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WO2001056933A2 - Procedes combinant une dispersion d'epuration et des membranes liquides sur support, et agents d'extraction - Google Patents

Procedes combinant une dispersion d'epuration et des membranes liquides sur support, et agents d'extraction Download PDF

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Publication number
WO2001056933A2
WO2001056933A2 PCT/US2001/040028 US0140028W WO0156933A2 WO 2001056933 A2 WO2001056933 A2 WO 2001056933A2 US 0140028 W US0140028 W US 0140028W WO 0156933 A2 WO0156933 A2 WO 0156933A2
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Prior art keywords
phenylphosphonic acid
acid
strip
solution
alkyl
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PCT/US2001/040028
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WO2001056933A3 (fr
Inventor
W. S. Winston Ho
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Commodore Separation Technologies Inc
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Commodore Separation Technologies Inc
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Priority claimed from US09/541,925 external-priority patent/US6433163B1/en
Application filed by Commodore Separation Technologies Inc filed Critical Commodore Separation Technologies Inc
Priority to AU2001247956A priority Critical patent/AU2001247956A1/en
Publication of WO2001056933A2 publication Critical patent/WO2001056933A2/fr
Anticipated expiration legal-status Critical
Publication of WO2001056933A3 publication Critical patent/WO2001056933A3/fr
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Classifications

    • 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
    • B01D61/24—Dialysis ; Membrane extraction
    • B01D61/246—Membrane extraction
    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

Definitions

  • the present invention relates to the removal and recovery of target species, such as metals, radionuclides, penicillin, and organic acids, from feed solutions, such as waste waters and process streams, using supported liquid membrane technology.
  • target species such as metals, radionuclides, penicillin, and organic acids
  • 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 semi-permeable membrane for the transport of the target species from the feed solution to the strip solution.
  • the organic liquid in the SLM is immiscible in the aqueous feed and strip streams and contains an extractant, a diluent which is generally an inert organic solvent, and sometimes a modifier.
  • Nechaev et al A. F. Nechaev, V. V. Projaev, V. P. Kapranchik, "Supported Liquid Membranes in Radioactive Waste Treatment Processes: Recent Experience and Prospective", in S. Slate, R. Baker, and G. Benda, eds., Proceedings of Fifth International Conference on Radioactive Waste
  • SLMs SLMs
  • 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
  • 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 from aqueous feed solutions have also been long pursued in the scientific and industrial community.
  • ELMs for the removal of metals including cobalt, copper, zinc, nickel, mercury, lead, cadmium, silver, europium, lanthanum, and neodymium, have been described in detail (W. S.
  • Wiencek "Emulsion Liquid Membranes for Wastewater Treatment. Equilibrium Models for Some Typical Metal-Extractant Systems," Environ. Sci. Technol.. 28, 1090-1098 (1994); M.T.A. Reis and J.M.R. Carvalho, "Recovery of Heavy Metals by a Combination of Two Processes: Cementation and Liquid Membrane Permeation," Minerals Eng.. 7, 1301-131 1 (1994); T. Kakkoi, M. Goto, K.
  • ELMs to remove penicillin and organic acids from aqueous feed solutions has long been pursued in the scientific and industrial community.
  • 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 generally to a process for the removal and recovery of target species from a feed solution using a combined SLM/strip dispersion.
  • the invention also relates to a new family of extractants that are useful for the removal and recovery of such target species.
  • the present invention relates to a process for the removal and recovery of one or more metals from a feed solution which comprises the following steps. First, a feed solution containing one or more metals is passed on one side of the SLM embedded in a microporous support material and treated to remove the metals 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 metal solution.
  • the present invention relates to a process for the removal and recovery of one or more radionuclides from a feed solution which comprises the following steps.
  • a feed solution containing one or more radionuclides is passed on one side of the SLM embedded in a microporous support material and treated to remove the radionuclides 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.
  • 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 radionuclide solution.
  • the present invention relates to a process for the removal and recovery of penicillins and organic acids from a feed solution which comprises the following steps.
  • a feed solution containing penicillin or organic acids is passed on one side of the SLM embedded in a microporous support material to remove the penicillin or organic acids 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.
  • the strip dispersion, or a part of the strip dispersion is then allowed to stand, resulting in separation into two phases: the organic liquid phase and the aqueous strip solution phase containing a concentrated solution of the target species.
  • penicillin shall be inclusive of all members of the group of antibiotics biosynthesized by several species of molds and any synthetic derivatives.
  • 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.
  • the present invention relates to an SLM embedded in a microporous support material having an interfacial polymerized layer or layers.
  • the present invention relates to a process for the removal and recovery of one or more target species, such as metals, radionuclides, penicillins, and organic acids, from a feed solution which comprises the following steps.
  • a feed solution containing one or more of the target species is passed on one side of the SLM embedded in a microporous support material with an interfacial polymerized layer or layers to remove the target species 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.
  • the strip dispersion, or a part of the strip dispersion is then allowed to stand, resulting in separation into two phases: the organic liquid phase and the aqueous strip solution phase containing a concentrated solution of the target species.
  • the continuous organic phase of the strip dispersion readily wets the pores of a microporous support to form a stable SLM.
  • the present invention relates to a family of new extractants, alkyl phenylphosphonic acids, e.g., 2-butyl-l-octyl phenylphosphonic acid (BOPPA) and 2-octyl-l-dodecyl phenylphosphonic acid (C20 ODPPA), which are useful in both conventional SLMs and the process of the present invention for the removal and recovery of radionuclide and/or metal species, also called herein the "target species.”
  • BOPPA 2-butyl-l-octyl phenylphosphonic acid
  • C20 ODPPA 2-octyl-l-dodecyl phenylphosphonic acid
  • Use of the new extractants result in improved extraction and an increased concentration of the target species in the aqueous strip solution.
  • the invention also relates to a method for the production of these alkyl phenylphosphonic acids.
  • the invention relates to new class of extractants that include dialkyl phosphoric acids containing alkyl chains of at least 8 to 12 carbon atoms.
  • dialkyl phosphoric acids containing alkyl chains of at least 8 to 12 carbon atoms.
  • di(2-butyloctyl)monothiophosphoric acid C12
  • MTPA MTPA
  • the invention also relates to a method for the production of these dialkyl phosphoric acids.
  • BOPPA 2-butyl-l-octyl phenylphosphonic acid
  • BOPPA 2-butyl-l-octyl phenylphosphonic acid
  • Figure 1 is a schematic representation of the combined supported liquid membrane/strip dispersion of the present invention.
  • FIG. 2 is an enlarged view of the schematic representation of the combined supported liquid membrane/strip dispersion of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the present invention relates to a process for the removal and recovery of a target species 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 target species is a metal.
  • Preferred metal species include, but are not limited to, cobalt, copper, zinc, nickel, mercury, lead, cadmium, silver, europium, lanthanum, neodymium, praseodymium, gadolinium, and selenium.
  • Other preferred metals include calcium, magnesium, and zinc.
  • the process of the invention comprises the following steps. First, a feed solution containing one or more metals is passed on one side of the SLM embedded in a microporous support material and treated to remove the metal or metals 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 metal solution.
  • the target species is a radionuclide.
  • Preferred radionuclide species include, but are not limited to, strontium, cesium, technetium, uranium, boron, plutonium, cobalt, and americium.
  • the process of the invention comprises the following steps. First, a feed solution containing one or more radionuclides is passed on one side of the SLM embedded in a microporous support material and treated to remove the radionuclide or radionuclides 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 radionuclide solution.
  • the target species is a penicillin.
  • Preferred penicillin species include, but are not limited to, penicillin G and penicillin V.
  • the process of the invention comprises the following steps. First, a feed solution containing one or more penicillins is passed on one side of the SLM embedded in a microporous support material and treated to remove the penicillin 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 penicillin solution.
  • the target species is an organic acid.
  • Preferred organic acid species include, but are not limited to, phenylalanine, acrylic acid, lactic acid, proprionic acid, citric acid, and acetic acid.
  • the process of the invention comprises the following steps. First, a feed solution containing one or more organic acids is passed on one side of the SLM embedded in a microporous support material and treated to remove the organic acid or acids 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 organic acid 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 the target species 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 continuous replenishment of the strip dispersion as shown in Figure 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 Figure 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, P a which is typically less than approximately 2 psi, is applied on the feed solution side of the SLM.
  • the pressure P a is greater than the pressure, P 0 , 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 have 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 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 is the product of this process.
  • the feed solution includes, but is not limited to, waste waters or process streams containing metals.
  • the metals include, but are not limited to, cobalt, copper, zinc, nickel, mercury, lead, cadmium, silver, europium, lanthanum, neodymium, praseodymium, gadolinium, chromium, calcium, magnesium, and selenium.
  • the radionuclides include, but are not limited to, strontium, cesium, technetium, uranium, boron, plutonium, cobalt, and americium.
  • the penicillins include, but are not limited to, penicillin G and penicillin V.
  • the organic acids include, but are not limited to phenylalanine, acrylic acid, lactic acid, proprionic acid, and acetic acid.
  • microporous support employed in the invention is comprised of, for example, microporous polypropylene, polytetrafluoroethylene, polyethylene, polysulfone, polyethersulfone, polyetheretherketone, polyimide, polyamide, or mixtures thereof.
  • the preferred microporous support is microporous polypropylene hollow fibers.
  • the aqueous portion of the strip dispersion comprises an aqueous acid solution or an aqueous base solution.
  • the aqueous portion of the strip dispersion comprises an aqueous acid solution, such as a mineral acid.
  • acids useful in the present invention include, but are not limited to, sulfuric acid (H 2 SO 4 ), hydrochloric acid (HC1), nitric acid (HNO 3 ), phosphoric acid (H 3 PO 4 ), 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 3 M.
  • the aqueous portion of the strip dispersion comprises an aqueous base solution.
  • bases useful in the present invention include, but are not limited to, sodium carbonate (Na 2 CO 3 ), sodium bicarbonate (NaHCO 3 ), sodium hydroxide (NaOH), ammonium hydroxide (NH 4 OH), and tetramethylammonium hydroxide ((CH) 4 NOH).
  • the base is advantageously present in a concentration between about 0.01 M and about 16 M, more preferably between about 0.2 M and about 2M.
  • the continuous organic liquid phase into which the aqueous strip solution is dispersed contains an extractant or extractants.
  • any extractant capable of extracting the target species contained in the feed solution can be used in the present invention.
  • Typical extractants which are known in the art for extraction of species from waste waters or process streams may be employed in the present strip dispersion.
  • Some nonlimiting examples of such extractants include, di(2,4,4- trimethylpentyl)dithiophosphonic acid), a nonylsalicyl aldoxime and ketoxime extractant system 9 e.g., LIX 973N containing about 46% nonylsalicyl aldoxime, 18% ketoxime, 6% nonylphenol, and 30% diluent), di(2-ethylhexyl)phosphoric acid (D2EHPA), oleic acid, and those disclosed in the references listed in the background ssection.
  • D2EHPA di(2-ethylhexyl)phosphoric acid
  • the present invention also comprises a new families of extractants.
  • One of these families of extractants are alkyl phenylphosphonic acids. These alkyl phenylphosphonic acids have advantageous properties over prior art extractants.
  • the alkyl group of the alkyl phenylphosphonic acid is paraffinic (saturated) and includes from 6 to 26 carbon atoms.
  • the new alkyl phenylphosphonic acids include
  • the new extractants are useful for the removal and recovery of radionuclides, such as strontium, cesium, plutonium, cobalt, and americium, and metal species, such as calcium, magnesium, and zinc.
  • the alkyl phenylphosphonic acid is employed as the extractant in the strip dispersion in the process of the invention.
  • the alkyl phenylphosphonic acid has significantly increases the extraction of strontium from feed solutions.
  • the new extractant also extends the SLM operation to a lower pH range to better utilize the available surface area of the hollow-fiber module. For example, for the removal of strontium, the pH has been reduced from 4.5 to 3.
  • the alkyl phenylphosphonic acid may be synthesized, for example, by reacting an alcohol containing from 6 to 26 carbon atoms and phenylphosphonyl dichloride in an organic solvent, such as pyridine. Preferred temperatures for the reaction are between about 0 and 10°C. The reaction is quenched by adding concentrated HCl and ice to the reaction mixture, resulting in a solution having a pH of 1. The alkyl phenylphosphonic acid can then be extracted from the reaction mixture using a solvent, such as toluene. The alkyl phenylphosphonic acid/solvent solution was washed with 1 M HCl solution and dried, for example, with MgSO 4 to produce a clear solution. The alkyl phenylphosphonic acid can then be recovered by evaporating the solvent from the solution in any manner.
  • an organic solvent such as pyridine. Preferred temperatures for the reaction are between about 0 and 10°C.
  • the reaction is quenched by adding concentrated HCl and
  • BOPPA may be synthesized, for example, by reacting 2-butyl-l-octanol and phenylphosphonyl dichloride in an organic solvent. Preferred temperatures for the reaction are between about 0 and 10°C. The reaction is quenched by adding concentrated HCl and ice to the reaction mixture, resulting in a solution having a pH of 1. The BOPPA can then be extracted from the reaction mixture using a solvent, such as toluene. The BOPP A/solvent solution was washed with 1 M HCl solution and dried, for example, with MgSO 4 to produce a clear solution. The BOPPA can then be recovered by evaporating the solvent from the solution in any manner.
  • alkyl phenylphosphonic acids including 2-hexyl- l -decyl (C 16) phenylphosphonic acid, 2-octyl-l-decyl/2-hexyl-l -dodecyl (C18) phenylphosphonic acid, 2-octyl-l-dodecyl (C20) phenylphosphonic acid, can be synthesized in a similar manner.
  • the present invention also comprises another family of novel extractants.
  • This new class of extractants include dialkyl phosphoric acids containing alkyl chains of at least 8 to 12 carbon atoms.
  • the compound di(2- butyloctyl)monothiophosphoric acid (C12 MTPA) is particularly useful for the removal and recovery of nickel.
  • These dialkyl monothiophosphoric acids can be produced, for example, by the following process. In general, the process involves reacting phosphorus pentasulfide (P 2 S 5 ) with an alcohol under heat to provide multiple alkyl thiophosphate intermediates.
  • dialkyl monothiophosphoric acid that corresponds to the alcohol used
  • the method can be carried out as a two-step synthesis, and can conveniently be performed in a single reaction vessel.
  • a solvent such as toluene or other hydrocarbon solvents, can optionally be employed in the reaction of the phosphorus pentasulfide and alcohol; however, use of a solvent is not necessary.
  • the hydrolysis reaction can be monitored, for example by fourier transfer infrared (FTIR) spectrometer, to determine when to stop the reaction, by-products of the reaction, such as phosphoric acid and residual alcohols, are easily removed.
  • FTIR Fourier transfer infrared
  • the phosphoric acid formed during the process can be removed, for example, by washing the final reaction mixture with water.
  • any residual alcohol can be separated from the monothiophosphates, for example, by distillation under vacuum.
  • R alkyl chains of 8 to 12 carbon atoms.
  • Alcohols that can be used in the present process include, but are not limited to, 2-ethyl-l-hexanol (C8); 3,5,5-trimethyl-l-hexanol (C9); 3,7-dimethyl-l-octanol (CIO); and 2-butyl-l-octanol (C12).
  • a preferred alcohol is 2-butyl-l-octanol.
  • Dialkyl monothiophosphoric acids that can be produced by the process include, but are not limited to, di(2-ethylhexyl)rnonothiophosphoric acid; di(3,5,5- trimethylhexyl) monothiophosphoric acid ; di(3,7-dimethyloctyl) monothiophosphoric acid; and di(2-butylocty ⁇ )monothiophosphoric acid.
  • a preferred monothiophosphoric acid is di(2-butyloctyl)monothiophosphoric acid.
  • Mineral acids which can be used to hydrolyze the P 2 S 5 include, but are not limited to, sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ), and hydrochloric acid (HCl), with about 2 normal to about 4 normal HCl being preferred.
  • Solvents that can be used in the process include but are not limited to toluene, benzene, p-xylene, and m-xylene. Toluene is the preferred solvent, however, it is not necessary to use a solvent for dissolving the P 2 S 5 in the present invention.
  • the reaction mixture can be heated, advantageously, the reaction mixture can be heated to a temperature in the range of about 60°C to about 160°C for a period of about 1 hour to about 60 hours.
  • the reaction mixture is heated to a temperature from about 70°C to about 145°C for a period of about 1 to about 24 hours, more preferably to a temperature from about 80°C to about 100°C for a period from about 4 hours to about 6 hours.
  • the hydrolysis reaction can be heated.
  • the reaction can be heated to a temperature in the range of about
  • reaction parameters include either heating to a temperature of about 80°C to about 100°C for a period of about 6 hours to about 8 hours, or to a temperature of about 100°C to about 120°C for about 3 hours to about 4 hours.
  • the process of the present invention is similar to the reaction of phosphorous pentoxide (P 2 O 5 ) with alcohol. However, the use of phosphorus pentasulfide P 2 S 5 has several advantages.
  • 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.
  • Hydrocarbon solvents that are useful in the present invention include, but are not limited to, 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 comprises 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.
  • alcohols that can be used in the present invention include, but are not limited to, 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 mixtures 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% - 100% (approximately 0.05M - 3M) extractant and about 0% - 20% modifier in a hydrocarbon solvent or mixture. More preferably, the organic liquid of the present strip dispersion comprises about 5% - 40% extractant and about 1% - 10% modifier in a hydrocarbon solvent or mixture. Even more preferably, the organic liquid comprises about 5% - 40% extractant and about 1% - 10% dodecanol in an isoparaffinic hydrocarbon solvent or in n-dodecane. All percentages are by weight unless specified otherwise.
  • the present invention has several advantages over conventional SLM technology. These advantages include increased membrane stability, reduced costs, increased simplicity of operation, improved flux, and improved recovery of target species concentration. These advantages also include increased simplicity of operation, reduction of capital and operation costs, and increased efficiency of target species removal.
  • the present invention provides a constant supply of the organic membrane solution into the pores of the hollow fiber support. 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. It further 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 many targeted species. For example, fluxes of about 3 g/(m 2 *hr) or higher for treatment of the feed solution are typical for the present invention.
  • unexpectedly high flux results with the present invention as compared to those observed with conventional SLM separation processes. Particularly advantageous fluxes result with the present process when it is used for the removal and recovery of cobalt.
  • the present invention comprises a new type of SLM which 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 target species in the aqueous strip solution.
  • the concentrated strip solution is a valuable product for resale or reuse.
  • the strip dispersion for each of the following examples was prepared by mixing an aqueous strip solution in a quantity of, for example, 200 ml, and an organic extractant solution (for example, dodecane containing 2 wt. % dodecanol and 8 wt. % extractant) in a quantity of, for example, 600 ml, in a Fisher brand mixer with a 2-inch diameter, 6-bladed, high-shear impeller at 500 rpm as measured by an Ono Sokki HT-4100 tachometer.
  • the mixer was plugged into a varistat to allow for adjustable speed control.
  • the impeller was initially started at 50% of its full power and the varistat at 80%.
  • the hollow-fiber moldule was 2.5 inches in diameter and 8 inches in length, providing a surface area of 1.4 m 2 .
  • the process was first started by passing water through the hollow fiber module. The pressures were adjusted to provide a positive pressure on the feed side of the hollow fiber module. Once the pressures were adjusted and stable, the water was replaced with the feed solution. A positive pressure was maintained on the feed side to prevent the organic phase in the shell side from passing through the pores of the hollow fibers.
  • the pressure of the inlet on the shell side was maintained at 1.25 psi and the outlet pressure of the feed side was set at 3.25 psi, thus maintaining a 2 psi differential between the two sides.
  • the feed flow was adjusted to give a flow rate of approximately 0.84 liter/min at these pressures.
  • the typical feed solution volume for these experiments was 4 liters.
  • Samples from the feed solution and the strip dispersion were taken at 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 and centrifuged to facilitate complete separation.
  • the aqueous phase samples from the strip dispersion samples and the feed solution samples were then analyzed by inductively coupled plasma (ICP) spectrometry.
  • ICP inductively coupled plasma
  • the flux of a species removed from the feed solution can be defined by the following formula:
  • V is the volume of the feed solution treated
  • ⁇ C is the concentration change in the feed solution
  • t is the time at which the sample was taken
  • A is the membrane surface area.
  • C is the initial concentration of the species in the feed solution
  • C is the concentration of the species in the feed solution at time t
  • t is the time
  • the rest of the symbols are as defined above.
  • the mass transfer coefficient k of the species was calculated from the above equation.
  • a fresh solution of 2.5 M H 2 SO 4 was prepared for use as the strip solution.
  • a strip dispersion was then prepared by mixing together 200 ml of the 2.5 M H 2 SO 4 solution and 600 ml of an organic solution containing 24 wt. % di(2,4,4- trimethylpentyl)dithiophosphinic acid (e.g., Cyanex 301), 2 wt. % dodecanol, and 74 wt. % Isopar L as described in the general procedure above.
  • This strip dispersion was then fed into the shell side of a 2.5-inch diameter polypropylene hollow fiber module (2.5 inches in diameter by 8 inches in length).
  • a feed solution containing a cobalt concentration of 489 parts per million (ppm) was passed into the tube side of the hollow fiber module.
  • the pH of the feed solution was maintained at 2.3 +/- 0.1 by adding 5 M NaOH as needed.
  • Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 1 below.
  • the cobalt was removed from the feed solution, concentrated, and recovered in the aqueous strip solution.
  • the cobalt flux of 8.777 g/(m 2 *hr) at a cobalt concentration of 233 ppm in the feed solution was unexpectedly high in comparison with the cobalt flux obtained under similar conditions with the conventional SLM as described in Example 3.
  • the extractant concentration of 24 wt. % was much lower than the extractant concentration for the conventional SLM in Example 3 which was about 37 wt. %.
  • a higher extractant concentration should give a higher flux.
  • the high flux of the seen with the present invention was an unexpected result.
  • Example 2 The experimental procedure for this example was the same as that described in Example 1 , except that a feed solution containing 571 ppm cobalt and the used strip dispersion from the preceding example were employed. The excess aqueous strip and organic solutions from the strip dispersion samples from the preceding example were returned to the strip dispersion tank before the start of this experiment. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 2.
  • the cobalt was removed from the feed solution, concentrated, and recovered in the aqueous strip solution.
  • the cobalt flux of 10.217 g/(m 2 *hr) at the cobalt concentration of 273 ppm in the feed solution was unexpectedly high in comparison with the cobalt flux obtained under the similar conditions with the conventional SLM described in Example 3.
  • the cobalt flux with the present invention was more than 5.2 times higher than that with the conventional SLM.
  • the extractant concentration of 24 wt. % was much lower than that of about 37 wt. % for the conventional SLM in Example 3.
  • a higher extractant concentration should generally give a higher flux.
  • the high flux was an unexpected result of the present invention. Table 2
  • the organic membrane phase of the conventional SLM (imbedded in a microporous support) was placed between two aqueous solutions - the feed solution and a strip solution that was not a strip dispersion.
  • the microporous support used for this example was the same type and same size of the hollow fiber module employed and described in Example 1.
  • the organic membrane solution was similar to that used in Example 1 except the concentration of the extractant, di(2,4,4-trimethylpentyl)dithiophosphinic acid (e.g., Cyanex 301), was higher, i.e., 1 M (approximately 37 wt. % instead of the 24 wt. % used in Example 1).
