TW201032881A - Indium recovery by supported liquid membrane with strip dispersion - Google 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

201032881 VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for removing and recovering indium from a solution. The method used in the present invention is a supported liquid membrane technique; the supported liquid membrane is used for dispersion to achieve the goal of recovering indium. [Prior Art] The conventional extraction and dispersion steps are carried out in two procedures, for example, extraction with a plurality of solutions, and the liquid film combines the two procedures into one. The single-programmed liquid membrane provides maximum zone power for the separation of the target product, maximizing the removal and recovery of the target product of this type (W_S. Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall , New York, 1992) ° Liquid membranes can be distinguished into two (1) supported liquid membranes (SLMs) and (2) emulsion liquid membranes (ELMs). In the supported liquid membrane, the liquid membrane is an organic liquid in a microporous substrate (for example, microporous polypropylene hollow fiber) (W. S. Winston Ho zero and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman &

Hall, New York, 1992). The basic principle is that when the organic solution is in contact with the surface of the micropores, the pores of the substrate are caused to be wet to form the supported liquid film. In order to extract the target product, the supported liquid film may be contained between the target product solution and the dispersion aqueous solution. The puff liquid membrane is a selective film which converts the target product in the target product solution to the dispersion by the selectivity of the selective liquid film. However, the organic solution in the supported liquid film is insoluble in the solution containing the target product and is also insoluble in the dispersion. The above organic solution contains extraction 3 201032881, a diluent (inert organic solution), and sometimes a modifier. Recently, in the scientific and industrial circles, the supported liquid film has been applied to remove metals, physical radioactive nucleus or olefinic metal elements in aqueous solutions containing target products. The above removable metals include: copper, zinc, ore. With put. (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, H Sep. Sci. Technol., 33, 537-549 (1998); J. Vander Linden and R. F. De Ketelaere, K Selective Recuperation of Copper by Supported

Liquid Membrane (SLM) Extraction, M J. Membrane Sci., 139, 125-135 (1998); Μ. 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); JC Lee, J. Jeong, JT Park, IJ Youn, and HS 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, 4 201032881 “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)) 〇In response to the removal of physical radionuclides, Dozol et al. revealed the use of extractants, aroma cups, or double crowns in supported liquid membranes. From high ionic strength

Removed from acidic solution (or alkaline solution) (JF Dozol, N. Simon, V. Lamaare, H. Rouquette, S. Eymard, B. Tournois, D. De Marc, and RM Macias, UA Solution for Cesium Removal From High-Salinity Acidic or Alkaline Liquid Waste: the Crown Calix arenes", Sep. Sci. Technol" 34, 877-909 (1999)). In addition, Kadney et al. disclose the recovery of plutonium (IV) by a supported liquid membrane having di(2-ethylhexyl) phosphoric acid (D2EHPA) as an ionophore. (CS Kedari, SS 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 )). Yafan et al. disclose the removal of olefinic metal elements by a supported liquid film, wherein the above-mentioned olefinic metal elements include: europium, lanthanum, neodymium, praseodymium And 釓 (by & plus 1 to ratio 111). (^11·

Yaftian, M. Burgard, C. B. Dieleman and D. Matt, MRare-earth Metal-ion Separation Using a Supported Liquid Membrane 5 201032881

Mediated by a Narrow Rim Phosphorylated Calix [4] arene, M J. Membrane Sci., 144, 57-64 (1998)) The disadvantage of supported liquid membranes is poor stability. The stability of the supported liquid membrane is poor, and the cause is related to the composition of the liquid membrane and the osmotic pressure. The feed solution and the dispersion solution do not contain liquid film components (organic solution, extract and modification solution), resulting in osmotic pressure difference (AJ B_ Kemperman, D. Bargeman, Th. Van Den Boomgaard, H. Strathmann, K Stability Of Supported Liquid Membranes: State of the Art", Sep. Sci. Technol., 31, 2733 (1996); TM Dreher and G. W Stevens, "Instability

Mechanisms of Supported Liquid Membranes", Sep. Sci. Technol., 33, 835-853 (1998); JF Dozol, J. Casas, and A. Sastre, w Stability of Flat Sheet Supported Liquid Membranes in the Transport of Radionuclides from Reprocessing Concentrate Solutions", J. Membrane Sci" 82, 237-246 (1993). In order to try to solve this problem, Winston et al. used a supported liquid membrane with two sets of hollow fiber modules, for example: hollow fiber inclusion Liquid film (WS Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992). In two sets of microporous fiber membrane structures, one set is used to carry an aqueous solution containing the target product, The other group is used to carry the dispersed aqueous solution, and 'the aqueous solution has a higher pressure, so that the organic solution is located between the two sets of microporous fibers. In addition, because the liquid film will continue to replenish, the hollow fiber liquid is promoted. The film has a high stability. However, this structure has the disadvantage of requiring two sets of fiber structures to achieve a low liquid film concentration. 201032881 Emulsion film is emulsion (emuls) Ion) as a product to selectively separate the liquid film. The emulsion film is obtained by dispersing the emulsion in the external continuous phase by stirring. Among them, the milk I» liquid is defined as two liquids which are not mutually soluble, and the droplets are different in size. Disperse in another liquid, for example: small droplets of organic liquid dispersed in water called water in oil emulsion. Emulsion is an oil phase liquid to separate internal water droplets from external continuous phase (WS Winston Ho and Kamalesh K. Sirkar, eds·, Membrane Handbook, Chapman & Hall, New York, 1992). In addition to φ, the emulsion contains a selective extractant, the internal water droplets contain a dispersing agent, and the surfactant can be used to increase the emulsion. Stability. The external continuous phase system contains the target product solution. Therefore, the solution with the target product can be extracted into the liquid film, and then the target product is dispersed and transferred into the small water droplets of the emulsion. The water droplets are taken out from the emulsion by electrostatic combination. Then, precipitation or electroplating is carried out to obtain the target product. In recent years, the chemical industry and the industry have used emulsion membrane technology to remove water containing the target product. The liquid metal, alkenyl earth elements and physical radionuclide. Among them, the metal removable by the emulsion film technology includes: beginning, copper, resignation, recording, mining, error, recording, silver. The rare earth elements removable with the emulsion film include: europium, lanthanum and neodymium (WS Winston Ho and Kamalesh K. Sirkar, eds.9 Membrane Handbook, Chapman & Hall, New York , 1992). A large number of literatures have been reported on the removal of precursors, recordings, minerals, mercury, and ship technology by emulsion membranes (B. Raghuraman, N. Tirmizi, and JM Wiencek, M Emulsion Liquid Membranes for Wastewater Treatment. Equilibrium Models for Some Typical 7 201032881

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);

RS Juang and JD 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); SYB

Hu and JM Wiencek, “Emulsion-Liquid-Membrane Extraction of Copper Using a Hollow-Fiber Contactor, M AIChE J., 570-581 (1998)). He and Shaka et al. reveal in detail the physical radioactive nuclear removal technology. Among them, the above physical radioactive nuclear species include: strontium, cesium, technetium and uranium (WS Winston Ho and Kamalesh K. Sirkar, eds., Membrane Handbook, Chapman & Hall, New York, 1992^ In addition, there are other literatures that disclose lithium removal by emulsion membranes (I. Eroglu, R. Kalpakci, and G. Gunduz, “Extraction of Strontium Ions with Emulsion Liquid Membrane Technique”, J. Membrane Sci ., 80, 319-325 (1993)). 8 201032881 The disadvantage of the emulsion membrane is that the liquid membrane swells when the liquid membrane is in contact with the target product solution for a long time. The liquid membrane swells to reduce the concentration of the dispersant in the water droplets. Influencing the rate of dispersion reaction. In addition, the liquid film expansion reduces the concentration of the target product in the water "drop, affecting the separation effect of the liquid film. In addition, the film expansion causes the film to be thin. The stability of the film is slammed. "Furthermore, the expansion of the liquid film increases the viscosity of the liquid film, and the high viscosity liquid film will increase the difficulty of decomposing the emulsion into a non-emulsion. Another disadvantage of the emulsion film is the rupture of the liquid film, resulting in The internal water droplets enter the target product solution φ, which reduces the efficiency of separation. Therefore, Lagulaman and Wynick reveal the use of microporous hollow fiber contactors to reduce the phenomenon of film expansion and liquid leakage. Among them, the disadvantage of emulsion film It also contains the necessary procedures for the preparation and lysis of the emulsion. In view of this, a highly stable supported liquid membrane, and can remove and recover metal, physical radioactive nucleus, penicillin and organic from the solution containing the target product. Acid is a technology that needs to be developed urgently. Therefore, how to disclose the combination of supporting liquid film and dispersion process to remove chromium (WS Winston Ho, 参 M Supported Liquid Membrane Process for Chromium Removal and Recovery), US Patent 6,171,563 ( 2001)), metal (WS

Winston Ho, M Combined Supported Liquid Membrane / Strip Dispersion Process for the Removal and Recovery of Radionuclides and Metals", U.S. Patent 6,328,782 (2001); W.S.

Winston Ho, "Combined Supported Liquid Membrane / Strip Dispersion Process for the Removal and Recovery of Metals", U. S. Patent 6,350, 419 (2002)), Physical Radionuclide (W.S. Winston 201032881)

Ho, wCombined Supported Liquid Membrane / Strip Dispersion Process for the Removal and Recovery of Radionuclides and Metals 1*, US Patent 6,328,782 (2001); WS Winston Ho, "Combined Supported Liquid Membrane / Strip Dispersion Process for the Removal and Recovery of Radionuclides", US Patent 6,696,589 (2004)), penicillin and organic acids (WS)

Winston Ho, "Combined Supported Liquid Membrane / .Strip Dispersion Process for the Removal and Recovery of Penicillin and Organic Acids", U.S. Patent 6, 433, 163 (2002)). In addition, techniques for removing metals with dialkyl monothiophosphoric acid extractants have also been disclosed. Among them, the dihydrocarbon monothioacidic acid extractant is applied to a supporting liquid film having a dispersion procedure. (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", US Patent 6,291,705 (2001)) So far, no one has disclosed the removal of indium by a supported liquid film with a dispersion process. Therefore, a high stability can be removed and recovered from industrial processes and wastewater. The invention relates to a method for removing and recovering indium from a solution. The method used in the present invention is a supported liquid film technology; The target is recovered by a supported liquid film to achieve the goal of recovering indium. 201032881 In an embodiment, the present invention discloses a procedure for removing and recovering steel from a feed solution. f first '- a feed solution containing la One end of the supported liquid film, wherein the liquid film comprises at least a porous cutting material, and the supporting liquid film is further used as a dispersion to disperse the indium; the dispersion of the indium may be dispersed in the aqueous phase. Taking the solution in an organic liquid ritual; wherein, the liquid of the machine can be a mixed liquid. Secondly, all or part of the above-mentioned dispersion of indium is separated into - organic phase by means of a stationary knife phase - the aqueous phase takes the solution, wherein the aqueous phase takes the solution towel to contain a concentrated (four) marriage. The organic phase of the dispersion of indium can be easily formed/occupied by the pores of the wet porous material--stable support liquid Membrane. The procedure disclosed in this publication has considerable advantages over conventional supported liquid membrane procedures or solvent extraction procedures. One object of the present invention is to provide a supported liquid membrane procedure for removal from solution. And the recovery of indium' and the stability of the film and the program. Another object of the present invention is to use a supported liquid film program to achieve high proportion and high content of indium removal and back.

Received. A further object of the present invention is to improve the efficiency and efficiency of indium recovery by the ❹_支楼魏膜程序, and (iv) - a high concentration of indium recovery liquid. [Embodiment] The present invention discloses a method for taking a dispersion of a liquid crystal film to remove and recover indium from a feed solution. In order to thoroughly understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details of those skilled in the art. On the other hand, the composition or steps of the public are not obsessed with the details to avoid the limitation of the present invention. The preferred embodiments of the present invention will be described in detail below, but the present invention may be widely practiced in other embodiments, and the scope of the present invention is not limited by the following detailed description. quasi. The present invention relates to a method of removing and recovering indium from a solution. The method used in the present invention is a supported liquid membrane technique: it is dispersed by a supported liquid membrane to achieve the goal of recovering indium. Suitable solutions can come from industrial processes and wastewater.

In one embodiment, the present invention discloses a procedure for removing and recovering indium from a feed solution. First, a feed solution containing indium passes through one end of a supported liquid membrane, wherein the liquid membrane comprises a porous (microporous) support material, and a dispersion is taken at the other end of the supported liquid membrane for taking and taking. Indium. The indium dispersion can be obtained by dispersing an aqueous phase to take a solution in an organic liquid; wherein the organic liquid can be a mixed liquid. Next, all or a portion of the dispersion in which indium is taken may be subjected to static phase separation to separate into an organic phase and a liquid phase to take the solution. Among them, the aqueous take-up solution contains concentrated indium. Any supported liquid membrane architecture can be used with the present invention. The one used in one embodiment is a hollow fiber membrane group. The hollow fiber membrane group contains miCroporous hollow fibers to form a shell_and_tube structure. In the present invention, the take-up liquid is passed through the shell end or the end of the shell in the shell structure, and the feed solution flows through the other end. The supported liquid membrane with hollow fiber structure provides stable support for the dispersion, thereby ensuring the stability of the process, as shown in the first figure 12 201032881 for the purpose of the present invention (recovering indium) It is defined as producing a mixed liquid having an aqueous phase and an organic phase. Wherein, the aqueous phase comprises an aqueous strip s〇luti〇n and the organic phase comprises one or more extracting agents (eXtractant) present in an organic liquid. The dispersion is formed by mixing the aqueous phase with the organic phase, as shown in the first figure. This combination allows the aqueous take-up solution to be present in the form of droplets in a continuous organic phase. During the extraction process, the dispersion is passed through the hollow fiber membrane membrane group so that the take-up dispersion is maintained. The organic phase of the dispersion is easily wetted by the hydrophilic pores of the porous hollow fiber to form a stable liquid film. The second figure is an enlarged schematic view of a device constructed in accordance with an embodiment of the present invention in which a supported liquid film is combined to take a dispersion to recover indium. The pressure of the supported liquid film at the end of the dispersion is p〇 during the progress of the procedure. At this time, at the end of the feed solution of the supported liquid membrane membrane group, a low pressure Pa (usually around 2 psi) is applied, wherein the pressure Pa is greater than the pressure p. . This pressure difference prevents the organic solution in the dispersion from penetrating through the pores of the hollow fiber to reach the feed solution end of the liquid film. The droplets dispersed in the aqueous phase take-up solution are about 80 to 800 microns (micr〇meter). This size has been several orders of magnitude larger than the size of the pores of the microporous support structure. Therefore, the end of the feed solution is reached at the end of the supporting liquid film where the droplets at the end of the dispersion do not pass through. In the selective liquid film take-up dispersion system disclosed in the present invention, the organic film solution, that is, the organic phase from which the dispersion is taken, is continuously supplied into the pores of the support. This continuous supply ensures stable and continuous operation of the supporting liquid film. In addition to the direct contact between the organic phase and the strip phase, this also provides an effective quality for the acquisition process. The organic phase and the take-up phase can even increase the * contact area between the two by mixing, such as high-shearing mixing. When the indium is removed, the mixer (e.g., the agitator) that takes the dispersion stops, and the dispersion is allowed to stand for phase separation until it is separated into two phases. The two phases are respectively an organic membrane solution and a concentrating φ strip solution, and the concentrated extract is the product of the procedure disclosed in the present invention. Among them, the feed solution may include a solution containing indium from industrial process liquid or waste water, and is not limited to industrial process liquid and waste water. The pore support material used in the present invention may comprise, for example, microporous polypropylene, polytetrafluoroethylene (PTFE), polyethylene, polysulfone, polyethersulfone. ), polyetheretherketone, polyimide, polyamide, polyaramide, or the like, or a mixture thereof. Among them, preferred support materials are microporous polypropylene and polytetrafluoroethylene hollow fibers. The aqueous phase portion of the dispersion contains at least one acidic aqueous phase solution, such as a mineral acid. The mineral acid may include, but is not limited to, hydrochloric acid (HC1), sulfuric acid (H2S04), nitric acid (hno3), and acetic acid (CH3COOH). Among them, the concentration of acid 201032881 is about 0.1 Μ to 18 。. Preferably, it can be between 1 至 and 6 Μ. The aqueous phase take-up solution is dispersed in a continuous organic phase containing one or more extractants. The extractant extracts the indium from the feed solution. Many extractants have been discovered and published for use in wastewater or industrial process liquors and can be used in the present invention.

