US20100224030A1 - Indium recovery by supported liquid membrane with strip dispersion - Google Patents

Indium recovery by supported liquid membrane with strip dispersion Download PDF

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US20100224030A1
US20100224030A1 US12/397,818 US39781809A US2010224030A1 US 20100224030 A1 US20100224030 A1 US 20100224030A1 US 39781809 A US39781809 A US 39781809A US 2010224030 A1 US2010224030 A1 US 2010224030A1
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Prior art keywords
acid
phosphoric acid
strip
phenylphosphonic
indium
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US12/397,818
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Ying-Ling Liu
Da-Ming Wang
Juin-Yih Lai
W.S. Winston Ho
Chung-Ching Lee
Chih-Hsieh Lee
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Chung Yuan Christian University
Solar Applied Material Technology Corp
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Chung Yuan Christian University
Solar Applied Material Technology Corp
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Priority to US12/397,818 priority Critical patent/US20100224030A1/en
Assigned to SOLAR APPLIED MATERIALS TECHNOLOGY CORP., CHUNG YUAN CHRISTIAN UNIVERSITY reassignment SOLAR APPLIED MATERIALS TECHNOLOGY CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LAI, JUIN-YIH, WANG, DA-MING, LIU, YING-LING, LEE, CHUNG-CHING, HO, W.S. WINSTON, LEE, CHIH-HSIEH
Priority to TW98121307A priority patent/TW201032881A/en
Priority to US12/611,910 priority patent/US20100226839A1/en
Priority to US12/873,334 priority patent/US20100329970A1/en
Publication of US20100224030A1 publication Critical patent/US20100224030A1/en
Abandoned legal-status Critical Current

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    • 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
    • C22B58/00—Obtaining gallium or indium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/38—Liquid-membrane separation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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 to the removal and recovery of indium from feed solutions, such as process streams and waste waters, using supported liquid membrane technology.
  • Liquid membranes combine extraction and stripping, which are normally carried out in two separate steps in conventional processes such as solvent extractions, into one step.
  • a one-step liquid membrane process provides the maximum driving force for the separation of a targeted species, leading to the best clean-up and recovery of the species (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992).
  • SLMs supported liquid membranes
  • ELMs emulsion liquid membranes
  • the liquid membrane phase is the organic liquid imbedded in pores of a microporous support, e.g., microporous polypropylene hollow fibers (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992).
  • a microporous support e.g., microporous polypropylene hollow fibers
  • the organic-based SLM is placed between two aqueous solutions—the feed solution and the strip solution where the SLM acts as a selective membrane for the transport of the target species from the feed solution to the strip solution.
  • the organic liquid in the SLM contains an extractant, a diluent which is generally an inert organic solvent, and sometimes a modifier, and it is immiscible in the aqueous feed and strip streams.
  • SLMs have been investigated to remove metals, radionuclides, and rare earth metals from aqueous feed solutions in the scientific and industrial community.
  • the removal of metals, including copper, zinc, cadmium, and palladium, with SLMs has been described (N. Aouad, G. Miquel-Mercier, E. Bienvenue, E. Tronel-Peyroz, G. Jerninet, J. Juillard, and P. Seta, “Lasalocid (X537A) as a Selective Carrier for Cd(II) in Supported Liquid Membranes,” J. Membrane Sci., 139, 167-174 (1998); J. A. Daoud, S. A. El-Reefy, and H.
  • SLMs SLMs
  • the organic phase is contained between the two sets of hollow fibers by maintaining the aqueous phases at a higher pressure than the organic phase.
  • the use of the hollow-fiber contained liquid membrane increases membrane stability, because the liquid membrane may be continuously replenished.
  • this configuration is not advantageous because it requires mixing two sets of fibers to achieve a low contained liquid membrane thickness.
  • an emulsion acts as a liquid membrane for the separation of the target species from a feed solution.
  • An ELM is created by forming a stable emulsion, such as a water-in-oil emulsion, between two immiscible phases, followed by dispersion of the emulsion into a third, continuous phase by agitation for extraction.
  • the membrane phase is the oil phase that separates the encapsulated, internal aqueous droplets in the emulsion from the external, continuous phase (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992).
  • the species-extracting agent is contained in the membrane phase, and the stripping agent is contained in the internal aqueous droplets. Emulsions formed from these two phases are generally stabilized by use of a surfactant.
  • the external, continuous phase is the feed solution containing the target species.
  • the target species is extracted from the aqueous feed solution into the membrane phase and then stripped into the aqueous droplets in the emulsion.
  • the target species can then be recovered from the internal aqueous phase by breaking the emulsion, typically via electrostatic coalescence, followed by electroplating or precipitation.
  • ELMs to remove metals, rare earth metals, and radionuclides from aqueous feed solutions has also been pursued in the scientific and industrial community.
  • the removal of metals including cobalt, nickel, cadmium, mercury, and lead with ELMs has been reported quite a lot in the literature (B. Raghuraman, N.
  • ELMs One disadvantage of ELMs is that the emulsion swells upon prolonged contact with the feed stream. This swelling causes a reduction in the stripping reagent concentration in the aqueous droplets which reduces stripping efficiency. It also results in dilution of the target species that has been concentrated in the aqueous droplets, resulting in lower separation efficiency of the membrane. The swelling further results in a reduction in membrane stability by making the membrane thinner. Finally, swelling of the emulsion increases the viscosity of the spent emulsion, making it more difficult to demulsify.
  • a second disadvantage of ELMs is membrane rupture, resulting in leakage of the contents of the aqueous droplets into the feed stream and a concomitant reduction of separation efficiency.
  • the present invention relates to a process for the removal and recovery of indium from a feed solution using a combined SLM/strip dispersion.
  • the present invention relates to a process for the removal and recovery of indium from a feed solution which comprises the following steps. First, a feed solution containing indium is passed on one side of the SLM embedded in a microporous support material and treated to remove the indium by the use of a strip dispersion on the other side of the SLM.
  • the strip dispersion can be formed by dispersing an aqueous strip solution in an organic liquid, for example, using a mixer.
  • Second, the strip dispersion, or a part of the strip dispersion is allowed to stand, resulting in separation of the dispersion into two phases: the organic liquid phase and the aqueous strip solution phase containing a concentrated indium solution.
  • the continuous organic phase of the strip dispersion readily wets the pores of a microporous support to form a stable SLM.
  • the process of the present invention provides a number of operational and economic advantages over the use of conventional SLMs or solvent extraction.
  • FIG. 1 is a schematic representation of the combined supported liquid membrane/strip dispersion of the present invention for the recovery of indium.
  • FIG. 2 is an enlarged view of the schematic representation of the combined supported liquid membrane/strip dispersion of the present invention for the recovery of indium.
  • FIG. 3 shows the indium concentrations in the feed and strip solutions as a function of time for the feed solution containing 200 ppm In 3+ in pH 1 H 2 SO 4 of 15.5 L.
  • the strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M di(2-ethyl-hexyl)phosphoric acid (D2EHPA) and 2 vol % dodecanol in Isopar-L.
  • D2EHPA di(2-ethyl-hexyl)phosphoric acid
  • FIG. 4 shows the indium concentrations in the feed and strip solutions as a function of time for the feed solution containing about 180 ppm In 3+ in pH 1 HNO 3 of 1 L.
  • the strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M D2EHPA and 2 vol % dodecanol in Isopar-L. Also shown are the indium concentrations in the feed solutions for the original feed solutions containing about 190 ppm In 3+ in pH 1 H 2 SO 4 and 160 ppm In 3+ in pH 1 HCl, all with the same feed volume of 1 L and the same strip dispersion.
  • FIG. 5 depicts the indium concentrations in the feed solutions originally containing about 200 ppm In 3+ in pH 1, 2 wt % H 2 C 2 O 4 as a function of time for 0.2M, 0.6M and 1M D2EHPA concentrations.
  • Each of the strip dispersions was prepared by mixing together 0.1 L (100 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing the specified D2EHPA concentration and 2 vol % dodecanol in Isopar-L.
  • FIG. 6 depicts the indium concentrations in the feed and strip solutions as a function of time for the feed solution containing 200 ppm In 3+ in pH 1, 2 wt % H 2 C 2 O 4 of 15.5 L.
  • the strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M D2EHPA and 2 vol % dodecanol in Isopar-L.
  • FIG. 7 shows the indium concentrations in the feed and strip solutions as a function of time for the ITO feed solution of 15.5 L containing about 140 ppm In 3+ at pH 0.9.
  • the strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M D2EHPA and 2 vol % dodecanol in Isopar-L. Also shown is the tin concentration in the feed solution as a function of time.
  • FIG. 8 depicts the indium concentrations in the feed and strip solutions as a function of time for the residual electrolyte feed solution of 0.5 L containing about 11000 ppm In 3+ at pH 1.
  • the strip dispersion was prepared by mixing together 0. 1 L (100 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M D2EHPA and 2 vol % dodecanol in Isopar-L.
  • both the indium concentration in the strip solution obtained experimentally, i.e., strip-exp, and that calculated from the feed concentration based on the material balance, i.e., strip-ideal (the ideal case) are included.
  • the present invention relates to a process for the removal and recovery of indium from a feed solution, such as waste waters or process streams.
  • This new process employs a combination of a supported liquid membrane (SLM) and a strip dispersion.
  • SLM supported liquid membrane
  • the present invention relates to a process for the removal and recovery of indium from a feed solution which comprises the following steps. First, a feed solution containing indium is passed on one side of the SLM embedded in a microporous support material and treated to remove the indium by the use of a strip dispersion on the other side of the SLM.
  • the strip dispersion can be formed by dispersing an aqueous strip solution in an organic liquid, for example, using a mixer.
  • Second, the strip dispersion, or a part of the strip dispersion is allowed to stand, resulting in separation of the dispersion into two phases: the organic liquid phase and the aqueous strip solution phase containing a concentrated indium solution.
  • the preferred configuration employs a hollow fiber module as the liquid membrane microporous support.
  • hollow fiber modules consist of microporous hollow fibers arranged in a shell-and-tube configuration.
  • the strip dispersion is passed through either the shell side of the module or the tube side of the module, and the aqueous feed solution containing indium for extraction is passed through the opposing side of the module.
  • the use of the hollow fiber system in the combined SLM/strip dispersion process allows constant supply of the strip dispersion as shown in FIG. 1 , ensuring a stable and continuous operation.
  • strip dispersion is defined as a mixture of an aqueous phase and an organic phase.
  • the aqueous phase of the dispersion comprises an aqueous strip solution, while the organic phase comprises an extractant or extractants in an organic liquid.
  • the dispersion is formed by the mixing of the aqueous and organic phases as shown in FIG. 1 . This combination results in droplets of the aqueous strip solution in a continuous organic phase.
  • the dispersion is maintained during the extraction process due to the flow of the dispersion through a membrane module, e.g., a hollow-fiber module.
  • the continuous organic phase of the strip dispersion readily wets the hydrophobic pores of the microporous hollow fibers in the module, forming a stable liquid membrane.
  • FIG. 2 shows an enlarged view of a schematic representation of the SLM with strip dispersion of the present invention.
  • a low pressure, Pa which is typically less than approximately 2 psi, is applied on the feed solution side of the SLM.
  • the pressure Pa is greater than the pressure, Po, on the strip dispersion side of the SLM. This difference in pressure prevents the organic solution of the strip dispersion from passing through the pores to come into the feed solution side.
  • the dispersed droplets of the aqueous strip solution in a typical size of about 80 to about 800 micrometers and are orders of magnitude larger than the pore size of the microporous support employed for the SLM, which is in the order of approximately 0.03 micrometer. Thus, these droplets are retained on the strip dispersion side of the SLM and cannot pass through the pores to go to the feed solution side.
  • the organic membrane solution i.e., the organic phase of the strip dispersion
  • This constant supply of the organic phase ensures a stable and continuous operation of the SLM.
  • the direct contact between the organic and strip phases provides efficient mass transfer for stripping.
  • the organic and strip phases can be mixed, for example, with high-shear mixing, to increase the contact area between the two phases.
  • the mixer for the strip dispersion is stopped, and the dispersion is allowed to stand until it separates into two phases, the organic membrane solution and the concentrated strip solution.
  • the concentrated strip solution containing indium is the product of this process.
  • the feed solution includes, but is not limited to, waste waters or process streams containing indium.
  • microporous support employed in the invention is comprised of, for example, microporous polypropylene, polytetrafluoroethylene, polyethylene, polysulfone, polyethersulfone, polyetheretherketone, polyimide, polyamide, polyaramide, or mixtures thereof.
  • the preferred microporous supports are microporous polypropylene and polytetrafluoroethylene hollow fibers.
  • the aqueous portion of the strip dispersion comprises an aqueous acid solution, such as a mineral acid.
  • aqueous acid solution such as a mineral acid.
  • mineral acids useful in the present invention include, but are not limited to, hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ), and acetic acid (CH 3 COOH).
  • the acid is present in a concentration between about 0.1 M and about 18 M.
  • the preferred concentration for the acid solution is between about 1 M and about 6 M.
  • the continuous organic liquid phase into which the aqueous strip solution is dispersed contains an extractant or extractants.
  • the extractant is capable of extracting indium contained in the feed solution.
  • Typical extractants which are known in the art for extraction of indium from waste waters or process streams may be employed in the present strip dispersion.
  • the extractants include dialkyl phosphoric acids and alkyl phenylphosphonic acids.
  • the dialkyl group of the dialkyl phosphoric acid is paraffinic (saturated) and has from 6 to 26 carbon atoms.
  • the dialkyl phosphoric acids are selected from the group consisting of di(2-ethyl-hexyl)phosphoric acid (D2EHPA), di(2-butyl-octyl)phosphoric acid, di(2-hexyl-decyl)phosphoric acid, di(2-octyl-decyl/2-hexyl-dodecyl)phosphoric acid, di(2-octyl-dodecyl)phosphoric acid, di(hexyl)phosphoric acid, di(heptyl)phosphoric acid, di(octyl)phosphoric acid, di(nonyl)phosphoric acid, di(decyl)phosphoric acid, di(undecyl)phosphoric acid, di
  • the alkyl group of the alkyl phenylphosphonic acid is paraffinic (saturated) and has from 6 to 26 carbon atoms.
  • the alkyl phenylphosphonic acids are selected from the group consisting of 2-butyl-1-octyl phenylphosphonic acid (BOPPA), 2-hexy-1-decyl phenylphosphonic acid, 2-octyl-1-decyl/2-hexyl-1-dodecyl phenylphosphonic acid, 2-octyl-1-dodecyl phenylphosphonic acid, hexyl phenylphosphonic acid, heptyl phenylphosphonic acid, octyl phenylphosphonic acid, nonyl phenylphosphonic acid, decyl phenylphosphonic acid, undecyl phenylphosphonic acid, dodecyl phenylphosphonic acid, tridecyl phenylphosphonic
  • the organic liquid of the present strip dispersion optionally comprises a hydrocarbon solvent or mixture.
  • the hydrocarbon solvent or mixture has a number of carbon atoms per solvent molecule ranging from 6 to 18, preferably from 10 to 14.
  • the hydrocarbon solvent includes, for example, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isoparaffinic hydrocarbon solvent (with a flash point of 92° C., a boiling point of 254° C., a viscosity of 3 cp (at 25° C.), and a density of 0.791 g/ml (at 15.6° C.)) or mixtures thereof.
  • the organic liquid of the present strip dispersion optionally contains a modifier to enhance the complexation and/or stripping of the target species.
  • the modifier can be, for example, an alcohol, a nitrophenyl alkyl ether, a trialkyl phosphate or mixtures thereof.
  • the alcohol can be, for example, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol or mixtures thereof.
  • the nitrophenyl ether can be, for example, o-nitrophenyl octyl ether (o-NPOE), o-nitrophenyl heptyl ether, o-nitrophenyl hexyl ether, o-nitrophenyl pentyl ether (o-NPPE), o-nitrophenyl butyl ether, o-nitrophenyl propyl ether or a mixture thereof.
  • the trialkyl phosphate can be, for example, tributyl phosphate, tris(2-ethylhexyl)phosphate or mixtures thereof.
  • the organic liquid of the present strip dispersion comprises about 2 volume % to about 100 volume % (approximately 0.05M to 3M) extractant and about 0 volume % to about 20 volume % modifier in a hydrocarbon solvent or mixture. More preferably, the organic liquid of the present strip dispersion comprises about 5 volume % to about 40 volume % extractant and about 1 volume % to about 10 volume % modifier in a hydrocarbon solvent or mixture. Even more preferably, the organic liquid comprises 5 volume % to about 40 volume % extractant and about 1 volume % to about 10 volume % dodecanol in an isoparaffinic hydrocarbon solvent or in n-dodecane. All percentages are by volume unless specified otherwise.
  • the present invention has several advantages over conventional SLM technology for removal and recovery of indium from aqueous feed solution. These advantages include increased membrane stability, reduced costs, increased simplicity of operation, improved flux, and improved recovery for indium.
  • the present invention provides a constant supply of the organic membrane solution into the pores of the hollow fiber support for removal and recovery of indium from aqueous feed solution.
  • This constant supply results in an SLM which is more stable than conventional SLMs, ensuring stable and continuous operation.
  • This constant supply also eliminates the need for recharging membrane modules, which is required with conventional SLMs. Further, it eliminates the need for a second set of membrane modules for use during recharging of the first set of membrane modules.
  • the present invention decreases not only operational costs but also the initial capital investment in the system.
  • the present invention also increases simplicity of the removal operation.
  • the present invention provides direct contact between the organic/extraction phase and aqueous strip phase. Mixing of these phases provides an extra mass transfer surface area in addition to the area given by the hollow fibers, leading to extremely efficient stripping of the target species from the organic phase. This efficient stripping enhances the flux for the extraction of indium.
  • the present invention comprises a new type of SLM for removal and recovery of indium, and it provides increased flexibility of aqueous strip/organic volume ratio. This flexibility allows the use of a smaller volume of aqueous strip solution to obtain a higher concentration of the recovered indium in the aqueous strip solution.
  • the concentrated strip solution is a valuable product for resale or reuse.
  • the supported liquid membranes (SLMs) with trip dispersion were used to extract indium from an aqueous feed solution to an organic solution, in which an aqueous strip solution was dispersed to continually strip the extracted indium.
  • the SLM system consisted of a hollow-fiber membrane module (Liquid-Cel®, extra-flow 2.5 ⁇ 8, Membrana-Charlotte, USA), a feed solution tank, a feed pump (model 7592-50, Cole-Parmer, USA) to drive the feed solution into the polypropylene hollow fibers in the module, a strip dispersion tank with a mixer (SS-NZ-1000, Eyela, Japan) to well disperse the aqueous strip solution in the organic solution, and another pump (model 7553-70, Cole-Parmer, USA) to drive the water-in-oil dispersion into the shell side of the module.
  • the hollow-fiber module was 6.35 cm (2.5 inches) in diameter and 20.3 cm (8 inches) in length, and it had a membrane surface area of
  • the organic solution also contained 2 vol % of 1-dodecanol (Merck), unless specified otherwise, as the modifier for the extractant.
  • the total volume of the organic solution was 0.90 L (900 ml), and that of the strip solution was 0.12 L (120 ml) unless specified otherwise. Both of the feed and dispersion tanks were thermo-stated at 25° C.
  • the process was first started by passing the feed solution through the tube side of the hollow fiber module. After the hollow fibers were filled with the feed solution, the water-in-oil dispersion was pumped into the shell side of the module. To prevent the organic phase form passing through the pores of the hollow fibers into the feed solution, the pressure in the tube side was maintained at a positive pressure, i.e., 4 to 5 psi higher than that in the shell side unless specified otherwise. Both the feed and dispersion solutions were pumped from the tanks to the module and then recycled back to the tanks. The pumping rate for both streams was kept at 1 L/min.
  • Feed Solution with about 200 ppm In 3+ in pH 1, 2 wt % H 2 C 2 O 4 of 1 L
  • Feed Solution with about 200 ppm In 3+ in pH 1, 2 wt % H 2 C 2 O 4 of 1 L
  • Feed Solution with about 200 ppm In 3+ in pH 1, 2 wt % H 2 C 2 O 4 of 1 L
  • Examples 1 to 10 have demonstrated that D2EHPA is an effective extractant in the supported liquid membranes (SLMs) with strip dispersion for the removal and recovery of indium from various aqueous feed solutions.
  • SLMs supported liquid membranes
  • These results of the SLMs with strip dispersion for indium are very much different from those for the metals and radionuclides disclosed in Ho's patents mentioned earlier (U.S. Pat. Nos. 6,291,705, 6,328,782, 6,350,419, 6,696,589) where D2EHPA was ineffective.
  • these results disclosed in this present invention are unexpected in view of the prior art disclosed in the Ho's patents.

Abstract

The present invention provides a process for the removal and recovery of indium from waste waters and process streams. The process of the present invention utilizes a combination of a supported liquid membrane (SLM) and a strip dispersion to improve extraction of indium while increasing membrane stability and decreasing processing costs. This novel process selectively removes indium from the feed stream, provides the increased flexibility of aqueous strip/organic volume ratio, and produces a concentrated strip solution of indium.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates to the removal and recovery of indium from feed solutions, such as process streams and waste waters, using supported liquid membrane technology.
  • 2. Description of the Prior Art
  • Liquid membranes combine extraction and stripping, which are normally carried out in two separate steps in conventional processes such as solvent extractions, into one step. A one-step liquid membrane process provides the maximum driving force for the separation of a targeted species, leading to the best clean-up and recovery of the species (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992).
  • There are two types of liquid membranes: (1) supported liquid membranes (SLMs) and (2) emulsion liquid membranes (ELMs). In SLMs, the liquid membrane phase is the organic liquid imbedded in pores of a microporous support, e.g., microporous polypropylene hollow fibers (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992). When the organic liquid contacts the microporous support, it readily wets the pores of the support, and the SLM is formed.
  • For the extraction of a target species from a feed solution, the organic-based SLM is placed between two aqueous solutions—the feed solution and the strip solution where the SLM acts as a selective membrane for the transport of the target species from the feed solution to the strip solution. The organic liquid in the SLM contains an extractant, a diluent which is generally an inert organic solvent, and sometimes a modifier, and it is immiscible in the aqueous feed and strip streams.
  • SLMs have been investigated to remove metals, radionuclides, and rare earth metals from aqueous feed solutions in the scientific and industrial community. The removal of metals, including copper, zinc, cadmium, and palladium, with SLMs has been described (N. Aouad, G. Miquel-Mercier, E. Bienvenue, E. Tronel-Peyroz, G. Jerninet, J. Juillard, and P. Seta, “Lasalocid (X537A) as a Selective Carrier for Cd(II) in Supported Liquid Membranes,” J. Membrane Sci., 139, 167-174 (1998); J. A. Daoud, S. A. El-Reefy, and H. F. Aly, “Permeation of Cd(II) Ions through a Supported Liquid Membrane Containing Cyanex-302 in Kerosene,” Sep. Sci. Technol., 33, 537-549 (1998); J. Vander Linden and R. F. De Ketelaere, “Selective Recuperation of Copper by Supported Liquid Membrane (SLM) Extraction,” J. Membrane Sci., 139, 125-135 (1998); M. E. Campderros, A. Acosta, and J. Marchese, “Selective Separation of Copper with LIX 864 in a Hollow Fiber Module,” Talanta, 47, 19-24 (1998); M. Rovira and A. M. Sastre, “Modelling of Mass Transfer in Facilitated Supported Liquid-Membrane Transport of Palladium(II) Using Di-(2-ethylhexyl)Thiophosphoric Acid,” J. Membrane Sci., 149, 241-250 (1998); J. C. Lee, J. Jeong, J. T. Park, I. J. Youn, and H. S. Chung, “Selective and Simultaneous Extractions of Zn and Cu Ions by Hollow Fiber SLM Modules Containing HEH(EHP) and LIX84,” Sep. Sci. Technol., 34, 1689-1701 (1999); F. Valenzuela, C. Basualto, C. Tapia, and J. Sapag, “Application of Hollow-Fiber Supported Liquid Membranes Technique to the Selective Recovery of a Low Content of Copper from a Chilean Mine Water,” J. Membrane Sci., 155, 163-168 (1999)).
  • On the removal of radionuclides, Dozol et al. (J. F. Dozol, N. Simon, V. Lamaare, H. Rouquette, S. Eymard, B. Tournois, D. De Marc, and R. M. Macias, “A Solution for Cesium Removal from High-Salinity Acidic or Alkaline Liquid Waste: the Crown Calix[4]arenes”, Sep. Sci. Technol., 34, 877-909 (1999)) have described the use of the extractant, Calix[4]arenes monocrown or biscrown, blocked in 1,3 alternative cone conformation, in SLMs for the removal of cesium from high-salinity acidic or alkaline liquid waste. Kedari et al. (C. S. Kedari, S. S. Pandit, and A. Ramanujam, “Selective Permeation of Plutonium (IV) through Supported Liquid Membrane Containing 2-Ethylhexyl 2-Ethylhexyl Phosphonic Acid as Ion Carrier”, J. Membrane Sci., 156, 187-196 (1999)) have studied the selective permeation of plutonium (IV) through a SLM containing 2-ethylhexyl 2-ethylhexyl phosphonic acid as the ion carrier.
  • On the extraction of rare earth metals, Yaftian et al. (M. R. Yaftian, M. Burgard, C. B. Dieleman and D. Matt, “Rare-earth Metal-ion Separation Using a Supported Liquid Membrane Mediated by a Narrow Rim Phosphorylated Calix[4]arene,” J. Membrane Sci., 144, 57-64 (1998)) has reported the use of SLMs for europium, lanthanum, neodymium, praseodymium, and gadolinium.
  • One disadvantage of SLMs is their instability due mainly to loss of the membrane liquid (organic solvent, extractant, and/or modifier) into the aqueous phases on each side of the membrane (A. J. B. Kemperman, D. Bargeman, Th. Van Den Boomgaard, H. Strathmann, “Stability of Supported Liquid Membranes: State of the Art”, Sep. Sci. Technol., 31, 2733 (1996); T. M. Dreher and G. W Stevens, “Instability Mechanisms of Supported Liquid Membranes”, Sep. Sci. Technol., 33, 835-853 (1998); J. F. Dozol, J. Casas, and A. Sastre, “Stability of Flat Sheet Supported Liquid Membranes in the Transport of Radionuclides from Reprocessing Concentrate Solutions”, J. Membrane Sci., 82, 237-246 (1993)). The prior art has attempted to solve this problem through the combined use of SLM with a module containing two set of hollow fibers, i.e., the hollow-fiber contained liquid membrane (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992). In this configuration with two sets of microporous hollow-fiber membranes, one carries the aqueous feed solution, and the other carries the aqueous strip solution. The organic phase is contained between the two sets of hollow fibers by maintaining the aqueous phases at a higher pressure than the organic phase. The use of the hollow-fiber contained liquid membrane increases membrane stability, because the liquid membrane may be continuously replenished. However, this configuration is not advantageous because it requires mixing two sets of fibers to achieve a low contained liquid membrane thickness.
  • In ELMs, an emulsion acts as a liquid membrane for the separation of the target species from a feed solution. An ELM is created by forming a stable emulsion, such as a water-in-oil emulsion, between two immiscible phases, followed by dispersion of the emulsion into a third, continuous phase by agitation for extraction. The membrane phase is the oil phase that separates the encapsulated, internal aqueous droplets in the emulsion from the external, continuous phase (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992). The species-extracting agent is contained in the membrane phase, and the stripping agent is contained in the internal aqueous droplets. Emulsions formed from these two phases are generally stabilized by use of a surfactant. The external, continuous phase is the feed solution containing the target species. The target species is extracted from the aqueous feed solution into the membrane phase and then stripped into the aqueous droplets in the emulsion. The target species can then be recovered from the internal aqueous phase by breaking the emulsion, typically via electrostatic coalescence, followed by electroplating or precipitation.
  • The use of ELMs to remove metals, rare earth metals, and radionuclides from aqueous feed solutions has also been pursued in the scientific and industrial community. The ELMs for the removal of metals, including cobalt, copper, zinc, nickel, mercury, lead, cadmium, and silver, and for the removal of rare earth metals, including europium, lanthanum, and neodymium, have been described in detail (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992). The removal of metals including cobalt, nickel, cadmium, mercury, and lead with ELMs has been reported quite a lot in the literature (B. Raghuraman, N. Tirmizi, and J. M. Wiencek, “Emulsion Liquid Membranes for Wastewater Treatment. Equilibrium Models for Some Typical Metal-Extractant Systems,” Environ. Sci. Technol., 28, 1090-1098 (1994); T. Kakkoi, M. Goto, K. Sugimoto, K. Ohto, and F. Nakashio, “Separation of Cobalt and Nickel with Phenylphosphonic Acid Mono-4-tert-octylphenyl Ester by Liquid Surfactant Membranes,” Sep. Sci. Technol., 30, 637-657 (1995); R. S. Juang and J. D. Jiang, “Recovery of Nickel from a Simulated Electroplating Rinse Solution by Solvent Extraction and Liquid Surfactant Membrane,” J. Membrane Sci., 100, 163-170 (1995); H. Kasaini, F. Nakashio, and M. Goto, “Application of Emulsion Liquid Membranes to Recover Cobalt Ions from a Dual-component Sulphate Solution Containing Nickel Ions,” J. Membrane Sci., 146, 159-168 (1998); S. Y. B. Hu and J. M. Wiencek, “Emulsion-Liquid-Membrane Extraction of Copper Using a Hollow-Fiber Contactor,” AIChE J., 570-581 (1998)).
  • On radionuclides, the removal of strontium, cesium, technetium, and uranium has also been described in detail by Ho and Sirkar (W. S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992). The extraction of strontium with the ELM technique has been investigated (I. Eroglu, R. Kalpakci, and G. Gunduz, “Extraction of Strontium Ions with Emulsion Liquid Membrane Technique”, J. Membrane Sci., 80, 319-325 (1993)).
  • One disadvantage of ELMs is that the emulsion swells upon prolonged contact with the feed stream. This swelling causes a reduction in the stripping reagent concentration in the aqueous droplets which reduces stripping efficiency. It also results in dilution of the target species that has been concentrated in the aqueous droplets, resulting in lower separation efficiency of the membrane. The swelling further results in a reduction in membrane stability by making the membrane thinner. Finally, swelling of the emulsion increases the viscosity of the spent emulsion, making it more difficult to demulsify. A second disadvantage of ELMs is membrane rupture, resulting in leakage of the contents of the aqueous droplets into the feed stream and a concomitant reduction of separation efficiency. Raghuraman and Wiencek (B. Raghuraman and J. Wiencek, “Extraction with Emulsion Liquid Membranes in a Hollow-Fiber Contactor”, AIChE J., 39, 1885-1889 (1993)) have described the use of microporous hollow-fiber contactors as an alternative contacting method to direct dispersion of ELMs to minimize the membrane swelling and leakage. This is due to the fact that the hollow-fiber contactors do not have the high shear rates typically encountered with the agitators used in the direct dispersion. Additional disadvantages include the necessary process steps for making and breaking the emulsion.
  • Thus, there has been a need in the art for an extraction process which maximizes the stability of the SLM membrane, resulting in efficient removal and recovery of metals, radionuclides, penicillin, and organic acids from the aqueous feed solutions. Ho recognized the need and invented the combined supported liquid membrane/strip dispersion process for the removal of chromium (W. S. Winston Ho, “Supported Liquid Membrane Process for Chromium Removal and Recovery”, U.S. Pat. No. 6,171,563 (2001)), metals (W. S. Winston Ho, “Combined Supported Liquid Membrane/Strip Dispersion Process for the Removal and Recovery of Radionuclides and Metals”, U.S. Pat. No. 6,328,782 (2001); W. S. Winston Ho, “Combined Supported Liquid Membrane/Strip Dispersion Process for the Removal and Recovery of Metals”, U.S. Pat. No. 6,350,419 (2002)), radionuclides (W. S. Winston Ho, “Combined Supported Liquid Membrane/Strip Dispersion Process for the Removal and Recovery of Radionuclides and Metals”, U.S. Pat. No. 6,328,782 (2001); W. S. Winston Ho, “Combined Supported Liquid Membrane/Strip Dispersion Process for the Removal and Recovery of Radionuclides”, U.S. Pat. No. 6,696,589 (2004)), and penicillin and organic acids (W. S. Winston Ho, “Combined Supported Liquid Membrane/Strip Dispersion Process for the Removal and Recovery of Penicillin and Organic Acids”, U.S. Pat. No. 6,433,163 (2002)). The synthesis of dialkyl monothiophosphoric acid extractants for the combined supported liquid membrane/strip dispersion process for the removal of metals has been reported (W. S. Winston Ho and Bing Wang, “Combined Supported Liquid Membrane/Strip Dispersion Process for the Removal and Recovery of Metals: Dialkyl Monothiophosphoric Acids and Their Use as Extractants”, U.S. Pat. No. 6,291,705 (2001)). But, none of these patents by Ho disclose the use of the combined supported liquid membrane/strip dispersion process for the removal and recovery of indium.
  • Thus, there is a need in the art for an extraction process which maximizes the stability and effectiveness of the SLM membrane for the efficient removal and recovery of indium from the aqueous feed solutions.
    • SUMMARY OF THE INVENTION
  • The present invention relates to a process for the removal and recovery of indium from a feed solution using a combined SLM/strip dispersion.
  • In one embodiment, the present invention relates to a process for the removal and recovery of indium from a feed solution which comprises the following steps. First, a feed solution containing indium is passed on one side of the SLM embedded in a microporous support material and treated to remove the indium by the use of a strip dispersion on the other side of the SLM. The strip dispersion can be formed by dispersing an aqueous strip solution in an organic liquid, for example, using a mixer. Second, the strip dispersion, or a part of the strip dispersion, is allowed to stand, resulting in separation of the dispersion into two phases: the organic liquid phase and the aqueous strip solution phase containing a concentrated indium solution.
  • The continuous organic phase of the strip dispersion readily wets the pores of a microporous support to form a stable SLM. The process of the present invention provides a number of operational and economic advantages over the use of conventional SLMs or solvent extraction.
  • Thus, it is an object of the present invention to provide an SLM process for the removal and recovery of indium which provides increased membrane stability.
  • It is another object of the invention to provide an SLM process having high indium removal and recovery.
  • It is yet another object of the present invention to provide an SLM process having improved recovery of indium to provide a concentrated strip solution of indium.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a schematic representation of the combined supported liquid membrane/strip dispersion of the present invention for the recovery of indium.
  • FIG. 2 is an enlarged view of the schematic representation of the combined supported liquid membrane/strip dispersion of the present invention for the recovery of indium.
  • FIG. 3 shows the indium concentrations in the feed and strip solutions as a function of time for the feed solution containing 200 ppm In3+ in pH 1 H2SO4 of 15.5 L. The strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M di(2-ethyl-hexyl)phosphoric acid (D2EHPA) and 2 vol % dodecanol in Isopar-L.
  • FIG. 4 shows the indium concentrations in the feed and strip solutions as a function of time for the feed solution containing about 180 ppm In3+ in pH 1 HNO3 of 1 L. The strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M D2EHPA and 2 vol % dodecanol in Isopar-L. Also shown are the indium concentrations in the feed solutions for the original feed solutions containing about 190 ppm In3+ in pH 1 H2SO4 and 160 ppm In3+ in pH 1 HCl, all with the same feed volume of 1 L and the same strip dispersion.
  • FIG. 5 depicts the indium concentrations in the feed solutions originally containing about 200 ppm In3+ in pH 1, 2 wt % H2C2O4 as a function of time for 0.2M, 0.6M and 1M D2EHPA concentrations. Each of the strip dispersions was prepared by mixing together 0.1 L (100 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing the specified D2EHPA concentration and 2 vol % dodecanol in Isopar-L.
  • FIG. 6 depicts the indium concentrations in the feed and strip solutions as a function of time for the feed solution containing 200 ppm In3+ in pH 1, 2 wt % H2C2O4 of 15.5 L. The strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M D2EHPA and 2 vol % dodecanol in Isopar-L.
  • FIG. 7 shows the indium concentrations in the feed and strip solutions as a function of time for the ITO feed solution of 15.5 L containing about 140 ppm In3+ at pH 0.9. The strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M D2EHPA and 2 vol % dodecanol in Isopar-L. Also shown is the tin concentration in the feed solution as a function of time.
  • FIG. 8 depicts the indium concentrations in the feed and strip solutions as a function of time for the residual electrolyte feed solution of 0.5 L containing about 11000 ppm In3+ at pH 1. The strip dispersion was prepared by mixing together 0. 1 L (100 ml) of the strip solution of 5M HCl and 0.9 L (900 ml) of the organic solution containing 0.6M D2EHPA and 2 vol % dodecanol in Isopar-L. In this figure, both the indium concentration in the strip solution obtained experimentally, i.e., strip-exp, and that calculated from the feed concentration based on the material balance, i.e., strip-ideal (the ideal case), are included.
    •  DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • The present invention relates to a process for the removal and recovery of indium from a feed solution, such as waste waters or process streams. This new process employs a combination of a supported liquid membrane (SLM) and a strip dispersion.
  • In one embodiment, the present invention relates to a process for the removal and recovery of indium from a feed solution which comprises the following steps. First, a feed solution containing indium is passed on one side of the SLM embedded in a microporous support material and treated to remove the indium by the use of a strip dispersion on the other side of the SLM. The strip dispersion can be formed by dispersing an aqueous strip solution in an organic liquid, for example, using a mixer. Second, the strip dispersion, or a part of the strip dispersion, is allowed to stand, resulting in separation of the dispersion into two phases: the organic liquid phase and the aqueous strip solution phase containing a concentrated indium solution.
  • While any SLM configuration may be employed in the process of the invention, the preferred configuration employs a hollow fiber module as the liquid membrane microporous support. Such hollow fiber modules consist of microporous hollow fibers arranged in a shell-and-tube configuration. In the present invention, the strip dispersion is passed through either the shell side of the module or the tube side of the module, and the aqueous feed solution containing indium for extraction is passed through the opposing side of the module. The use of the hollow fiber system in the combined SLM/strip dispersion process allows constant supply of the strip dispersion as shown in FIG. 1, ensuring a stable and continuous operation.
  • For the purposes of the invention, strip dispersion is defined as a mixture of an aqueous phase and an organic phase. The aqueous phase of the dispersion comprises an aqueous strip solution, while the organic phase comprises an extractant or extractants in an organic liquid. The dispersion is formed by the mixing of the aqueous and organic phases as shown in FIG. 1. This combination results in droplets of the aqueous strip solution in a continuous organic phase. The dispersion is maintained during the extraction process due to the flow of the dispersion through a membrane module, e.g., a hollow-fiber module. The continuous organic phase of the strip dispersion readily wets the hydrophobic pores of the microporous hollow fibers in the module, forming a stable liquid membrane.
  • FIG. 2 shows an enlarged view of a schematic representation of the SLM with strip dispersion of the present invention. A low pressure, Pa, which is typically less than approximately 2 psi, is applied on the feed solution side of the SLM. The pressure Pa is greater than the pressure, Po, on the strip dispersion side of the SLM. This difference in pressure prevents the organic solution of the strip dispersion from passing through the pores to come into the feed solution side. The dispersed droplets of the aqueous strip solution in a typical size of about 80 to about 800 micrometers and are orders of magnitude larger than the pore size of the microporous support employed for the SLM, which is in the order of approximately 0.03 micrometer. Thus, these droplets are retained on the strip dispersion side of the SLM and cannot pass through the pores to go to the feed solution side.
  • In this SLM/strip dispersion system, there is a constant supply of the organic membrane solution, i.e., the organic phase of the strip dispersion, into the pores. This constant supply of the organic phase ensures a stable and continuous operation of the SLM. In addition, the direct contact between the organic and strip phases provides efficient mass transfer for stripping. The organic and strip phases can be mixed, for example, with high-shear mixing, to increase the contact area between the two phases.
  • Once removal of indium is complete, the mixer for the strip dispersion is stopped, and the dispersion is allowed to stand until it separates into two phases, the organic membrane solution and the concentrated strip solution. The concentrated strip solution containing indium is the product of this process.
  • The feed solution includes, but is not limited to, waste waters or process streams containing indium.
  • The microporous support employed in the invention is comprised of, for example, microporous polypropylene, polytetrafluoroethylene, polyethylene, polysulfone, polyethersulfone, polyetheretherketone, polyimide, polyamide, polyaramide, or mixtures thereof. The preferred microporous supports are microporous polypropylene and polytetrafluoroethylene hollow fibers.
  • The aqueous portion of the strip dispersion comprises an aqueous acid solution, such as a mineral acid. Examples of mineral acids useful in the present invention include, but are not limited to, hydrochloric acid (HCl), sulfuric acid (H2SO4), nitric acid (HNO3), and acetic acid (CH3COOH). The acid is present in a concentration between about 0.1 M and about 18 M. The preferred concentration for the acid solution is between about 1 M and about 6 M.
  • The continuous organic liquid phase into which the aqueous strip solution is dispersed contains an extractant or extractants. The extractant is capable of extracting indium contained in the feed solution. Typical extractants which are known in the art for extraction of indium from waste waters or process streams may be employed in the present strip dispersion.
  • The extractants include dialkyl phosphoric acids and alkyl phenylphosphonic acids. The dialkyl group of the dialkyl phosphoric acid is paraffinic (saturated) and has from 6 to 26 carbon atoms. The dialkyl phosphoric acids are selected from the group consisting of di(2-ethyl-hexyl)phosphoric acid (D2EHPA), di(2-butyl-octyl)phosphoric acid, di(2-hexyl-decyl)phosphoric acid, di(2-octyl-decyl/2-hexyl-dodecyl)phosphoric acid, di(2-octyl-dodecyl)phosphoric acid, di(hexyl)phosphoric acid, di(heptyl)phosphoric acid, di(octyl)phosphoric acid, di(nonyl)phosphoric acid, di(decyl)phosphoric acid, di(undecyl)phosphoric acid, di(dodecyl)phosphoric acid, di(tridecyl)phosphoric acid, di(tetradecyl)phosphoric acid, di(pentadecyl)phosphoric acid, di(hexadecyl)phosphoric acid, di(heptadecyl)phosphoric acid, di(octadecyl)phosphoric acid, di(nonadecyl)phosphoric acid, di(decadecyl)phosphoric acid, di(undecadecyl)phosphoric acid, di(dodecadecyl)phosphoric acid, di(tridecadecyl)phosphoric acid, di(tetrdecadecyl)phosphoric acid, di(pentadadecyl)phosphoric acid, di(hexadecadecyl)phosphoric acid, and mixtures thereof. The preferred dialkyl phosphoric acid is di(2-ethyl-hexyl)phosphoric acid (D2EHPA).
  • The alkyl group of the alkyl phenylphosphonic acid is paraffinic (saturated) and has from 6 to 26 carbon atoms. The alkyl phenylphosphonic acids are selected from the group consisting of 2-butyl-1-octyl phenylphosphonic acid (BOPPA), 2-hexy-1-decyl phenylphosphonic acid, 2-octyl-1-decyl/2-hexyl-1-dodecyl phenylphosphonic acid, 2-octyl-1-dodecyl phenylphosphonic acid, hexyl phenylphosphonic acid, heptyl phenylphosphonic acid, octyl phenylphosphonic acid, nonyl phenylphosphonic acid, decyl phenylphosphonic acid, undecyl phenylphosphonic acid, dodecyl phenylphosphonic acid, tridecyl phenylphosphonic acid, tetradecyl phenylphosphonic acid, pentadecyl phenylphosphonic acid, hexadecyl phenylphosphonic acid, heptadecyl phenylphosphonic acid, octadecyl phenylphosphonic acid, nonadecyl phenylphosphonic acid, decadecyl phenylphosphonic acid, undecadecyl phenylphosphonic acid, dodecadecyl phenylphosphonic acid, tridecadecyl phenylphosphonic acid, tetrdecadecyl phenylphosphonic acid, pentadadecyl phenylphosphonic acid, hexadecadecyl phenylphosphonic acid, and mixtures thereof. The preferred alkyl phenylphosphonic acid is 2-butyl-1-octyl phenylphosphonic acid (BOPPA).
  • The organic liquid of the present strip dispersion optionally comprises a hydrocarbon solvent or mixture. The hydrocarbon solvent or mixture has a number of carbon atoms per solvent molecule ranging from 6 to 18, preferably from 10 to 14. The hydrocarbon solvent includes, for example, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isoparaffinic hydrocarbon solvent (with a flash point of 92° C., a boiling point of 254° C., a viscosity of 3 cp (at 25° C.), and a density of 0.791 g/ml (at 15.6° C.)) or mixtures thereof.
  • The organic liquid of the present strip dispersion optionally contains a modifier to enhance the complexation and/or stripping of the target species. The modifier can be, for example, an alcohol, a nitrophenyl alkyl ether, a trialkyl phosphate or mixtures thereof. The alcohol can be, for example, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol or mixtures thereof. The nitrophenyl ether can be, for example, o-nitrophenyl octyl ether (o-NPOE), o-nitrophenyl heptyl ether, o-nitrophenyl hexyl ether, o-nitrophenyl pentyl ether (o-NPPE), o-nitrophenyl butyl ether, o-nitrophenyl propyl ether or a mixture thereof. The trialkyl phosphate can be, for example, tributyl phosphate, tris(2-ethylhexyl)phosphate or mixtures thereof.
  • The organic liquid of the present strip dispersion comprises about 2 volume % to about 100 volume % (approximately 0.05M to 3M) extractant and about 0 volume % to about 20 volume % modifier in a hydrocarbon solvent or mixture. More preferably, the organic liquid of the present strip dispersion comprises about 5 volume % to about 40 volume % extractant and about 1 volume % to about 10 volume % modifier in a hydrocarbon solvent or mixture. Even more preferably, the organic liquid comprises 5 volume % to about 40 volume % extractant and about 1 volume % to about 10 volume % dodecanol in an isoparaffinic hydrocarbon solvent or in n-dodecane. All percentages are by volume unless specified otherwise.
  • The present invention has several advantages over conventional SLM technology for removal and recovery of indium from aqueous feed solution. These advantages include increased membrane stability, reduced costs, increased simplicity of operation, improved flux, and improved recovery for indium.
  • The present invention provides a constant supply of the organic membrane solution into the pores of the hollow fiber support for removal and recovery of indium from aqueous feed solution. This constant supply results in an SLM which is more stable than conventional SLMs, ensuring stable and continuous operation. This constant supply also eliminates the need for recharging membrane modules, which is required with conventional SLMs. Further, it eliminates the need for a second set of membrane modules for use during recharging of the first set of membrane modules. Thus, the present invention decreases not only operational costs but also the initial capital investment in the system. The present invention also increases simplicity of the removal operation.
  • The present invention provides direct contact between the organic/extraction phase and aqueous strip phase. Mixing of these phases provides an extra mass transfer surface area in addition to the area given by the hollow fibers, leading to extremely efficient stripping of the target species from the organic phase. This efficient stripping enhances the flux for the extraction of indium.
  • The present invention comprises a new type of SLM for removal and recovery of indium, and it provides increased flexibility of aqueous strip/organic volume ratio. This flexibility allows the use of a smaller volume of aqueous strip solution to obtain a higher concentration of the recovered indium in the aqueous strip solution. The concentrated strip solution is a valuable product for resale or reuse.
  • This invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. To the contrary, it is to be clearly understood that reading the description herein may suggest various other embodiments, modifications, and equivalents to those skilled in the art without departing from the spirit of the present invention and/or the scope of the appended claims.
    • EXAMPLES General Procedure
  • In all of the following examples, the supported liquid membranes (SLMs) with trip dispersion were used to extract indium from an aqueous feed solution to an organic solution, in which an aqueous strip solution was dispersed to continually strip the extracted indium. The SLM system consisted of a hollow-fiber membrane module (Liquid-Cel®, extra-flow 2.5×8, Membrana-Charlotte, USA), a feed solution tank, a feed pump (model 7592-50, Cole-Parmer, USA) to drive the feed solution into the polypropylene hollow fibers in the module, a strip dispersion tank with a mixer (SS-NZ-1000, Eyela, Japan) to well disperse the aqueous strip solution in the organic solution, and another pump (model 7553-70, Cole-Parmer, USA) to drive the water-in-oil dispersion into the shell side of the module. The hollow-fiber module was 6.35 cm (2.5 inches) in diameter and 20.3 cm (8 inches) in length, and it had a membrane surface area of 1.4 m2.
  • All of the following examples were run in the countercurrent mode with the feed solution passing through the tube side of the microporous polypropylene hollow fiber module whereas the strip dispersion passing through the shell side of the module. Indium in the feed solution was extracted to the organic solution in the membrane module, and the extracted indium was stripped into the dispersed strip solution both in the module and in the dispersion tank.
  • The aqueous feed solution, containing indium, was placed in the feed tank that was agitated by a magnetic stirring bar at a rate of 300 rpm. The strip solution, 5M HCl aqueous solution, was dispersed with a 2-bladed paddle (8.5 cm in diameter) at a rate of 300 rpm in the organic solution containing D2EHPA (Merck) as the extractant for indium in Isopar-L (ExxonMobil). The concentration of D2EHPA in Isopar-L was 0.6 M (20.5 vol %) for most of the experiments we performed unless specified otherwise. The organic solution also contained 2 vol % of 1-dodecanol (Merck), unless specified otherwise, as the modifier for the extractant. The total volume of the organic solution was 0.90 L (900 ml), and that of the strip solution was 0.12 L (120 ml) unless specified otherwise. Both of the feed and dispersion tanks were thermo-stated at 25° C.
  • The process was first started by passing the feed solution through the tube side of the hollow fiber module. After the hollow fibers were filled with the feed solution, the water-in-oil dispersion was pumped into the shell side of the module. To prevent the organic phase form passing through the pores of the hollow fibers into the feed solution, the pressure in the tube side was maintained at a positive pressure, i.e., 4 to 5 psi higher than that in the shell side unless specified otherwise. Both the feed and dispersion solutions were pumped from the tanks to the module and then recycled back to the tanks. The pumping rate for both streams was kept at 1 L/min.
  • During each experiment, samples from the feed and strip solutions were taken at certain timed intervals. The strip dispersion samples were allowed to stand until phase separation occurred. The aqueous phase from the strip dispersion sample was then collected. The aqueous phase samples from the strip dispersion samples and the feed solution samples were then analyzed to determine the indium concentrations by using an atomic absorption spectrophotometer (GBC 906, GBC, Australia) unless specified otherwise (for example, using an inductively coupled plasma (ICP) spectrometer).
  • Experiments with different feed compositions and volumes were carried out to investigate the performance of the process of SLM with strip dispersion. The performance maybe expressed in terms of indium recovery and concentrations in both the treated feed and strip solutions.
    • Example 1
  • Feed Solution with 200 ppm In3+ in pH 1 H2SO4 of 15.5 L.
      • Condition: Organic Solution=0.6M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L.
      • Strip=5M HCl, 0.12 L
        The feed solution contained 200 ppm In3+ in pH 1 H2SO4, and it had a volume of 15.5 L. The organic solution was 0.6M di(2-ethyl-hexyl)phosphoric acid (D2EHPA) and 2 vol % dodecanol in Isopar-L, and it had a volume of 0.9 L. The strip solution was 5M HCl with a volume of 0.12 L. A strip dispersion was prepared by mixing together 0.12 L (120 ml) of the strip solution and 0.9 L (900 ml) of the organic solution as described in the general procedure above. The feed solution containing about 200 ppm In3+ was pumped into the tube side of the polypropylene hollow fiber module. The strip dispersion was fed into the shell side of the hollow fiber module. Samples of the feed and strip solutions were collected at certain timed intervals as described in the general procedure above and analyzed by atomic absorption spectrophotometry. The indium concentrations in the feed and strip solution samples as a function of time are listed in Table 1. The results are shown in FIG. 3. Both the table and figure show that the SLM process with strip dispersion can produce the strip solution with a very high indium concentration of greater than 20000 ppm.
  • TABLE 1
    Time Feed Time Strip
    (min) (ppm) (min) (ppm)
    0 200.2 0 0
    5 172.0 10 4459
    10 141.5 20 8996
    15 125.9 30 12191
    20 105.9 40 15037
    25 90.07 50 17364
    30 79.76 60 18851
    35 65.73 70 20580
    40 49.63 80 21386
    45 48.40 90 21100
    50 41.26 100 22337
    55 34.82 110 22641
    60 29 120 23528
    70 21.71 140 22808
    80 14.62 160 22203
    90 9.48 180 22758
    100 5.09 200 21742
    110 2.94
    120 0.32
    130 0
    140 0
    150 0
    160 0
    170 0
    180 0
    195 0
    200 0
    • Example 2
  • Feed Solution with about 180 ppm In3+ in pH 1 HNO3 of 1 L.
      • Condition: Organic Solution=0.6M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L.
      • Strip=5M HCl, 0.12 L.
        The experimental procedure for this example was the same as that described in Example 1 except the feed solution with about 180 ppm In3+ in pH 1 HNO3 of 1 L was used instead of the feed solution with 200 ppm In3+ in pH 1 M H2SO4 of 15.5 L. The indium concentrations in the feed and strip solution samples as a function of time are listed in Table 2. The results are also shown in FIG. 4.
  • TABLE 2
    Time Feed Time Strip
    (min) (ppm) (min) (ppm)
    0 181.9 0 0
    1 89.5 5 1034
    3 16.8 10 1246
    5 0 15 1315
    20 1305
    25 1337
    30 1282
    40 1280
    50 1325
    60 1315
    • Example 3
  • Feed Solution with about 190 ppm In3+ in pH 1 H2SO4 of 1 L
      • Condition: Organic Solution=0.6M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L
      • Strip=5M HCl, 0.12 L
        The experimental procedure for this example was the same as that described in Example 1 except the feed solution with about 190 ppm In3+ in pH 1 H2SO4 of 1 L was used instead of the feed solution with 200 ppm In3+ in pH 1 M H2SO4 of 15.5 L. The indium concentrations in the feed solution samples as a function of time are listed in Table 3. The results are also shown in FIG. 4 for comparison. Both the table and figure show that the results for this example using the feed solution with pH 1 H2SO4 were very similar to those for Example 2 using the feed solution with pH 1 HNO3 while the other conditions were essentially the same.
  • TABLE 3
    Time Feed
    (min) (ppm)
    0 191.6
    1 99.01
    2 53.77
    3 25.17
    5 0
    • Example 4
  • Feed Solution with about 160 ppm In3+ in pH 1 HCl of 1 L
      • Condition: Organic Solution=0.6M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L
      • Strip=5M HCl, 0.12 L
        The experimental procedure for this example was the same as that described in Example 1 except the feed solution with about 160 ppm In3+ in pH 1 HCl of 1 L was used instead of the feed solution with 200 ppm In3+ in pH 1 M H2SO4 of 15.5 L. The indium concentrations in the feed solution samples as a function of time are listed in Table 4. The results are also shown in FIG. 4 for comparison. Both the table and figure show that the results for this example using the feed solution with pH 1 HCl were very similar to those for Example 2 using the feed solution with pH 1 HNO3 and Example 3 using the feed solution with pH 1 H2SO4 while the other conditions were essentially the same.
  • TABLE 4
    Time Feed
    (min) (ppm)
    0 156.6
    1 87.98
    3 29.48
    5 8.27
    7 0.72
    10 0
    • Example 5
  • Feed Solution with about 200 ppm In3+ in pH 1, 2 wt % H2C2O4 of 1 L
      • Condition: Organic Solution=0.2M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L
      • Strip=5M HCl, 0.1 L
        The experimental procedure for this example was the same as that described in Example 1 except (1) the feed solution with about 200 ppm In3+ in pH 1, 2 wt % H2CO4 (oxalic acid) of 1 L was used instead of the feed solution with 200 ppm In3+ in pH 1 M H2SO4 of 15.5 L, and (2) 0.2M D2EHPA was used instead of 0.6M, and (3) the volume of the strip solution used was 0.1 L (100 ml) instead of 0.12 L (120 ml). The indium concentrations in the feed solution samples as a function of time are listed in Table 5. The results are also shown in FIG. 5.
  • TABLE 5
    Time Feed
    (min) (ppm)
    0 208.0
    1 194.9
    3 189.7
    5 183.8
    7 176.5
    10 167.2
    15 150.0
    20 128.7
    25 124.2
    30 111.7
    40 87.16
    50 69.80
    60 55.66
    72 40.14
    80 30.03
    90 21.90
    100 16
    110 13.48
    120 10.98
    130 9.58
    140 8.35
    155 7.05
    160 6.11
    170 4.67
    190 2.89
    • Example 6
  • Feed Solution with about 200 ppm In3+ in pH 1, 2 wt % H2C2O4 of 1 L
      • Condition: Organic Solution=0.6M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L
      • Strip=5M HCl, 0.1 L
        The experimental procedure for this example was identical to that described in Example 5 except 0.6M D2EHPA was used instead of 0.2M, i.e., the experimental procedure was similar to that for Example 1. The indium concentrations in the feed solution samples as a function of time are listed in Table 6. The results are also shown in FIG. 5 for comparison. Both the table and figure show that the results for this example using the 0.6M D2EHPA were much better than those for Example 5 using 0.2M D2EHPA.
  • TABLE 6
    Time Feed
    (min) (ppm)
    0 205.7
    1 169.3
    3 137.1
    5 107.2
    7 86.34
    10 60.57
    15 31.99
    20 13.82
    25 3.99
    30 0
    • Example 7
  • Feed Solution with about 200 ppm In3+ in pH 1, 2 wt % H2C2O4 of 1 L
      • Condition: Organic Solution=1M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L
      • Strip=5M HCl, 0.1 L
        The experimental procedure for this example was identical to that described in Example 5 except 1M D2EHPA was used instead of 0.2M, i.e., the experimental procedure was similar to that for Example 1. The indium concentrations in the feed solution samples as a function of time are listed in Table 7. The results are also shown in FIG. 5 for comparison. Both the table and figure show that the results for this example using the 0.6M D2EHPA were better than those for Example 6 using 0.6M D2EHPA and much better than those for Example 5 using 0.2M D2EHPA. These results indicated that 0.6M D2EHPA was suitable and effective for the extraction of indium from the feed solution containing the oxalic acid.
  • TABLE 7
    Time Feed
    (min) (ppm)
    0 194.2
    1 141.5
    3 109.6
    5 81.82
    7 59.68
    10 34.33
    12.5 18.34
    15 10.85
    17.5 6.28
    20 0
    • Example 8
  • Feed Solution with 200 ppm In3+ in pH 1, 2 wt % H2C2O4 of 15.5 L
      • Condition: Organic Solution=0.6M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L
      • Strip=5M HCl, 0. 12 L
        The experimental procedure for this example was identical to that described in Example 1 except the feed solution with 200 ppm In3+ in pH 1, 2 wt % H2C2l O 4 was used instead of that in pH 1 H2SO4. The indium concentrations in the feed and strip solution samples as a function of time are listed in Table 8. The results are also shown in FIG. 6. Both the table and figure show that the SLM with strip dispersion can recover and concentrate indium in the strip solution with 18000 ppm or higher from the feed solution containing the oxalic acid.
  • TABLE 8
    Time (min) Feed (ppm) Time (min) Strip (ppm)
    0 200.1 0 0
    5 196.6 10 1057
    10 190.7 20 2209
    15 185.5 30 3253
    20 180.1 40 4399
    25 179.0 50 5560
    30 172.9 60 6399
    35 169.3 70 7181
    40 163.2 80 7965
    45 158.6 90 8078
    50 153.4 100 10162
    55 148.9 110 10953
    60 144.4 120 11491
    70 137.6 140 12445
    80 129.5 160 13741
    90 124.9 180 14744
    100 116.5 200 15453
    110 112.0 220 16166
    120 105.0 240 16762
    130 99.03 270 17308
    140 93.15 330 18200
    150 88.31 360 17725
    160 83.72 390 18258
    170 80.51 420 18320
    180 75.44 450 18342
    195 70.85 480 18274
    200 67.99 510 18272
    210 66.24 540 18662
    220 62.07 570 17853
    240 55.45 600 17168
    255 51.75 630 17127
    270 47.97 660 17305
    285 43.52
    300 39.39
    315 36.43
    330 34.09
    345 31.97
    360 29.08
    375 26.32
    390 24.23
    405 21.68
    420 20.54
    435 17.99
    450 17.01
    465 15.19
    480 14.16
    500 11.97
    510 12.21
    540 9.74
    560 8.23
    570 7.57
    600 6.16
    630 5.98
    660 4.48
    • Example 9
  • ITO Feed Solution with about 140 ppm In3+ and pH 0.9 of 15.5 L
      • Condition: Organic Solution=0.6M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L
      • Strip=5M HCl, 0. 12 L
        The experimental procedure for this example was identical to that described in Example 1 except the ITO (indium tin oxide) feed solution with about 140 ppm In3+ and pH 0.9 was used instead of that with 200 ppm In3+ in pH 1 H2SO4. The indium concentrations in the feed and strip solution samples as a function of time are given in Table 9. The results are also shown in FIG. 7. Both the table and figure show that the SLM with strip dispersion can recover and concentrate indium in the strip solution with 11000 ppm or higher from the ITO feed solution. Also given in this table are the tin concentrations in the feed solution samples as a function of time and those in the strip solution samples at the beginning and end of the experiment. Also shown in the figure are the tin concentrations in the feed solution samples as a function of time. These results indicate that the tin was hardly extracted from the feed solution and nor concentrated in the strip solution. Thus, the SLM with strip dispersion was effective for the removal and recovery of indium form the ITO feed solution.
  • TABLE 9
    Feed Strip
    Time In Sn Time In Sn
    (min) (ppm) (ppm) (min) (ppm) (ppm)
    0 143.5 14.52 0 0  0
    10 136.6 14.67 20 1240 —
    20 131.7 17.15 40 2538 —
    30 124.8 16.11 60 3485 —
    40 123.4 19.97 80 4564 —
    50 113.4 15.79 120 6222 —
    60 109.5 17.28 180 8692 —
    80 101.4 17.13 240 10532 —
    100 92.53 19.39 300 11177 —
    120 84.62 12.99 420 11631 —
    140 75.69 18.2 480 11695 —
    160 75.94 22.28 540 11606 —
    180 59.28 18.81 600 11581 —
    210 54.21 19.60 660 10932 —
    240 45.84 16.17 720 11018 20
    270 35.88 14.71
    300 34.15 14.42
    330 29.21 14.83
    360 23.93 17.00
    390 20.03 10.33
    420 17.43 9.97
    450 13.81 10.30
    480 12.71 12.51
    510 8.71 13.50
    540 6.76 16.48
    570 6.19 15.20
    600 5.72 13.31
    630 4.12 13.29
    660 3.32 13.45
    690 2.64 14.23
    720 2.26 12.34
    • Example 10
  • Residual Electrolyte Feed Solution with about 11000 ppm In3+ and pH 0.9 of 0.5 L
      • Condition: Organic Solution=0.6M D2EHPA, 2 vol % dodecanol in Isopar-L, 0.9 L
      • Strip=5M HCl, 0.1 L
        The experimental procedure for this example was identical to that described in Example 1 except the residual electrolyte feed solution with about 11000 ppm In3+ and pH 1 was used instead of that with 200 ppm In3+ in pH 1 H2SO4. The indium concentrations in the feed and strip solution samples as a function of time are given in Table 10. In this table, both the indium concentration in the strip solution obtained experimentally, i.e., strip-exp, and that calculated from the feed concentration based on the material balance, i.e., strip-ideal (the ideal case), are included. The results are also shown in FIG. 8. Both the table and figure show that the SLM with strip dispersion can recover and concentrate indium in the strip solution with 25000 ppm or higher (strip-exp) from the feed solution of residual electrolyte.
  • TABLE 10
    Time Feed Strip-ideal Time Strip-exp.
    (min) (ppm) (ppm) (min) (ppm)
    0 11018 0 0 0
    0.5 10798 1103 6 4738
    1 10309 3545 10 7412
    1.5 9966 5261 20 11440
    2 9723 6476 30 12791
    2.5 9690 6641 45 15170
    3 9335 8414 60 18783
    3.5 9154 9321 150 25206
    4 9154 9321
    5 8605 12068
    6 8422 12981
    7 8403 13076
    8 8329 13448
    10 8121 14488
    12 7775 16214
    15 7687 16658
    20 7460 17789
    25 7269 18745
    30 7437 17908
    40 7337 18404
    50 7019 19998
    60 6897 20606
    100 6022 24980
    150 5262 28779
  • Examples 1 to 10 have demonstrated that D2EHPA is an effective extractant in the supported liquid membranes (SLMs) with strip dispersion for the removal and recovery of indium from various aqueous feed solutions. These results of the SLMs with strip dispersion for indium are very much different from those for the metals and radionuclides disclosed in Ho's patents mentioned earlier (U.S. Pat. Nos. 6,291,705, 6,328,782, 6,350,419, 6,696,589) where D2EHPA was ineffective. Thus, these results disclosed in this present invention are unexpected in view of the prior art disclosed in the Ho's patents.
    • Example 11 2-Butyl-1-Octyl Phenylphosphonic Acid (BOPPA) Extractant
  • Feed Solution with 200 ppm In3+ in pH 1 H2SO4 of 1 L
      • Condition: Organic Solution=0.6M BOPPA, 2 vol % dodecanol in Isopar-L, 0.8 L
      • Strip=5M HCl, 0. 12 L
        The experimental procedure for this example was similar to that described in Example 1 except the extractant of 0.6M 2-butyl-1-octyl phenylphosphonic acid (BOPPA; C12 alkyl group) was used instead of that of 0.6M D2EHPA. The indium concentrations in the feed and strip solution samples as a function of time are given in Table 11. The results are also shown in FIG. 9. Both the table and figure show that the SLM with strip dispersion can effectively recover and concentrate indium in the strip solution with 20000 ppm or higher from the feed solution.
  • TABLE 11
    Time Feed Time Strip
    (min) (ppm) (min) (ppm)
    0 173.6 0 0
    5 137.5 5 1044
    10 98.2 10 1584
    15 69.2 15 2207
    20 48.5 20 2567
    25 32.1 25 2849
    30 20.4 30 3010
    40 9.7 40 2940
    50 3.0 50 3125
    60 1.4 60 3021
    120 0.1 120 3130

Claims (22)

1. A combined supported liquid membrane (SLM)/strip dispersion process for the removal and recovery of indium from a feed solution containing the indium comprising
(1) treating a feed solution containing indium on one side of the SLM embedded in a microporous support material to remove the indium by the use of a strip dispersion on the other side of the SLM, the strip dispersion being formed by dispersing an aqueous strip solution in an organic liquid comprising an extractant using a mixer; and
(2) allowing the strip dispersion or a part of the strip dispersion to separate into two phases, the organic liquid phase and the aqueous strip solution phase containing a concentrated indium solution.
2. The process of claim 1, wherein the feed solution is treated to remove indium to a concentration of 5 parts per million (ppm) or lower.
3. The process of claim 1, wherein the aqueous strip solution of the strip dispersion comprises an acid.
4. The process of claim 3, wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and mixtures thereof.
5. The process of claim 1, wherein the organic liquid of the strip dispersion further comprises a modifier in a hydrocarbon solvent or mixture.
6. The process of claim 1, wherein the organic liquid of the strip dispersion comprises about 2 volume % to about 100 volume % extractant and about 0 volume % to about 20 volume % modifier in a hydrocarbon solvent or mixture.
7. The process of claim 6, wherein the organic liquid of the strip dispersion comprises about 5 volume % to about 40 volume % extractant and about 1 volume % to about 10 volume % modifier in a hydrocarbon solvent or mixture.
8. The process of claim 5, wherein the modifier is selected from the group consisting of alcohols, nitrophenyl alkyl ethers, trialkyl phosphates, and mixtures thereof.
9. The process of claim 8 wherein the alcohol is selected from the group consisting of hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadacanol, octadecanol, and mixtures thereof.
10. The process of claim 8 wherein the nitrophenyl alkyl ether is selected from the group consisting of o-nitrophenyl octyl ether (o-NPOE), o-nitrophenyl heptyl ether, o-nitrophenyl hexyl ether, o-nitrophenyl pentyl ether (o-NPPE), o-nitrophenyl butyl ether, o-nitrophenyl propyl ether, and mixtures thereof.
11. The process of claim 8, wherein the trialkyl phosphate is selected from the group consisting of tributyl phosphate, tris(2-ethylhexyl)phosphate, and mixtures thereof.
12. The process of claim 5, wherein the hydrocarbon solvent is selected from a group consisting of n-decane; n-undecane; n-dodecane; n-tridecane; n-tetradecane; isodecane; isoundecane; isododecane; isotridecane; isotetradecane; isoparaffinic hydrocarbon solvent having a flash point of 92° C., a boiling point of 254° C., a viscosity of 3 cp at 25° C., and a density of 0.791 g/ml at 15.6° C.; and mixtures thereof.
13. The process of claim 1, wherein the microporous support material is selected from the group consisting of polypropylene, polytetrafluoroethylene, polyethylene, polysulfone, polyethersulfone, polyetheretherketone, polyimide, polyamide, polyaramide, and mixtures thereof.
14. The process of claim 1, wherein the microporous support material is polypropylene.
15. The process of claim 1, wherein the extractant comprises a dialkyl phosphoric acid.
16. The process of claim 15, wherein the dialkyl group of the dialkyl phosphoric acid is paraffinic (saturated) and has from 6 to 26 carbon atoms.
17. The process of claim 15, wherein the dialkyl phosphoric acid is selected from the group consisting of di(2-ethyl-hexyl)phosphoric acid (D2EHPA), di(2-butyl-octyl)phosphoric acid, di(2-hexyl-decyl)phosphoric acid, di(2-octyl-decyl/2-hexyl-dodecyl)phosphoric acid, di(2-octyl-dodecyl)phosphoric acid, di(hexyl)phosphoric acid, di(heptyl)phosphoric acid, di(octyl)phosphoric acid, di(nonyl)phosphoric acid, di(decyl)phosphoric acid, di(undecyl)phosphoric acid, di(dodecyl)phosphoric acid, di(tridecyl)phosphoric acid, di(tetradecyl)phosphoric acid, di(pentadecyl)phosphoric acid, di(hexadecyl)phosphoric acid, di(heptadecyl)phosphoric acid, di(octadecyl)phosphoric acid, di(nonadecyl)phosphoric acid, di(decadecyl)phosphoric acid, di(undecadecyl)phosphoric acid, di(dodecadecyl)phosphoric acid, di(tridecadecyl)phosphoric acid, di(tetrdecadecyl)phosphoric acid, di(pentadadecyl)phosphoric acid, di(hexadecadecyl)phosphoric acid, and mixtures thereof.
18. The process of claim 15 wherein the dialkyl phosphoric acid is di(2-ethyl-hexyl)phosphoric acid (D2EHPA).
19. The process of claim 1 wherein the extractant comprises an alkyl phenylphosphonic acid.
20. The process of claim 19 wherein the alkyl group of the alkyl phenylphosphonic acid is paraffinic (saturated) and has from 6 to 26 carbon atoms.
21. The process of claim 19 wherein the alkyl phenylphosphonic acid is selected from the group consisting of 2-butyl-1-octyl phenylphosphonic acid (BOPPA), 2-hexyl-1-decyl phenylphosphonic acid, 2-octyl-1-decyl/2-hexyl-1-dodecyl phenylphosphonic acid, 2-octyl-1-dodecyl phenylphosphonic acid, hexyl phenylphosphonic acid, heptyl phenylphosphonic acid, octyl phenylphosphonic acid, nonyl phenylphosphonic acid, decyl phenylphosphonic acid, undecyl phenylphosphonic acid, dodecyl phenylphosphonic acid, tridecyl phenylphosphonic acid, tetradecyl phenylphosphonic acid, pentadecyl phenylphosphonic acid, hexadecyl phenylphosphonic acid, heptadecyl phenylphosphonic acid, octadecyl phenylphosphonic acid, nonadecyl phenylphosphonic acid, decadecyl phenylphosphonic acid, undecadecyl phenylphosphonic acid, dodecadecyl phenylphosphonic acid, tridecadecyl phenylphosphonic acid, tetrdecadecyl phenylphosphonic acid, pentadadecyl phenylphosphonic acid, hexadecadecyl phenylphosphonic acid, and mixtures thereof.
22. The process of claim 19 wherein the alkyl phenylphosphonic acid is 2-butyl-1-octyl phenylphosphonic acid (BOPPA).
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