  • Example 3 In a manner similar to Example 1, a feed solution containing 472 ppm cobalt and a sulfuric acid strip solution were used in Example 3. In the same way as in Example 1 , the pH of the feed solution was maintained by adding 5 M NaOH as needed. Also in a similar countercurrent flow configuration, the feed solution was passed into the tube side of the hollow fiber module, whereas the strip solution was fed into the shell side of the module. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 3.
  • the experimental procedure for this example was the same as that described in Example 1, except that a feed solution containing 562 ppm cobalt and an organic solution of the strip dispersion containing 8 wt. % di(2,4,4-trimethylpentyl)dithio- phosphinic acid (e.g., Cyanex 301), 2 wt. % dodecanol, and 90 wt. % Isopar L were used. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 4.
  • a feed solution containing 562 ppm cobalt and an organic solution of the strip dispersion containing 8 wt. % di(2,4,4-trimethylpentyl)dithio- phosphinic acid e.g., Cyanex 301
  • 2 wt. % dodecanol e.g., 2 w
  • the cobalt was removed from the feed solution, concentrated, and recovered in the aqueous strip solution.
  • the cobalt flux of 7.406 g/(m 2 *hr) at a cobalt concentration of 346 ppm in the feed solution was unexpectedly high in comparison with the cobalt flux obtained under the similar conditions with the conventional SLM described in Example 3.
  • the cobalt flux with the present invention was at least 3.8 times higher than that with the conventional SLM.
  • the extractant concentration of 8 wt. % for the present Example was much lower than that of about 37 wt. % for the conventional SLM in Example 3.
  • a higher extractant concentration should generally give a higher flux.
  • the high flux of the present invention was an unexpected result. Table 4
  • Example 4 The experimental procedure for this example was the same as that described in Example 4, except that a feed solution containing 567 ppm cobalt and the used strip dispersion from the Example 4 were used. The excess aqueous strip and organic solutions from the strip dispersion samples of Example 4 were returned to the strip dispersion tank before the start of the run for this experiment. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 5.
  • the cobalt was removed from the feed solution, concentrated, and recovered in the aqueous strip solution.
  • the cobalt flux of 8.023 g/(m 2 *hr) at a cobalt concentration of 333 ppm in the feed solution was unexpectedly high in comparison with the cobalt flux obtained under the similar conditions with the conventional SLM described in Example 3.
  • the cobalt flux with the present invention was more than 4.1 times higher than that with the conventional SLM.
  • the extractant concentration of 8 wt. % for the present Example was much lower than that of about 37 wt. % for the conventional SLM in Example 3.
  • a higher extractant concentration should generally give a higher flux. Again, the high flux was an unexpected result of the present invention.
  • the experimental procedure for this example was the same as that described in Examples 1 and 4, except that a feed solution containing 562 ppm cobalt and an organic solution of the strip dispersion containing 8 wt. % di(2,4,4- trimethylpentyl)dithio-phosphinic acid (e.g., Cyanex 301), 3 wt. % dodecanol, and 89 wt. % Isopar L were used. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 6.
  • the cobalt was removed from the feed solution, concentrated, and recovered in the aqueous strip solution.
  • the cobalt flux of 6.960 g/(m 2 *hr) at the cobalt concentration of 359 ppm in the feed solution was unexpectedly high in comparison with the cobalt flux obtained under the similar conditions with the conventional SLM described in Example 3.
  • the flux for the latter at a similar cobalt concentration of 358 ppm in the feed solution was only 1.954 g/(m 2 *hr).
  • the cobalt flux with the present invention was more than 3.6 times higher than that with the conventional SLM.
  • the extractant concentration of 8 wt. % for the present example was much lower than that of about 37 wt. % for the conventional SLM in Example 3.
  • a higher extractant concentration should generally give a higher flux.
  • the high flux was an unexpected result of the present invention. Table 6
  • Example 7 The experimental procedure for this example was the same as that described in Example 6, except that a feed solution containing 551 ppm cobalt and the used strip dispersion from Example 6 were employed. The excess aqueous strip and organic solutions from the strip dispersion samples from Example 6 were returned to the strip dispersion tank before the start of this experiment. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 7.
  • the cobalt was removed from the feed solution, concentrated, and recovered in the aqueous strip solution.
  • the cobalt flux of 6.926 g/(m 2 *hr) at the cobalt concentration of 349 ppm in the feed solution was unexpectedly high in comparison with the cobalt flux obtained under the similar conditions with the conventional SLM described in Example 3.
  • the flux for the latter, even at a higher cobalt concentration of 358 in the feed solution, was only 1.954 g/(m 2 *hr).
  • the cobalt flux with the present invention was more than 3.5 times higher than that with the conventional SLM.
  • the extractant concentration of 8 wt. % for the present Example was much lower than that of about 37 wt. % for the conventional SLM in Example 3.
  • a higher extractant concentration should generally give a higher flux. Again, the high flux was an unexpected result of the present invention.
  • Examples 4 - 7 also served to investigate the effect of dodecanol concentration on cobalt flux. As shown in Table 7, the effect of dodecanol concentration on cobalt flux in these examples was not very significant for dodecanol concentrations of 2 wt. % and 3 wt. %.
  • the experimental procedure for this example was the same as that described in Examples 1 , 4, and 6, except that a feed solution containing 576 ppm cobalt and an organic solution of the strip dispersion containing 8 wt. % di(2,4,4- trimethylpentyl)dithio-phosphinic acid (e.g., Cyanex 301), 1 wt. % dodecanol, and 91 wt. % Isopar L were used. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above.
  • a feed solution containing 576 ppm cobalt and an organic solution of the strip dispersion containing 8 wt. % di(2,4,4- trimethylpentyl)dithio-phosphinic acid (e.g., Cyanex 301), 1 wt. % dodecanol, and 91 wt. % Isopar L were used. Samples of the feed
  • the cobalt was removed from the feed solution, concentrated, and recovered in the aqueous strip solution.
  • the cobalt flux of 6.171 g/(m 2 *hr) at the cobalt concentration of 396 ppm in the feed solution was unexpectedly high in comparison with the cobalt flux obtained under the similar conditions with the conventional
  • Example 8 The experimental procedure for this example was the same as that described in Example 8, except that a feed solution containing 570 ppm cobalt and the used strip dispersion from Example 8 were employed. The excess aqueous strip and organic solutions from the strip dispersion samples from Example 8 were returned to the strip dispersion tank before the start of this experiment. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 9.
  • the cobalt was removed from the feed solution, concentrated, and recovered in the aqueous strip solution.
  • the cobalt flux of 7.269 g/(m 2 *hr) at the cobalt concentration of 358 ppm in the feed solution was unexpectedly high in comparison with the cobalt flux obtained under the similar conditions with the conventional SLM described in Example 3.
  • the flux for the latter, even at the same cobalt concentration of 358 in the feed solution, was only 1.954 g/(m 2 *hr).
  • the cobalt flux with the present invention was more than 3.7 times higher than that with the conventional SLM.
  • the extractant concentration of 8 wt. % for the present example was much lower than that of about 37 wt. % for the conventional SLM in Example 3.
  • a higher extractant concentration should generally give a higher flux. Again, the high flux was an unexpected result of the present invention.
  • Examples 4 - 9 also served to investigate the effect of the concentration of the modifier, dodecanol, on cobalt flux. As shown from these examples, the effect of dodecanol concentration on cobalt flux was not very significant for dodecanol concentrations ranging from 1 wt. % to 3 wt. %. In other words, dodecanol concentrations ranging from 1 wt. % to 3 wt. % were effective.
  • the experimental procedure for this example was the same as that described in Example 1, except that a 1 -liter feed solution containing 524 ppm cobalt with pH 2; an 800-ml organic solution of 8 wt. % di(2,4,4-trimethylpentyl)dithiophosphinic acid (e.g., Cyanex 301), 2 wt. % dodecanol; and 90 wt. % Isopar L, and a 60-ml strip solution of 5 M hydrochloric acid were used.
  • the pH of the feed solution was maintained at 2.0 +/- 0.1 by adding 5 M NaOH as needed. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above.
  • the experimental procedure for this example was the same as that described in Example 1 , except that a 40-liter feed solution containing 492 ppm cobalt with pH 2; a 900-ml organic solution of 8 wt. % di(2,4,4-trimethylpentyl)dithiophosphinic acid (e.g., Cyanex 301), 2 wt. % dodecanol, and 90 wt. % Isopar L; and a 105-ml strip solution of 6.5 M hydrochloric acid were used.
  • the pH of the feed solution was maintained at 2.0 +/- 0.1 by adding 5 M NaOH as needed. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 11.
  • the cobalt was removed from the feed solution, recovered, and concentrated to more than 96,000 ppm in the aqueous strip solution in 6 hours using the recycle mode of operation for both the feed solution and the strip dispersion.
  • the cobalt concentration in the strip solution was more than 195 times the original feed concentration.
  • the experimental procedure for this example was the same as that described in Example 1, except that a 5-liter feed solution containing 151 ppm copper and 556 ppm zinc with pH 1.9; a 950-ml organic solution of 15 wt. % nonylsalicyl aldoxime and ketoxime extractant system (e.g., LIX 973N containing about 46% nonylsalicyl aldoxime, 18% ketoxime, 6% nonylphenol, and 30% diluent), 2 wt. % dodecanol, and 83 wt. % n-dodecane; and a 50-ml strip solution of 3 M sulfuric acid were used.
  • a 5-liter feed solution containing 151 ppm copper and 556 ppm zinc with pH 1.9 a 950-ml organic solution of 15 wt. % nonylsalicyl aldoxime and ketoxime extractant system (e.g., LIX 973N containing about 46% nonyl
  • the pH of the feed solution was maintained at 1.9 +/- 0.1 by adding 5 M NaOH as needed.
  • Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 12.
  • the copper concentration of the feed solution was changed from 151 ppm to 0.07 ppm in just 90 minutes using the recycle mode of operation for both the feed solution and the strip dispersion.
  • the copper was recovered and concentrated to more than 10,000 ppm in the aqueous strip solution in 2 hours.
  • the copper concentration in the strip solution was more than 70 times the original feed concentration.
  • the experimental procedure for this example was the same as that described in Examples 1 and 12, except that the 5-liter feed solution treated in Example 12 containing 556 ppm zinc with pH 1.9; a 850-ml organic solution of 8 wt. % di(2,4,4- trimethyl-pentyl)dithiophosphinic acid (e.g., Cyanex 301), 2 wt. % dodecanol, and 90 wt. % n-dodecane; and a 150-ml strip solution of 3 M sulfuric acid were used.
  • the pH of the feed solution was maintained at 1.9 +/- 0.1 by adding 5 M NaOH as needed.
  • the experimental procedure for this example was the same as that described in Example 1, except that a 2-liter feed solution containing 2,216 ppm nickel with pH 3; a 750-ml organic solution of 24 wt. % of the new extractant, di(2-butyloctyl) monothiophosphoric acid (C12 MTPA), 4 wt. % dodecanol, and 72 wt. % n- dodecane; and a 250-ml strip solution of 2.5 M sulfuric acid were used.
  • the pH of the feed solution was maintained at 3 +/- 0.1 by adding 5 M NaOH as needed. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 14.
  • the nickel was removed from the feed solution, recovered, and concentrated to more than 10,000 ppm in the aqueous strip solution in 30 minutes in the recycle mode of operation for both the feed solution and the strip dispersion.
  • the nickel concentration in the strip solution was more than 4.8 times the original feed concentration.
  • the experimental procedure for this example was the similar to that described in example 14, except that a feed solution containing 2,469 ppm nickel with pH 4.5 and a organic solution containing 24 wt. % of the conventional extractant, di(2-ethylhexyl) phosphoric acid (D2EHPA), were used.
  • the pH of the feed solution was maintained at 4.5 +/- 0.1 by adding 5 M NaOH as needed.
  • Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 15.
  • the nickel fluxes at the nickel concentrations of 2,335 ppm and 1,915 ppm in the feed solution at pH 4.5 were 2.30 and 1.93 g/(m 2 *hr), respectively. These fluxes were significantly lower than those with the new extractant, C12 MTPA, described in Example 14, i.e., 3.31 and 2.79 g/(m 2 *hr) at even lower nickel concentrations of 2,023 ppm and 1,860 ppm in the feed solution at an even lower pH of 3, respectively.
  • the flux of a metal increases as the concentration of the metal in the feed solution increases.
  • an extractant operable at a lower pH can better utilize the length of the module than an extractant operable at a higher pH.
  • the new extractant, C12 MTPA outperformed the conventional extractant,
  • the experimental procedure for this example was the same as that described in Example 1, except that a 2-liter feed solution containing 0.388 ppm mercury with pH 2.5; a 525-ml organic solution of 10 wt. % oleic acid, 10 wt. % dodecanol, and 80 wt. % Isopar L; and a 175-ml strip solution of 3 M nitric acid containing 3 wt. % sodium iodide were used.
  • the pH of the feed solution was maintained at 2.5 +/- 0.1 by adding 5 M NaOH as needed.
  • Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above. Fluxes and k values were then calculated and are reported in Table 16.
  • the mercury concentration in the feed solution was changed from 0.388 ppm to 0.00084 ppm in just 15 minutes using the recycle mode of operation for both the feed solution and the strip dispersion.
  • the mercury was further reduced to less than 0.00084 ppm in the feed solution, i.e., below the detection limit by ICP spectrometry, in the total run time of just 30 minutes, and it was recovered and concentrated to 21.2 ppm in the aqueous strip solution at the same time.
  • the mercury concentration in the strip solution was more than 54 times the original feed concentration.
  • the experimental procedure for this example was the same as that described in examples 1 and 16, except that a 2-liter feed solution containing 3.01 ppm mercury with pH 2.5; a 525-ml organic solution of 10 wt. % oleic acid, 2.5 wt. % dodecanol, and 87.5 wt. % Isopar 1; and a 175-ml strip solution of 3 M nitric acid containing 3 wt. % sodium iodide were used.
  • the pH of the feed solution was maintained at 2.5 +/- 0.1 by adding 5 M NaOH as needed. Samples of the feed and strip solutions were collected at timed intervals and analyzed by ICP as described in the general procedure above.
  • the alcohol 2-butyl-l-octanol 893 ml (4 moles) was mixed with 222g (1 mole) phosphorus pentasulfide (P 2 S 5 ) and heated to about 90°C for a period of about at least 4 hours.
  • the intermediate reaction products were hydrolyzed with about 100 ml of 4N HCl at a temperature of about 100°C to about 120°C for a period of about 3 hours to about 4 hours.
  • the hydolysis reaction was monitored by FTIR to determine when the reaction was complete.
  • the reaction mixture was then washed with water to remove any thiophosphoric acid (H 3 PSO 4 ) formed.
  • the reaction mixture was then distilled under vacuum to remove any unreacted 2-butyl- l-octanol.
  • a fresh solution of 3 M H 2 SO 4 was prepared for use as the strip solution.
  • a strip dispersion was then prepared by mixing together 250 ml of the 3 M H 2 SO 4 solution and 750 ml of n-dodecane containing 2% dodecanol and 8% 2-butyl-l-octyl phenylphosphonic acid (BOPPA) as described in the general procedure above.
  • BOPPA 2-butyl-l-octyl phenylphosphonic acid
  • a feed solution containing the following metals was passed into the tube side of the hollow fiber module: strontium (Sr; 5 ppm), calcium (Ca; 80 ppm), magnesium (Mg; 20 ppm), or zinc (Zn; 50 ppm).
  • the pH of the feed solution was maintained at 3.0 +/- 0.1 by adding 5 M NaOH as needed.
  • Samples of the feed and strip solutions were collected at timed intervals as described in the general procedure above and analyzed by ICP. Fluxes and k values were then calculated and are reported in Tables 18 to 21.
  • a fresh solution of 1 M HCl was prepared for use as the strip solution.
