US20180282887A1 - Solvent extraction and stripping system - Google Patents

Solvent extraction and stripping system Download PDF

Info

Publication number
US20180282887A1
US20180282887A1 US16/001,830 US201816001830A US2018282887A1 US 20180282887 A1 US20180282887 A1 US 20180282887A1 US 201816001830 A US201816001830 A US 201816001830A US 2018282887 A1 US2018282887 A1 US 2018282887A1
Authority
US
United States
Prior art keywords
copper
organic
phase
permeable body
housing
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
Application number
US16/001,830
Inventor
William Daniel Ernt
George M. Galik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Minextech LLC
Original Assignee
Minextech LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Minextech LLC filed Critical Minextech LLC
Priority to US16/001,830 priority Critical patent/US20180282887A1/en
Publication of US20180282887A1 publication Critical patent/US20180282887A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
    • B04B—CENTRIFUGES
    • B04B1/00—Centrifuges with rotary bowls provided with solid jackets for separating predominantly liquid mixtures with or without solid particles
    • B04B1/04—Centrifuges with rotary bowls provided with solid jackets for separating predominantly liquid mixtures with or without solid particles with inserted separating walls
    • B04B1/06—Centrifuges with rotary bowls provided with solid jackets for separating predominantly liquid mixtures with or without solid particles with inserted separating walls of cylindrical shape
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0476—Moving receptacles, e.g. rotating receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/45—Mixing liquids with liquids; Emulsifying using flow mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
    • B01F25/3133—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit characterised by the specific design of the injector
    • B01F25/31331—Perforated, multi-opening, with a plurality of holes
    • B01F25/313311—Porous injectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/431—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
    • B01F25/4314—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor with helical baffles
    • B01F25/43141—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor with helical baffles composed of consecutive sections of helical formed elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/431—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
    • B01F25/43197—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor characterised by the mounting of the baffles or obstructions
    • B01F25/431971—Mounted on the wall
    • B01F3/0861—
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0086—Treating solutions by physical methods
    • C22B3/0005—
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • B01F2005/0637—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/45—Mixing in metallurgical processes of ferrous or non-ferrous materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/431—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
    • B01F25/43197—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor characterised by the mounting of the baffles or obstructions
    • B01F25/431972—Mounted on an axial support member, e.g. a rod or bar
    • 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
    • Y02P10/234—

Definitions

  • the present invention relates solvent extraction and stripping systems, i.e. methods and apparatus.
  • the invention has particular utility in connection with the processing of solutions containing metals, such as, for example, the production of copper by solvent extraction of copper containing solutions followed by electrowinning of a rich copper electrolyte obtained by stripping copper from a copper containing solvent, and will be described in connection with such utility, although other utilities are contemplated.
  • liquid-liquid extraction where two mutually insoluble liquids contact each other
  • the mining industry has used liquid-liquid ion exchange for many years to recover metal from aqueous leaching solutions, such as described in U.S. Pat. No. 5,196,095 to Sudderth et al, and U.S. Pat. No. 4,683,310 to Dalton et al.
  • Liquid-liquid ion exchange has also been used for years to recover dissolved copper from etching solutions, such as described in U.S. Pat. No. 3,705,061 to King, in accordance with a recovery process such as that disclosed in U.S. Pat. No. 5,466,375 to Galik.
  • etching solutions such as described in U.S. Pat. No. 3,705,061 to King
  • recovery process such as that disclosed in U.S. Pat. No. 5,466,375 to Galik.
  • Stripping can be ion exchange for all types or deprotonation for primary, secondary and tertiary amines and trialkylguanidines
  • Tertiary amines and trialkylguanidines are more selective than primary and secondary amines
  • extraction must be at pH below the pk b of the extractant
  • Selectivity can be pH dependent
  • Primary, secondary and tertiary amines are relatively simple to produce
  • the leachant typically is a weak solution of sulfuric acid and usually is obtained as a recycle stream from a downstream process step such as a raffinate stream from an organic copper extraction step.
  • the copper-rich weakly acidic aqueous solution typically is referred to as a pregnant leach solution (PLS) and is mixed with an organic solvent in a mixer.
  • the organic solvent which is substantially immiscible in the aqueous solution, extracts copper from the pregnant leach solution to form what is commonly termed a loaded organic stream.
  • the mixture comprising the pregnant leach solution and organic extractant are then transferred to a settler tank where the organic phase and aqueous phases are allowed to separate to form an upper, copper loaded organic phase and a lower, copper depleted acidic aqueous phase called a “raffinate phase”.
  • the lower aqueous raffinate phase is removed from the settler tank and typically is recycled and used as a leachant to leach more copper from the ore in the heap.
  • the loaded organic phase is transferred to a second mixer and mixed with lean electrolyte which is obtained from a downstream electrowinning cell.
  • the mixture is transferred to a second settler and the organic and aqueous phases allowed to separate.
  • the lean electrolyte which typically is a highly acidic sulfuric acid stream extracts the copper from the loaded organic phase and forms a rich copper electrolyte aqueous phase.
  • the rich copper electrolyte aqueous phase is fed to an electrowinning cell to form the copper product.
  • lean electrolyte Depleted electrolyte from the electrowinning cell termed “lean electrolyte” is recycled and the stream mixed with the loaded organic phase in the mixer and settler to extract more copper from the loaded organic phase.
  • the loaded organic phase which is now largely depleted of the extracted copper typically is termed the “stripped organic phase” and this phase typically is recycled to the first mixer to contact and extract more copper from new pregnant leach solution.
  • entrained water in the loaded organic phase decreases the efficiency of stripping copper from the loaded organic phase in the stripping step of the process and adds to the load on the mixer and stripper. This entrained water also transfers undesirable contaminates from the leach solution to the stripping solution or electrolyte.
  • the loaded organic stream then is mixed with an aqueous acidic stream, to extract copper from the loaded organic stream to produce a stripped organic extractant process stream and a copper rich aqueous electrolyte process stream which aqueous electrolyte process stream is fed into an electrowinning cell and copper produced by electrowinning, the method comprising feeding one or more of the liquid process streams to one or more cyclones to remove entrained water or entrained organic extractant from the stream before the stream is used further in the process.
  • the present invention overcomes the aforesaid and other problems of the prior art, by providing, in one aspect, is a unique micro dispersion device, which significantly improves mass transfer and thus stage efficiency.
  • the micro dispersion device of the present invention can create different dispersed phase droplet sizes and thus an optimum droplet size can be determined for a specific application. Optimum droplet sizes are determined to maximize mass transfer as well as maximizing phase separation efficiency.
  • a disadvantage of prior art liquid-liquid ion exchange systems for dispersing one liquid in another is that air bubbles are entrained during the dispersing step. The entrained air interferes with material transfer and with coalescensce of the dispersed liquid, and delays separation of the two liquids.
  • Our micro dispersion device avoids the formation of air bubbles as one liquid is dispersed in the other, thus providing a more efficient recovery of the desired material.
  • Our micro dispersion device also allows the dispersion of a specific phase independent of phase volume or flow ratio.
  • the organic to aqueous (O/A) ratio is for example, 4:1
  • the organic phase can be dispersed using our micro dispersion device without having to recycle the aqueous phase.
  • Our micro dispersion device produces a more uniform distribution of droplet sizes within the continuous phase compared to heretofore existing phase mixing devices available.
  • the micro dispenser device controls which solution phase is dispersed and which solution phase is continuous.
  • Conventional prior art mixers do not control the dispersed or continuous phase but rather the solution flow to the mixer controls this parameter. It follows that regardless of which solution has the overall larger volume, the micro dispenser device of the present invention does not require the larger solution volume (or a recycle on the lower solution volume) to ensure a continuous phase for the mixer. This provides the operator with more operational flexibility and avoids the costs of recycling a lower volume solution which needs to be the continuous phase.
  • a further advantage associated with the control of the dispersed phase through the use of the micro dispenser device is that entrainment can be reduced. Entrainments, as general principle, in the dispersed phase is much less than entrainment in the continuous phase.
  • micro dispenser device of the present invention ensures the optimum droplet size is created for the dispersed phase which leads to improved mass transfer and improved stage efficiency.
  • the micro dispenser device of the present invention also ensures a uniform droplet size which will improve phase separation.
  • the micro dispenser device of the present invention is a closed system, which does not introduce air into the system. This reduces the formation of a third (air) phase into the settler or centrifuge and thus improves phase separation. Additionally, the reduction or elimination of air in the system will reduce the degradation of organic as well as lessening organic/solvent losses.
  • centrifuge separator which allows high phase separation efficiency due to the high ‘g’ force created in a rotating bowl.
  • the centrifuge separator of the present invention has a lower cost compared to other centrifugal extractors and separators.
  • the economical design and manufacturing techniques allows the use of a centrifugal separator in, for example, hydrometallurgical solvent extractors operations.
  • centrifugal contactors and separators are too costly and are uneconomical to use in most solvent extractors operations.
  • Our centrifuge separator offers the advantages over other currently available process equipment such as low hold-up, low residence time, and low organic/solvent inventory.
  • the rotating bowl of our centrifuge separator imparts the liquid in a practically rigid body rotation.
  • the inner surface of the rotating liquid has almost a vertical shape because of the high ‘g’ force.
  • the dispersion entering at the bottom gets separated as it moves upward.
  • the rate of separation depends upon the drop size distribution, their settling velocities under the centrifugal action (r ⁇ 2 )—where r is the radius of the centrifuge bowl and ⁇ is the rotational speed, plus densities, viscosities and coalescing behavior of the two phases.
  • r ⁇ 2 the settling velocities under the centrifugal action
  • centrifuge separator is unique. These design techniques eliminate or significantly reduce the shortcomings found in existing centrifugal based systems.
  • Our centrifuge separator (with or without our micro dispenser device) is designed so the entering flow does not contain, or contains very little, entrained air. Feed pipes and the separation chamber are occupied essentially 100% by liquid. This avoids air entrainment, which increases phase separation times. This also eliminates a third phase in the centrifuge chamber—thus increasing the volume occupied by the liquids and hence increasing residence times compared to existing centrifuge designs of the same size.
  • centrifuge separator which is significantly less expensive to make. This makes the use of a centrifuge separator much more economically viable.
  • centrifugal separator is independent of the mixing step.
  • the mixer is operated at the same speed as the separating bowl.
  • the mixing operation is dependent on the separation RPM and vice versa.
  • Mixing and separation are two discrete operations and should be independent.
  • Our centrifugal separator is totally separate from the mixing operation.
  • a closed system greatly reduces, if not eliminates VOC emissions as well as organic/solvent losses due to evaporation.
  • our micro dispersion device and our centrifuge separator significantly improve mass transfer and stage efficiency, while at the same time, improve separation and reduce entrainment losses all at a lower cost than conventional solvent extraction systems and existing centrifuge systems.
  • our solvent extraction system is an essentially closed solvent extraction system, which minimizes organic solvent loss from evaporation.
  • the present invention provides a micro dispersion apparatus for mixing of two liquids of different densities which liquids are substantially insoluble in one another, said apparatus comprising a hollow permeable body having a recess for receiving a first fluid which can flow from the recess through the permeable body to an exterior of the permeable body; a housing surrounding and spaced from the exterior of the permeable body, said housing having an inlet for a second fluid and an outlet for a mixture of the first and second fluid; and a baffle or baffles in the space between the exterior of the permeable body and the housing, the baffle or baffles being spaced to define a mixing channel in the space between the exterior of the permeable body and the housing so that the second fluid can enter the housing inlet and flow through the mixing channel to the outlet, while picking up fluid on the exterior of the permeable body.
  • the mixing channel is substantially in the shape of a helix, or the baffle is formed of a series of elongated segments formed end-to-end.
  • the permeable body has pores in the range of 0.2 to 400 microns, preferably 20 to 200 microns, more preferably 60 to 100 microns.
  • micro dispersion device is similar to the device described in our prior U.S. Published Application US 2003/0029795 A1. However, unlike the micro dispersion device described in our prior U.S. Published Application US 2003/0029795 A1, the permeable body is filed, at least in part, with loosely packed finely divided media or frits.
  • the present invention also provides an apparatus for separating and recovery of a metal such as copper from a metal-containing source such as a copper-containing source by a solvent extraction/electrowinning process, comprising a mixing device for mixing a metal-containing aqueous solution and an immiscible organic extractant, wherein the mixing device comprises apparatus as above described, the apparatus further comprising a centrifugal separator, and a mixing conduit connecting the mixing device with a centrifugal separator.
  • the mixing conduit is sized and shaped to provide a travel or residence time between the mixing device and the centrifugal separator of 5-120 seconds, preferably 20-60 seconds, more preferably 35-45 seconds.
  • the centrifugal separator separates the mixture into two streams, a heavy phase and a light phase, the heavy phase comprising primarily an aqueous phase containing copper, said apparatus further comprising a conduit carrying the heavy phase to an electrowinning stage.
  • the apparatus further comprises a conduit carrying the light phase conduit to the mixing device.
  • the invention also provides a method for separating a mixture of a first and a second fluid of different densities, which fluids are substantially insoluble in one another, said method comprising providing an apparatus as above described, flowing the first fluid from an interior of the permeable body to an exterior of the permeable body; and contacting the first fluid on the exterior of the permeable body with the second fluid.
  • the permeable body has pores in the range of 0.2 to 400 microns, preferably 20 to 200 microns, more preferably 60 to 100 microns.
  • the permeable body is filled, at least in part, with loosely packed finely divided media or flits, and including the step of flowing the first fluid through the media or flit.
  • the aqueous based solution compromises an aqueous acid solution, while the organic solution comprises an organic solvent, such as kerosene.
  • the present invention also provides a method for separating and recovery of metals such as copper from a metal-containing source by a solvent extraction electrowinning process, comprising providing a copper-containing aqueous solution and an immiscible organic extractant to a mixing device, wherein the mixing device comprises an apparatus as above described; whereupon the organic extractant is dispersed in the copper-containing aqueous solution and extracts metal from the aqueous solution, passing the resulting dispersion through a mixing conduit to a centrifugal separator, and separating the organic extractant containing metal from the aqueous solution.
  • the mixing conduit is sized and shaped to provide a travel or residence time between the mixing device and the centrifugal separator of 5-120 seconds, preferably 20-60 seconds, more preferably 35-45 seconds.
  • the centrifugal separator separates the mixture into two streams, a heavy phase and a light phase, the heavy phase comprising primarily an aqueous phase containing copper; including the steps of passing the heavy phase to an electrowinning stage.
  • Yet another embodiment of the method includes the step of returning the light phase, at least in part, to the mixing device.
  • FIG. 1 is flow diagram of a system for the hydrometallurgical production of a metal such as copper in accordance with one aspect the present invention
  • FIG. 1A is a side elevational view, in cross section, showing details of an apparatus for dispersing an organic fluid such as kerosene into an aqueous-based solution in accordance with another aspect of the present invention
  • FIG. 2 is a side elevational view, in cross section, of a centrifugal contactor-separator employed in accordance with the present invention
  • FIG. 2A is a cross-sectional view of the rotating cylinder portion of the centrifugal contractor—separator of FIG. 2 ;
  • FIG. 3 is a flow diagram, similar to FIG. 1 , of an alternative system for the hydrometallurgical production of a metal such as copper in accordance with the present invention.
  • a copper containing pregnant leach solution (PLS) 10 from a copper oxide ore heap 12 is fed to a first mixing vessel 14 A where the pregnant leach solution is mixed with an organic liquid extractant such as a hydroxyl oxime ion exchanger in kerosene supplied from tank 16 .
  • mixing vessel 14 A comprises an elongate cylindrical housing 18 having an inlet 20 at one end, and an outlet 22 at the other end.
  • a permeable body 24 in the shape of a cylindrical tube is coaxially disposed within the cylindrical housing 18 .
  • housing and permeable body 24 need not be cylindrical—they may be square, or rectangular or have other geometric shapes in cross-section.
  • the permeable body 24 is connected to the housing inlet 20 at one end 26 , and a disc 28 closes the end of permeable body 24 adjacent the housing outlet 22 .
  • the outer wall of permeable body 24 is spaced from the interior wall of housing 18 .
  • a helical baffle 30 is located within the annular space between the outer wall of permeable body 24 and the inner wall of housing 18 .
  • Baffle 30 may be a continuous elongated helical strip or formed as a series of segments.
  • Mixing vessel 14 A also has a lateral inlet 32 adjacent the inlet 20 end.
  • Permeable body 24 can be made of permeable or porous metal, and is filled with loosely packed finely divided media or frits such as powdered metal particles or ceramic particles.
  • Various permeable and porous metals are available commercially from a variety of vendors including Mott Metallurgical Corporation of Farmington, Conn.
  • the permeable or porous metal used in this invention preferably has substantially uniform pore sizes, or at least most of the pores are within an acceptable range for the intended purpose, and typically are in the range of 0.2 to 400 microns, preferably 20 to 200 microns, more particularly 60 to 100 microns.
  • the porous media or flits should be inert to the liquids being handled.
  • the media or flits can be made of particles of ceramic, or stainless steel, Nickel 200, MONEL® nickel-copper alloy 400, INCONEL® nickel-chromium alloy 600, HASTELLOY® nickel-molybdenum-chromium alloy C276, Alloy 20, gold, platinum, silver, and titanium.
  • the media or flits by their nature, cause the droplets of the organic solvent to finally divide, dispersing fine droplets on the outer surface of the permeable body 24 , where they are picked up by the PLS.
  • the organic liquid extractant in kerosene is introduced through inlet 20 into the interior of permeable body 24 .
  • PLS is introduced into the interior of mixing vessel 14 A through lateral inlet 32 , into the space between the outer wall of permeable body 24 and the inner wall of mixing vessel 14 A.
  • the organic liquid extractant is forced through the permeable body 24 and emerges from the permeable body in the form of a fine organic liquid extractant droplets where the droplets are picked up by the flowing PLS, forming a dispersion of kerosene droplets in the PLS.
  • the PLS preferably is flowed under turbulent conditions so that the droplets of the organic liquid extractant are quickly dispersed before having an opportunity to coalesce.
  • the organic liquid extractant which is substantially immiscible with the aqueous based PLS solution, extracts copper from the pregnant leach solution, and emerges from the mixing vessel 14 A via outlet 22 .
  • the PLS may be introduced into the interior of permeable body 24 , and the organic liquid extractant introduced into the interior of the mixing vessel 14 A through lateral inlet 32 , into the space between the outer wall of permeable body 24 and the inner wall of mixing vessel 14 A.
  • the PLS is forced through the permeable body 24 , and emerges from the permeable body in the form of fine droplets which are picked up by the flowing organic liquid extractant, forming a dispersion of aqueous droplets in the kerosene.
  • Conduit 34 A includes inline baffles shown in phantom as 98 A for maintaining the fluid in a mixed condition.
  • Conduit 34 A is sized and shaped relative to the flow of fluid from mixing vessel 14 A to provide a travel or residence time sufficient to permit substantial mass transfer of copper in the aqueous solution to the organic liquid extractant.
  • a residence time of 5-120 seconds, preferably 20-60 seconds, more preferably 35-45 seconds is sufficient before the fluid is introduced into a centrifugal separator 100 A.
  • one or more loops may be included in the conduit 34 A, or the cross sectional size of the conduit 34 A increased so that the flow from mixing vessel 14 A is controlled to within the target residence time of 5-120 seconds.
  • centrifuge separator 100 A creates two exit streams—a light phase (organic) and a heavy phase (aqueous raffinate).
  • the aqueous raffinate is recycled to the leach heap to dissolve more copper.
  • the organic phase exiting the centrifuge 100 A is transferred to another mixing vessel 14 B, similar to mixing vessel 14 A, where it is mixed with lean electrolyte from the electrowinning stage 60 as will be discussed below.
  • the organic liquid extractant is forced through the permeable body 24 contained in mixing vessel 14 B, and emerges from the permeable body in the form of a fine organic liquid extractant droplets where the droplets are picked up by the flowing electrolyte, forming a dispersion of kerosene droplets in the electrolyte.
  • the electrolyte preferably is flowed under turbulent conditions so that the droplets of the organic liquid extractant are quickly dispersed before having an opportunity to coalesce.
  • the electrolyte or stripping solution which is substantially immiscible with the organic liquid extractant removes (strips) copper from the organic liquid extractant and emerges from the mixing vessel 14 B, where it is passed via conduit 34 B which also contains inline baffles shown in phantom as 98 B, similar to conduit 34 A, for maintaining the fluid in a mixed condition.
  • conduit 34 B is sized and shaped relative to the flow of the fluid from mixing vessel 14 A to provide a travel or residence time sufficient to permit substantial mass transfer of copper in the aqueous solution to the organic liquid extractant.
  • the fluid then passed to a second strip stage centrifuge 100 B which is similar in construction to centrifuge 100 A as will be described in detail below, and in which a light organic phase is partially stripped of copper and returned to tank 16 , and a rich copper electrolyte phase is passed to an electrowinning cell 60 .
  • centrifugal separator 100 A which is similar to the centrifugal separator described in our prior U.S. Pat. No. 6,440,054, comprises a rotatable cylinder 102 in the shape of a vertical right cylinder contained in a housing 104 having vertical side wall 106 bottom wall 108 and top wall 109 .
  • a vertical drive shaft 112 is suspended at the upper end of housing 104 by an upper thrust bearing.
  • Centrifugal separator 100 A has an inlet 116 for input of an organic/aqueous mixed phase, i.e., from conduit 34 A.
  • the solution enters the central opening (orifice) 140 of the rotating cylinder 102 .
  • the dispersion entering central orifice 140 gets deflected towards the outside wall of the cylinder by a horizontal deflecting baffle 142 provided close to the entrance.
  • a horizontal deflecting baffle 142 provided close to the entrance.
  • the mixing box at the bottom of the centrifugal separator is eliminated, and the upper end of rotating cylinder 102 provided with a plurality of vertical baffles 146 which create several chambers ranging from 4 to 8. In a preferred embodiment, we create four (4) chambers.
  • the rotating cylinder 102 imparts to the liquid a practically rigid body rotation.
  • the inner surface of the rotating liquid has almost a vertical shape because of high ‘g’ except a small parabolic portion adjacent the bottom.
  • the dispersion entering at the bottom region 148 gets separated as it moves upwards.
  • the rate of separation depends upon the droplet size distribution, their settling velocities under the centrifugal action (r ⁇ 2), where r is the radius of the bowl/chamber and ⁇ is the rotation speed), densities, viscosities and coalescing behavior of the two phases. For complete separation, adequate height needs to be provided for a given level of (r ⁇ 2).
  • the solution is separated into two phases—a light phase which is discharged through the ports 144 and exits the unit through the top port 110 , and a heavy phase which is discharged through outlet ports 156 and leaves the unit through outlet 158 .
  • the heavy phase outlet ports 156 have variable positions which are selected and changed according to the relative flow rates of the heavy and light phases and the relative volumes of each phase within the centrifugal separator 100 A.
  • FIG. 3 shows an alternative embodiment of the invention.
  • the FIG. 3 embodiment includes two mixing vessels 14 A 1 and 14 A 2 , and 14 B 1 and 14 B 2 for both the extract stage as well as the strip stage connected through valving and conduits 10 A, 10 B, 34 A, 34 B, so that one mixing vessel may remain in service, while the other mixing vessel is taken off line for maintenance or cleaning.
  • the present invention provides various advantages over prior art processes. For one, the system is closed. Thus, loss of organic solvent, i.e. due to evaporation is avoided. Also, by passing the organic phase through finely divided media or frits, and a permeable body before the organic phase is mixed with the PLS, a micro dispersion of the organic phase is formed in the PLS. Thus, less organic solvent is needed in the overall process. Also, higher throughput may be achieved with smaller equipment overall, thus adding to equipment savings, as well as operational savings.
  • Uranium may be recovered as ‘yellow cake’ (approximately 80% U3O8) by precipitation and calcining of ammonium uranyl sulfate.
  • some recovery systems employ crystallization to create a nickel sulfate or copper sulfate crystal.
  • electrowinning creates 99.99+ pure copper at the cathode, other metals, for example, zinc, are also electrowon.
  • some operations also use spray drying technology to create a metal salt dust. Still other changes including recovery of other metals including, but not limited to zinc, nickel, cobalt and uranium, using appropriate extractants, e.g. as above described, are possible.

Abstract

An apparatus for separating a mixture of two liquids of different densities which liquids are substantially insoluble in one another includes a hollow permeable body having a recess for receiving a first fluid which can flow from the recess through the permeable body to an exterior of the permeable body. A housing surrounds and is spaced from the exterior of the permeable body. The housing has an inlet for a second fluid and an outlet for a mixture of the first and second fluid. A baffle or baffles are provided in the space between the exterior of the permeable body and the housing, and to define a mixing channel in space between the exterior of the permeable body and the housing so that the second fluid can enter the housing inlet and flow through the mixing channel to the outlet, while picking up fluid on the exterior of the permeable body.

Description

  • This application is a divisional application of U.S. patent application Ser. No. 15/051,352, entitled, “Solvent Extraction and Stripping System” filed Feb. 23, 2016, the entire disclosure of which is incorporated herein by reference.
    • FIELD OF THE INVENTION
  • The present invention relates solvent extraction and stripping systems, i.e. methods and apparatus. The invention has particular utility in connection with the processing of solutions containing metals, such as, for example, the production of copper by solvent extraction of copper containing solutions followed by electrowinning of a rich copper electrolyte obtained by stripping copper from a copper containing solvent, and will be described in connection with such utility, although other utilities are contemplated.
    • DESCRIPTION OF RELATED ART
  • In many industries it often is useful to disperse a first fluid of one type in a second fluid of a different type. For example, carbon dioxide gas is dispersed (dissolved) in water to form carbonated water. In another example, liquid-liquid extraction (where two mutually insoluble liquids contact each other) is used to produce pharmaceuticals and other chemicals, treat water, process food, and recover metals from ore. For example, the mining industry has used liquid-liquid ion exchange for many years to recover metal from aqueous leaching solutions, such as described in U.S. Pat. No. 5,196,095 to Sudderth et al, and U.S. Pat. No. 4,683,310 to Dalton et al. Liquid-liquid ion exchange has also been used for years to recover dissolved copper from etching solutions, such as described in U.S. Pat. No. 3,705,061 to King, in accordance with a recovery process such as that disclosed in U.S. Pat. No. 5,466,375 to Galik. Each of the four patents mentioned above are incorporated herein by reference.
  • The four classes of extractants typically employed in the industry are:
      • 1. Chelation Extractants
      • 2. Ion Pair Extractants
      • 3. Neutral or Solvating Extractants
      • 4. Organic Acid Extractants
        These extractants are compared in Tables 1 to 4 below:
  • TABLE 1
    Chelation Extractants
    EXTRACTANT CLASS CHELATING AGENTS
    FORMULA OR STRUCTURE
    Figure US20180282887A1-20181004-C00001
    EXTRACTION CHEMISTRY
    Figure US20180282887A1-20181004-C00002
    MODIFIERS ALCOHOLS, PHENOLS, ESTERS (TXIB)
    KETOXIMES/ALDOXIME MIXTURES
    SPECIAL FEATURES
    Main commercial extractants for copper
    Operate on hydrogen ion cycle. Stripping is reverse of extraction
    Function with acid and ammoniacal leach solutions
    More selective than other extractant classes
    Kinetically slower than ion pair extractants
    Have good physical properties in terms of phase separation, low aqueous solubility, chemical stability
    Relatively expensive to manufacture
  • TABLE 2
    ION-PAIR EXTRACTANTS
    EXTRACTANT CLASS ION-PAIR EXTRACTANTS
    FORMULA OR STRUCTURE
    Quaternary Amines R3R′N+Cl−
    Primary Amines RNH2
    Secondary Amines R2NH
    Tertiary Amines R3N
    Trialkyl Guanidines
    EXTRACTION CHEMISTRY-QUATERNARY AND TERTIARY
    AMINES
    Figure US20180282887A1-20181004-C00003
    Figure US20180282887A1-20181004-C00004
    MODIFIERS ISODECANOL OR TRIDECANOL,
    AROMATIC DILUENT
    SPECIAL FEATURES
    Commercial extractants for uranium, thorium, vanadium, gold, cobalt
    and other metals
    Modifiers promote solubility of the extractant-metal complex in the
    diluent
    Kinetics, both extraction and stripping are fast
    Extraction is usually of a metal anion complex such as Au(CN)2 −
    or UO2(SO4)3 4−
    Selectivity is not high. Other anions can compete with the metal
    being extracted
    Stripping can be ion exchange for all types or deprotonation for
    primary, secondary and tertiary amines and trialkylguanidines
    Tertiary amines and trialkylguanidines are more selective than
    primary and secondary amines
    For all except quaternary amines, extraction must be at pH below
    the pkb of the extractant
    Selectivity can be pH dependent
    Primary, secondary and tertiary amines are relatively simple to
    produce
  • TABLE 3
    NEUTRAL OR SOLVATING EXTRACTANTS
    EXTRACTANT CLASS NEUTRAL OR SOLVATING
    EXTRACTANTS
    FORMULA OR STRUCTURE
    Tri Octyl Phosphine Oxide R3P = O R = CH3 and (CH3)2CHCH2
    (TOPO)
    Tri Butyl Phosphate (TBP) (RO)3PO
    Ketones (MIBK) R2CO
    Alcohols ROH
    EXTRACTION CHEMISTRY
    Extraction is by adduct formation
    Figure US20180282887A1-20181004-C00005
    Stripping is with concentrated HNO3
    SPECIAL FEATURES
    TBP is used extensively in nuclear fuel reprocessing
    Kinetically fast
    Extract neutral metal complexes
    Selectivity is low
    Organometallic complex must be organic soluble
  • TABLE 4
    ORGANIC ACID EXTRACTANTS
    EXTRACTANT CLASS ORGANIC ACID EXTRACTANTS
    FORMULA OR STRUCTURE
    Phosphinic Acids R3 P(O)OH
    Sulphonic Acids R SO2OH
    Carboxlic Acids R3C—COOH, Versatic Acid
    Phosphoric Acids (C4H9CH(C2H5)CH2O)2 POOH,
    D2EHPA
    EXTRACTION CHEMISTRY
    Figure US20180282887A1-20181004-C00006
    SPECIAL FEATURES
    Phosphinic acids are widely used for cobalt extraction
    Versatic acids can be used for Cu and Ni extraction
    D2EHPA extracts a wide range of metals
    Operate on a hydrogen ion cycle but do not display hydrogen ion
    stoichiometry. Often between 1 and 2 moles of extractant are
    required for each mole of hydrogen produced during extraction.
    This is because adduct formation is also involved in the extraction
    Selectivity is poor and careful pH control may be required to
    achieve reasonable selectivity
  • By way of example, in the recovery of copper, copper ore, typically a copper oxide ore or other copper source, is formed into a particulate mass, a so-called “heap” and a leaching solution trickled over and through the heap to dissolve copper in the ore, forming a copper containing solution. The leachant typically is a weak solution of sulfuric acid and usually is obtained as a recycle stream from a downstream process step such as a raffinate stream from an organic copper extraction step. The copper-rich weakly acidic aqueous solution typically is referred to as a pregnant leach solution (PLS) and is mixed with an organic solvent in a mixer. The organic solvent, which is substantially immiscible in the aqueous solution, extracts copper from the pregnant leach solution to form what is commonly termed a loaded organic stream. The mixture comprising the pregnant leach solution and organic extractant are then transferred to a settler tank where the organic phase and aqueous phases are allowed to separate to form an upper, copper loaded organic phase and a lower, copper depleted acidic aqueous phase called a “raffinate phase”.
  • The lower aqueous raffinate phase is removed from the settler tank and typically is recycled and used as a leachant to leach more copper from the ore in the heap. The loaded organic phase is transferred to a second mixer and mixed with lean electrolyte which is obtained from a downstream electrowinning cell. The mixture is transferred to a second settler and the organic and aqueous phases allowed to separate. The lean electrolyte which typically is a highly acidic sulfuric acid stream extracts the copper from the loaded organic phase and forms a rich copper electrolyte aqueous phase. The rich copper electrolyte aqueous phase is fed to an electrowinning cell to form the copper product. Depleted electrolyte from the electrowinning cell termed “lean electrolyte” is recycled and the stream mixed with the loaded organic phase in the mixer and settler to extract more copper from the loaded organic phase. In the mixer/settler operations the loaded organic phase which is now largely depleted of the extracted copper typically is termed the “stripped organic phase” and this phase typically is recycled to the first mixer to contact and extract more copper from new pregnant leach solution.
  • In a typical prior art copper solvent extraction-electrowinning process, there are a number of process streams which are either recycled or used in subsequent steps of the process. Because of the nature of the mixer and settler operations and the physical and chemical characteristics of the process streams, these process streams typically contain entrained liquids which are detrimental to subsequent steps or recycle steps or which may be lost in the process causing a significant replacement cost and/or environmental problem. For example, when the raffinate stream is recycled and used to leach more copper ore, entrained organic solvent, typically kerosene, will be lost in the leaching operation adding a make-up expense to the process economics and also creating environmental and other process problems including safety hazards. Similarly, entrained water in the loaded organic phase decreases the efficiency of stripping copper from the loaded organic phase in the stripping step of the process and adds to the load on the mixer and stripper. This entrained water also transfers undesirable contaminates from the leach solution to the stripping solution or electrolyte.
  • In U.S. Pat. No. 4,874,534 an improved method of separating organic solvents from aqueous process streams is disclosed in connection with a copper solvent extraction/electrowinning process. Aqueous solutions such as a raffinate process stream having droplets of an organic solvent entrained therein are fed into the upper part of a vertically extending vessel having air bubbles rising therein from an air inlet near the bottom of the vessel. The entrained organic solvent in the raffinate is collected and removed from the top of the vessel and recycled in the process.
  • U.S. Pat. Nos. 4,269,676, 4,272,492 and 5,176,802 show typical solvent extraction processes for recovering copper from copper sulfide ores, waste products from the pyrometallurgical processing of copper ores and copper containing acidic chloride solutions.
  • See also U.S. Pat. No. 5,849,172 in which is disclosed a method of removing entrained liquids from liquid process streams obtained in a copper solvent extraction electrowinning process wherein a copper containing pregnant leach solution is mixed with an immiscible organic extractant to extract the copper from the pregnant leach solution to form an aqueous raffinate process stream and a copper loaded organic process stream. The loaded organic stream then is mixed with an aqueous acidic stream, to extract copper from the loaded organic stream to produce a stripped organic extractant process stream and a copper rich aqueous electrolyte process stream which aqueous electrolyte process stream is fed into an electrowinning cell and copper produced by electrowinning, the method comprising feeding one or more of the liquid process streams to one or more cyclones to remove entrained water or entrained organic extractant from the stream before the stream is used further in the process.
  • The above prior art processes and other prior art processes are somewhat inefficient, due to inefficient mass transfer, necessitating large volumes of organic extractant/solvent during the extraction process, and use of open tanks with long residence time resulting in large amounts of organic extractant/solvent being lost to the atmosphere. The loss of organic extractant/solvent is both costly, and creates environmental and safety hazards.
    • SUMMARY OF THE INVENTION
  • The present invention overcomes the aforesaid and other problems of the prior art, by providing, in one aspect, is a unique micro dispersion device, which significantly improves mass transfer and thus stage efficiency. The micro dispersion device of the present invention can create different dispersed phase droplet sizes and thus an optimum droplet size can be determined for a specific application. Optimum droplet sizes are determined to maximize mass transfer as well as maximizing phase separation efficiency. A disadvantage of prior art liquid-liquid ion exchange systems for dispersing one liquid in another is that air bubbles are entrained during the dispersing step. The entrained air interferes with material transfer and with coalescensce of the dispersed liquid, and delays separation of the two liquids. Our micro dispersion device avoids the formation of air bubbles as one liquid is dispersed in the other, thus providing a more efficient recovery of the desired material. Our micro dispersion device also allows the dispersion of a specific phase independent of phase volume or flow ratio. Thus, in a system where the organic to aqueous (O/A) ratio is for example, 4:1, the organic phase can be dispersed using our micro dispersion device without having to recycle the aqueous phase. Our micro dispersion device produces a more uniform distribution of droplet sizes within the continuous phase compared to heretofore existing phase mixing devices available.
  • The micro dispenser device controls which solution phase is dispersed and which solution phase is continuous. Conventional prior art mixers do not control the dispersed or continuous phase but rather the solution flow to the mixer controls this parameter. It follows that regardless of which solution has the overall larger volume, the micro dispenser device of the present invention does not require the larger solution volume (or a recycle on the lower solution volume) to ensure a continuous phase for the mixer. This provides the operator with more operational flexibility and avoids the costs of recycling a lower volume solution which needs to be the continuous phase.
  • A further advantage associated with the control of the dispersed phase through the use of the micro dispenser device is that entrainment can be reduced. Entrainments, as general principle, in the dispersed phase is much less than entrainment in the continuous phase.
  • Additionally, the micro dispenser device of the present invention ensures the optimum droplet size is created for the dispersed phase which leads to improved mass transfer and improved stage efficiency.
  • The micro dispenser device of the present invention also ensures a uniform droplet size which will improve phase separation.
  • The micro dispenser device of the present invention is a closed system, which does not introduce air into the system. This reduces the formation of a third (air) phase into the settler or centrifuge and thus improves phase separation. Additionally, the reduction or elimination of air in the system will reduce the degradation of organic as well as lessening organic/solvent losses.
  • In another aspect we provide a unique centrifuge separator, which allows high phase separation efficiency due to the high ‘g’ force created in a rotating bowl. The centrifuge separator of the present invention has a lower cost compared to other centrifugal extractors and separators. The economical design and manufacturing techniques allows the use of a centrifugal separator in, for example, hydrometallurgical solvent extractors operations. Currently available centrifugal contactors and separators are too costly and are uneconomical to use in most solvent extractors operations. Our centrifuge separator offers the advantages over other currently available process equipment such as low hold-up, low residence time, and low organic/solvent inventory. The rotating bowl of our centrifuge separator imparts the liquid in a practically rigid body rotation. The inner surface of the rotating liquid has almost a vertical shape because of the high ‘g’ force. The dispersion entering at the bottom gets separated as it moves upward. The rate of separation depends upon the drop size distribution, their settling velocities under the centrifugal action (rΩ2)—where r is the radius of the centrifuge bowl and Ω is the rotational speed, plus densities, viscosities and coalescing behavior of the two phases. For complete separation, adequate height needs to be provided for a given level of centrifugal action—(rΩ2). The outlet ports at the top are positioned in such a way that only very clean light and heavy phases exit the unit after separation.
  • The design of our centrifuge separator is unique. These design techniques eliminate or significantly reduce the shortcomings found in existing centrifugal based systems. Our centrifuge separator (with or without our micro dispenser device) is designed so the entering flow does not contain, or contains very little, entrained air. Feed pipes and the separation chamber are occupied essentially 100% by liquid. This avoids air entrainment, which increases phase separation times. This also eliminates a third phase in the centrifuge chamber—thus increasing the volume occupied by the liquids and hence increasing residence times compared to existing centrifuge designs of the same size.
  • Moreover, our centrifuge separator, which is significantly less expensive to make. This makes the use of a centrifuge separator much more economically viable.
  • Furthermore, the rotational speed of our centrifugal separator is independent of the mixing step. In conventional centrifugal based extraction systems, the mixer is operated at the same speed as the separating bowl. Thus the mixing operation is dependent on the separation RPM and vice versa. Mixing and separation are two discrete operations and should be independent. Our centrifugal separator, is totally separate from the mixing operation.
  • Finally, unlike conventional settlers, in our system separation of the phases occurs within a closed system. A closed system greatly reduces, if not eliminates VOC emissions as well as organic/solvent losses due to evaporation.
  • Working together, our micro dispersion device and our centrifuge separator significantly improve mass transfer and stage efficiency, while at the same time, improve separation and reduce entrainment losses all at a lower cost than conventional solvent extraction systems and existing centrifuge systems. Moreover, our solvent extraction system is an essentially closed solvent extraction system, which minimizes organic solvent loss from evaporation. By way of example, as applied to production of copper by solvent extraction, in accordance with present invention, we provide a solvent extraction process in which an aqueous based leach solution is mixed with an immiscible organic solvent that is passed through a permeable or porous body, forming micro dispersed droplets of the organic solution in a continuous aqueous phase solution. The resulting dispersion is then passed through a centrifugal separator.
  • More particularly, in one aspect the present invention provides a micro dispersion apparatus for mixing of two liquids of different densities which liquids are substantially insoluble in one another, said apparatus comprising a hollow permeable body having a recess for receiving a first fluid which can flow from the recess through the permeable body to an exterior of the permeable body; a housing surrounding and spaced from the exterior of the permeable body, said housing having an inlet for a second fluid and an outlet for a mixture of the first and second fluid; and a baffle or baffles in the space between the exterior of the permeable body and the housing, the baffle or baffles being spaced to define a mixing channel in the space between the exterior of the permeable body and the housing so that the second fluid can enter the housing inlet and flow through the mixing channel to the outlet, while picking up fluid on the exterior of the permeable body.
  • In one embodiment, wherein the mixing channel is substantially in the shape of a helix, or the baffle is formed of a series of elongated segments formed end-to-end.
  • In one embodiment, the permeable body has pores in the range of 0.2 to 400 microns, preferably 20 to 200 microns, more preferably 60 to 100 microns.
  • The micro dispersion device is similar to the device described in our prior U.S. Published Application US 2003/0029795 A1. However, unlike the micro dispersion device described in our prior U.S. Published Application US 2003/0029795 A1, the permeable body is filed, at least in part, with loosely packed finely divided media or frits.
  • The present invention also provides an apparatus for separating and recovery of a metal such as copper from a metal-containing source such as a copper-containing source by a solvent extraction/electrowinning process, comprising a mixing device for mixing a metal-containing aqueous solution and an immiscible organic extractant, wherein the mixing device comprises apparatus as above described, the apparatus further comprising a centrifugal separator, and a mixing conduit connecting the mixing device with a centrifugal separator.
  • In one embodiment, the mixing conduit is sized and shaped to provide a travel or residence time between the mixing device and the centrifugal separator of 5-120 seconds, preferably 20-60 seconds, more preferably 35-45 seconds.
  • In one embodiment, the centrifugal separator separates the mixture into two streams, a heavy phase and a light phase, the heavy phase comprising primarily an aqueous phase containing copper, said apparatus further comprising a conduit carrying the heavy phase to an electrowinning stage.
  • In another embodiment, the apparatus further comprises a conduit carrying the light phase conduit to the mixing device.
  • The invention also provides a method for separating a mixture of a first and a second fluid of different densities, which fluids are substantially insoluble in one another, said method comprising providing an apparatus as above described, flowing the first fluid from an interior of the permeable body to an exterior of the permeable body; and contacting the first fluid on the exterior of the permeable body with the second fluid.
  • In one embodiment, the permeable body has pores in the range of 0.2 to 400 microns, preferably 20 to 200 microns, more preferably 60 to 100 microns.
  • In another embodiment of the method the permeable body is filled, at least in part, with loosely packed finely divided media or flits, and including the step of flowing the first fluid through the media or flit.
  • In one aspect of the invention, as applied specifically to processing of copper sulfate, the aqueous based solution compromises an aqueous acid solution, while the organic solution comprises an organic solvent, such as kerosene.
  • The present invention also provides a method for separating and recovery of metals such as copper from a metal-containing source by a solvent extraction electrowinning process, comprising providing a copper-containing aqueous solution and an immiscible organic extractant to a mixing device, wherein the mixing device comprises an apparatus as above described; whereupon the organic extractant is dispersed in the copper-containing aqueous solution and extracts metal from the aqueous solution, passing the resulting dispersion through a mixing conduit to a centrifugal separator, and separating the organic extractant containing metal from the aqueous solution.
  • In one embodiment, the mixing conduit is sized and shaped to provide a travel or residence time between the mixing device and the centrifugal separator of 5-120 seconds, preferably 20-60 seconds, more preferably 35-45 seconds.
  • In another embodiment of the method, the centrifugal separator separates the mixture into two streams, a heavy phase and a light phase, the heavy phase comprising primarily an aqueous phase containing copper; including the steps of passing the heavy phase to an electrowinning stage.
  • Yet another embodiment of the method includes the step of returning the light phase, at least in part, to the mixing device.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • Further features and advantages of the present invention will be seen from the following detailed description, taken in conjunction with the accompanying drawings, wherein like numerals depict like parts, and wherein:
  • FIG. 1 is flow diagram of a system for the hydrometallurgical production of a metal such as copper in accordance with one aspect the present invention;
  • FIG. 1A is a side elevational view, in cross section, showing details of an apparatus for dispersing an organic fluid such as kerosene into an aqueous-based solution in accordance with another aspect of the present invention;
  • FIG. 2 is a side elevational view, in cross section, of a centrifugal contactor-separator employed in accordance with the present invention;
  • FIG. 2A is a cross-sectional view of the rotating cylinder portion of the centrifugal contractor—separator of FIG. 2; and
  • FIG. 3 is a flow diagram, similar to FIG. 1, of an alternative system for the hydrometallurgical production of a metal such as copper in accordance with the present invention.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • The invention will now be described in connection with the production of copper from a copper-containing ore. Referring first to FIGS. 1 and 1A, a copper containing pregnant leach solution (PLS) 10 from a copper oxide ore heap 12, is fed to a first mixing vessel 14A where the pregnant leach solution is mixed with an organic liquid extractant such as a hydroxyl oxime ion exchanger in kerosene supplied from tank 16. Referring in particular to FIG. 1A, mixing vessel 14A comprises an elongate cylindrical housing 18 having an inlet 20 at one end, and an outlet 22 at the other end. A permeable body 24 in the shape of a cylindrical tube is coaxially disposed within the cylindrical housing 18. However, housing and permeable body 24 need not be cylindrical—they may be square, or rectangular or have other geometric shapes in cross-section. The permeable body 24 is connected to the housing inlet 20 at one end 26, and a disc 28 closes the end of permeable body 24 adjacent the housing outlet 22.
  • The outer wall of permeable body 24 is spaced from the interior wall of housing 18. A helical baffle 30 is located within the annular space between the outer wall of permeable body 24 and the inner wall of housing 18. Baffle 30 may be a continuous elongated helical strip or formed as a series of segments. Mixing vessel 14A also has a lateral inlet 32 adjacent the inlet 20 end.
  • Permeable body 24 can be made of permeable or porous metal, and is filled with loosely packed finely divided media or frits such as powdered metal particles or ceramic particles. Various permeable and porous metals are available commercially from a variety of vendors including Mott Metallurgical Corporation of Farmington, Conn. The permeable or porous metal used in this invention preferably has substantially uniform pore sizes, or at least most of the pores are within an acceptable range for the intended purpose, and typically are in the range of 0.2 to 400 microns, preferably 20 to 200 microns, more particularly 60 to 100 microns. The porous media or flits should be inert to the liquids being handled. For example, the media or flits can be made of particles of ceramic, or stainless steel, Nickel 200, MONEL® nickel-copper alloy 400, INCONEL® nickel-chromium alloy 600, HASTELLOY® nickel-molybdenum-chromium alloy C276, Alloy 20, gold, platinum, silver, and titanium. As will be described below, the media or flits, by their nature, cause the droplets of the organic solvent to finally divide, dispersing fine droplets on the outer surface of the permeable body 24, where they are picked up by the PLS.
  • In use, the organic liquid extractant in kerosene is introduced through inlet 20 into the interior of permeable body 24. PLS is introduced into the interior of mixing vessel 14A through lateral inlet 32, into the space between the outer wall of permeable body 24 and the inner wall of mixing vessel 14A. The organic liquid extractant is forced through the permeable body 24 and emerges from the permeable body in the form of a fine organic liquid extractant droplets where the droplets are picked up by the flowing PLS, forming a dispersion of kerosene droplets in the PLS. The PLS preferably is flowed under turbulent conditions so that the droplets of the organic liquid extractant are quickly dispersed before having an opportunity to coalesce. The organic liquid extractant, which is substantially immiscible with the aqueous based PLS solution, extracts copper from the pregnant leach solution, and emerges from the mixing vessel 14A via outlet 22.
  • Alternatively, the PLS may be introduced into the interior of permeable body 24, and the organic liquid extractant introduced into the interior of the mixing vessel 14A through lateral inlet 32, into the space between the outer wall of permeable body 24 and the inner wall of mixing vessel 14A. In such case, the PLS is forced through the permeable body 24, and emerges from the permeable body in the form of fine droplets which are picked up by the flowing organic liquid extractant, forming a dispersion of aqueous droplets in the kerosene.
  • The solution emerging from outlet 22 is passed via conduit 34A to an extract stage centrifugal separator 100A as will be described in detail below. Conduit 34A includes inline baffles shown in phantom as 98A for maintaining the fluid in a mixed condition. Conduit 34A is sized and shaped relative to the flow of fluid from mixing vessel 14A to provide a travel or residence time sufficient to permit substantial mass transfer of copper in the aqueous solution to the organic liquid extractant. Ordinarily, a residence time of 5-120 seconds, preferably 20-60 seconds, more preferably 35-45 seconds, is sufficient before the fluid is introduced into a centrifugal separator 100A. Alternatively, one or more loops may be included in the conduit 34A, or the cross sectional size of the conduit 34A increased so that the flow from mixing vessel 14A is controlled to within the target residence time of 5-120 seconds.
  • As will be described below, centrifuge separator 100A creates two exit streams—a light phase (organic) and a heavy phase (aqueous raffinate). The aqueous raffinate is recycled to the leach heap to dissolve more copper. The organic phase exiting the centrifuge 100A is transferred to another mixing vessel 14B, similar to mixing vessel 14A, where it is mixed with lean electrolyte from the electrowinning stage 60 as will be discussed below. As before, the organic liquid extractant is forced through the permeable body 24 contained in mixing vessel 14B, and emerges from the permeable body in the form of a fine organic liquid extractant droplets where the droplets are picked up by the flowing electrolyte, forming a dispersion of kerosene droplets in the electrolyte. As before, the electrolyte preferably is flowed under turbulent conditions so that the droplets of the organic liquid extractant are quickly dispersed before having an opportunity to coalesce. The electrolyte or stripping solution, which is substantially immiscible with the organic liquid extractant removes (strips) copper from the organic liquid extractant and emerges from the mixing vessel 14B, where it is passed via conduit 34B which also contains inline baffles shown in phantom as 98B, similar to conduit 34A, for maintaining the fluid in a mixed condition. As before, conduit 34B is sized and shaped relative to the flow of the fluid from mixing vessel 14A to provide a travel or residence time sufficient to permit substantial mass transfer of copper in the aqueous solution to the organic liquid extractant. The fluid then passed to a second strip stage centrifuge 100B which is similar in construction to centrifuge 100A as will be described in detail below, and in which a light organic phase is partially stripped of copper and returned to tank 16, and a rich copper electrolyte phase is passed to an electrowinning cell 60.
  • Referring in particular to FIG. 2, there is shown centrifugal separator 100A. However, centrifugal separator 100B is essentially the same. Centrifugal separator 100A, which is similar to the centrifugal separator described in our prior U.S. Pat. No. 6,440,054, comprises a rotatable cylinder 102 in the shape of a vertical right cylinder contained in a housing 104 having vertical side wall 106 bottom wall 108 and top wall 109. A vertical drive shaft 112 is suspended at the upper end of housing 104 by an upper thrust bearing. Centrifugal separator 100A has an inlet 116 for input of an organic/aqueous mixed phase, i.e., from conduit 34A. The solution enters the central opening (orifice) 140 of the rotating cylinder 102. The dispersion entering central orifice 140, gets deflected towards the outside wall of the cylinder by a horizontal deflecting baffle 142 provided close to the entrance. Referring also to FIG. 2A, unlike the centrifugal separator described in our aforesaid U.S. Pat. No. 6,440,054, the mixing box at the bottom of the centrifugal separator is eliminated, and the upper end of rotating cylinder 102 provided with a plurality of vertical baffles 146 which create several chambers ranging from 4 to 8. In a preferred embodiment, we create four (4) chambers. The rotating cylinder 102 imparts to the liquid a practically rigid body rotation. The inner surface of the rotating liquid has almost a vertical shape because of high ‘g’ except a small parabolic portion adjacent the bottom. The dispersion entering at the bottom region 148 gets separated as it moves upwards. The rate of separation depends upon the droplet size distribution, their settling velocities under the centrifugal action (rΩ2), where r is the radius of the bowl/chamber and Ω is the rotation speed), densities, viscosities and coalescing behavior of the two phases. For complete separation, adequate height needs to be provided for a given level of (rΩ2). Inside the bowl/chamber the solution is separated into two phases—a light phase which is discharged through the ports 144 and exits the unit through the top port 110, and a heavy phase which is discharged through outlet ports 156 and leaves the unit through outlet 158. The heavy phase outlet ports 156 have variable positions which are selected and changed according to the relative flow rates of the heavy and light phases and the relative volumes of each phase within the centrifugal separator 100A.
  • FIG. 3 shows an alternative embodiment of the invention. The FIG. 3 embodiment includes two mixing vessels 14A1 and 14A2, and 14B1 and 14B2 for both the extract stage as well as the strip stage connected through valving and conduits 10A, 10B, 34A, 34B, so that one mixing vessel may remain in service, while the other mixing vessel is taken off line for maintenance or cleaning.
  • The present invention provides various advantages over prior art processes. For one, the system is closed. Thus, loss of organic solvent, i.e. due to evaporation is avoided. Also, by passing the organic phase through finely divided media or frits, and a permeable body before the organic phase is mixed with the PLS, a micro dispersion of the organic phase is formed in the PLS. Thus, less organic solvent is needed in the overall process. Also, higher throughput may be achieved with smaller equipment overall, thus adding to equipment savings, as well as operational savings.
  • Also, from studies and tests we found that entrainment of the organic phase in the aqueous is generated in the mixing step and not influenced by the separator. The quantity of entrainment is substantially effected by air ingestion. Using the hollow permeable body mixing apparatus as above described greatly reduces the possibility of air entrainment in the liquid and thus improves separation in the downstream separator (any separator for that matter).
  • Also, if air is excluded from the dispersion in the mixer, then organic-in-aqueous entrainment is minimized and aqueous-in-organic entrainment essentially reduced essentially to undetectable levels. Thus, our mixing apparatus as above described allows for a reduction, if not essentially elimination of air entrainment in the liquid thus reducing entrainment of one phase in the other phase. Conventional prior art mixing devices cannot achieve this since by design conventional mixing systems are exposed to the atmosphere and draw air into the liquid.
  • Various changes may be made in the above invention without the departing from the spirit and scope thereof. While the recovery of copper by electrowinning (post solvent extraction) has been described in the above working example, recovery of other metals, or other post-solvent extraction steps are possible. By way of example, Uranium may be recovered as ‘yellow cake’ (approximately 80% U3O8) by precipitation and calcining of ammonium uranyl sulfate. Also, some recovery systems employ crystallization to create a nickel sulfate or copper sulfate crystal. And, while electrowinning creates 99.99+ pure copper at the cathode, other metals, for example, zinc, are also electrowon. And some operations also use spray drying technology to create a metal salt dust. Still other changes including recovery of other metals including, but not limited to zinc, nickel, cobalt and uranium, using appropriate extractants, e.g. as above described, are possible.

Claims (5)

1. A centrifugal separator, comprising a rotatable tank in the shape of a vertical right cylinder in a housing, at least one inlet adjacent a lower end of the housing and a plurality of outlets adjacent an upper end of the housing, and wherein an upper end of the rotatable tank is provided with a plurality of vertical baffles which create a plurality of chambers in the upper end of the rotatable tank.
2. The centrifugal separator as claimed in claim 1, further including one or more additional inlets between the inlet adjacent the lower end of the housing and the outlets.
3. The centrifugal separator as claimed in claim 1, wherein the plurality of outlets adjacent the upper end of the housing have variable positions.
4. The centrifugal separator as claimed in claim 1, wherein the upper end of the rotatable tank is divided into four to eight chambers.
5. The centrifugal separator as claimed in claim 1, wherein the upper end of the rotatable tank is divided into four chambers.
US16/001,830 2016-02-23 2018-06-06 Solvent extraction and stripping system Abandoned US20180282887A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/001,830 US20180282887A1 (en) 2016-02-23 2018-06-06 Solvent extraction and stripping system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15/051,352 US9994962B2 (en) 2016-02-23 2016-02-23 Solvent extraction and stripping system
US16/001,830 US20180282887A1 (en) 2016-02-23 2018-06-06 Solvent extraction and stripping system

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US15/051,352 Division US9994962B2 (en) 2016-02-23 2016-02-23 Solvent extraction and stripping system

Publications (1)

Publication Number Publication Date
US20180282887A1 true US20180282887A1 (en) 2018-10-04

Family

ID=59629742

Family Applications (2)

Application Number Title Priority Date Filing Date
US15/051,352 Expired - Fee Related US9994962B2 (en) 2016-02-23 2016-02-23 Solvent extraction and stripping system
US16/001,830 Abandoned US20180282887A1 (en) 2016-02-23 2018-06-06 Solvent extraction and stripping system

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US15/051,352 Expired - Fee Related US9994962B2 (en) 2016-02-23 2016-02-23 Solvent extraction and stripping system

Country Status (9)

Country Link
US (2) US9994962B2 (en)
CN (1) CN109312241A (en)
AR (1) AR107713A1 (en)
AU (1) AU2017223707A1 (en)
BR (1) BR112018017346A2 (en)
CL (1) CL2018002412A1 (en)
EC (1) ECSP18071821A (en)
MX (1) MX2018010157A (en)
WO (1) WO2017147313A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190184313A1 (en) * 2017-12-15 2019-06-20 Minextech Llc Method and apparatus for separating insoluble liquids of different densities
US20190233959A1 (en) * 2018-01-26 2019-08-01 Minextech Llc Extraction and recovery of lithium from brine
JP2022041565A (en) * 2020-09-01 2022-03-11 株式会社神戸製鋼所 Phase separator, phase separation system with the same and phase separation method
JP7394731B2 (en) * 2020-10-02 2023-12-08 株式会社神鋼環境ソリューション extraction system
CN113373310B (en) * 2021-06-08 2023-04-11 安徽惠宏科技有限公司 Uniform nickel sulfate extraction equipment based on waste battery metal recovery process

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB405349A (en) * 1931-08-08 1934-02-08 Richard Leiser Process of and apparatus for treating a liquid with a second liquid that is not miscible therewith
US3705061A (en) 1971-03-19 1972-12-05 Southern California Chem Co In Continuous redox process for dissolving copper
CH615360A5 (en) * 1977-03-08 1980-01-31 Chemap Ag Appliance in a recycle reactor for admixing liquids with gases
PL117268B1 (en) 1978-07-26 1981-07-31 Politechnika Gdanska Method of recovery of copper and accompanying metals from sulphide ores,post-flotation deposits and waste products in metallurgical processing of copper oresiz sernistykh rud,flotacionnykh osadkov i iz proizvodstvennykh otchodov metallurgicheskojj pererabotki mednykh rud
US4272492A (en) 1979-05-31 1981-06-09 Jensen Wayne H Selective extraction and recovery of copper
DE3037898A1 (en) 1980-10-07 1982-05-06 Bruker Analytische Meßtechnik GmbH, 7512 Rheinstetten MIXING CHAMBER
EP0057797B1 (en) 1981-02-03 1986-06-25 Imperial Chemical Industries Plc Process for the extraction of metal values and novel metal extractants
US4595571A (en) 1984-09-05 1986-06-17 Galik George M Liquid-liquid extractor and method for using same
US4874534A (en) 1988-01-11 1989-10-17 Magma Copper Company Method for removal of organic solvents from aqueous process streams
US5196095A (en) 1990-04-03 1993-03-23 Henkel Corporation Process for recovering a metal from an aqueous solution comprising a mixture of metal chlorides
US5176802A (en) 1991-07-19 1993-01-05 Willem P. C. Duyvesteyn Treatment of copper sulfide concentrates
GB9226129D0 (en) * 1992-12-15 1993-02-10 Baker Salah A A process vessel
US5466375A (en) 1993-07-21 1995-11-14 Galik; George M. Liquid-liquid extraction
US5849172A (en) 1997-06-25 1998-12-15 Asarco Incorporated Copper solvent extraction and electrowinning process
US6440054B1 (en) 2000-09-18 2002-08-27 George M. Galik Apparatus for liquid-liquid extraction
US20030029795A1 (en) 2001-08-07 2003-02-13 Galik George M. Apparatus and methods for dispersing one fluid in another fluid using a permeable body
WO2012086685A1 (en) * 2010-12-22 2012-06-28 独立行政法人国立高等専門学校機構 Fluid mixer and fluid mixing method
US9771279B2 (en) * 2015-03-31 2017-09-26 General Electric Technology Gmbh Foam intercept system

Also Published As

Publication number Publication date
CL2018002412A1 (en) 2019-01-18
CN109312241A (en) 2019-02-05
US9994962B2 (en) 2018-06-12
AU2017223707A1 (en) 2018-10-11
ECSP18071821A (en) 2019-08-30
BR112018017346A2 (en) 2018-12-26
US20170241028A1 (en) 2017-08-24
WO2017147313A1 (en) 2017-08-31
MX2018010157A (en) 2019-01-31
AR107713A1 (en) 2018-05-23

Similar Documents

Publication Publication Date Title
US20180282887A1 (en) Solvent extraction and stripping system
US10512884B2 (en) Process for the recovery of gold from anode slimes
EP2614868B1 (en) Liquid-liquid extraction unit, multistage liquid-liquid extraction apparatus using the unit, and multistage continuous extraction system for rare earth elements
US7507343B2 (en) Mixing and settling method and device in solvent extraction processes to recover high-purity products
US5849172A (en) Copper solvent extraction and electrowinning process
EP0020026A1 (en) Solvent extraction apparatus and process
Morı́s et al. Solvent extraction of molybdenum and tungsten by Alamine 336 and DEHPA in a rotating disc contactor
AU699079B2 (en) Method of recovering extractant
Sole Solvent extraction in the hydrometallurgical processing and purification of metals: process design and selected applications
CN100441261C (en) Method and apparatus for purification of slightly water-soluble organic solution from aqueous entrainment
WO2019148105A1 (en) Extraction and recovery of lithium from brine
CN100558438C (en) Be used for purify aqueous solutions to remove the method and apparatus of extraction solution drop
US6315899B1 (en) Apparatus for separating entrained aqueous from loaded organic in an SX process
US11898222B2 (en) System and method for liquid-organic particle separation
US9145309B2 (en) Phase separation tank
CA1112602A (en) Process and apparatus for mixing and separation in a solvent extraction
US4450144A (en) Ammonium hydroxide stripping of tungsten from organic solvents
US20130153518A1 (en) System and method for liquid-liquid separation
CA2872341C (en) Solvent extraction method for uranium
US20180001230A1 (en) System and method for separating liquid mixtures

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION