216. In an exemplary embodiment,conditioning 216 can be a solid liquid phase separation step configured to yield metal-bearingsolution 217 and a metal-bearing solid. In various embodiments, metal-bearingsolution 217 is subjected tofirst metal recovery 225 to recoverfirst metal value 28.First metal recovery 225 comprisesvalve 222 in communication withconditioning 216, and firststationary phase 23A and secondstationary phase 23B connected in parallel withvalve 222.Valve 222 can control flow of metal-bearingsolution 217 to either firststationary phase 23A or secondstationary phase 23B. In various embodiments, metal-bearingsolution 217 passes through a firststationary phase 23A until firststationary phase 23A is loaded withmetal value 28 to near capacity. Thenvalve 222 switches the flow of metal-bearingsolution 217 to pass through secondstationary phase 23B. Aftervalve 222 switches,elution solution 25A can be passed throughstationary phase 23A to elutemetal value 28. When secondstationary phase 23B is loaded withmetal value 28 to near capacity,valve 222 switches flow of metal-bearingsolution 217 back tostationary phase 23A. Aftervalve 222 switches the second time,elution solution 25B can be passed throughstationary phase 23B to elutemetal value 28. - In various embodiments,
remainder solution 24 may be subjected tometal recovery 218 to yieldmetal value 220. In exemplary embodiments,metal recovery 218 can compriseelectrowinning remainder solution 24 to yield recoveredmetal value 220 as a cathode. In a preferred embodiment,metal recovery 218 may be configured to feedremainder solution 24 directly into an electrowinning circuit to recover a desiredmetal value 220. In an especially preferred embodiment,metal value 220 is copper. - Moving to
FIG. 4 , a secondexemplary process 40 for recovering rhenium and a second metal value from a metal-bearingmaterial 212 is illustrated according to various embodiments of the present invention. After metal-bearingmaterial 212 has been suitably prepared, processed metal-bearingmaterial 213 is subjected toreactive processing 214 to put a metal value or metal values in processed metal-bearingmaterial 213 in a condition for later metal recovery steps, namelyfirst metal recovery 225 andsecond metal recovery 218. In accordance with an exemplary embodiment of the present invention,reactive processing 214 comprises a leaching process. - In various embodiments,
reactive processing 214 provides metal-bearingslurry 215 forconditioning 216. In an exemplary embodiment,conditioning 216 can be a solid liquid phase separation step configured to yield metal-bearingsolution 217 and a metal-bearing solid. In various embodiments, metal-bearingsolution 217 is subjected tofirst metal recovery 225 to recoverfirst metal value 28.First metal recovery 225 comprisesvalve 222 in communication withconditioning 216, and firststationary phase 23A and secondstationary phase 23B connected in parallel withvalve 222.Valve 222 can control flow of metal-bearingsolution 217 to either firststationary phase 23A or secondstationary phase 23B. In various embodiments, metal-bearingsolution 217 passes through a firststationary phase 23A until firststationary phase 23A is loaded withmetal value 28 to near capacity. Thenvalve 222 switches the flow of metal-bearingsolution 217 to pass through secondstationary phase 23B. Aftervalve 222 switches,elution solution 25A can be passed throughstationary phase 23A to elutemetal value 28. When secondstationary phase 23B is loaded withmetal value 28 to near capacity,valve 222 switches flow of metal-bearingsolution 217 back tostationary phase 23A. After thevalve 222 switches the second time,elution solution 25B can be passed throughstationary phase 23B to elutemetal value 28. - In various embodiments,
remainder solution 24 can be subjected tosolvent extraction 230. In accordance with various aspects of this embodiment of the present invention,solvent extraction 230 can be configured to selectively extract a metal value, such as, for example copper. Duringsolvent extraction 230, a metal value, such as, for example copper, from metal-bearing solution may be loaded selectively onto an organic chelating agent, for example, an aldoxime/ketoxime blend, resulting in a metal value containing organic stream and a raffinate solution. In various embodiments, the metal value containing organic stream may comprise a copper compound.Solvent extraction 230 can be configured to select for a metal value, such as copper by the selection of an appropriate mixture of ketoximes and/or aldoximes.Solvent extraction 230 can produce a raffinate solution and arich electrolyte 32. In various embodiments,solvent extraction 230 can yield arich electrolyte 32 comprising a metal value. - Raffinate from
solvent extraction 230 advantageously may be used in a number of ways. For example, all or a portion of raffinate may be recycled toreactive processing 214, such as, for example to aid with temperature control or solution balancing, or it may be used in other leaching operations, or it may be used for any combination thereof. The use of raffinate inreactive processing 214 may be beneficial because the acid values contained in raffinate may act to optimize the potential for leaching oxide and/or sulfide ores that commonly dominate heap leaching operations. It should be appreciated that the properties of raffinate, such as component concentrations, may be adjusted in accordance with the desired use of raffinate. - In various embodiments,
rich electrolyte 32 may be subjected tometal recovery 218 to yieldmetal value 220. In exemplary embodiments,metal recovery 218 can comprise electrowinningrich electrolyte 32 to yield recoveredmetal value 220 as a cathode. In a preferred embodiment,metal recovery 218 may be configured to feedrich electrolyte 32 directly into an electrowinning circuit to recover a desiredmetal value 220. In an especially preferred embodiment,metal value 220 is copper. - With reference to
FIG. 5 , a thirdexemplary process 50 for recovering rhenium and a second metal value from a metal-bearingmaterial 212 is illustrated according to various embodiments of the present invention. After metal-bearingmaterial 212 has been suitably prepared, processed metal-bearingmaterial 213 is subjected toreactive processing 214 to put a metal value or metal values in processed metal-bearingmaterial 213 in a condition forlater metal recovery 218. In accordance with an exemplary embodiment of the present invention,reactive processing 214 comprises a leaching process. In various embodiments,reactive processing 214 provides metal-bearingslurry 215 forconditioning 216. - With further reference to
FIG. 5 , in various embodiments, metal-raffinate 36 may be passed throughstationary phase 23. As described above,metal value 28 can be adsorbed ontostationary phase 23. Aremainder solution 24 can be removed fromstationary phase 23.Metal value 28 can be eluted offstationary phase 23 withelution solution 25.Elution solution 25 can be heated as described above. In a preferable embodiment,metal value 28 is rhenium. - With reference to
FIG. 6 , anexemplary method 60 for recovery of rhenium is illustrated according to various embodiments of the present invention. A column comprising a stationary phase, such as activatedcarbon 302, can be placed in communication with a rhenium-rich pregnant leach solution 304 (“Re-rich PLS 304”). In an exemplary embodiment,Re-rich PLS 304 can comprise rhenium and copper.Re-rich PLS 304 can originate from an active copper leach or a stockpile copper leach, for example, residing in a pond or a pit. In an exemplary embodiment,Re-rich PLS 304 can be an acid blow-down stream or leach of molybdenite roaster flue fumes and dusts. In another exemplary embodiment,Re-rich PLS 304 can be a raffinate stream. One skilled in the art will appreciate that any solution comprising rhenium, in any concentration, is suitable for use herewith, For example, solutions containing more or less than 1 mg/L rhenium, even in the presence of iron, copper, molybdenum, vanadium and other metals, are suitable for use herewith. One skilled in the art will further appreciate that flow through a plurality of columns, in series, in parallel, or in any other arrangement, is within the scope of this disclosure. - Rhenium can be adsorbed 306 onto activated
carbon 302 of the column and a rhenium-leanpregnant leach solution 308 can exit from the column. The rhenium-loadedcolumn 310 can be placed in communication withelution solution 312.Elution solution 312 can be heated 314 to a temperature. In various embodiments,elution solution 312 can comprise any eluate, which can extract rhenium off of the loadedcolumn 310. In general,elution solution 312 can be an aqueous solution having a pH greater than about 7. - In an exemplary embodiment,
elution solution 312 can comprise a hydroxide salt in an aqueous solution. For example, a hydroxide salt can be at least one of sodium hydroxide, ammonium hydroxide, lithium hydroxide, and potassium hydroxide. In an exemplary embodiment,elution solution 312 can be an aqueous solution comprising sodium hydroxide in an amount from about 0.1% to about 10% or preferably an amount from about 0.2% to about 5%, or more preferably an amount from about 0.5% to about 2.5%. In another exemplary embodiment,elution solution 312 can be an aqueous solution comprising ammonium hydroxide in an amount from about 0.1% to about 10% or preferably an amount from about 0.2% to about 5%, or more preferably an amount from about 0.5% to about 2.5%. - In various embodiments,
elution solution 312 can be heated 314 to a temperature greater than or equal to 80° C. In an exemplary embodiment,elution solution 312 can be heated 314 to a temperature from about 80° C. to about 130° C., and preferably to a temperature from about 90° C. to about 120° C., and more preferably to a temperature from about 105° C. to about 115° C., and even more preferably to a temperature from about 108° C. to about 110° C. In an aspect of the invention, as the temperature ofelution solution 312 is increased 314, the amount of the hydroxide salt in the aqueous solution can be decreased. As the temperature ofelution solution 312 is increased 314, the elution efficiency increases. In addition, as the temperature ofelution solution 312 is increased 314, the costs of theelution solution 312 decrease. - In various embodiments, rhenium can be eluted 316 from rhenium-loaded
column 310 to produce Re-richaqueous eluate 318. Optionally, the stationary phase of the column can be regenerated 320 and recycled as activatedcarbon 302. Optionally,Re-rich eluate 318 can be subjected to arhenium recovery 322 to producepure rhenium 326 and Re-leanaqueous eluate 324. OptionallyRe-lean eluate 324 can be recycled 328 toelution solution 312. - Finally turning to
FIG. 7 ,plant scale process 70 for recovering rhenium is illustrated according to various embodiments of the present invention. According toplant scale process 70, rheniumrich PLS 704 flows into afirst adsorption column 728 containing first partially loadedcarbon 730 fromsecond adsorption column 732. Any suitable adsorption column may be used with the present invention, for example, a twelve-foot diameter by twelve-foot high adsorption column. - First partially adsorbed
rhenium PLS 734 flows fromfirst adsorption column 728 intosecond adsorption column 732 containing second partially loadedcarbon 736 fromthird adsorption column 738. The amount of rhenium adsorbed onto second partially loadedcarbon 736 can be less than that adsorbed onto first partially loadedcarbon 730. - Second partially adsorbed