  • a strip dispersion was then prepared by mixing together 250 ml of the 1 M HCl solution and 750 ml of n-dodecane containing 2% dodecanol and 8% BOPPA as described in the general procedure above.
  • the strip dispersion was fed into the shell side of a polypropylene hollow fiber module.
  • a feed solution containing the following metals was passed into the tube side of the hollow fiber module: strontium (Sr; 5 ppm), calcium (Ca; 80 ppm), magnesium (Mg; 20 ppm), or zinc (Zn; 50 ppm).
  • the pH of the feed solution was maintained at 3.0 +/- 0.1 by adding 5 M NaOH as needed.
  • EXAMPLE 21 A fresh solution of 3 M HCl was prepared for use as the strip solution.
  • a strip dispersion was then prepared by mixing together 250 ml of the 3 M HCl solution and 750 ml of n-dodecane containing 2% dodecanol and 8% BOPPA as described in the general procedure above.
  • the strip dispersion was fed into the shell side of a polypropylene hollow fiber module.
  • a feed solution containing the following metals was passed into the tube side of the hollow fiber module: strontium (Sr; 5 ppm), calcium (Ca; 80 ppm), magnesium (Mg; 20 ppm), or zinc (Zn; 50 ppm).
  • the pH of the feed solution was maintained at 3.0 +/- 0.1 by adding 5 M NaOH as needed.
  • Samples of the feed and strip solutions were collected at timed intervals as described in the general procedure above and analyzed by ICP. Fluxes and k values were then calculated and are reported in Tables 26. No obvious improvement was seen using the 3 M HCL strip solution over the 1 M HCl strip solution.
  • EXAMPLE 22 A fresh solution of 1 M HCl was prepared for use as the strip solution.
  • a strip dispersion was then prepared by mixing together 250 ml of the 1 M HCl solution and 750 ml of n-dodecane containing 2% dodecanol and 8% BOPPA as described in the general procedure above.
  • the strip dispersion was fed into the shell side of a polypropylene hollow fiber module.
  • a feed solution containing the following metals was passed into the tube side of the hollow fiber module: strontium (Sr; 5 ppm), calcium (Ca; 80 ppm), magnesium (Mg; 20 ppm), or zinc (Zn; 50 ppm).
  • the pH of the feed solution was maintained at 2.5 +/- 1.0 by adding 5 M NaOH as needed.
  • Samples of the feed and strip solutions were collected at timed intervals as described in the general procedure above and analyzed by ICP. Fluxes and k values were then calculated and are reported in Tables 30 to 33.
  • the results of the extraction at pH 2.5 was slightly worse than those at pH 3, but most of the Sr was removed after 70 minutes.
  • EXAMPLE 24 The experimental procedure for this example was the same as that described in Example 20, except that 2-hexyl-l-decyl phenylphosphonic acid (C16 HDPPA) was used instead of BOPPA. Fluxes and k values for strontium were calculated and are reported in Table 35. As shown in this table, the C16 HDPPA extractant removed strontium very well.
  • C16 HDPPA 2-hexyl-l-decyl phenylphosphonic acid
  • C16 DEHPA di(2-hexyl-l- decyl)phosphoric acid
  • the strip dispersion with C16 DEHPA turned into an emulsion, and it was difficult to separate into two phases, the organic liquid phase and the aqueous strip phase, upon standing.
  • the C16 HDPPA extractant was much better than the C16 DEHPA extractant for the removal of strontium.
  • EXAMPLE 26 The experimental procedure for this example was the same as that described in Example 20, except that a mixture of 2-hexyl-l-dodecyl/2-octyl-l-decyl phenylphosphonic acids (C18 HDPPA/ODPPA) was used instead of BOPPA. Fluxes and k values for strontium were calculated and are reported in Table 37. As shown in this table, the C18 HDPPA/ODPPA extractant mixture removed strontium very well. Table 37
  • EXAMPLE 27 The experimental procedure for this example was the same as that described in Example 20, except that 2-octyl-l-dodecyl phenylphosphonic acid (C20 ODPPA) was used instead of BOPPA. Fluxes and k values for strontium were calculated and are reported in Table 38. As shown in this table, the C20 ODPPA extractant removed strontium very well.
  • C20 ODPPA 2-octyl-l-dodecyl phenylphosphonic acid
  • the first organic solution was freshly prepared with a composition of 8 wt % C20 ODPPA, 2 wt % dodecanol, and 90 wt % dodecane (42.6 g of C20 ODPPA), which was used in Experiments #1, 2, 3, and 4 with a low feed concentration of 317 pico Curie per liter (pCi/L) strontium-90 and Experiment #9 with a low feed concentration of 1,000 pCi/L. This solution was also used later in Experiment #10 with a high feed concentration of 487,000 pCi/L Sr-90.
  • the strip dispersions were made up of 1.0 M HCl and the previously mentioned organic solutions.
  • the total strip dispersion volume used was about 1 L (0.25 L acid strip solution and 0.75 L organic solution), except for Experiments #7, 8, and 10 where 0.6 L was used (#7 and 8 with 0.1 L acid strip solution and 0.5 L organic solution, #10 with 0.040 L acid solution and 0.560 L organic solution). A fresh acid strip solution was used for each experiment.
  • the aqueous feed solutions for Experiments #4, 6, 8, and 9 had calcium, magnesium, and zinc added to them to make their concentrations of about 80 ppm, 20 ppm, and 50 ppm, respectively.
  • the feed outlet pressure was maintained between 4 - 4.5 psi, and the strip dispersion inlet pressure was maintained between 1 - 2 psi.
  • the feed inlet pressure was maintained between 5 - 5.5 psi.
  • Samples were taken during the experiments from the discharge of the module and not from the bulk solution. The sample volumes taken were at least 100 mL. Two strip samples were analyzed after diluting the sample 1 : 100. The strontium-90 concentrations were measured by filtering the sample through 3M's EMPORE® filter paper, which selectively traps about 97% of Sr-90. The samples were prepared in the following manner per the manufacturer's directions. Concentrated nitric acid was added to the sample to make a 2.0 N nitric acid solution. The sample was then stirred and allowed to sit. One of the filter papers was placed in a filter support and conditioned with 10 mL of methanol for approximately 1 minute.
  • the methanol was pulled through the filter, followed immediately by 20 mL of 2.0 M HNO 3 .
  • the sample was added to the filter.
  • Most of the samples were passed through the filter at no more than 25 mL/min; this ensured the capture of Sr-90 by the filter.
  • the sample was immediately followed by 20 mL of 2.0 M HNO 3 .
  • the filter was then dried under a heat lamp and was analyzed by a gas flow proportional counter, Tennelec 1000 series, Low Background Alpha/Beta Counting
  • Sr-90 can be removed from ground water solutions effectively with the combined supported liquid membrane/strip dispersion process of the present invention.
  • This process was very effective to remove Sr-90 from feed solutions containing about 300 - 1,000 pCi/L Sr-90 to the target concentration of less than 8 pCi/L in the treated feed solutions.
  • this target concentration was also achieved from a ground water solution containing about 1,000 pCi/L Sr-90, 80 ppm calcium, 20 ppm magnesium, and 50 ppm zinc.
  • the feed solutions used containing these ions simulated the ground waters at Brookhaven National Laboratory and West Valley, NY.
  • the new extractant, C20 ODPPA, was very effective for the removal of Sr- 90, and it gave consistent results below 8 pCi/L Sr-90 in the treated feed solutions.
  • the treated feed and used strip solution samples that were analyzed did not have any problems while filtering and did not have any cloudiness, indicating insignificant solubility of this extractant in the aqueous feed and strip solutions.
  • Mass transfer coefficients were calculated using 317 pCi/L, 1,000 pCi/L, 27,941 pCi/L and 487,000 pCi/L feed concentrations for the respective experiments.
  • 2-Butyl-l-octyl (C12) phenylphosphonic acid (BOPPA) was synthesized by the following reaction.
  • a solution of 45 g of 2-butyl-l-octanol in 100ml of pyridine was prepared.
  • a solution of 51 g of phenylphosphonyl dichloride in 100 ml of pyridine was also prepared.
  • the 2-butyl-l-octanol solution was added dropwise to the phenyl phosphonyl dichloride solution at a temperature between 5 and 10°C over a period of 30 minutes. The reaction was then allowed to continue at the same temperature for an additional hour while the mixture was stirred.
  • BOPPA was also synthesized by the following reaction (with different reactant amounts from those used in Example 29).
  • a solution of 31.5 g of 2-butyl- l-octanol in 70ml of pyridine was prepared.
  • a solution of 44 g of phenylphosphonyl dichloride in 70 ml of pyridine was also prepared.
  • the 2-butyl-l- octanol solution was added dropwise to the phenyl phosphonyl dichloride solution at a temperature between 5 and 10°C over a period of 30 minutes. The reaction was then allowed to continue at the same temperature for an additional 4 - 8 hours while the mixture was stirred.
  • 2-Octyl-l -dodecyl phenylphosphonic acid (C20 ODPPA) was synthesized by the use of the same procedure described in Example 30 except 50.5 g of 2-octyl-l- dodecanol was used instead of 31.5 g of 2-butyl- 1 -octanol.
  • the strip dispersion for each of the following examples was prepared by mixing an aqueous strip solution in a quantity, for example, 200 ml, of an organic extractant solution.
  • the organic extractant solution can be, for example, Isopar L, an isoparaffinic hydrocarbon solvent with a flash point of 62°C, a boiling point of
  • a quantity of combined aqueous strip solution/organic extractant solution for example, 800 ml, was introduced into a Fisher brand mixer with a 2-inch diameter, 6-bladed, high-shear impeller at 500 rpm as measured by Ono Sokki HT-4100 tachometer.
  • the mixer was plugged into a varistat to allow for adjustable speed control.
  • the impeller was initially started at 50% of the full power and varistat at 80%.
  • microporous polypropylene hollow-fiber module of 2.5 inches in diameter and 8 inches in length, providing a surface area of 1.4 square meters.
  • the process was first started by passing water through the hollow fiber module. Once pressures were adjusted and stable, the water was then replaced with the feed solution. A positive pressure was maintained on the feed side to prevent the organic phase in the shell side from passing through the pores of the hollow fibers.
  • the pressure of the inlet on the shell side was maintained at 1.5 psi and the outlet pressure of the feed side was set at 11.5 psi, thus maintaining a 10 psi differential between the two sides.
  • the feed flow was adjusted to give a flow rate of approximately 0.84 liter/min at these pressures.
  • the typical feed solution volume for these experiments was 1 liter.
  • the flux of a species removed from the feed solution can be defined by the following formula:
  • V is the volume of the feed solution treated
  • ⁇ C is the concentration change in the feed solution
  • t is the time at which the sample is taken
  • A is the membrane surface area.
  • the mass transfer coefficient k of the species removed from the feed solution can be defined by the following formula:
  • V C 0 ln ( - ⁇ ) t A C t
  • a strip dispersion was prepared by mixing together 200 ml of the 1.2 M sodium carbonate (Na 2 CO 3 ) solution and 800 ml of an organic solution containing 10 wt. % N-lauryl-N-trialkylmethylamine with a molecular weight of 372 (a total number of 25.3 carbon atoms per amine molecule, e.g., Amberlite LA-2), 1 wt. % o- nitrophenyl octyl ether (o-NPOE), and 89 wt. % Isopar L as described in the general procedure above.
  • the strip dispersion was fed into the shell side of a 2.5-inch polypropylene hollow fiber module.
  • Penicillin G was removed from a high concentration of 8,840 ppm to a relatively low concentration of 1,161 ppm in the feed solution in 2.5 hours in the recycle mode of operation for both the feed solution and the strip dispersion.
  • the penicillin G was recovered and concentrated to a high concentration of 40,802 ppm in the aqueous strip solution at the same time. This represented a recovery efficiency of 92.3%.
  • the penicillin G was removed to a low concentration of less than 600 ppm in the feed solution, and it was recovered and concentrated to about 40,000 ppm in the aqueous strip solution.
  • Table 40 The results of the experiment are listed in Table 40 below.
  • a strip dispersion was prepared by mixing together 200 ml of the 1.2 M sodium carbonate (Na 2 CO 3 ) solution and 800 ml of an organic solution containing
  • Penicillin G was removed from a high concentration of 9,609 ppm to a concentration of 2,837 ppm in the feed solution in 2.5 hours in the recycle mode of operation for both the feed solution and the strip dispersion. Penicillin G was recovered and concentrated to a high concentration of 44,739 ppm in the aqueous strip solution at the same time. This represented a recovery efficiency of 83.6%. At the 5 hours in the recycle operation, the penicillin G was removed to a concentration of 1,540 ppm in the feed solution, and it was recovered and concentrated to a very high concentration of 55,064 ppm in the aqueous strip solution. This represented a recovery efficiency of 90.5%. The penicillin G flux at the penicillin G concentration of 6,499 ppm in the feed solution at pH 4 was 4.44 g/(m 2 *hr), which was lower than the flux at pH 3 described in Example 34.
  • a strip dispersion was prepared by mixing together 200 ml of the 1.2 M sodium carbonate (Na 2 CO 3 ) solution and 800 ml of an organic solution containing 10 wt. % N-lauryl-N-trialkylmethylamine with a molecular weight of 372 (a total number of 25.3 carbon atoms per amine molecule, e.g., Amberlite LA-2), 1 wt. % o- nitrophenyl octyl ether (o-NPOE), and 89 wt. % Isopar L as described in the general procedure above.
  • the strip dispersion was fed into the shell side of a 2.5-inch polypropylene hollow fiber module.
  • the penicillin G was removed from a high concentration of 9,125 ppm to a concentration of 6,547 ppm in the feed solution in
  • Penicillin G was recovered and concentrated to a concentration of 7,434 ppm in the aqueous strip solution at the same time. This represented a recovery efficiency of 16.3%.
  • the penicillin G was removed to a concentration of 4,544 ppm in the feed solution, and it was recovered and concentrated to a concentration of 24,579 ppm in the aqueous strip solution.
  • a microporous polypropylene hollow-fiber module of 2.5 inches in diameter by 8 inches in length (with a surface area of 1.4 m 2 ) was used in the in-situ interfacial polymerization for the preparation of the microporous support with an interfacial polymerized layer for use with the supported liquid membrane (SLM) with a strip dispersion.
  • SLM supported liquid membrane
  • the module was mounted vertically.
  • a 1 -liter aqueous solution of 2.54 wt. % L-lysine monohydrate in distilled water was recycled upwards vertically through the tube side of the module at a flow rate of 1 liter/min.
  • the pressure at the outlet of this aqueous stream from the module was adjusted to 10 psig.
  • Isopar G which was an isoparaffinic hydrocarbon solvent (with a flash point of 41°C, a boiling point of 176°C, a viscosity of 1 cp (at 25°C), and a density of 0.747 g/ml (at 15.6°Q), was recycled through the shell of the module for 10 minutes, and it was then drained.
  • the interfacial polymerization was carried out by recycling a 1 -liter organic solution of 0.12% (w/v) trimesoyl chloride (TMC) in Isopar G (0.12 g TMC per 100 ml Isopar G) upwards vertically through the shell side of the module for 1.5 minutes.
  • TMC trimesoyl chloride
  • the interfacial polymerization reaction was terminated by washing the tube side (the aqueous amine solution side) with water by recycling 2-liter water upwards vertically through the tube side at a flow rate of 1 liter/min and an outlet pressure of
  • the experimental procedure for this example was the same as that described in Examples 37 and 38 except a 1 -liter aqueous solution of 2 wt. % l-(2- aminoethyl)piperazine in distilled water and an interfacial polymerization time of 2 minutes were used.
  • Example 37 The experimental procedure for this example was the same as that described in Example 37 except a 0.75-liter aqueous solution of 2.27 wt. % triethylenetetraamine in distilled water was used.
  • the experimental procedure for this example was the same as that described in Example 37 except a 0.75-liter aqueous solution of 1.80 wt. % hexamefhylenediamine in distilled water and an outlet pressure of 5 psig for the aqueous solution were used.
  • a strip dispersion is then prepared by mixing together 250 ml of the 1 M HCl solution and 750 ml of n-dodecane containing 2% dodecanol and 8% 2-butyl-l- octyl phenylphosphonic acid (BOPPA) in a Fisher brand mixer with a 2-inch diameter, 6-bladed, high-shear impeller at 500 rpm as measured by Ono Sokki HT- 4100 tachometer. The mixer is plugged into a varistat to allow for adjustable speed control. The impeller is initially started at 50% of the full power and varistat at 80%. The strip dispersion is fed into the shell side of a hollow fiber module of microporous polypropylene support with an interfacial polymerized layer prepared from the in-situ interfacial polymerization technique described in Example 37.
  • BOPPA 2-butyl-l- octyl phenylphosphonic acid
  • the run using the SLM with the strip dispersion is conducted in countercurrent fashion with the feed (or tube) side of the module started first using water.
  • the water is then replaced with the feed solution once the pressures are adjusted and stable.
  • a positive pressure is maintained on the feed side to prevent the organic phase in the shell side from passing through the pores of the hollow fibers.
  • the pressure of the inlet on the shell side is maintained at 1.25 psi and the outlet pressure of the feed side is set at 3.25 psi, thus maintaining a 2 psi differential between the sides.
  • the feed flow is adjusted to give a flow rate of approximately
  • a 2-liter feed solution containing the following metals is passed into the tube side of the hollow fiber module: strontium (Sr; 5 ppm), calcium (Ca; 80 ppm), magnesium (Mg; 20 ppm), or zinc (Zn; 50 ppm).
  • the pH of the feed solution is maintained at 3.0 +/- 0.1 by adding 5 M NaOH as needed.
  • Samples of the feed and strip solutions are taken at timed intervals.
  • the strip dispersion samples are allowed to stand until a decent phase separation is seen.
  • the aqueous phase from the strip dispersion sample is then collected and centrifuged to facilitate complete separation.
  • the aqueous phase samples from the strip dispersion samples and the feed solution samples are analyzed by inductively coupled plasma (ICP) spectrometry.
  • ICP inductively coupled plasma
  • the experimental procedure for this example is the same as that described in Example 43 except a 4-liter feed solution containing 562 ppm cobalt at pH 2.3, a 600-ml organic solution containing 8 wt. % di(2,4,4-trimethylpentyl) dithiophosphinic acid (e.g., Cyanex 301), 2 wt. % dodecanol, and 90 wt.
  • a 4-liter feed solution containing 562 ppm cobalt at pH 2.3 a 600-ml organic solution containing 8 wt. % di(2,4,4-trimethylpentyl) dithiophosphinic acid (e.g., Cyanex 301), 2 wt. % dodecanol, and 90 wt.
  • Isopar L isoparaffinic hydrocarbon solvent with a flash point of 62°C, a boiling point of 207°C, a viscosity of 1.5 cp (at 25°C), and a density of 0.767 g/ml (at 15.6°Q)
  • a 200-ml aqueous strip solution of 2.5 M H 2 SO 4 are used.
  • the pH of the feed solution is maintained at 2.3 +/- 0.1 by adding 5 M NaOH as needed.
  • Example 43 except a 1 -liter feed solution containing a penicillin G concentration of 8,840 ppm at pH 3, a 800-ml organic solution containing 10 wt. % N-lauryl-N- trialkylmethylamine with a molecular weight of 372 (a total number of 25.3 carbon atoms per amine molecule, e.g., Amberlite LA-2)), 1 wt. % o-nitrophenyl octyl ether (o-NPOE), and 89 wt. % Isopar, an aqueous strip solution of 200 ml of 1.2 M sodium carbonate (Na 2 CO 3 ), a differential pressure of 10 psi between the feed and strip dispersion sides are used. The pH of the feed solution is maintained at 3 +/- 0.1 by adding 3 M sulfuric acid as needed.

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Abstract

L'invention concerne un nouveau procédé d'extraction et de récupération d'espèces cibles, telles que des métaux, radionucléides, pénicillines et acides organiques, à partir d'eaux usées et de flux de traitement. Dans ce procédé on utilise une combinaison d'une membrane liquide sur support et d'une dispersion d'épuration, afin d'améliorer l'extraction des espèces cibles tout en augmentant la stabilité des membranes et en réduisant les coûts de traitement. L'invention concerne également une membrane liquide sur support, incorporée dans un matériau support microporeux comprenant au moins une couche d'interface polymérisée. En outre, l'invention concerne des nouvelles classes d'agents d'extraction ainsi que des procédés de fabrication de ces agents. Ces nouvelles classes comprennent des acides phénylphosphoniques d'alkyle et des acides phosphoriques de dialkyle. Le procédé de fabrication des agents d'extraction à base d'acide phosphorique de dialkyle consiste à mélanger du pentasulfure phosphoreux avec un alcool, puis à exécuter une hydrolyse des réactifs intermédiaires, à l'aide d'un acide minéral.
PCT/US2001/040028 2000-02-04 2001-02-05 Procedes combinant une dispersion d'epuration et des membranes liquides sur support, et agents d'extraction Ceased WO2001056933A2 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2409414C2 (ru) * 2009-02-25 2011-01-20 Дэвон Инвестмент Лимитед Жидкая мембрана для выделения спиртов или эфиров из водных растворов и способ выделения спиртов или эфиров
EP2537576A1 (fr) 2011-06-24 2012-12-26 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Procédé de pertraction
WO2018112577A1 (fr) * 2016-12-22 2018-06-28 Universidade Estadual De Campinas - Unicamp Procédé de fermentation et système intégré pour la production d'acides organiques
CN113667843A (zh) * 2020-05-13 2021-11-19 厦门稀土材料研究所 一种采用低共熔溶剂分离钍的方法
CN114315565A (zh) * 2021-12-07 2022-04-12 河北科技大学 一种乙醇酸/丙氨酸天然低共熔离子液体及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0167736B1 (fr) * 1984-05-21 1988-08-10 Akzo GmbH Procédé de transfert d'ions métalliques par utilisation de membranes microporeuses
NL8903039A (nl) * 1989-12-11 1991-07-01 Tno Emulsie-pertractie.
AU2824997A (en) * 1996-05-02 1997-11-19 Commodore Separation Technologies, Inc. Supported liquid membrane separation
US6171563B1 (en) * 1999-01-21 2001-01-09 Commodore Separation Technologies, Inc. Supported liquid membrane process for chromium removal and recovery
US6328782B1 (en) * 2000-02-04 2001-12-11 Commodore Separation Technologies, Inc. Combined supported liquid membrane/strip dispersion process for the removal and recovery of radionuclides and metals

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2409414C2 (ru) * 2009-02-25 2011-01-20 Дэвон Инвестмент Лимитед Жидкая мембрана для выделения спиртов или эфиров из водных растворов и способ выделения спиртов или эфиров
EP2537576A1 (fr) 2011-06-24 2012-12-26 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Procédé de pertraction
WO2012177134A1 (fr) 2011-06-24 2012-12-27 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Processus de pertraction
WO2018112577A1 (fr) * 2016-12-22 2018-06-28 Universidade Estadual De Campinas - Unicamp Procédé de fermentation et système intégré pour la production d'acides organiques
CN113667843A (zh) * 2020-05-13 2021-11-19 厦门稀土材料研究所 一种采用低共熔溶剂分离钍的方法
CN114315565A (zh) * 2021-12-07 2022-04-12 河北科技大学 一种乙醇酸/丙氨酸天然低共熔离子液体及其制备方法和应用
CN114315565B (zh) * 2021-12-07 2023-12-19 河北科技大学 一种乙醇酸/丙氨酸天然低共熔离子液体及其制备方法和应用

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