The extractant comprises dialkyl phosphoric acids and alkyl phenylphosphonic acids. The above dialkyl phosphoric acids may be selected from one of the following groups or a mixture thereof: di(2-ethyl-hexyl) phosphoric acid (D2EHPA), Di(2-butyl-octyl phosphoric acid), di(2-hexyl-decyl) phosphoric acid, di(2-hexyl-decyl) phosphoric acid -(octyl-decyl/2-hexyl-dodecyl phosphoric acid), di(2-octyl-12)-destroyed acid Di(2-octyl-dodecyl) phosphoric acid], di(hexyl) phosphoric acid, di(heptyl) phosphoric acid, di(octyl) acid [di(octyl) phosphoric acid], di(nonyl) phosphoric acid, di(decyl) phosphoric acid, di(-}--alkyl) Acid (di(undecyl) phosphoric acid], di(dodecyl) phosphoric acid, di(tridecyl) phosphoric acid, di(tridecyl) phosphoric acid Fourteen bases) acidity [di(t Etradecyl) phosphoric acid], two (five-firing) 15 201032881 phosphoric acid [di(pentadecyl) phosphoric acid], di(hexadecyl) phosphoric acid], two (seventeen-sodium) dish Acid [di(heptadecyl) phosphoric acid], bis(octadecyl)phosphoric acid, [di(octadecyl) phosphoric acid], di(nonadecyl) phosphoric acid, di (twenty) Di(decadecyl phosphoric acid), di(undecadecyl) phosphoric acid, di(docalcyl) phosphoric acid [di(dodecadecyl) phosphoric] Acid], di(tridecadecyl) phosphoric acid, di(tetrdecadecyl) phosphoric acid, di (twenty-five) Acid [di (pentadadecyl) phosphoric acid], di (hexadecadecyl) phosphoric acid [di (hexadecadecyl) phosphoric acid]. Preferably, it may be di(2-ethyl-hexyl) phosphoric acid (D2EHPA). 〇 The alkyl group of the above-mentioned alkyl phenylphosphonic acid may be a paraffinic (or say saturated) and may contain 6 to 26 carbon atoms. The above alkylbenzene phosphite may be selected from one of the following groups or a mixture thereof: (2-butyl-1-octyl)benzenephosphite [2-butyl-1 _octyl phenylphosphonic acid (ΒΟΡΡΑ)], (2- 2-hexyl-l-decyl phenylphosphonic acid '(2-octyl-1-indenyl-2-hexyl-1-dodecyl)phenylphosphoric acid (2) -octyl-l-decyl/2-hexyl-l-dodecyl phenylphosphonic acid) ' (2- 16 201032881

2-octyl-l-dodecyl phenylphosphonic acid, hexyl phenylphosphonic acid, heptyl phenylphosphonic acid, xin Octyl phenylphosphonic acid, nonyl phenylphosphonic acid, decyl phenylphosphonic acid '-\-undecyl phenylphosphonic acid, Dodecyl phenylphosphonic acid, tridecyl phenylphosphonic acid, tetradecyl phenylphosphonic acid, fifteen phenyl phthalate (pentadecyl phenylphosphonic acid), hexadecyl phenylphosphonic acid, heptadecyl phenylphosphonic acid, octadecyl phenylphosphonic acid, ten Nonadecyl phenylphosphonic acid, decadecyl phenylphosphonic acid, undecadecyl phenylphosphon Ic acid), dodecadecyl phenylphosphonic acid, tridecadecyl phenylphosphonic acid, tetrdecadecyl phenylphosphonic acid, Pentadadecyl phenylphosphonic acid, hexadecadecyl phenylphosphonic acid. Among them, preferred is (2-butyl-1-octyl phenylphosphonic acid 17 201032881 (ΒΟΡΡΑ)]. The take-up dispersion used in the present invention may optionally further comprise a carbohydrate hydrating solvent or a mixture. The hydrocarbon solvent or mixture may have from 6 to 18 carbon atoms, preferably from 1 to 14 carbon atoms. The hydrocarbon solvent includes: n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane ), isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isoparaffic hydrocarbon Solvent) [haves a flash point of 92 ° C, a 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 a mixture thereof. The take-up dispersion provided by the present invention may comprise a modifier to enhance its complexation and/or handleability to the target material. The modifier may be an alcohol, a nitraphenyl-alkyl ether, a trialkyl phosphate or a mixture thereof. Among them, the alcohol may be, for example, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanoyl ), tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadacanol, octadecanol or mixtures thereof. Further, the nitr〇phenyl alkyl ether may be, for example, o-nitrophenyloctyl ether [0_nitr0phenyl octyl ether (o-NPOE)], o-nitrophenyl hep-yet (0_nit; r〇phenyl heptyl ether) ), 邻为18 201032881 o-nitrophenyl hexyl ether, nitrophenyl pentyl ether (o-NPPE), o-nitrophenyl butyl ether, neighbor Nitrophenyl propyl "ether" or a mixture thereof. Further, the triaikyl phosphate may be, for example, tributyl phosphate or tris(2-ethylhexyl) phosphate. The extracting liquid disclosed in the present invention has an organic liquid containing an extractant having a volume percentage of 2 φ to 100 (that is, a molar volume concentration of about 0.05 M to 3 M), and a modifier having a volume percentage of 0 to 20 present in the hydrocarbon. Compound solvent or a mixture thereof. Preferably, the dispersion is taken from an organic liquid containing 5 to 4 liters of the extractant, and the modifier having a volume percentage of 丨 to 1 Torr is present in the hydrocarbon solvent or a mixture thereof. More preferably, the organic liquid containing the dispersion contains 5 to 40 parts by volume of the extractant, and the volume of 1 to 1 〇 of dodecyl alcohol (deCan〇1) is present in the aliphatic hydrocarbon solvent (isoparaffinic hydrocarbon ® S〇). 1Vent) or n-dodecane. It should be noted that the above percentages are percentages unless otherwise specified. Compared to conventional supported liquid film technology, the present inventors have considerable advantages in the application of self-feeding/gluten removal of recovered indium. These advantages include better film stability, lower cost, simplified process operation, better flux, and better indium recovery. The technique disclosed herein stabilizes the supply of the organic film solution to the pores/same of the hollow fiber support for removal and recovery of the indium from the feed solution. Such a stable supply of 201032881 makes the supporting liquid film disclosed in the present invention more stable than the conventional liquid film, so that (4) is more stable and carried out. In addition, the present invention requires (four) two sets of thin chess films for rotation operation and recharging. Therefore, the technique of the present invention can simultaneously reduce the cost of hardware and operation. Meanwhile, the invention discloses the removal. The technology is simpler to operate than the conventional technology. In the technique disclosed in the present invention, the organic/extracted phase can be directly contacted to take the aqueous phase. The mixing of the two phases makes the mass transfer surface provided by the original hollow fiber. More mass transfer surface area can be utilized, thereby increasing the efficiency of the target material from the organic phase. The improved extraction efficiency further enhances the mass transfer flux when the indium is extracted. The technology disclosed by the present invention provides A new type of supporting liquid film for removing and recovering the insult' and taking the water phase to be more elastic than the volume of the organic phase. This elasticity allows the invention to use a smaller volume of aqueous phase to take the solution (aqueous stnp Phase) to achieve a higher concentration of recovered indium solution. High concentration of recycled indium solution liquid high value products can be reused or sold directly. The present invention can be made by the following examples It should be noted that the examples are not intended to limit the scope of the invention; rather, the examples are intended to illustrate various ways in which the invention may be practiced, and various possibilities of embodiments. Modifications. The scope of the invention should be defined by the following claims. Example Basic Preparation Procedure In the following example, a supporting liquid film technique combined with a take-up dispersion (strip 20 201032881 dispersion) will be used to feed from one aqueous phase. The solution extracts indium into an organic solution, wherein an aqueous phase strip solution is dispersed to continuously take the extracted indium. The supporting liquid membrane system comprises a hollow fiber membrane membrane group' (Liquid -Cel, extra-flow 2.5x8, Membrana-Charlotte, USA), a feed solution tank, a feed pump (model 7592-50, Cole-Parmer, USA) to transfer the feed to polypropylene At the hollow fiber, a dispersion tank is taken, and the take-up dispersion tank is provided with a stirrer (SS, NZ-1000, Eyela, φ Japan) to completely disperse the aqueous phase and take the solution in the organic solution. membrane The system further contains another pump (model 7553-70, Cole-Parmer, USA) to transport the oil phase material containing the aqueous phase material to the shell side of the membrane membrane group. The diameter of the hollow fiber membrane group is 6.35 cm (2.5 inches) with a length of 20.3 cm (8 inches) and a film surface area of 1.4 square meters. The following example is operated in a countercurrent membrane. The feed solution flows through the micropores. The tube φ side of the polypropylene hollow fiber membrane group; the extracted indium is taken into the membrane membrane group and the dispersion tank, and is dispersed in the take-up solution. The aqueous phase feed solution containing indium was placed in a feed tank and oscillated at 300 rpm with a magnetic shock rod. The solution was taken as a 5 盐酸 hydrochloric acid solution which was dispersed in an organic solution at a speed of 300 rpm by a double blade stirring paddle (8.5 cm in diameter). The organic solution contains di(2-ethyl-hexyl)phosphic acid (D2EHPA) (supplied by Merck) in a heterogeneous hydrocarbon solvent (Is〇par-L) (provided by ExxonMobil) Used as a 21 201032881 extractant for steel. In most of the following experiments, unless otherwise specified, bis(2-ethylhexyl)disc. (D2EHPA) is in the isoparaffin solvent (the concentration of ~ρ 巾 towel is care (20.5 vol%). a modified thorn containing 12% by volume of dodecanol (1-dode(10)D (supplied by Merck) as an extractant (in the following examples, if not otherwise specified, dodecyl alcohol is used as a modifier for the extractant). Unless otherwise specified, the total volume of the organic solution is about L9L (9〇〇mi), and the volume of the solution is about 0.12L (120ml). The temperature of the feed and dispersion tank is maintained at a 〇C. The feed solution flows through the tube end of the hollow fiber membrane group. When the hollow fabric membrane is filled with the feed solution, the oil phase material containing the aqueous phase substance is sent to the shell end of the hollow fiber membrane group by the pump. The organic phase enters the feed solution through the pores of the hollow fiber, and the tube end is subjected to a positive pressure, for example, about 4 to 5 psi higher than the shell end. In the following example, if the scale is specified, the secret will be Under this pressure difference • Read. When the system is running, the 'feeding and dispersing solution is sent from the tank to the membrane membrane group. And then sent back to the tank. The speed of the pump transporting the fluid is about i L / min. In the experiment, the feed and the take-up solution are sampled at a fixed time. The sample taken by taking the dispersion solution is placed. The phase is until the phase separation occurs. Then, the aqueous phase sample taken from the dispersion solution and the feed solution is analyzed to determine the concentration of indium. In the following examples, the analysis is performed by atomic adsorption spectrometry unless otherwise specified. Completed by atomic absorption spectrophotometer (GBC 906, GBC, Australia). Other analytical methods may include, for example, electricity 22 201032881

Inductively coupled plasma spectrometer (ICP spectrometer). • Different feed solution compositions and volumes were tested in the experiments to verify the performance of the disclosed supported liquid film of the present invention, wherein this property can be expressed as the concentration of recovered indium in the feed and take-up solution. A feed bath. 15.5L 'pH 1 sulfuric acid (jj2S〇4) solution, and contains an initial 0 concentration of 200 ppm of trivalent indium (In3+). Organic solution. 0.9 L, organic solution is isothermal burning hydrocarbon The solvent (is〇par_L) is a solvent' and contains one of di(2-ethyl-hexyl) phosphoric acid (D2EHPA) and a volume percent concentration (v〇l%). Take a solution of 2dodecanol: 0.12 L of 5 Μ hydrochloric acid (HC1) solution. The feed solution is a volume of 15.5 L 'pH 1 sulfuric acid (H2S04) solution, and φ contains an initial concentration of 200 ppm. Trivalent indium (In3+). The volume of the organic solution is 0.9 1^, which is an isocratic hydrocarbon solvent (18 (^&1>1^) as a solvent and contains 〇.6 1^1 bis (2_ Diethyl 2-hexylphosphoric acid (D2EHPA) and the percent atomicity (vol%) of dodecanol (dodecanol). The solution was a volume of 0.12 L of a 5 Μ hydrochloric acid (HC1) solution. The dispersion was taken by mixing 0.12 L (12 ml) of the take-up solution and 0.9 L (900 ml) of the organic solution. The details of the preparation were as described above. The preparation procedure is described in this section and will not be described here. 23 201032881 A feed solution containing trivalent indium at a concentration of 200 ppm is first introduced into the tube end of a polypropylene hollow fiber membrane group by a pump. Then enter into the shell end of the hollow fiber membrane group. Each time interval, the feed solution _ and the take-up solution are separately sampled and analyzed by an atomic adsorption spectrophotometer, as described in the "Basic Preparation Procedure" section above. The change in concentration of indium in the feed solution and the take-up solution is recorded in Table 1 and is drawn into a third figure. As shown in the table and the figure, the supported liquid film disclosed in the present invention A high concentration of the indium concentration of more than 20,000 ppm can be obtained by taking the dispersion technique.

Table 1 Time Minutes (min) Feed Solution Indium Concentration (ppm) Time Minutes (min) Take Indium Concentration (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 24 201032881 110 2.94 120 0.32 130 0 140 0 150 0 160 0 170 0 180 0 195 0 200 0 Example two feed solution: 1 L, a pH 1 nitric acid (HN〇3) solution with an initial concentration of 180 ppm of trivalent indium ( In3+). Organic solution: 0.9 L, organic solution is isoparaffin solvent (Isopar-L) as solvent and contains 0.6 bis(2-ethyl-hexyl) phosphoric acid, D2EHPA And a volume percent concentration (vol%) of 2 dodecanols. Take the solution: 0.12 L of 5 Μ hydrochloric acid (HC1) solution. The experimental operation of this example is the same as that of the first example. The only difference is that in this example, the feed solution is a volume of 1 L, a pH 1 nitric acid (ΗΝ〇3) solution, and contains an initial concentration of 180 ppm of trivalent marriage (Ιη3+). The feed solution in Comparative Example 1 was a 15.5 L, pH 1 sulfuric acid (H2S04) solution and contained an initial concentration of 200 ppm of trivalent indium (In3+). The concentration of indium in the feed solution and the take-up solution is recorded in Table 2 as a function of time and is plotted as a fourth figure. 25 201032881

table

Feed solution: 1 L ′ of a sulfuric acid (1) (H2S〇4) solution of pH 1 and containing an initial concentration of 190 ppm of trivalent indium (In3+).

Organic solution: 0.9 L, (d) solution is based on isophthalic acid solvent (is〇par L) as solvent 'and contains 0.6 bis (2-ethylhexyl) phosphoric acid [di(2 ethyl hexyl) phosphoric acid, D2EHPA] And a hoarding percentage (vol%) of 2 dodecanols. Take the solution: 0.12 L of 5 Μ hydrochloric acid (HC1) solution. The experimental operation of this example is the same as that of the first example. The only difference is that in this example, the feed solution is a volume of 1 L, a pH 1 sulfuric acid (H2S〇4) solution, and contains an initial concentration of 190 ppm of trivalent indium ( In3+), the feed solution in Comparative Example 1 was a volume of 15.5 L, a pH 1 sulfuric acid (H2S04) solution and contained an initial concentration of 200 ppm of trivalent indium (In3+). The change in indium concentration in the feed solution and the take-up solution is reported in Table 3 and is plotted in Figure 4 for comparison to 26 201032881. As shown in the figure and table, this example is similar to the experimental results of Example 2. The difference between this example and the second example is only the feed solution, and the rest of the experimental conditions are the same. The feed solution of this example is a pH 1 sulfuric acid (HJO4) solution, and the sample feed solution of Example 2 is a pH 1 nitric acid (HN〇3) solution. Table 3 Time Minutes (min) Indium concentration of the feed solution (ppm) 0 191.6 1 99.01 2 1---- 53.77 3 25.17 5 0 --------

Example four feed solution: 11 ^, 1511 value 1 of 1 ^ 1 solution, and contains an initial concentration of 16 〇卯 111 of trivalent indium (In 3 +) organic solution: 0.9 L, the organic solution is an isoparaffin solvent ( Is〇par L) is a solvent and contains 0.6 bis (2-ethylhexyl) phosphoric acid [di(2 ethyl hexyl) phosphoric acid, D2EHPA] and a volume percentage concentration (v〇1%) of 2, dodecyl alcohol (dodecanol). Take the solution: 0.12 L of 5 Μ hydrochloric acid (HC1) solution The experimental operation of this example is the same as that of the first example, except that in the present example, the feed solution is a condensed 1 L, pH 丨 HC1 solution, and Containing trivalent indium (In 3+) at an initial concentration of 160 ppm, the feed solution in Comparative Example 1 is a body 27 201032881 with a volume of 15.5 L, a pH 1 sulfuric acid (ΗΑΟ4) solution and contains an initial concentration of 2 〇〇 ppm. Trivalent indium (In3+). The change in concentration of indium in the feed solution and the take-up solution is reported in Table 4 and is plotted in the fourth panel for comparison. As shown in the figure and table, this example is similar to the experimental results of Example 2 and Example 3. The difference between this example and the second and third examples is only the feed solution, and the rest of the experimental conditions are the same. The feed solution of this example is a pH 1 HCl solution' and the sample feed solution of Example 2 is a pH 1 nitric acid (HNO3) solution, and the sample feed solution of Example 3 is 硫酸^ value ❹ 1 of sulfuric acid (h2so4) Solution. Φ Example 5 Table 4 Time Minutes (min) Indium solution concentration (ppm) 0 156.6 1 87.98 3 29.48 5 8.27 7 0.72 10 0 — Feed solution: 1 L, pH 1 oxalic acid (H2C204) solution, its weight The percentage (wt%) is 2 and contains trivalent indium (In3+) at an initial concentration of 200 ppm. Organic solution: 0.9 L, organic solution with isoparaffin solvent (lS0par_L) as solvent, and containing 0.2 bis(2-ethyl-hexyl) phosphoric acid, D2EHPA and volume Percent concentration (vol%) is 2, dodecanos 〇28 201032881 Take solution: 0.1L of 5M hydrochloric acid (HC1) solution

The experimental operation of this example is the same as that of the first example, except that (1) in this example, the feed solution is a volume of 1 L, pH 1 of oxalic acid (H2C204) solution, the weight percentage (wt ° / 〇) is 2 and contains trivalent indium (In 3+) with an initial concentration of 200 ppm. The feed solution in the first example is a sulfuric acid (H2S04) solution with a volume of 15.5 L, pH 1, and contains trivalent indium at an initial concentration of 200 ppm. (In3+); (2) In this example, the organic solution contains 0.2 bis(2-ethylhexyl)phosphoric acid (D2EHPA), 0.6 Μ of Comparative Example 1, and (3) the volume of the solution taken in this example. 0.1 L (100 ml), 0.12 L (120 ml) of the control example 1. The change in concentration of indium in the feed solution and the take-up solution is reported in Table 5 and is plotted in Figure 5. Table 5 Time Minutes (min) Indium Solution Concentration (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 29 201032881 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 Feed solution: 1 L, pH 1 oxalic acid (H2C2〇4) solution, the weight percentage (wt ° / 〇) is 2 and contains the initial 200 ppm of trivalent indium (In3+). Example six

Organic solution: 0.9L, the organic solution is isoparaffin solvent (Isopar-L) as solvent, and contains 〇.6 1^ bis(2-ethylhexyl)phosphoric acid [^(2-61^1-1^) 71) phosphoric acid, D2EHPA] and a volume percent concentration (vol%) of 2 dodecanols. Take the solution: 0.1 L of 5 Μ hydrochloric acid (HC1) solution

The experimental operation of this example is the same as that of the fifth example. The only difference is that the 'organic' gluten solution contains 一·6 Μ of “one (2-ethylhexyl) disc acid (D2EHPA), and the comparison example 5 is 0.2 Μ. . That is, the experimental operation of this example is similar to the first example. The change in concentration of indium in the feed solution and the take-up solution is reported in Table 6 and is based on the fifth enthalpy for comparison. As shown in the figure and table, this example uses 0.6Μbis(2-ethylhexyl)linic acid (D2EHPA), and the experimental results obtained are much better than those with 0.2Μ (example 5). Table 6 Time infusion liquid indium strontium 1 30 201032881 minutes (min) degrees (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: 1 L, a solution of oxalic acid (H2C2〇4) having a pH of 1, and having a weight percentage (wt%) of 2 and containing an indium indium (In 3+) having an initial concentration of 200 ppm. Organic solution: 0.9 L, organic solution with isoparaffin solvent (Isopar-L) as solvent and containing 1 (2-ethyl-hexyl) phosphoric acid, D2EHPA And a volume percent concentration (vol%) of 2 dodecanols. Take the solution: 0.1 L of 5M hydrochloric acid (HC1) solution.

The experimental procedure of this example is the same as that of Example 5. The only difference is that in this example, the organic solution contains 1M bis(2-ethylhexyl)phosphoric acid (D2EHPA), which is 0.2M of Comparative Example 5. That is, the experimental operation of this example is similar to the first example. The change in concentration of indium in the feed solution and the take-up solution is reported in Table VII' and is plotted in Figure 5 for comparison. As shown in the figure and table, this example uses 0.6M bis(2-ethylhexyl)phosphoric acid (D2EHPA), and the experimental results obtained are better than those using 0.6 ( (such as Example 6) and farther than those using 0.2 Μ. (as in example 5) is better. Such a junction 31 201032881 shows that if the indium is to be extracted from the feed solution containing oxalic acid, the preferred choice of the concentration of di(2-ethylhexyl)phosphoric acid (D2EHPA) is 〇.6Μβ. Minute (min) Indium concentration of the feed solution (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 A feed solution of M5.5L, a solution of oxalic acid (??4) having a pH of 1 and having a weight percentage (wt%) of 2 and containing an initial concentration of 200 ppm of trivalent indium (In3+). ® Organic solution: 〇.9L, organic solution with isoparaffin solvent (lS0par_L) as solvent and containing 6.6]^1 bis(2-ethylhexyl)phosphoric acid [(11(2_6也^_1^^) 1) Phosphoric acid, D2EHPA] and volume percent concentration ~ 〇 1%) are 2 dodecanols. Take the solution: 0.12L of 5 Μ hydrochloric acid (HC1) solution. The experimental operation of this example is the same as that of the first example. The only difference is that in this example, the feed solution is a limulus value of 1 and a weight percentage (wt%) of 2/4)/liquid mixture and contains an initial concentration of 2 The trivalent indium (ιη 3+) of 〇〇ρρ^, the feed solution in Comparative Example No. 32 201032881 is a sulfuric acid (H2S04) solution of pH 1, and contains trivalent indium (In3+) having an initial concentration of 200 ppm. The change in indium concentration in the feed solution and the take-up solution is reported in Table 8 and is plotted in Figure 6. As shown in the table and the figure, the supported liquid film take-up and dispersion technique disclosed in the present invention can obtain a high-concentration take-up solution having an indium concentration of 18,000 ppm or more. Table eight

Time Feed Indium Concentration Time Take Liquid Indium Concentration Minutes (min) (ppm) Minutes (min) (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 33 201032881

。 。 。 。 。 。 。 。 510 12.21 540 9.74 560 8.23 570 7.57 600 6.16 630 5.98 660 4.48 范例 Example 9 feed solution: 15·5 L, pH 0.9 indium tin oxide (IT〇) solution containing an initial concentration of 140 ppm of trivalent indium ( Ιη3+) organic solution, (4) solution using isomeric combustion solvent (Is〇parL) as solvent, and containing 0.6M bis(2-ethylhexyl) disc acid [di(2_ethyi_hexyi) phosphoric acid, mEHPA] and volume percentage The concentration (¥〇1%) is 2dodecanol. 34 201032881 Take the solution: 0.12 L of 5 Μ hydrochloric acid (11 (^) solution The experimental operation of this example is the same as the first example, the only difference is this example. The towel, the feed solution is the oxidation surface of the positive value 〇.9 Tin (ΙΤ0) solution, and contains the initial. The lightness of 140 Peng's trivalent she, the control sample - the feed solution is ρΗ value of 1 sulphuric acid postal 4) solution 'and contains the initial concentration of 2 〇〇 三 trivalent Face ο. The change in concentration of indium in the feed solution and the take-up solution is reported in Table IX and is compiled in the seventh chart. As shown in the table and the figure, the present invention can be used to obtain a high concentration take-up solution of indium soil HOOOppm or higher from the ITO feed solution. Table 9 also shows the concentration of tin (4) in the feed solution sample, the change, and the concentration of tin in the take-up solution at the beginning and end of the actual shutdown. The seventh plot also shows the change in kick concentration versus time in the feed solution sample. As shown in the figure, 'tin is not extracted from the feed solution, and the solution is taken from the _. Therefore, it can be seen that the Wei film take-up dispersion technique disclosed in the present invention can effectively remove and recover indium from the ITG feed solution Φ. Table 9 Feed Solution*—. Minutes 丨miy Indium In Concentration (ppm) Tin Sn concentration (ppm) f fp (mini 0 143.5 14.52 - 10 136.6 14.67 20 20 131.7 17.15 40, 30 124.8 16.11 60, 40 123.4 19.97 80, 50 113.4 15.79 120^ Take liquid indium In concentration tin Sn concentration (Ppm) (ppm) -〇' 0 ^ 1240 ^ 2538 • ^ 3485 • 4564 . ^ 6222 - 35 201032881 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 ten feed solution Solution solution organic solution. 0.5 L PH value of 0.9 residual electrolyte residUal electrolyte), which contains trivalent indium (In 3+) • 0.9L at an initial concentration of 11 〇〇〇ppm, and the organic solution is treated with an isomeric smouldering solvent (is〇par_L) and contains 0.6 ——( 2-(2-ethyl-hexyl) phosphoric acid, D2EHPA, and a volume percent concentration (v〇i%) are 2dodecanol. Take solution: 0.1 L of 5 Μ hydrochloric acid (HC1) solution 36 201032881 The experimental operation of this example is the same as that of Example 1, except that in this example, the feed solution is a residual electrolyte feed solution with a pH of 0.9, and The trivalent indium (In3+) having an initial concentration of 10.0 ppm was used, and the feed solution in the first example was a pH 1 sulfuric acid (H2S04) solution and contained an initial concentration of 200 ppm of trivalent indium (In 3+). The change in the concentration of indium in the feed solution and the take-up solution is reported in Table 10. Note that in Table 10, the changes in indium concentration obtained through calculation and experiment are simultaneously displayed, and are respectively indicated as the take-up solution (experimental value) and the take-up solution (real φ test value) curve. Among them, the calculation data is obtained by mass balance calculation of the feed solution. The above results are plotted in the eighth figure. As shown in the table and the figure, the supported liquid film take-up and dispersion technique disclosed in the present invention can obtain a high concentration take-up solution having an indium concentration of more than 25,000 ppm from the residual electrolyte feed solution. Table ten

Time minutes (min) Feed solution Indium concentration (ppm) Ideal value (calculated indium concentration) (ppm) Time minute (min) Experimental value (indium concentration obtained experimentally) (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 37 201032881 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 The results of examples 1 to 10 show the choice of di(2-ethylhexyl)phosphoric acid (D2EHPA) When it is an extractant, better results can be obtained by removing and recovering indium from the aqueous phase feed solution by the supported liquid film take-up dispersion technique disclosed in the present invention. The results show that the present invention is significantly different from those skilled in the art of recovering metals and radioisotopes by using a supported liquid film take-up dispersion technique and using bis(2-ethylhexyl) squaric acid (D2EHPA) as an extractant. The utility of bis(2-ethylhexyl)phosphoric acid (D2EHPA) in the prior art is not apparent. US Patent No. 6,291,705, 6,328,782, 6,350,419, 6,696,589. Therefore, the techniques disclosed in the present invention are unexpected by the prior art. Example 11 Extractant: (2-Butyl-l-Octyl Phenylphosphonic Acid (ΒΟΡΡΑ)]. Feed solution: 1 L, a sulfuric acid (ΗΘΟ4) solution of pH 1, and containing trivalent indium (In 3+) at an initial concentration of 200 ppm. Organic solution: 0.8 L, the organic solution is an isoparaffin solvent (Is〇par_L) as a solvent, and contains (2-butyl-1 -octyl)benzene phosphate (8〇1)1) And volume 38 201032881 concentration (vol%) is 2 dodecanos (dodecanol) 〇 take solution: 0.12 L of 5 Μ hydrochloric acid (HC1) solution. The experimental operation of this example is the same as that of the first example. The only difference is that in this example, the extractant is selected as 0.6 Μ (2-butyl-1-octyl) benzoic acid (ΒΟΡΡΑ), which is compared with the sample one. The extractant is 〇.6 bis(2-ethylhexyl)phosphoric acid (D2EHPA). The change in concentration of indium in the feed solution and the take-up solution is reported in Table XI and is plotted as ninth. As shown in the table and the figure, the push-pull liquid film take-up and dispersion technique disclosed in the present invention can obtain a high-concentration take-up solution having an indium concentration of more than 20,000 ppm from the feed solution. Table 11 Time Minute imin丨 Indium solution of feed solution τ (ppm)

Time time (min) (minutes)_g_ ίο 15 20 25 30 40 50 60 T20 Take solution indium concentration (ppm) 0 1044 — 1584 ~ 2207 — 2567 — 2849 — 3010 — 2940 — 3125 ~~ —3021 — 3130 ', The invention is also described in the above embodiments, and the invention may be varied and varied. Therefore, it is necessary to recite the above detailed description within the scope of the appended claims. The above-described apparatus can be widely used in other embodiments of the present invention, and is not intended to limit the scope of the invention as claimed in the present invention; The equivalent changes or modifications to be completed shall be included in the following: [Simplified illustration]

The first diagram is based on the construction of the embodiment of the present invention. The schematic diagram of the apparatus for recovering indium in combination with the slit liquid film (SLM) technique and the method of taking the dispersion technique is constructed according to the embodiment of the present invention. , an enlarged schematic diagram of a combination of a slit liquid film (SLM) technique and a device for taking a dispersion technique to recover a marriage. The third figure is the line hiding _ take the dispersion in the 'indium concentration change with time. The feed liquid system is - sulfuric acid (h2so4) solution, the hoarding is 15.5L, the pH is 1, and ▲ 丄 ^ And contains an initial concentration of 200 ppm of trivalent (ln3+) 〇 In addition, the take-up system is a mixed liquid, which is a solution of 0.12 L (120 ml) of 5 M hydrochloric acid (HC1) as a strip solution. ) and mix it with a 0.9 L (900 ml) organic solution. Among them, the organic solution is an isoparaffin solvent (Isopar-L) as a solvent, and contains di(2-ethyl-hexyl) phosphoric acid, D2EHPA, and a volume percent concentration ( Vol ° /.) is 2 dodecanols. The fourth graph is a schematic representation of the change in indium concentration over time in the feed solution. Of which, 201032881

The feed solution was a nitric acid (HNO3) solution having a volume of 1 l, a pH of 1, and containing an initial concentration of 180 ppm of trivalent indium (In 3+). In addition, the take-up dispersion is a mixed liquid consisting of 0.12 L (120 ml) of a 5 Μ hydrochloric acid (HC1) solution as a strip solution, and mixed with a 〇.9L (900 ml). Organic solution. Among them, the organic solution is an isoparaffin solvent (Is〇par_L) as a solvent, and contains 0.6 di(2-ethyl-hexyl) phosphoric acid, D2EHPA, and a volume percent concentration. (v〇i%) is didecyl alcohol (d〇decan〇l). The fourth figure also shows that when the feed solution is a solution of trivalent indium (In3+) sulfuric acid (h2S〇4) having a pH of 1 and containing an initial concentration of WOppm, and when the feed solution is at a pH of 丨A schematic diagram showing the change of indium concentration in the feed solution over time when the HC1 solution of trivalent indium (In3+) having an initial concentration of 16 〇ppm is contained. Among them, the feed volume was 1 L, and the dispersion was taken up in the same manner as in the third figure.第五 The fifth figure is a schematic diagram of the change of indium concentration with time in the feed solution. Among them, the feed solution was a sulfuric acid (h2so4) solution having a pH of 1, a weight concentration (wt%) of 2, and an initial concentration of 200 ppm of divalent indium (In3+). The fifth graph shows the change of indium concentration with time when the concentration of di(2-ethylhexyl)phosphoric acid (D2EHPA) in the dispersion is 0.2 M, 0-6 Μ and M. The above three kinds of taking knife liquid are mixed liquids, which are 0.1 L (l〇〇ml) of 5 Μ hydrochloric acid (HC1) ♦ liquid as a take solution (stHp solution), and mixed with a 〇 9L (9 〇〇ml) Machine z liquid. Among them, the organic solution is an isomeric hydrocarbon solvent (Isopar-L) as a solvent of 201032881, and contains two (2-ethylhexyl) acid at different concentrations (〇·2 Μ, 0.6 Μ, 1 Μ). (2-ethyl-hexyl) phosphoric acid, D2EHPA] and volume percent concentration (vol%) is 2dodecanol (dodecanol). The sixth figure is the change of indium concentration with time in the feed solution and the take-up solution. schematic diagram. Wherein, the feed solution is a sulfuric acid (H2S04) solution having a weight concentration (wt%) of 2, which has a volume of 15·5 L′, a pH value of 1, and contains trivalent indium having an initial concentration of 200 ppm 0 ( In3+). In addition, 'take the dispersion liquid as a mixed liquid, which is a 0.12 L (l2 〇 ml) solution of 5 Μ hydrochloric acid (HC1) as a strip solution, and mix it with a 〇9 L (900 Ml) of organic solution. Among them, the organic solution is an isomerization hydrocarbon solvent (Is〇par-L) as a solvent, and contains one (2-ethylhexyl) phosphoric acid. D2EHPA] and the volume percentage concentration (vol%) is 2dodecanol (dodecanol) 〇m The seventh figure is a schematic diagram of the change of indium concentration with time in the feed solution and the take-up solution. The 'feed solution is an indium tin oxide (IT0) solution having a volume of 15.5 L, a pH of 0.9' and containing an initial concentration of 14 〇ppm of trivalent indium (Ιη3+)β. In addition, the dispersion is taken as a a mixed liquid consisting of 0.12 L (120 ml) of 5 Μ hydrochloric acid (HC1)' solution as a take-up solution (4) s〇iuti〇n), and mixed with a 9 L (900 ml) organic solution . Among them, the organic solution is an isoparaffin solvent (Isopar-L) as a solvent, and contains 〇6 μ bis (2-ethylhexyl) linic acid 42 201032881 [di(2-ethyl-hexyl) phosphoric acid, D2EHPA] And the volume percent concentration (vol%) is 2dodecanol. Figure 7 also shows the tin concentration in the feed solution as a function of time. The eighth figure is a graph showing the change of indium concentration with time in the feed solution and the take-up solution. The 'feeding liquid' is a residual electrolyte feed solution having a reservoir of L.5 L, a pH of 1, and containing trivalent indium (In3+) having an initial concentration of ❹ n000 PPm. In addition, the take-up dispersion is a mixed liquid consisting of 0.1 L (100 ml) of a 5 Μ hydrochloric acid (HC1) solution as a strip solution, and mixed with a 0.9 l (900 ml) Organic solution. Among them, the organic solution is an isoparaffinated hydrocarbon solvent (ISOpar_L) as a solvent, and contains 〇6 M (2-ethyl-hexyl) phosphoric acid, D2EHPA, and volume percentage The concentration (vol%) is 2. dodecanoyl. In this figure, the indium concentration and φ obtained by calculation and experiment are also shown, and are respectively labeled as taking the experiment and taking the ideal curve. Among them, the calculated data portion is calculated by mass balance of the feed solution. [Main component symbol description] 43

Claims (1)

201032881 VII. Patent application scope: 1. A supported liquid film take-up dispersion process, which is removed and recovered from the feed solution, indium, comprising: - (1) a liquid film with a microporous support material The feed solution is treated at one end so as to remove indium at the other end of the liquid medium by strip dispersion, wherein the take-up dispersion uses a take-up dispersion, and the take-up dispersion is passed through a a mixer dispersing an aqueous phase to take a solution in an organic liquid, and the organic liquid contains an extracting agent; and (2) separating a part or all of the taken dispersion into an organic phase and an aqueous phase, wherein The aqueous phase is an aqueous phase take-up solution, and the aqueous phase take-up solution comprises a concentrated indium solution. 2. The supported liquid film take-up dispersion procedure of claim 1, wherein the feed solution is treated to remove indium until its concentration falls below 5 ppm or less. 3. The supported liquid film take-up dispersion process of claim 1, wherein the aqueous take-up solution for taking the dispersion comprises at least one acid. 4. The supported liquid film take-up dispersion process according to claim 3, wherein the acid is selected from one of the following groups or a mixture thereof: hydrochloric acid (HC1), sulfuric acid (h2so4), nitric acid (hno3) ), as well as acetic acid (CH3C00H). 201032881 5. The supported liquid film take-up dispersion process as described in claim 1, wherein the organic liquid obtained by taking the dispersion further comprises a modifier, and the modified agent is present. In a hydrocarbon solvent or a mixture. 6. The supported liquid film take-up dispersion process according to claim 1, wherein the organic liquid containing the dispersion contains the extractant having a volume percentage of about 2 to 100, and the volume percentage is about 0. The modifier to 20' and the extractant and the modifier are present in a hydrocarbon solvent or mixture. ❹ 7. The supported liquid film take-up dispersion procedure as described in claim 6 wherein the organic liquid from which the dispersion is taken contains an extractant having a volume percentage of about 5 to 40, and the percentage of accumulation is about 1 to 1 2 3 modifier 'The extractant and the modifier are present in a hydrocarbon solvent or mixture. 45 1 The supported liquid film take-off dispersion procedure as described in claim 5 of the patent application' The modifiers referred to above are selected from one of the following groups or a mixture thereof: alcohol, nitrophenyl alkyl ether, and trialkyl phosphate. 2 The supported liquid film take-up dispersion procedure of claim 8 wherein the alcohol is selected from one of the following groups or a mixture thereof: hexanol, heptanol, Octanol (octanoD, nonano1, decan〇l, undecanol, dodecano1, tridecano1, ten 201032881 tetradecanol, fifteen Alcohol (pentadecanol), hexadecanol (hexadecanol), heptadecanocanol, octadecanocan (octadecanol). 10. The supported liquid film take-up dispersion procedure of claim 8 wherein the above The nitrophenyl alkyl ether is selected from one of the following groups or a mixture thereof: 〇-nitrophenyl octyl ether (o-NPOE), o-nitrophenylheptyl ether ( O-nitrophenyl heptyl ether), o-nitrophenyl hexyl ether, nitrophenyl pentyl ether (o-NPPE), ortho-phenylphenyl butyl Ether), 〇-nitr〇phenyl propyl ether. 11. The supported liquid film take-up dispersion process of claim 8, wherein the above trialkyl phosphate is selected from one of the following groups or a mixture thereof: a tributyl phosphate, a tris(2-ethylhexyl) phosphate, and a supported liquid film take-up dispersion process as described in claim 5, wherein the above The hydrocarbon solvent is selected from one of the following groups or a mixture thereof: n-decane, n-undecane, n-dodecane, and thirteen (n-tridecane), n-tetradecane, isodecane, isoundecane, isododecane, isotridecane, isotetradecene Isotetradecane, isothermal hydrocarbon solvent 46 201032881 (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 791 791 g / ml (at 15.6 °C)]. 13. The supported liquid film take-up dispersion process of claim 1, wherein the microporous support material is selected from one of the following groups or a mixture thereof: polypropylene, polytetra Fluorinated tetrafluoroethylene (PTFE), polyethylene, polysulfone, polyethersulfone, polyetheretherketone, polyimide, polyamine (polyamide), cyclic polyaramide. 14. The supported liquid film take-up dispersion process of claim 1, wherein the microporous support material is polypropylene. 15. The supported liquid film take-up dispersion process of claim 1, wherein the extractant comprises a dialkyl phosphoric acid. Ο 16. The supported liquid film take-up dispersion process of claim 15, wherein the above-mentioned dialkyl phosphoric acid has 6 to 26 carbon atoms and is saturated (paraffinic). 17. The supported liquid film take-up dispersion process of claim 5, wherein the above-mentioned dialkyl phosphoric acids may be selected from one of the following groups or a mixture thereof: two (2-B) Base-hexyl phosphate [diG-dhykexy1) 201032881 Phosphoric acid (D2EHPA)], di(2-butyl-octyl) phosphoric acid, di(2-hexyl-decyl) phosphoric acid 】, (2-octyl-fluorenyl-2-hexyl-dodecyl) phosphoric acid [di(2-octyl-decyl/2-hexyl-dodecyl) phosphoric acid], bis(2-octyl- 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((diyl) phosphoric acid) Di(undecyl) phosphoric acid, di(dodecyl) phosphoric acid, di(tridecyl) phosphoric acid, di(tridecyl) phosphoric Acid], di (tetradecyl phosphoric acid), di(pentadecyl) phosphoric acid, di(hexadecyl) phosphoric acid [di] (hexad Ecyl) phosphoric acid 】, di(heptadecyl) phosphoric acid, di(octadecyl) phosphoric acid, di(octadecyl)phosphoric acid [di(nonadecyl) phosphoric acid], di(decadecyl) phosphoric acid, di(undecadecyl) phosphoric acid, di (twenty) Di(dodecadecyl) phosphoric acid, di(decadelatelyl) phosphoric acid, di(quaternary) pyricic acid, di(tetradecadecyl) phosphoric Acid], two (25) base acid [di (pentadadecyl) phosphoric acid], two (26 burning base) acid 48 201032881 [di (hexadecadecyl) phosphoric acid]. * 18. The supported liquid film take-up dispersion procedure described in claim 15 wherein the above-mentioned dialkyl phosphoric acid is di(2-ethyl-hexyl) acid. Di(2-ethyl_hexyl) phosphoric acid (D2EHPA)]. 19. The supported liquid film take-up dispersion process of claim 1, wherein the extractant comprises an alkyl phenylphosphonic acid. 20. The supported liquid film take-up dispersion process of claim 19, wherein the alkyl group of the above alkyl phenylphosphonic acid has 6 to 26 broken atoms and Is a saturated state (paraffinic) 〇 21. The supported liquid film take-up dispersion procedure of claim 19, wherein the alkylbenzene phosphite described above may be selected from one of the following groups or a mixture thereof :(2_butyl-1-octyl)benzene acid acid [2-butyl_l-octyl phenylphosphonic acid (ΒΟΡΡΑ)], (2·hexyl-1-fluorenyl) phenylphosphite (2-hexyl-1-decyl phenylphosphonic) Acid, (2-octyl-1-indenyl-2-hexyl-1-dodecylphenylphosphonic acid), (2-octyl·l-decyl/2-hexyl-1-dodecyl phenylphosphonic acid), 2-octyl-l-dodecyl phenylphosphonic acid, hexyl phenylphosphonic acid, heptyl phenylphosphonic acid , octyl phenylphosphonic acid > octyl phenylphosphonic acid > nonyl phenylphosphonic acid Decyl phenylphosphonic 'acid' H undecyl phenylphosphonic acid, dodecyl phenylphosphonic acid, tridecyl benzoaric acid ( Tridecyl phenylphosphonic acid, tetradecyl phenylphosphonic acid, pentadecyl phenylphosphonic acid, hexadecyl phenyl phenylphosphonic acid, seventeen Heptadecyl phenylphosphonic acid, octadecyl phenylphosphonic acid, nonadecyl phenylphosphonic acid, decanoyl phthalic acid (decadecyl) Phenylphosphonic acid), undecadecyl phenylphosphonic acid, dodecadecyl phenylphosphonic acid, tridecadecyl 10 phenylphosphonic acid , tetradecadecyl phenylphosphonic acid, pentadadecyl phenyl Phosphonic acid), hexadecadecyl phenylphosphonic acid, 22. The supported liquid film take-up dispersion process as described in claim 19, wherein the above-mentioned pyridyl benzoic acid ( The alkyl phenylphosphonic acid) is (2-butyl-1-octyl phenylphosphonic acid 50 201032881 (ΒΟΡΡΑ)].