rhenium PLS 740 flows fromsecond adsorption column 732 intothird adsorption column 738 containing a third partially loadedcarbon 742 from afourth adsorption column 744. The amount of rhenium adsorbed onto third partially loadedcarbon 742 is less than that adsorbed onto second partially loadedcarbon 736. - Third partially adsorbed
rhenium PLS 746 flows fromthird adsorption column 738 intofourth adsorption column 744 containing fourth partially loadedcarbon 748 fromfifth adsorption column 750. The amount of rhenium adsorbed onto fourth partially loadedcarbon 748 is less than that adsorbed onto third partially loadedcarbon 742. - Fourth partially adsorbed
rhenium PLS 752 flows fromfourth adsorption column 744 intofifth adsorption column 750 containing stripped activatedcarbon 702. Rheniumlean PLS 708 flows away, for example, for other metal recovery. Loaded activatedcarbon 710 fromfirst adsorption column 728 flows to anelution vessel 754. Any suitable elution vessel may be used with the present invention, for example, one or a plurality of 2600 gallon elution vessels. One skilled in the art will appreciate that flow through any number of columns, in series, in parallel, or in any other arrangement, is within the scope of this disclosure. -
Water 756 andeluate 758 are mixed inmix tank 760 to yield anelution solution 712. In an exemplary embodiment,elution solution 712 comprises one or more of sodium hydroxide, ammonium hydroxide, lithium hydroxide, and potassium hydroxide.Boiler 762 heatswater 764 recycled through aplate heat exchanger 766. One or a plurality of heat exchanges can be used.Plate heat exchanger 766 in turn heatselution solution 712 to yieldheated elution solution 768, which flows toelution vessel 754. In an exemplary embodiment, the temperature ofelution solution 712 is increased, for example, to about 100° C. to about 140° C., or to about 100° C. to about 120° C., or to about 100° C.-110° C. -
Spent carbon 770 flows fromelution vessel 754 tocarbon pre-treatment tank 772.New carbon 774 is washed withwater 776 inwash tank 778 to yield washedcarbon 780, which also flows tocarbon pre-treatment tank 772.Wash 782 with reject fine carbon flows to acarbon super sack 784. Carbon super sack 784 can be drained ofexcess water 786. Carbon incarbon pre-treatment tank 772 flows throughcarbon rotary kiln 773 for re-activation of carbon viapumps carbon rotary kiln 773 is rated at 200 lb/hour. Stripped activatedcarbon 702 then flows intofifth adsorption column 750 viapump 779. - A
rhenium eluate 781 flows fromelution vessel 754, viapump 783, toeluate tank 785, where it is mixed withaqueous solution 788. Any suitable eluate tank may be used with the present invention, for example, one or a plurality of 15000 gallon eluate tanks. In an exemplary embodiment,aqueous solution 788 is sulfuric acid. A resulting rhenium richaqueous eluate 718 flows to a solvent extraction (SX)process tank 790. Any suitableSX process tank 790 may be used with the present invention, for example, one or a plurality of 1000 gallon SX process tanks. - Rich organic 792 flows to a
solvent extraction stripper 794, where it is stripped with astriping solution 796. In an exemplary embodiment,solvent extraction stripper 794 is rated at 20 gal/minute. In an exemplary embodiment, strippingsolution 796 is sodium hydroxide. Lean organic 798 returns toSX process tank 790. A resulting rhenium leanaqueous eluate 724 flows to a raffinate pond or is recycled and reused.Concentrated rhenium 726 is available for storage and use. - A stationary phase comprising activated carbon was loaded with rhenium. Three aqueous elution solutions comprised ammonium hydroxide in varying concentrations can be prepared (see Table 1). Ammonium hydroxide was formed by adding ammonia to water. Each elution solution was heated to a temperature of about 108° C. to about 110° C. and passed through the stationary phase at a rate of about 1.5 bed volumes per hour to about 2.0 bed volumes per hour. The complete elution cycle was about 4 bed volumes to about 6 bed volumes. Rhenium can be recovered through the elution and results are shown in Table 1.
-
TABLE 1 Rhenium Yields at varying Concentrations of Ammonia Eluate Conc. % Re Yield, % NH3 0.5 95.2 NH3 1.0 95.9 NH3 2.5 96.1 - A stationary phase comprising activated carbon was loaded with rhenium. Eight aqueous elution solutions comprised ammonium hydroxide in varying concentrations can be prepared (see Table 2). Ammonium hydroxide was formed by adding ammonia to water. Each elution solution was heated to a temperature (see Table 2) and passed through the stationary phase at a rate of about 1.5 bed volumes per hour to about 2.0 bed volumes per hour. The complete elution cycle was an average of about 16 bed volumes. Rhenium was recovered through the elution and results are shown in Table 2.
-
TABLE 2 Rhenium Yields at varying Concentrations of Ammonia Eluate Conc. % Temp, ° C. Re Yield, % NH3 15 22 80.8 NH3 15 50 92.0 NH3 15 80 91.4 NH3 29 22 88.1 NH3 5 50 88.0 NH3 5 75 93.3 NH3 5 50 87.2 NH3 5 50 89.4 - A stationary phase comprising activated carbon was loaded with rhenium. Three aqueous elution solutions comprised sodium hydroxide in varying concentrations can be prepared (see Table 3). Each elution solution was heated to a temperature of about 108° C. to about 110° C. and passed through the stationary phase at a rate of about 1.5 bed volumes per hour to about 2.0 bed volumes per hour. The complete elution cycle was about 6 bed volumes to about 8 bed volumes. Rhenium was recovered through the elution and results are shown in Table 3.
-
TABLE 3 Rhenium Yields at varying Concentrations of Sodium Hydroxide Eluate Conc. % Re Yield, % NaOH 1.0 98.6 NaOH 2.0 97.1 NaOH 5.0 96.9 - A stationary phase comprising activated carbon was loaded with rhenium. Eight aqueous elution solutions comprised sodium hydroxide in varying concentrations can be prepared (see Table 4). Each elution solution was heated to a temperature (see Table 4) and passed through the stationary phase at a rate of about 1.5 bed volumes per hour to about 2.0 bed volumes per hour. The complete elution cycle was an average of 16 bed volumes. Rhenium was recovered through the elution and results are shown in Table 4
-
TABLE 4 Rhenium Yields at varying Concentrations of Sodium Hydroxide Eluate Conc. % Temp, ° C. Re Yield, % NaOH 15 22 59.0 NaOH 15 50 88.3 NaOH 15 80 93.6 NaOH 40 23 69.9 NaOH 40 50 85.3 NaOH 40 50 79.6 NaOH 40 50 84.7 NaOH 40 80 89.0 - A copper heap leach solution was contacted with four columns in series containing a stationary phase comprising activated carbon. The copper leach solution contains 0.65 mg/L of dissolved rhenium. Other metals, such as aluminum, cadmium, calcium, cobalt, copper, iron, magnesium, manganese, sodium, nickel, silicon, vanadium, yttrium and zinc, were present in the copper leach solution at concentrations greater than the concentration of dissolved rhenium. The copper leach solution was contacted with the stationary phase at a rate of 0.125 bed volume per minute for a period of 3 to 4 days. Rhenium was measured in the recovered elution solution exiting each column and results are shown as in Table 5. The average rhenium recovery from the copper leach solution was 96%. The average rhenium loading onto the stationary phase in column 1 was greater than 2000 mg Re per kg carbon.
-
TABLE 5 Average Rhenium Concentration of Copper Leach Solution exiting a Series of Four Activated Carbon Columns Column Rhenium Concentration, mg/L 1 0.314 2 0.155 3 0.072 4 0.025 - Finally, as used herein, the terms “comprise”, “comprises”, “comprising”, “having”, “including”, “includes”, or any variation thereof, are intended to reference a non-exclusive inclusion, such that a process, method, article, composition or apparatus that comprises a list of elements does not include only those elements recited, but can also include other elements not expressly listed and equivalents inherently known or obvious to those of reasonable skill in the art. Other combinations and/or modifications of structures, arrangements, applications, proportions, elements, materials, or components used in the practice of the instant invention, in addition to those not specifically recited, can be varied or otherwise particularly adapted to specific environments, manufacturing specifications, design parameters or other operating requirements without departing from the scope of the instant invention and are intended to be included in this disclosure.
- Moreover, unless specifically noted, it is the Applicants' intent that the words and phrases in the specification and the claims be given the commonly accepted generic meaning or an ordinary and accustomed meaning used by those of reasonable skill in the applicable arts. In the instance where these meanings differ, the words and phrases in the specification and the claims should be given the broadest possible, generic meaning. If it is intended to limit or narrow these meanings, specific, descriptive adjectives will be used. Absent the use of these specific adjectives, the words and phrases in the specification and the claims should be given the broadest possible meaning. If any other special meaning is intended for any word or phrase, the specification will clearly state and define the special meaning.
- Various embodiments and the examples described herein are exemplary and not intended to be limiting in describing the full scope of compositions and methods of this invention. Equivalent changes, modifications and variations of various embodiments, materials, compositions and methods may be made within the scope of the present invention, with substantially similar results.
Claims (20)
1. A method for recovering rhenium, the method comprising:
feeding a metal-bearing leach solution comprising rhenium over activated carbon;
adsorbing said rhenium onto said activated carbon;
heating a basic aqueous solution to a temperature greater than 80° C.; and
eluting said rhenium from said activated carbon with said basic aqueous solution.
2. The method according to claim 1 further comprising removing a rhenium lean metal-bearing leach solution from said activated carbon.
3. The method according to claim 2 further comprising recovering at least one metal value from said rhenium lean metal-bearing leach solution.
4. The method according to claim 3 , wherein said at least one metal value is at least copper.
5. The method according to claim 1 further comprising recovering rhenium metal.
6. The method according to claim 1 further comprising leaching a metal-bearing material to yield said metal-bearing leach solution.
7. The method according to claim 1 , wherein said basic aqueous solution comprises at least one of sodium hydroxide, ammonium hydroxide, lithium hydroxide, and potassium hydroxide.
8. The method according to claim 1 , wherein said basic aqueous solution comprises sodium hydroxide in an amount from about 0.5% to about 2.5%.
9. The method according to claim 1 , wherein said basic aqueous solution comprises ammonium hydroxide in an amount from about 0.5% to about 3%.
10. The method according to claim 1 , wherein heating a basic aqueous solution to a temperature greater than 80° C. is to a temperature from about 100° C. to about 115° C.
11. The method according to claim 1 , wherein heating a basic aqueous solution to a temperature greater than 80° C. is to a temperature from about 108° C. to about 110° C.
12. A system for the recovery of rhenium from a metal-bearing leach solution, the system comprising:
a metal-bearing leach solution feedstream;
at least one bed of activated carbon in communication with said metal-bearing leach solution feedstream;
an elutate feedstream in communication with said at least one bed of activated carbon;
a heater element coupled to said eluate feedstream; and
at least one exit port in communication with said at least one bed of activated carbon, said at least one exit port distal to said metal-bearing leach solution feedstream and said eluate feedstream.
13. The system according to claim 12 wherein said at least one exit port is at least one metal-bearing leach solution exit port and at least one eluate exit port.
14. The system according to claim 13 further comprising a metal recovery apparatus in communication with said at least one metal-bearing leach solution exit port.
15. The system according to claim 14 wherein said metal-bearing recovery apparatus is an electrowinning circuit.
16. The system according to claim 12 further comprising a rhenium recovery apparatus in communication with said eluate exit port.
17. The system according to claim 16 wherein said rhenium recovery apparatus is at least one of a solvent extraction apparatus, an ion exchange apparatus, and a crystallization apparatus.
18. The system according to claim 12 further comprising a leaching apparatus coupled to said metal-bearing leach solution feedstream and operably producing a metal-bearing leach solution.
19. A method for recovering two metal values, the method comprising:
leaching a material comprising two metal values to produce a leach solution comprising two metal values;
subjecting said leach solution to activated carbon;
adsorbing a first metal value on said activated carbon;
removing a solution comprising a second metal value from said activated carbon;
heating an elutate solution;
eluting said first metal value with said elutate solution;
recovering said first metal value; and
recovering said second metal value.
20. The method according to claim 19 wherein said two metal values are copper and rhenium.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/424,863 US20100263490A1 (en) | 2009-04-16 | 2009-04-16 | Methods and systems for recovering rhenium from a copper leach |
PE2011001815A PE20121114A1 (en) | 2009-04-16 | 2010-02-23 | METHODS AND SYSTEMS TO RECOVER RENIUM FROM COPPER LEACHING |
AU2010236985A AU2010236985B2 (en) | 2009-04-16 | 2010-02-23 | Methods and systems for recoverying rhenium from a copper leach |
EP10705741.6A EP2419545B1 (en) | 2009-04-16 | 2010-02-23 | Methods and systems for recoverying rhenium from a copper leach |
PCT/US2010/025031 WO2010120405A1 (en) | 2009-04-16 | 2010-02-23 | Methods and systems for recoverying rhenium from a copper leach |
CA2758884A CA2758884A1 (en) | 2009-04-16 | 2010-02-23 | Methods and systems for recovering rhenium from a copper leach |
CL2011002584A CL2011002584A1 (en) | 2009-04-16 | 2011-10-14 | Methods for recovering rhenium, which comprises feeding metal leaching solution comprising rhenium on activated carbon, adsorbing said rhenium on said activated carbon, heating basic aqueous solution at a temperature between 108 ° C and 110 ° C and eluting said rhenium; rhenium recovery system. |
US13/588,448 US8361192B2 (en) | 2009-04-16 | 2012-08-17 | Methods and systems for recovering rhenium from a copper leach |
US13/724,860 US8491700B2 (en) | 2009-04-16 | 2012-12-21 | Methods and systems for recovering rhenium from a copper leach |
US13/921,539 US20130276586A1 (en) | 2009-04-16 | 2013-06-19 | Methods and systems for recovering rhenium from a copper leach |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/424,863 US20100263490A1 (en) | 2009-04-16 | 2009-04-16 | Methods and systems for recovering rhenium from a copper leach |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/588,448 Division US8361192B2 (en) | 2009-04-16 | 2012-08-17 | Methods and systems for recovering rhenium from a copper leach |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100263490A1 true US20100263490A1 (en) | 2010-10-21 |
Family
ID=42045297
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/424,863 Abandoned US20100263490A1 (en) | 2009-04-16 | 2009-04-16 | Methods and systems for recovering rhenium from a copper leach |
US13/588,448 Expired - Fee Related US8361192B2 (en) | 2009-04-16 | 2012-08-17 | Methods and systems for recovering rhenium from a copper leach |
US13/724,860 Active US8491700B2 (en) | 2009-04-16 | 2012-12-21 | Methods and systems for recovering rhenium from a copper leach |
US13/921,539 Abandoned US20130276586A1 (en) | 2009-04-16 | 2013-06-19 | Methods and systems for recovering rhenium from a copper leach |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/588,448 Expired - Fee Related US8361192B2 (en) | 2009-04-16 | 2012-08-17 | Methods and systems for recovering rhenium from a copper leach |
US13/724,860 Active US8491700B2 (en) | 2009-04-16 | 2012-12-21 | Methods and systems for recovering rhenium from a copper leach |
US13/921,539 Abandoned US20130276586A1 (en) | 2009-04-16 | 2013-06-19 | Methods and systems for recovering rhenium from a copper leach |
Country Status (7)
Country | Link |
---|---|
US (4) | US20100263490A1 (en) |
EP (1) | EP2419545B1 (en) |
AU (1) | AU2010236985B2 (en) |
CA (1) | CA2758884A1 (en) |
CL (1) | CL2011002584A1 (en) |
PE (1) | PE20121114A1 (en) |
WO (1) | WO2010120405A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170357052A1 (en) * | 2015-01-16 | 2017-12-14 | The Regents Of The University Of California | Multi-mode waveguide using space-division multiplexing |
CN110501327B (en) * | 2019-05-29 | 2022-11-11 | 金川集团股份有限公司 | Separation detection method for rhenium in high-copper matrix solid material and liquid material |
Citations (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2809092A (en) * | 1955-04-11 | 1957-10-08 | Kennecott Copper Corp | Extraction of rhenium incidental to manufacture of mol ybdenum oxide |
US2876065A (en) * | 1955-04-11 | 1959-03-03 | Kennecott Copper Corp | Process for producing pure ammonium perrhenate and other rhenium compounds |
US2945743A (en) * | 1958-02-27 | 1960-07-19 | Kennecott Copper Corp | Process for purifying impure rhenium-bearing solutions by ion exchange |
US2972531A (en) * | 1958-04-18 | 1961-02-21 | Kennecott Copper Corp | Process for production of ultra-high purity rhenium |
US3244475A (en) * | 1962-10-31 | 1966-04-05 | Philip E Churchward | Solvent extraction process for separating rhenium from molybdenum |
US3458277A (en) * | 1966-07-21 | 1969-07-29 | Kennecott Copper Corp | Process for the recovery of molybdenum values as high purity ammonium paramolybdate from impure molybdenum-bearing solution,with optional recovery of rhenium values if present |
US3495934A (en) * | 1967-02-07 | 1970-02-17 | Forsch Inst Fuer Ne Metalle | Method for extracting rhenium from aqueous solutions |
US3558268A (en) * | 1967-11-13 | 1971-01-26 | Kennecott Copper Corp | Process for recovering rhenium values from ion exchange materials |
US3672874A (en) * | 1970-11-12 | 1972-06-27 | Universal Oil Prod Co | Recovery of rhenium values from a spent catalyst |
US3739057A (en) * | 1971-07-09 | 1973-06-12 | Molybdenum Corp | Process for the recovery of rhenium and molybdenum values from molybdenite concentrate |
US3751555A (en) * | 1972-03-22 | 1973-08-07 | Molybdenum Corp | Solvent extraction process for the recovery of molybdenum and rhenium from molybdenite |
US3798305A (en) * | 1972-05-19 | 1974-03-19 | Gte Sylvania Inc | Recovering rhenium values from organic extractant solutions |
US3855385A (en) * | 1973-11-12 | 1974-12-17 | Universal Oil Prod Co | Recovery of rhenium from a spent catalyst |
US3856915A (en) * | 1972-05-19 | 1974-12-24 | Gte Sylvania Inc | Solvent recycle process for recovery of rhenium from molybdate solutions |
US3862292A (en) * | 1973-08-24 | 1975-01-21 | Us Interior | Recovery of rhenium |
US3915690A (en) * | 1973-12-28 | 1975-10-28 | Hoeganaes Ab | Composition and method of making alloy steel powder |
US3932579A (en) * | 1973-12-06 | 1976-01-13 | Universal Oil Products Company | Recovery of rhenium |
US4000244A (en) * | 1973-01-30 | 1976-12-28 | Molyscand Ab | Wet-chemical digestion of molybdenum sulphide containing material |
US4006212A (en) * | 1975-09-10 | 1977-02-01 | Gte Sylvania Incorporated | Process for recovery of molybdenum and rhenium from ores |
US4049771A (en) * | 1974-09-12 | 1977-09-20 | Gte Sylvania Incorporated | Extraction process for recovery of rhenium |
US4185078A (en) * | 1974-09-12 | 1980-01-22 | Gte Sylvania Incorporated | Extraction process for recovery of rhenium |
US4188208A (en) * | 1978-05-22 | 1980-02-12 | Newmont Exploration Limited | Recovery of gold from carbonaceous gold-bearing ores |
US4278641A (en) * | 1979-08-07 | 1981-07-14 | Institute Po Obshta I Neorganichna Chimia | Method for extracting rhenium and tungsten from wastes of rhenium-tungsten alloys |
US4521381A (en) * | 1984-11-07 | 1985-06-04 | Gte Products Corporation | Recovery of rhenium |
US4557906A (en) * | 1984-11-07 | 1985-12-10 | Gte Products Corporation | Recovery of rhenium |
US4572823A (en) * | 1983-05-13 | 1986-02-25 | Nihon Kogyo Kabushiki Kaisha | Process for rhenium recovery |
US4599153A (en) * | 1983-01-13 | 1986-07-08 | American Cyanamid Company | Selective extraction of rhenium from aqueous sulfuric acid solutions |
US4774003A (en) * | 1983-08-25 | 1988-09-27 | University Of Utah | Ion exchange extraction of metallic and non-metallic anions by control of the basicity of amine extractants |
US4816235A (en) * | 1987-02-24 | 1989-03-28 | Batric Pesic | Silver and manganese recovery using acidified thiourea |
US5215574A (en) * | 1992-01-03 | 1993-06-01 | Betz Laboratories, Inc. | Method of improving precious metal yield in a Merrill-Crowe recovery process |
US5427606A (en) * | 1990-11-15 | 1995-06-27 | Bruno Sceresini Holding Pty. Ltd. | Base metals recovery by adsorption of cyano complexes on activated carbon |
US5605563A (en) * | 1993-02-25 | 1997-02-25 | Ann Huber | Method for removing copper from an anion exchange material loaded with precious metals |
US5804151A (en) * | 1997-09-16 | 1998-09-08 | Cyprus Amax Minerals Company | Process for autoclaving molybdenum disulfide |
WO2002077302A2 (en) * | 2001-03-23 | 2002-10-03 | Mintek | Recovery of gold from carbon eluate cyanide solution |
US6494932B1 (en) * | 2000-06-06 | 2002-12-17 | Birch Mountain Resources, Ltd. | Recovery of natural nanoclusters and the nanoclusters isolated thereby |
US20030200839A1 (en) * | 1998-03-27 | 2003-10-30 | Jenkins Alexander E. | Recovery of precious metals and copper from copper/gold ores using resin technology |
US6936090B2 (en) * | 2001-11-09 | 2005-08-30 | H. C. Starck Gmbh | Process for isolating rhenium |
US20070014709A1 (en) * | 2002-12-31 | 2007-01-18 | John Moyes | Recovering metals from sulfidic materials |
US20080118422A1 (en) * | 2006-11-21 | 2008-05-22 | Peter Amelunxen | System and method for conversion of molybdenite to one or more molybdenum oxides |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60258434A (en) | 1984-06-04 | 1985-12-20 | Nippon Mining Co Ltd | Method for recovering rhenium |
RO98782B1 (en) | 1987-11-18 | 1990-04-30 | Institutul De Cercetari Inginerie Tehnologica | Process for recovering rhenium from residual solutions at hydroelectric plant of low head for molybdenum |
PL160950B1 (en) | 1988-06-24 | 1993-05-31 | Gorniczo Hutniczy Miedzi | Method of recovering rhenium from acid waste solutions encountered in non-ferrous metals industry |
AUPO944297A0 (en) | 1997-09-25 | 1997-10-16 | Advance R & D Pty Ltd | Modular and transportable processing plant and mobile mineral process evaluation unit |
-
2009
- 2009-04-16 US US12/424,863 patent/US20100263490A1/en not_active Abandoned
-
2010
- 2010-02-23 PE PE2011001815A patent/PE20121114A1/en active IP Right Grant
- 2010-02-23 WO PCT/US2010/025031 patent/WO2010120405A1/en active Application Filing
- 2010-02-23 EP EP10705741.6A patent/EP2419545B1/en not_active Not-in-force
- 2010-02-23 AU AU2010236985A patent/AU2010236985B2/en not_active Ceased
- 2010-02-23 CA CA2758884A patent/CA2758884A1/en not_active Abandoned
-
2011
- 2011-10-14 CL CL2011002584A patent/CL2011002584A1/en unknown
-
2012
- 2012-08-17 US US13/588,448 patent/US8361192B2/en not_active Expired - Fee Related
- 2012-12-21 US US13/724,860 patent/US8491700B2/en active Active
-
2013
- 2013-06-19 US US13/921,539 patent/US20130276586A1/en not_active Abandoned
Patent Citations (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2809092A (en) * | 1955-04-11 | 1957-10-08 | Kennecott Copper Corp | Extraction of rhenium incidental to manufacture of mol ybdenum oxide |
US2876065A (en) * | 1955-04-11 | 1959-03-03 | Kennecott Copper Corp | Process for producing pure ammonium perrhenate and other rhenium compounds |
US2945743A (en) * | 1958-02-27 | 1960-07-19 | Kennecott Copper Corp | Process for purifying impure rhenium-bearing solutions by ion exchange |
US2972531A (en) * | 1958-04-18 | 1961-02-21 | Kennecott Copper Corp | Process for production of ultra-high purity rhenium |
US3244475A (en) * | 1962-10-31 | 1966-04-05 | Philip E Churchward | Solvent extraction process for separating rhenium from molybdenum |
US3458277A (en) * | 1966-07-21 | 1969-07-29 | Kennecott Copper Corp | Process for the recovery of molybdenum values as high purity ammonium paramolybdate from impure molybdenum-bearing solution,with optional recovery of rhenium values if present |
US3495934A (en) * | 1967-02-07 | 1970-02-17 | Forsch Inst Fuer Ne Metalle | Method for extracting rhenium from aqueous solutions |
US3558268A (en) * | 1967-11-13 | 1971-01-26 | Kennecott Copper Corp | Process for recovering rhenium values from ion exchange materials |
US3672874A (en) * | 1970-11-12 | 1972-06-27 | Universal Oil Prod Co | Recovery of rhenium values from a spent catalyst |
US3739057A (en) * | 1971-07-09 | 1973-06-12 | Molybdenum Corp | Process for the recovery of rhenium and molybdenum values from molybdenite concentrate |
US3751555A (en) * | 1972-03-22 | 1973-08-07 | Molybdenum Corp | Solvent extraction process for the recovery of molybdenum and rhenium from molybdenite |
US3798305A (en) * | 1972-05-19 | 1974-03-19 | Gte Sylvania Inc | Recovering rhenium values from organic extractant solutions |
US3856915A (en) * | 1972-05-19 | 1974-12-24 | Gte Sylvania Inc | Solvent recycle process for recovery of rhenium from molybdate solutions |
US4000244A (en) * | 1973-01-30 | 1976-12-28 | Molyscand Ab | Wet-chemical digestion of molybdenum sulphide containing material |
US3862292A (en) * | 1973-08-24 | 1975-01-21 | Us Interior | Recovery of rhenium |
US3855385A (en) * | 1973-11-12 | 1974-12-17 | Universal Oil Prod Co | Recovery of rhenium from a spent catalyst |
US3932579A (en) * | 1973-12-06 | 1976-01-13 | Universal Oil Products Company | Recovery of rhenium |
US3915690A (en) * | 1973-12-28 | 1975-10-28 | Hoeganaes Ab | Composition and method of making alloy steel powder |
US4185078A (en) * | 1974-09-12 | 1980-01-22 | Gte Sylvania Incorporated | Extraction process for recovery of rhenium |
US4049771A (en) * | 1974-09-12 | 1977-09-20 | Gte Sylvania Incorporated | Extraction process for recovery of rhenium |
US4006212A (en) * | 1975-09-10 | 1977-02-01 | Gte Sylvania Incorporated | Process for recovery of molybdenum and rhenium from ores |
US4188208A (en) * | 1978-05-22 | 1980-02-12 | Newmont Exploration Limited | Recovery of gold from carbonaceous gold-bearing ores |
US4278641A (en) * | 1979-08-07 | 1981-07-14 | Institute Po Obshta I Neorganichna Chimia | Method for extracting rhenium and tungsten from wastes of rhenium-tungsten alloys |
US4599153A (en) * | 1983-01-13 | 1986-07-08 | American Cyanamid Company | Selective extraction of rhenium from aqueous sulfuric acid solutions |
US4572823A (en) * | 1983-05-13 | 1986-02-25 | Nihon Kogyo Kabushiki Kaisha | Process for rhenium recovery |
US4774003A (en) * | 1983-08-25 | 1988-09-27 | University Of Utah | Ion exchange extraction of metallic and non-metallic anions by control of the basicity of amine extractants |
US4521381A (en) * | 1984-11-07 | 1985-06-04 | Gte Products Corporation | Recovery of rhenium |
US4557906A (en) * | 1984-11-07 | 1985-12-10 | Gte Products Corporation | Recovery of rhenium |
US4816235A (en) * | 1987-02-24 | 1989-03-28 | Batric Pesic | Silver and manganese recovery using acidified thiourea |
US5427606A (en) * | 1990-11-15 | 1995-06-27 | Bruno Sceresini Holding Pty. Ltd. | Base metals recovery by adsorption of cyano complexes on activated carbon |
US5215574A (en) * | 1992-01-03 | 1993-06-01 | Betz Laboratories, Inc. | Method of improving precious metal yield in a Merrill-Crowe recovery process |
US5605563A (en) * | 1993-02-25 | 1997-02-25 | Ann Huber | Method for removing copper from an anion exchange material loaded with precious metals |
US5804151A (en) * | 1997-09-16 | 1998-09-08 | Cyprus Amax Minerals Company | Process for autoclaving molybdenum disulfide |
US20030200839A1 (en) * | 1998-03-27 | 2003-10-30 | Jenkins Alexander E. | Recovery of precious metals and copper from copper/gold ores using resin technology |
US6494932B1 (en) * | 2000-06-06 | 2002-12-17 | Birch Mountain Resources, Ltd. | Recovery of natural nanoclusters and the nanoclusters isolated thereby |
WO2002077302A2 (en) * | 2001-03-23 | 2002-10-03 | Mintek | Recovery of gold from carbon eluate cyanide solution |
US6936090B2 (en) * | 2001-11-09 | 2005-08-30 | H. C. Starck Gmbh | Process for isolating rhenium |
US20070014709A1 (en) * | 2002-12-31 | 2007-01-18 | John Moyes | Recovering metals from sulfidic materials |
US20080118422A1 (en) * | 2006-11-21 | 2008-05-22 | Peter Amelunxen | System and method for conversion of molybdenite to one or more molybdenum oxides |
Non-Patent Citations (1)
Title |
---|
D.A. Bartlett, The Fundamentals of Heat Exchangers, The Industrial Physicist, December 1996, pp. 18-21 * |
Also Published As
Publication number | Publication date |
---|---|
CA2758884A1 (en) | 2010-10-21 |
WO2010120405A1 (en) | 2010-10-21 |
EP2419545A1 (en) | 2012-02-22 |
CL2011002584A1 (en) | 2012-03-23 |
AU2010236985B2 (en) | 2013-08-29 |
US8491700B2 (en) | 2013-07-23 |
US8361192B2 (en) | 2013-01-29 |
PE20121114A1 (en) | 2012-08-12 |
AU2010236985A1 (en) | 2011-11-10 |
US20120304827A1 (en) | 2012-12-06 |
US20130118310A1 (en) | 2013-05-16 |
US20130276586A1 (en) | 2013-10-24 |
EP2419545B1 (en) | 2014-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8003064B2 (en) | Controlled copper leach recovery circuit | |
US20020034465A1 (en) | Method for recovering metal values from metal-containing materials using high temperature pressure leaching | |
US11584974B2 (en) | System and method including multi-circuit solution extraction for recovery of metal values from metal-bearing materials | |
US8920773B2 (en) | Systems and methods for metal recovery | |
US10036096B2 (en) | System and method for parallel solution extraction of one or more metal values from metal-bearing materials | |
AU2001277182A1 (en) | Method for Recovering Copper from Sulfide Ore Materials Using High Temperature Pressure Leaching, Solvent Extraction and Electrowinning | |
US8491700B2 (en) | Methods and systems for recovering rhenium from a copper leach | |
US20070041884A1 (en) | Resin and process for extracting non-ferrous metals | |
AU2004235837A2 (en) | A resin and process for extracting non-ferrous metals |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: FREEPORT-MCMORAN CORPORATION, ARIZONA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WATERMAN, BRETT T;DIXON, STEVE NELS;MORELLI, THERESA LINNE;AND OTHERS;SIGNING DATES FROM 20090604 TO 20090624;REEL/FRAME:022954/0353 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |