Use and method of amino-containing neutral phosphine extractants for the extraction separation of gallium and indium

Abstract

The present application relates to the use and method of the amino-containing neutral phosphine extractant of general formula I for the extraction separation of gallium and indium, wherein R1 and R2 are each independently selected from C6-C 14 alkyl; R3 and R4 are each independently selected from hydrogen, C1-C8 alkyl, C3-C 10 cycloalkyl and C6-C 10 aryl; R5 and R6 are each independently selected from C4-C 16 alkyl. The method of the present application can preferentially extract gallium, thereby realizing the separation of gallium and indium. Unlike the conventional gallium-indium separation extractant such as P204 which preferentially extracts indium, the present application has a significant advantage in separating low-gallium high-indium feed solution. In addition, the extractant used in the present application is a neutral extractant, which does not need to be saponified before use, reducing the consumption of acid and alkali reagents; and the synthesis method is simple, the raw materials are easy to obtain, the cost is low, and it has high industrial application value.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for extracting and separating gallium and indium, and in particular, to the use and method of a class of amino-containing neutral phosphine extractant for extracting and separating gallium and indium. BACKGROUND

[0002] With the increasing demand for gallium and indium in the fields of semiconductor materials, energy materials, catalysts and pharmaceutical preparations, efficient separation and production of gallium and indium are of great significance to the development of science and technology in China.

[0003] The existing method for separating gallium and indium from solution is mainly P204 extraction method. CN201510277326.3 discloses a method for separating and extracting indium and gallium from an indium-gallium solution. The method uses an acidic phosphorus extractant such as P204 to co-extract indium and gallium, and then uses concentrated hydrochloric acid and oxalic acid to stepwise back-extract indium and gallium to obtain indium-rich and gallium-rich solutions, respectively. The purity of the indium and gallium products obtained by the method is not high and further refining is required. In addition, the acid consumption is too high, and the operation environment and economy are poor.

[0004] JP2012102062A discloses an amino-containing neutral or acidic phosphine extractant represented by the following formula:

[0005]

[0006] wherein R 1 and R 2 are each independently a substituted or unsubstituted straight-chain or branched-chain C 1-18 alkyl, C 2-18 alkenyl or C 2-18 alkynyl, or a substituted or unsubstituted straight-chain or branched-chain C 7-18 aralkyl or C 8-18 aralkenyl; R 3 and R 4 are each independently hydrogen, a substituted or unsubstituted straight-chain or branched-chain C 1-4 alkyl, C 2-4 alkenyl or C 2-4 alkynyl, or a substituted or unsubstituted straight-chain or branched-chain C 7-18 arylalkyl or C 8-18 arylalkenyl, and relates to a method for selectively extracting indium or gallium from a solution containing indium, gallium and zinc using the same. However, according to the results of the examples in JP2012102062A, the amino-containing neutral phosphine extractant therein has poor separation performance for gallium and indium, and only part of the amino-containing acidic phosphine extractant has good separation performance for gallium and indium.

[0007] Therefore, it is of great significance to develop an extractant with high selectivity for gallium and indium to promote the efficient separation and recovery of gallium and indium resources. SUMMARY

[0008] The inventors of the present application have developed a method for the extraction separation of thorium, cerium, zirconium, hafnium, uranium, and copper using amino-containing neutral phosphine extractants, see CN 105734289 A, CN 105734288 A, CN 107287419 A, CN 106521190 A, CN 106521153 A, CN 107674974 A, CN 109097570 A. In recent experiments, the inventors used part of the amino-containing neutral phosphine extractants for the extraction separation of gallium and indium, unexpectedly achieved good extraction separation effect, thereby completing the present application. The amino-containing neutral phosphine extractants used are stable in nature and easy to synthesize. The significant feature of the present application is that the extractant is a neutral extractant, no need for saponification, reducing the consumption of acid and alkali reagents; and in the extraction process, gallium is preferentially extracted into the extraction liquid, and indium is left in the aqueous phase, thereby realizing the separation of gallium and indium; unlike the conventional gallium-indium separation extractant P204, which preferentially extracts indium into the extraction liquid and leaves gallium in the aqueous phase, when treating a low-gallium high-indium feed solution, the amount of gallium to be extracted is small, thereby saving the amount of extractant and the consumption of chemical raw materials in the extraction process, thereby improving the economy of the separation process. Therefore, the present application has significant advantages in separating low-gallium high-indium feed solutions.

[0009] It is an object of the present application to provide the use of an amino-containing neutral phosphine extractant for the extraction separation of gallium and indium.

[0010] It is another object of the present application to provide a method for the extraction separation of gallium and indium using the amino-containing neutral phosphine extractant.

[0011] One aspect of the present application provides the use of an amino-containing neutral phosphine extractant of the following general formula I for the extraction separation of gallium from a feed solution comprising gallium and indium:

[0012]

[0013] wherein,

[0014] R1and R2are each independently selected from the group consisting of C6-C 14 alkyl;

[0015] R3and R4are each independently selected from the group consisting of hydrogen, C1-C8alkyl, C3-C 10 cycloalkyl, and C6-C 10 aryl;

[0016] R5and R6are each independently selected from the group consisting of C4-C 16 alkyl.

[0017] Another aspect of the present application provides a method for separating gallium and indium, which comprises the step of extracting gallium from a feed solution containing gallium and indium using an amino-containing neutral phosphine extractant of general formula I.

[0018] The method for separating gallium and indium according to the present application can be carried out by a method of solvent extraction, for example, by formulating the amino-containing neutral phosphine extractant of the present application into a liquid extraction system, or by a method of solid-liquid extraction, for example, by formulating the amino-containing neutral phosphine extractant of the present application into a solid separation material such as a liquid ion exchange resin.

[0019] Advantages

[0020] The present application has the remarkable feature of preferentially extracting gallium, thereby achieving the separation of gallium and indium. Unlike conventional gallium-indium separation extractants such as P204, which preferentially extract indium, the present application has a significant advantage in separating a feed solution containing low gallium and high indium. The extractant used in the present application is a neutral extractant, which does not need to be saponified before use, thereby reducing the consumption of acid and alkali reagents. Moreover, the synthesis method is simple, the raw materials are readily available, and the cost is low, thereby having high industrial application value. DETAILED DESCRIPTION

[0021] The present application will be described in more detail below, but the present application is not limited to the following.

[0022] The present application provides, in one aspect, the use of an amino-containing neutral phosphine extractant of general formula I for extracting and separating gallium from a feed solution containing gallium and indium:

[0023]

[0024] wherein,

[0025] R1and R2are each independently selected from the group consisting of C6-C 14 alkyl, preferably C7-C 12 alkyl, more preferably C8-C 12 alkyl;

[0026] R3and R4are each independently selected from the group consisting of hydrogen, C1-C8alkyl, C3-C 10 cycloalkyl, and C6-C 10 aryl; preferably from the group consisting of hydrogen, C1-C6alkyl, C3-C8cycloalkyl, and C6-C8aryl;

[0027] R5and R6are each independently selected from the group consisting of C4-C 16 alkyl, preferably C5-C 12 alkyl, more preferably C6-C 10 alkyl, most preferably C6-C8alkyl.

[0028] In the formula I, R1and R2are the same or different. In addition, R1and R2are preferably the same alkyl, more preferably the same C8-C12 alkyl.

[0029] Preferably, the total number of carbon atoms in R1 and R2 is an integer between 14 and 24, including but not limited to 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24 carbon atoms, and more preferably an integer between 16 and 24.

[0030] R3 and R4 may be the same or different. Preferably, R3 and R4 are each independently selected from hydrogen, C1-C4 alkyl, C3-C6 alicyclic alkyl, and C6-C8 aryl, with hydrogen, methyl, ethyl, cyclohexyl, and phenyl being more preferred. In particular, R3 is selected from hydrogen, C1-C4 alkyl, C3-C6 alicyclic alkyl, and C6-C8 aryl, with hydrogen, methyl, ethyl, cyclohexyl, and phenyl being more preferred; R4 is selected from hydrogen and C1-C4 alkyl, with hydrogen, methyl, and ethyl being more preferred.

[0031] Preferably, the total number of carbon atoms in R3 and R4 is an integer between 0 and 12, including but not limited to 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12 carbon atoms, and is preferably an integer between 0 and 7.

[0032] R5 and R6 may be the same or different, preferably the same C6 to C8 alkyl group. Preferably, the total number of carbon atoms in R5 and R6 is an integer between 10 and 24, including but not limited to 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24 carbon atoms, and more preferably an integer between 12 and 20.

[0033] Preferably, in the amino-containing neutral phosphine extractant of Formula I of the present invention, the total number of carbon atoms of R1, R2, R3, R4, R5 and R6 is 30 to 48, including but not limited to 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 and 48 carbon atoms, preferably 30 to 42, more preferably 32 to 40.

[0034] Preferably, the amino-containing neutral phosphine extractant of general formula I is one or more selected from the group consisting of N,N'-di(2-ethylhexyl)aminomethylphosphonic acid di(2-ethylhexyl) ester, N,N'-di(2-ethylhexyl)aminomethylphosphonic acid didodecyl ester, 1-(N,N'-di(2-ethylhexyl)amino)-1-ethylphosphonic acid di(2-ethylhexyl) ester, 1-(N,N'-di(2-ethylhexyl)amino)-1-ethylpropylphosphonic acid di(2-ethylhexyl) ester, 1-(N,N'-dihexylamino)-1-phenylmethylphosphonic acid di(2-ethylhexyl) ester, 1-(N,N'-di(2-ethylhexyl)amino)-1-cyclohexylmethylphosphonic acid di(2-ethylhexyl) ester, 1-(N,N'-di(2-ethylhexyl)amino)-1-methylethylphosphonic acid di(2-ethylhexyl) ester.

[0035] The amino-containing neutral phosphine extractant of general formula I can be synthesized according to known or similar methods in the prior art (such as CN201410765062.1, CN201611012369.X) or methods similar to the methods disclosed in the examples.

[0036] For example, the amino-containing neutral phosphine extractant of general formula I can be obtained by subjecting compound II, compound III and compound IV to an aminomethylation reaction, as shown in reaction formula 1:

[0037]

[0038] wherein R1, R2, R3, R4, R5 and R6 are defined as in general formula I.

[0039] According to another aspect of the present application, there is provided a method for extracting and separating gallium from a gallium and indium-containing feed solution, the method comprising the step of using the above-mentioned amino-containing neutral phosphine extractant of general formula I to extract gallium from the gallium and indium-containing feed solution.

[0040] In one embodiment, the method for extracting and separating gallium according to the present application can be carried out by a solvent extraction method, the method comprising: mixing a neutral phosphine extraction system comprising the amino-containing neutral phosphine extractant of general formula I with the gallium and indium-containing feed solution to carry out extraction to obtain a gallium-containing extract and an indium-containing raffinate.

[0041] The neutral phosphine extraction system comprises the amino-containing neutral phosphine extractant of general formula I, an optional auxiliary extractant, an optional phase modifier and a diluent. Preferably, the neutral phosphine extraction system consists of the above-mentioned components.

[0042] In the present application, the neutral phosphine extraction system is sometimes referred to as an organic phase.

[0043] The auxiliary extractant mainly plays a role of assisting extraction and can enhance the extraction performance of the neutral phosphine extractant containing amino group on gallium. The auxiliary extractant can be selected from the phosphorus (phosphine) extractants of the following general formula V:

[0044]

[0045] wherein,

[0046] Z is O or S;

[0047] R7is selected from the group consisting of hydrogen, C1-C 16 alkyl, C1-C 16 alkoxy, -SH and -NH2substituted with at least one substituent selected from the group consisting of C1-C 16 alkyl, and the like, preferably selected from the group consisting of hydrogen, C1-C 12 alkyl, C1-C 12 alkoxy, -SH and -NH2substituted with at least one substituent selected from the group consisting of C4-C 12 alkyl, and the like; more preferably selected from the group consisting of C1-C 10 alkyl and C1-C 10 alkoxy;

[0048] R8and R9are each independently selected from the group consisting of C4-C 12 alkyl, C4-C 12 alkoxy and -NH2substituted with at least one substituent selected from the group consisting of C4-C 12 alkyl, and the like, preferably selected from the group consisting of C4-C 10 alkyl, C4-C 10 alkoxy and -NH2substituted with at least one substituent selected from the group consisting of C4-C 10 alkyl, and the like, more preferably selected from the group consisting of C4-C 10 alkyl and C4-C 10 alkoxy.

[0049] Suitable auxiliary extractants can be selected from: neutral phosphorus (phosphine) extractants, such as straight-chain trialkyl phosphine oxide (Cyanex 923), branched-chain trialkyl phosphine oxide (Cyanex 925), trioctyl phosphine oxide (TOPO), dimethylheptyl methyl phosphonate (P350), di(-2-ethylhexyl) 2-ethylhexyl phosphonate, tri-butyl phosphate (TBP); acidic phosphorus (phosphine) extractants, such as di(2,4,4-trimethylpentyl) dithiophosphonate (Cyanex 301), di(2,4,4-trimethylpentyl) thiophosphonate (Cyanex 302), di(2-ethylhexyl) phosphoric acid (P204), mono-2-ethylhexyl 2-ethylhexyl phosphonate (P507), di(2,4,4-trimethylpentyl) phosphonic acid (Cyanex 272), di(2-ethylhexyl) phosphonic acid (P227 or P229); neutral phosphonamide extractants, such as the neutral phosphonamide extractants disclosed in CN201410409451.0 and CN201410040023.5, such as triisooctyl phosphonamide, diisooctyl-isooctyloxy phosphonamide, isooctyl-diisooctyloxy phosphonamide, tris(diisobutyl) phosphonamide, di(diisobutyl)-isooctyloxy phosphonamide, tridecyl phosphonamide, and dihexyl-decyloxy phosphonamide, etc.; and mixed extractants of the above extractants in any proportion.

[0050] The phase modifier mainly plays a role in improving the physical phenomenon of extraction, which can be selected from C4-C 10 one or more of alkanols and tri-butyl phosphate, preferably one or more selected from n-octanol, isooctanol, 2-methylheptanol, and mixed alcohols of the above three alcohols in any proportion and tri-butyl phosphate; more preferably mixed alcohols or 2-methylheptanol.

[0051] The diluent is selected from: C5-C 16 alkanes, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, etc.; aviation kerosene; sulfonated kerosene, liquid paraffin, such as 250-400℃ light lubricating oil fraction, etc.; C5-C 16 cycloalkanes, such as cyclopentane, C1-C4 alkyl-substituted cyclopentane, cyclohexane, C1-C4 alkyl-substituted cyclohexane, decalin, etc.; C6-C 10 aromatic hydrocarbons, such as benzene, toluene, xylene (including o-, m-, p-xylene and mixed xylene), etc. Preferably, the diluent is one or more selected from aviation kerosene, sulfonated kerosene, heptane and xylene.

[0052] In the amino group-containing neutral phosphine extraction system, the volume ratio of the amino group-containing neutral phosphine extractant, the optional auxiliary extractant, the optional phase modifier, and the diluent can be: amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = about 1-60: about 0-40: about 0-20: about 40-110, more preferably amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = about 10-40: about 0-20: about 0-20: about 50-100; and still more preferably amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = about 15-35: about 0-15: about 0-15: about 55-90, for example, amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = about 15-35: about 3-15: 0: about 55-90, or amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = about 15-35: 0: about 3-15: about 55-90, or amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = about 15-35: 0: 0: about 55-90.

[0053] The feed solution is a hydrochloric acid solution containing gallium and indium in the form of trivalent ions, wherein the concentration of gallium and the concentration of indium can each independently be about 0.0001 to about 2 mol / L, for example, 0.001, 0.010, 0.020, 0.030, 0.040, 0.050, 0.10, 0.20, 0.30, 0.50 mol / L, etc., but not limited thereto.

[0054] In some embodiments, the hydrochloric acid concentration of the feed solution is about 0.1 to about 6 mol / L, preferably about 1 to about 5 mol / L, for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 mol / L, etc., but not limited thereto.

[0055] In some embodiments, the molar ratio of indium to gallium in the feed solution can be about 500:1 to about 1:500, for example, 50:1 to 1:50, 100:1 to 1:100, 150:1 to 1:150, 200:1 to 1:200, 250:1 to 1:250, 300:1 to 1:300, 350:1 to 1:350, 400:1 to 1:400, 450:1 to 1:450, etc., but not limited thereto.

[0056] In some embodiments, the molar concentration of indium in the feed solution is not less than the molar concentration of gallium, for example, the molar ratio of indium to gallium can be 1:1 to 100:1, for example, 1:1 to 10:1, 1:1 to 20:1, 1:1 to 30:1, 1:1 to 40:1, 1:1 to 50:1, 1:1 to 60:1, 1:1 to 70:1, 1:1 to 80:1, 1:1 to 90:1, etc., but not limited thereto.

[0057] The raw material for preparing the feed solution is not limited as long as it contains gallium and indium. The raw material suitable for preparing the feed solution includes various raw materials containing gallium and indium, such as indium copper sulfide, zinc blende, tetrahedrite, gallium-indium-containing waste devices, etc. The raw material can be pretreated by physical, chemical or other methods, and dissolved in hydrochloric acid to prepare the feed solution of the present application.

[0058] In some embodiments, the volume ratio of the neutral phosphine extraction system to the feed solution can be 0.1-20:1, preferably about 0.5-10:1.

[0059] The extraction stage of the extraction can be 1-20 stages, preferably 1-10 stages.

[0060] In some embodiments, the extraction is carried out in a countercurrent extraction manner.

[0061] A small amount of indium can be entrained in the gallium-containing extraction solution. Generally, in the gallium-containing extraction solution, the content of indium can be controlled to be 10% or less, normally 5% or less, based on the total moles of indium and gallium; the content of gallium is 90% or more, normally 95% or more.

[0062] The obtained indium-containing raffinate can be further treated, for example, distilled to remove acid and water to obtain the corresponding indium salt, or precipitated with alkali to obtain indium hydroxide precipitate, or adjusted to acid and then replaced with zinc or aluminum to obtain elemental indium. Therefore, the method according to the present application can further comprise a step of treating the indium-containing raffinate to recover indium.

[0063] The method according to the present application further comprises a step of stripping gallium from the gallium-containing extraction solution with a stripping agent to obtain a gallium-containing stripping product.

[0064] In some embodiments, the stripping agent (which can also be referred to as a reverse liquid, a stripping liquid, a stripping solution) can be selected from acid solutions such as hydrochloric acid, sulfuric acid, nitric acid, etc. or mixed solutions of the above acids in any proportion. The molar concentration of hydrogen ions in the stripping agent can be 1 x 10 -8 - 6 mol / L, preferably 0.01-5 mol / L.

[0065] The stripping stage of the stripping can be 1-10 stages, preferably 2-6 stages.

[0066] The volume ratio of the gallium-containing extraction solution to the stripping agent can be 0.1-10:1, preferably about 0.5-5:1.

[0067] In some embodiments, the stripping is carried out in a countercurrent stripping manner.

[0068] The organic phase after stripping can be recycled and used again to extract and separate gallium from the gallium- and indium-containing feed solution.

[0069] The method for separating gallium and indium according to the present application can further comprise a step of recovering gallium from the gallium-containing stripping product.

[0070] The step of recovering gallium from the gallium-containing stripping product is not particularly limited and any method known in the art for recovering gallium can be used.

[0071] For example, a small amount of indium can be present in the gallium-containing stripping product. Therefore, in an embodiment, the method for recovering gallium can use the method disclosed in CN202111581742.4 to extract indium from the gallium-containing stripping product with high selectivity, leaving gallium in the raffinate aqueous phase, and then recovering gallium from the gallium-containing raffinate aqueous phase.

[0072] In the solvent extraction method according to the present application, the extraction and stripping can be carried out using a liquid-liquid separation device known in the art, preferably in a series of liquid-liquid separation funnels, mixed-settling extraction tanks or centrifugal extractors, more preferably in mixed-settling extraction tanks or centrifugal extractors.

[0073] In the solvent extraction method according to the present application, the above-mentioned extraction and stripping can be carried out intermittently or continuously, preferably continuously.

[0074] The results show that, after extraction and separation, the yield of indium is greater than 95%, and the purity of indium is greater than 99%, effectively achieving the separation of gallium and indium.

[0075] In addition, through the step of recovering gallium, the yield of gallium is greater than 98%, and the purity of gallium is greater than 99%.

[0076] In another embodiment, the method for extracting and separating gallium and indium according to the present application is carried out by a solid-liquid extraction method, which comprises separating and purifying gallium and indium using a solid separation material prepared using an amino-containing neutral phosphine extractant of general formula I. More specifically, the method comprises contacting the solid separation material prepared using an amino-containing neutral phosphine extractant of general formula I with a gallium- and indium-containing feed solution to carry out solid-liquid extraction to obtain a gallium-containing solid separation material and an indium-containing raffinate.

[0077] In an embodiment, the solid-liquid extraction method is carried out in a resin column, wherein the solid separation material is added to the resin column, and then the gallium- and indium-containing feed solution is added to contact the solid separation material with the gallium- and indium-containing feed solution to carry out solid-liquid extraction.

[0078] The indium-containing raffinate in the solid-liquid extraction method is sometimes also referred to as indium-containing tail liquid. The content of gallium in the indium-containing tail liquid is not particularly limited, but is preferably not greater than about 1 mg / L, more preferably not greater than about 0.1 mg / L, thereby improving the purity of indium.

[0079] The obtained indium-containing raffinate can be further treated, for example, distilled to remove acid and water to obtain a corresponding indium salt, or precipitated by adding alkali to obtain an indium hydroxide precipitate, or replaced by zinc or aluminum after being adjusted to an acid to obtain elemental indium. Therefore, the method according to the present application can further comprise a step of treating the indium-containing raffinate to recover indium.

[0080] The description of the solution containing gallium and indium in the solvent extraction method is also applicable to the solid-liquid extraction method, and thus is not repeated here.

[0081] The solid separation material can be a resin, porous silica ball, diatomite, etc. loaded with the amino-containing neutral phosphine extractant of general formula I. Preferably, the solid separation material can be prepared by a conventional method in the art, for example, by loading the neutral phosphine extractant of general formula I on a resin, porous silica ball, diatomite, etc. by impregnation, in-situ polymerization, chemical bonding, etc., preferably by impregnation, in-situ polymerization, etc.

[0082] In a preferred embodiment, the solid separation material is a chelating resin. The method for preparing the chelating resin is not particularly limited as long as it is loaded with the amino-containing neutral phosphine extractant of general formula I. For example, a chelating resin can be prepared by first preparing resin microparticles by dispersion polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc., and then loading the neutral phosphine extractant of general formula I on the resin microparticles, or by adding the neutral phosphine extractant of general formula I before or during polymerization to prepare the chelating resin by in-situ polymerization.

[0083] In an embodiment, the chelating resin can be prepared by dispersion polymerization of the amino-containing neutral phosphine extractant of general formula I with styrene-based monomers and divinylbenzene monomers. For example, the neutral phosphine extractant of general formula I is mixed with a mixture of styrene-based monomers and divinylbenzene monomers, an initiator is added in an amount of 2% of the total mass of the oil phase to prepare an oil phase; 10 times the volume of the oil phase of deionized water is taken, 3% gelatin and 0.5% ammonium thiocyanate are added to the mass of the water phase, and mixed to prepare a water phase; the water phase is heated to 50°C, after the gelatin is dissolved, the oil phase is slowly added, and incubated for half an hour, then the temperature is raised to 80°C, and the polymerization reaction is carried out for 5 hours; the temperature is then raised to 90°C to solidify the resin for half an hour, the resin is taken out, washed, and sieved, and then air-dried to obtain the desired chelating resin. The styrene-based monomers can be styrene, methylstyrene, ethylstyrene, etc.

[0084] In another embodiment, the solid separation material is porous silica spheres, diatomite, etc. loaded with the amino group-containing neutral phosphine extractant of general formula I. There is no particular limitation on the method for loading the amino group-containing neutral phosphine extractant of general formula I on the porous silica spheres, diatomite, etc., as long as the amino group-containing neutral phosphine extractant of general formula I can be loaded on the porous silica spheres, diatomite, etc. For example, the amino group-containing neutral phosphine extractant of general formula I can be dissolved in a diluent (e.g., dichloromethane, trichloromethane, benzene, toluene, etc., which are volatile and inert solvents), and the porous silica spheres, diatomite, etc. separation material can be added, and the diluent can be slowly evaporated under stirring to obtain the desired solid separation material.

[0085] In one embodiment, the solid-liquid extraction method according to the present application further comprises the step of stripping the gallium in the gallium-containing solid separation material with a stripping agent to obtain a gallium-containing stripping product. The stripping agent after stripping can be collected, and when the gallium content in the stripping agent is less than 0.1 mg / L, the addition of the stripping agent can be stopped. The solid separation material after stripping can be recycled and used again to extract and separate gallium from the gallium- and indium-containing feed solution.

[0086] The description of the stripping agent in the solvent extraction method is also applicable to the solid-liquid extraction method, and thus is not repeated here.

[0087] The description of the recovery of gallium from the gallium-containing stripping product in the solvent extraction method is also applicable to the solid-liquid extraction method, and thus is not repeated here.

[0088] As an example, the solid-liquid extraction method according to the present application can be operated as follows: the solid separation material is added to a resin column, and then the feed solution is added from the inlet for solid-liquid extraction, and the raffinate is collected from the outlet, and the gallium content in the raffinate is analyzed periodically, and when the gallium content in the raffinate reaches 0.1 mg / L, the addition of the feed solution is stopped; the gallium extracted in the solid separation material is stripped with a stripping solution, and the stripping solution is collected, and when the gallium content in the stripping solution is less than 0.1 mg / L, the addition of the stripping solution is stopped.

[0089] The term

[0090] The term "C1-Cnalkyl" as used herein refers to a straight-chain or branched-chain alkyl group having 1 to n carbon atoms, for example, a straight-chain or branched-chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 carbon atoms, and includes, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, etc. C1-Cnalkyl 16 The term "C1-Cnalkyl" as used herein refers to a straight-chain or branched-chain alkyl group having 1 to n carbon atoms, for example, a straight-chain or branched-chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 carbon atoms, and includes, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, etc. C1-Cnalkyl 12 The term "C1-Cnalkyl" as used herein refers to a straight-chain or branched-chain alkyl group having 1 to n carbon atoms, for example, a straight-chain or branched-chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 carbon atoms, and includes, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, etc. C1-Cnalkyl 10 The term "C1-Cnalkyl" as used herein refers to a straight-chain or branched-chain alkyl group having 1 to n carbon atoms, for example, a straight-chain or branched-chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 carbon atoms, and includes, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, etc. C1-Cnalkyl 12alkyl, C4-C 10 alkyl, C6-C 14 alkyl, and C7-C 12 The meanings of alkyl, C4-C

[0091] The term C1-C 16 Alkoxy means a straight-chain or branched alkoxy group having 1 to 16 carbon atoms, for example a straight-chain or branched alkoxy group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15 or 16 carbon atoms, including, without limitation, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, i-butoxy, n-pentoxy, neopentoxy, i-pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy and the like. C1-C 12 alkoxy, and C4-C 10 The meanings of alkoxy, C4-C

[0092] The term C3-C 10 Alicyclic alkyl means a saturated cyclic alkyl group having 3 to 10 carbon atoms, including the carbon atoms of the substituents, which can be a monocyclic or bicyclic group, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like, which can be substituted by one or more substituents selected from C1-C4 alkyl. The meanings of C3-C8 alicyclic alkyl and the like are analogous.

[0093] The term C6-C 10 Aryl means an aromatic group having 6 to 10 carbon atoms, including the carbon atoms of the substituents, for example phenyl and phenyl substituted by one or more substituents selected from C1-C4 alkyl, for example tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl and the like. The meanings of C6-C8 aryl and the like are analogous.

[0094] The term C4-C 10 Alkanol means a straight-chain or branched alkanol having 4 to 10 carbon atoms, for example a straight-chain or branched alkanol having 4, 5, 6, 7, 8, 9 or 10 carbon atoms, including, without limitation, n-butanol, t-butanol, i-butanol, n-pentanol, neopentanol, i-pentanol, hexanol, heptanol, octanol, nonanol, decanol and the like.

[0095] The term C5-C 16Alkanes refer to straight-chain or branched alkanes containing 5 to 16 carbon atoms, straight-chain or branched alkanes having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 carbon atoms, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and the like.

[0096] The term C5-C16 alkanes as used in the present invention refers to saturated alkanes containing 5 to 16 carbon atoms, which can be straight-chain or branched, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and the like. 16 Alicyclic alkanes refer to saturated cyclic alkanes containing 5 to 16 carbon atoms, which can be monocyclic or bicyclic, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decalin, and the like, including one or more substituents selected from C1-C4 alkyl groups.

[0097] The term C6-C10 arenes as used in the present invention refers to arenes containing 6 to 10 carbon atoms, such as benzene and benzene substituted with one or more substituents selected from C1-C4 alkyl groups, such as benzene, toluene, xylene, and the like. 10 Alicyclic alkanes refer to saturated cyclic alkanes containing 5 to 16 carbon atoms, which can be monocyclic or bicyclic, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decalin, and the like, including one or more substituents selected from C1-C4 alkyl groups.

[0098] Unless otherwise specified, the numerical ranges set forth in the present invention include the end point values and all points in between the end point values in increments of the smallest unit of the end point values and all sub-ranges composed of these points.

[0099] Examples

[0100] In order to further illustrate the scheme of the present invention, specific examples of the present invention are provided to help those skilled in the art to understand and implement the present invention, but the present invention is not limited to these examples.

[0101] Reagents and sources

[0102] Dialkyl phosphite, organic amine, aldehyde, ketone, toluene, p-toluenesulfonic acid, aviation kerosene, sulfonated kerosene, heptane, TBP, fatty alcohol, and other reagents were purchased from Aldrich Reagent Co., Ltd.

[0103] Feed solution, washing solution, and stripping agent were self-made in the laboratory.

[0104] Other reagents (such as acid, etc.) were commercially available analytical reagents.

[0105] The purity of the products was determined by ICP-OES (instrument model: PQ9000, manufacturer: Analytikjena).

[0106] Nuclear magnetic resonance instrument was Bruker AVANCE NEO.

[0107] Preparation Example 1: Preparation of N,N'-di(2-ethylhexyl)aminomethylphosphonic acid di(2-ethylhexyl) ester

[0108]

[0109] To a single neck flask equipped with a mechanical stirrer and a condenser reflux apparatus, di(2-ethylhexyl) phosphite (1 mol), paraformaldehyde (1.1 mol), di(2-ethylhexyl) amine (1.1 mol), toluene (800 ml) and p-toluene sulfonic acid (0.8 g) were added, stirred and refluxed at 80-90°C for 12 h. Toluene and unreacted starting materials were removed by rotary evaporation to obtain the target product.

[0110] 1 H NMR (500 MHz, CDC13): δ 3.81-3.89 (m, 4H, CH2), 2.86-3.10 (m, 4H, CH2), 1.74 (dd, 2H, CH2), 1.56-1.62 (m, 4H, CH), 1.38-1.42 (m, 12H, CH2), 1.3-1.18 (m, 20H, CH2), 0.87-0.97 (m, 24H, CH3).

[0111] Preparation Example 2: Preparation of N,N'-di(2-ethylhexyl)aminomethylphosphonic acid didodecyl ester

[0112]

[0113] The target product was prepared using the same procedure as in Preparation Example 1 except that di(dodecyl) phosphite was used instead of di(2-ethylhexyl) phosphite.

[0114] 1 H NMR (500 MHz, CDC13): δ 3.86-3.97 (m, 4H, CH2), 2.84-2.95 (m, 4H, CH2), 1.79 (dd, 2H, CH2), 1.73-1.76 (m, 2H, CH2), 1.69-1.72 (m, 4H, CH2), 1.52-1.56 (m, 4H, CH2), 1.27-1.35 (m, 48H, CH2), 0.84-0.98 (m, 18H, CH3).

[0115] Preparation Example 3: Preparation of 1-(N,N'-di(2-ethylhexyl)amino)-1-ethylphosphonic acid di(2-ethylhexyl) ester

[0116]

[0117] The target product was prepared by the same process as in Preparation Example 1 except that acetaldehyde was used instead of paraformaldehyde.

[0118] 1 H NMR (500 MHz, CDC13): δ 3.83-3.92 (m, 4H, CH2), 3.3 (q, 1H, CH), 2.94-3.02 (m, 4H, CH2), 1.68-1.74 (m, 4H, CH), 1.52-1.56 (m, 8H, CH2), 1.25-1.31 (m, 24H, CH2), 1.2 (d, 3H, CH3), 0.88-0.99 (m, 24H, CH3).

[0119] Preparation Example 4: Preparation of di(2-ethylhexyl) 1-(N,N'-di(2- ethylhexyl)amino)-1-ethylpropylphosphonate

[0120]

[0121] The target product was prepared by the same process as in Preparation Example 1 except that 3-pentanone was used instead of paraformaldehyde.

[0122] 1 H NMR (500 MHz, CDC13): δ 3.83-3.92 (m, 4H, CH2), 3.3 (q, 1H, CH), 2.94-3.02 (m, 4H, CH2), 1.68-1.74 (m, 4H, CH), 1.52-1.56 (m, 8H, CH2), 1.25-1.31 (m, 24H, CH2), 1.2 (d, 3H, CH3), 0.88-0.99 (m, 24H, CH3).

[0123] Preparation Example 5: Preparation of di(2-ethylhexyl) 1-(N,N'-dihexylamino)-1- phenylmethylphosphonate

[0124]

[0125] The target product was prepared by the same process as in Preparation Example 1 except that benzaldehyde was used instead of paraformaldehyde and dihexylamine was used instead of di(2-ethylhexyl)amine.

[0126] 1H NMR (500 MHz, CDC13): δ 7.29-7.33 (m, 4H, CH2), 7.19-7.21 (m, 1H, CH), 3.90-3.98 (m, 4H, CH), 3.8 (q, 1H, CH), 2.94 (dd, 4H, CH2), 1.64-1.75 (m, 2H, CH), 1.47-1.58 (m, 4H, CH2), 1.29-1.34 (m, 28H, CH2), 0.88-0.96 (m, 18H, CH3).

[0127] Preparation Example 6: Preparation of 1-(N,N'-di(2-ethylhexyl)amino)-1- cyclohexylmethylphosphonic acid di(2-ethylhexyl) ester

[0128]

[0129] The target product was prepared by the same process as in Preparation Example 1, except that cyclohexylcarboxaldehyde was used instead of paraformaldehyde.

[0130] 1 H NMR (500 MHz, CDC13): δ 7.29-7.33 (m, 4H, CH2), 7.19-7.21 (m, 1H, CH), 3.90-3.98 (m, 4H, CH), 3.8 (q, 1H, CH), 2.94 (dd, 4H, CH2), 1.64-1.75 (m, 2H, CH), 1.47-1.58 (m, 4H, CH2), 1.29-1.34 (m, 28H, CH2), 0.88-0.96 (m, 18H, CH3).

[0131] Preparation Example 7: Preparation of 1-(N,N'-di(2-ethylhexyl)amino)-1- methylethylphosphonic acid di(2-ethylhexyl) ester

[0132]

[0133] The target product was prepared by the same process as in Preparation Example 1, except that acetone was used instead of paraformaldehyde.

[0134] 1 H NMR (500 MHz, CDC13): δ 7.29-7.33 (m, 4H, CH2), 7.19-7.21 (m, 1H, CH), 3.90-3.98 (m, 4H, CH), 3.8 (q, 1H, CH), 2.94 (dd, 4H, CH2), 1.64-1.75 (m, 2H, CH), 1.47-1.58 (m, 4H, CH2), 1.29-1.34 (m, 28H, CH2), 0.88-0.96 (m, 18H, CH3).

[0135] Examples 1-7

[0136] Preparation of organic phase: The seven extractants synthesized in Preparation Examples 1-7 were each mixed with n-heptane to form an organic phase, the molar concentration of the extractant in the organic phase being 0.1 mol / L based on the total volume of the organic phase.

[0137] Preparation of feed solution: Single solutions of indium chloride and gallium chloride were taken respectively, mixed, and then diluted with distilled water and hydrochloric acid to the required concentration and acidity (i.e. hydrogen ion concentration), the indium and gallium concentrations both being 0.005 mol / L, the total concentration being 0.01 mol / L, and the acidity being 4.0 mol / L.

[0138] The organic phase and the feed solution were mixed in a volume ratio of 1:1, and single-stage extraction was carried out at room temperature. During the extraction process, the phases separated rapidly, equilibrium was reached within 1 minute, the phase interface was clear, and no emulsion or third phase was produced.

[0139] After the extraction was complete, the separation factor β of gallium (Ga) and indium (In) was calculated Ga / In (see Table 1).

[0140] The separation factor β of gallium (Ga) and indium (In) was calculated as follows Ga / In

[0141]

[0142] where D is the distribution ratio of the metal ion, and is calculated as follows:

[0143]

[0144] where [M] (aq,init) and [M] (aq) are the initial concentration and the equilibrium concentration of the metal ion in the aqueous phase respectively.

[0145] Comparative Example 1

[0146] N,N'-di(2-ethylhexyl)aminomethylphosphonic acid dibutyl ester disclosed in JP2012102062A was used as the extractant, and its structural formula is shown below.

[0147]

[0148] In addition to using N,N'-di(2-ethylhexyl)aminomethylphosphonic acid dibutyl ester as the extractant, extraction experiments were carried out in the manner of Examples 1-7, and the separation factor β of gallium and indium was Ga / In see Table 1.

[0149] Comparative Example 2

[0150] ​(2-ethylhexyl) aminomethylphosphonic acid di(2-ethylhexyl) ester disclosed in ZL201710904948.3, the structural formula of which is shown below.

[0151]

[0152] In addition to using (2-ethylhexyl) aminomethylphosphonic acid di(2-ethylhexyl) ester as the extractant, the extraction experiments were carried out according to the methods of Examples 1-7, and the separation factor β of gallium and indium Ga / In See Table 1.

[0153] Comparative Example 3

[0154] 2-((2-ethylhexyl)amino)-ethylphosphonic acid di(2-ethylhexyl) ester disclosed in CN202111581742.4, the structural formula of which is shown below.

[0155]

[0156] In addition to using 2-((2-ethylhexyl)amino)-ethylphosphonic acid di(2-ethylhexyl) ester as the extractant, the extraction experiments were carried out according to the methods of Examples 1-7, and the separation factor β of gallium and indium Ga / In See Table 1.

[0157] Comparative Example 4

[0158] N,N'-di(2-ethylhexyl) aminomethylphosphonic acid mono(2-ethylhexyl) ester was obtained by hydrolysis of N,N'-di(2-ethylhexyl) aminomethylphosphonic acid di(2-ethylhexyl) ester synthesized in Preparation Example 1, and the structural formula of the amino-containing acidic phosphine extractant is shown below.

[0159]

[0160] In addition to using N,N'-di(2-ethylhexyl) aminomethylphosphonic acid mono(2-ethylhexyl) ester as the extractant and using the acidity conditions in Table 2, the extraction experiments under a series of acidity conditions were carried out according to the methods of Examples 1-7, and the separation factor β of gallium and indium Ga / In See Table 2.

[0161] Table 1 Separation factor β of gallium and indium in each example and comparative example Ga / In

[0162]

[0163] Table 2 Separation factor β of gallium and indium under a series of acidity conditions in Comparative Example 4 Ga / In

[0164]

[0165] The results of Examples 1 to 7 and Comparative Examples 1 to 4 show that the separation factor of the extraction system of the present application for gallium and indium is obviously greater than that of N,N'-bis(2-ethylhexyl)aminomethylphosphonic acid dibutyl ester, (2-ethylhexyl)aminomethylphosphonic acid di(2-ethylhexyl) ester, 2-((2-ethylhexyl)amino)-ethylphosphonic acid di(2-ethylhexyl) ester and the amino-containing acidic phosphine extractant N,N'-bis(2-ethylhexyl)aminomethylphosphonic acid mono(2-ethylhexyl) ester system.

[0166] Separation Example 1

[0167] Indium extraction recovery:

[0168] Preparation of the organic phase: 0.5 L of 2-((2-ethylhexyl)amino)-ethylphosphonic acid di(2-ethylhexyl) ester was mixed with 9.5 L of n-heptane to prepare the organic phase.

[0169] The feed solution was a gallium-indium mixed solution, in which the concentration of indium was 0.0475 mol / L, the concentration of gallium was 0.0025 mol / L, and the solution acidity was 2.68 mol / L hydrochloric acid.

[0170] The stripping agent was 2.50 mol / L sulfuric acid.

[0171] The organic phase was mixed with the feed solution at a volume ratio of 1:1 to carry out 3-stage countercurrent extraction, to obtain a gallium-containing extraction solution and an indium-containing raffinate aqueous phase. Then the gallium-containing extraction solution was mixed with the stripping agent at a volume ratio of 1:1 to carry out 2-stage countercurrent stripping, to obtain a gallium-containing stripping solution. Element analysis of the obtained indium-containing raffinate aqueous phase showed that the purity of indium was 99.95% and the yield was 95%.

[0172] Gallium extraction recovery:

[0173] Preparation of the organic phase: 0.5 L of 2-((2-ethylhexyl)amino)-ethylphosphonic acid di(2-ethylhexyl) ester was mixed with 9.5 L of n-heptane to prepare the organic phase.

[0174] The feed solution was a gallium-containing stripping solution.

[0175] The stripping agent was 2.0 mol / L hydrochloric acid solution.

[0176] The gallium-containing stripping solution was mixed with the organic phase at a volume ratio of 2:1 to carry out 2-stage countercurrent extraction, to obtain a gallium-containing raffinate aqueous phase and an indium-containing extraction solution. Then the indium-containing extraction solution was mixed with the stripping agent at a volume ratio of 1:1 to carry out 2-stage countercurrent stripping, to obtain an indium-containing stripping solution, which was returned to the indium extraction recovery step for indium separation and recovery. Element analysis of the obtained gallium-containing raffinate aqueous phase showed that the purity of gallium was 99.9% and the yield was 98.2%.

[0177] Separation Example 2

[0178] Extraction recovery of indium:

[0179] Preparation of organic phase: 3L of N,N'-di(2-ethylhexyl)aminomethylphosphonic acid bis(dodecyl) ester was mixed with 7L of sulfonated kerosene to prepare the organic phase.

[0180] The feed solution was a gallium-indium mixed solution, in which the concentration of indium was 0.2 mol / L, the concentration of gallium was 0.2 mol / L, and the acidity of the solution was 3.9 mol / L hydrochloric acid.

[0181] The stripping agent was 1.50 mol / L sulfuric acid.

[0182] The organic phase was mixed with the feed solution in a volume ratio of 1:1 to carry out 5-stage countercurrent extraction, to obtain gallium-containing extraction solution and indium-containing raffinate aqueous phase. Then the gallium-containing extraction solution was mixed with the stripping agent in a volume ratio of 2:1 to carry out 3-stage countercurrent stripping, to obtain gallium-containing stripping solution. The indium-containing raffinate aqueous phase obtained was subjected to elemental analysis, and the results showed that the purity of indium was 99.98%, and the yield was 95.5%.

[0183] Extraction recovery of indium:

[0184] Preparation of organic phase: 3L of N,N'-di(2-ethylhexyl)aminomethylphosphonic acid bis(dodecyl) ester was mixed with 7L of sulfonated kerosene to prepare the organic phase.

[0185] The feed solution was a gallium-indium mixed solution, in which the concentration of indium was 0.2 mol / L, the concentration of gallium was 0.2 mol / L, and the acidity of the solution was 3.9 mol / L hydrochloric acid.

[0186] The stripping agent was 1.50 mol / L sulfuric acid.

[0187] The organic phase was mixed with the feed solution in a volume ratio of 1:1 to carry out 5-stage countercurrent extraction, to obtain gallium-containing extraction solution and indium-containing raffinate aqueous phase. Then the gallium-containing extraction solution was mixed with the stripping agent in a volume ratio of 2:1 to carry out 3-stage countercurrent stripping, to obtain gallium-containing stripping solution. The indium-containing raffinate aqueous phase obtained was subjected to elemental analysis, and the results showed that the purity of indium was 99.98%, and the yield was 95.5%.

[0188] Separation Example 3

[0189] Extraction recovery of indium:

[0190] Preparation of organic phase: 3L of N,N'-di(2-ethylhexyl)aminomethylphosphonic acid bis(dodecyl) ester was mixed with 7L of sulfonated kerosene to prepare the organic phase.

[0191] The feed solution is a gallium-indium mixed solution, in which the concentration of indium is 0.3 mol / L, the concentration of gallium is 0.01 mol / L, and the solution acidity is 3.02 mol / L hydrochloric acid.

[0192] The stripping agent is 3.0 mol / L sulfuric acid.

[0193] The organic phase and the feed solution are mixed in a ratio of 1:5 by volume to carry out 7-stage countercurrent extraction, to obtain gallium-containing extraction solution and indium-containing raffinate aqueous phase. Then the gallium-containing extraction solution is mixed with the stripping agent in a ratio of 5:1 by volume to carry out 5-stage countercurrent stripping, to obtain gallium-containing stripping extraction solution. The indium-containing raffinate aqueous phase obtained is subjected to elemental analysis, and the results show that the purity of indium is 99.96%, and the yield is 95.8%.

[0194] Gallium extraction recovery:

[0195] Preparation of the organic phase: 3L of 1-methyl-2-((2-ethylhexyl)amino)-propyl phosphonic acid bis(2-ethylhexyl) ester is mixed with 7L of sulfonated kerosene to prepare the organic phase.

[0196] The feed solution is gallium-containing stripping extraction solution.

[0197] The stripping agent is 3.5 mol / L hydrochloric acid solution.

[0198] The gallium-containing stripping extraction solution and the organic phase are mixed in a ratio of 2:1 by volume to carry out 5-stage countercurrent extraction, to obtain gallium-containing raffinate aqueous phase and indium-containing extraction solution. Then the indium-containing extraction solution is mixed with the stripping agent in a ratio of 5:1 by volume to carry out 3-stage countercurrent stripping, to obtain indium-containing stripping extraction solution, which is returned to the indium extraction recovery step for indium separation and recovery. The gallium-containing raffinate aqueous phase obtained is subjected to elemental analysis, and the results show that the purity of gallium is 99.98%, and the yield is 98.8%.

[0199] Separation Example 4

[0200] Indium extraction recovery:

[0201] Preparation of the organic phase: 3L of 1-(N,N'-di(2-ethylhexyl)amino)-1-ethylpropyl phosphonic acid bis(2-ethylhexyl) ester is mixed with 7L of sulfonated kerosene to prepare the organic phase.

[0202] The feed solution is a gallium-indium mixed solution, in which the concentration of indium is 0.5 mol / L, the concentration of gallium is 0.1 mol / L, and the solution acidity is 2.32 mol / L hydrochloric acid.

[0203] The stripping agent is 3.5 mol / L sulfuric acid.

[0204] The organic phase and the feed solution were mixed in a ratio of 1:10 by volume and subjected to 5-stage countercurrent extraction to obtain a gallium-containing extraction solution and an indium-containing raffinate aqueous phase. The gallium-containing extraction solution and a stripping agent were then mixed in a ratio of 10:1 by volume and subjected to 7-stage countercurrent stripping to obtain a gallium-containing stripping solution. The indium purity of the obtained indium-containing raffinate aqueous phase was 99.99% and the indium yield was 96% as determined by elemental analysis.

[0205] Gallium extraction recovery:

[0206] Preparation of the organic phase: 1 L of 1-methyl-2-((2-ethylhexyl)amino)-propyl phosphonic acid bis(2-ethylhexyl) ester, 1 L of TBP and 8 L of aviation kerosene were mixed to prepare the organic phase.

[0207] The feed solution was a gallium stripping solution.

[0208] The stripping agent was a 2.5 mol / L hydrochloric acid solution.

[0209] The gallium-containing stripping solution and the organic phase were mixed in a ratio of 5:1 by volume and subjected to 3-stage countercurrent extraction to obtain a gallium-containing raffinate aqueous phase and an indium-containing extraction solution. The indium-containing extraction solution and a stripping agent were then mixed in a ratio of 3:1 by volume and subjected to 5-stage countercurrent stripping to obtain an indium-containing stripping solution, which was returned to the indium extraction recovery step for indium separation and recovery. The gallium purity of the obtained gallium-containing raffinate aqueous phase was 99.95% and the gallium yield was 98% as determined by elemental analysis.

[0210] Separation Example 5

[0211] Indium extraction recovery:

[0212] Preparation of the organic phase: 4 L of 1-(N,N'-dihexylamino)-1-phenylmethyl phosphonic acid bis(2-ethylhexyl) ester and 6 L of aviation kerosene were mixed to prepare the organic phase.

[0213] The feed solution was a gallium-indium mixed solution, in which the indium concentration was 0.05 mol / L, the gallium concentration was 0.5 mol / L, and the solution acidity was 3.0 mol / L hydrochloric acid.

[0214] The stripping agent was a 4.0 mol / L sulfuric acid solution.

[0215] The organic phase and the feed solution were mixed in a ratio of 1:1 by volume and subjected to 10-stage countercurrent extraction to obtain a gallium-containing extraction solution and an indium-containing raffinate aqueous phase. The gallium-containing extraction solution and a stripping agent were then mixed in a ratio of 1:1 by volume and subjected to 7-stage countercurrent stripping to obtain a gallium-containing stripping solution. The indium purity of the obtained indium-containing raffinate aqueous phase was 99.5% and the indium yield was 96.5% as determined by elemental analysis.

[0216] Gallium extraction recovery:

[0217] Preparation of the organic phase: 0.5 L of 2-((2-ethylhexyl)amino)-pentylphosphonic acid di(2-ethylhexyl) ester was mixed with 9.5 L of aviation kerosene to obtain the organic phase.

[0218] The feed solution was a gallium-containing stripping solution.

[0219] The stripping agent was 4.5 mol / L hydrochloric acid solution.

[0220] The gallium-containing stripping solution was mixed with the organic phase at a volume ratio of 10:1 to perform 5-stage countercurrent extraction, to obtain a gallium-containing raffinate aqueous phase and an indium-containing extraction solution. Then the indium-containing extraction solution was mixed with the stripping agent at a volume ratio of 5:1 to perform 3-stage countercurrent stripping, to obtain an indium-containing stripping solution, which was returned to the indium extraction and recovery step for indium separation and recovery. The obtained gallium-containing raffinate aqueous phase was subjected to elemental analysis, and the results showed that the purity of gallium was 99.98%, and the yield was 99%.

[0221] Separation Example 6

[0222] Indium extraction and recovery:

[0223] Preparation of the organic phase: 1 L of 1-(N,N'-di(2-ethylhexyl)amino)-1- cyclohexylmethylphosphonic acid di(2-ethylhexyl) ester was mixed with 9 L of aviation kerosene to obtain the organic phase.

[0224] The feed solution was a gallium-indium mixed solution, in which the concentration of indium was 0.025 mol / L, the concentration of gallium was 0.001 mol / L, and the solution acidity was 2.5 mol / L hydrochloric acid.

[0225] The stripping agent was 2.5 mol / L sulfuric acid.

[0226] The organic phase was mixed with the feed solution at a volume ratio of 1:10 to perform 6-stage countercurrent extraction, to obtain a gallium-containing extraction solution and an indium-containing raffinate aqueous phase. Then the gallium-containing extraction solution was mixed with the stripping agent at a volume ratio of 10:1 to perform 3-stage countercurrent stripping, to obtain a gallium-containing stripping solution. The obtained indium-containing raffinate aqueous phase was subjected to elemental analysis, and the results showed that the purity of indium was 99.99%, and the yield was 95.5%.

[0227] Gallium extraction and recovery:

[0228] Preparation of the organic phase: 0.5 L of 2-((2-ethylhexyl)amino)-pentylphosphonic acid di(2-ethylhexyl) ester was mixed with 9.5 L of aviation kerosene to obtain the organic phase.

[0229] The feed solution was a gallium-containing stripping solution.

[0230] The stripping agent was 3.5 mol / L hydrochloric acid solution.

[0231] The gallium-containing stripping solution and the organic phase were mixed in a volume ratio of 2:1 and subjected to 3-stage countercurrent extraction to obtain a gallium-containing raffinate aqueous phase and an indium-containing extract. The indium-containing extract was then mixed with a stripping agent in a volume ratio of 10:1 and subjected to 5-stage countercurrent stripping to obtain an indium-containing stripping solution, which was returned to the indium extraction recovery step for the separation and recovery of indium. The gallium-containing raffinate aqueous phase obtained was subjected to elemental analysis, and the results showed that the purity of gallium was 99.99% and the yield was 98.5%.

[0232] Separation Example 7

[0233] Indium extraction recovery:

[0234] Preparation of the organic phase: 3L of 2-((2-ethylhexyl)amino)-pentyl phosphonic acid di(2-ethylhexyl) ester and 7L of aviation kerosene were mixed to prepare the organic phase.

[0235] The feed solution was a gallium-indium mixed solution, in which the concentration of indium was 1.0 mol / L, the concentration of gallium was 0.5 mol / L, and the solution acidity was 4.0 mol / L hydrochloric acid.

[0236] The stripping agent was a 3.5 mol / L hydrochloric acid solution.

[0237] The organic phase and the feed solution were mixed in a volume ratio of 1:2 and subjected to 5-stage countercurrent extraction to obtain a gallium-containing extract and an indium-containing raffinate aqueous phase. The gallium-containing extract was then mixed with a stripping agent in a volume ratio of 10:1 and subjected to 5-stage countercurrent stripping to obtain a gallium-containing stripping solution. The indium-containing raffinate aqueous phase obtained was subjected to elemental analysis, and the results showed that the purity of indium was 99.98% and the yield was 97.5%.

[0238] Gallium extraction recovery:

[0239] Preparation of the organic phase: 3L of 2-((2-ethylhexyl)amino)-pentyl phosphonic acid di(2-ethylhexyl) ester and 7L of aviation kerosene were mixed to prepare the organic phase.

[0240] The feed solution was a gallium-containing stripping solution.

[0241] The stripping agent was a 3.5 mol / L hydrochloric acid solution.

[0242] The gallium-containing stripping solution and the organic phase were mixed in a volume ratio of 1:1 and subjected to 5-stage countercurrent extraction to obtain a gallium-containing raffinate aqueous phase and an indium-containing extract. The indium-containing extract was then mixed with a stripping agent in a volume ratio of 10:1 and subjected to 5-stage countercurrent stripping to obtain an indium-containing stripping solution, which was returned to the indium extraction recovery step for the separation and recovery of indium. The gallium-containing raffinate aqueous phase obtained was subjected to elemental analysis, and the results showed that the purity of gallium was 99.99% and the yield was 99%.

[0243] Separation Example 8

[0244] (1) Preparation of the extract resin

[0245] Take 50 mL N,N'-di(2-ethylhexyl) amino methyl phosphonic acid di(2-ethylhexyl) ester and 50 mL styrene-divinylbenzene mixed solution to prepare oil phase, wherein the volume ratio of styrene to divinylbenzene is 2:1. Take 500 mL deionized water, add 15 g gelatin, 2.5 g thiocyanate, heat to 50℃, after the gelatin is completely dissolved, slowly add the oil phase, stir for half an hour, then heat to 80℃, react for 5 hours, then heat to 90℃, solidify for half an hour. Take out and filter the resin, wash with water, air dry, get 75 g extract resin.

[0246] (2) Separation and purification experiment

[0247] Dissolve the indium chloride solid with a purity of 99% to prepare a feed solution, which is a hydrochloric acid solution containing 0.10 mol / L indium and 0.001 mol / L gallium, and the concentration of hydrochloric acid is 2.5 mol / L.

[0248] Take 50 grams of extract resin into the separation column, inject the feed solution into the separation column, the flow rate of the feed solution is 2 mL / min, take samples every 5 minutes for monitoring. When the content of gallium in the raffinate reaches 0.1 mg / L, stop adding the feed solution. The obtained raffinate is precipitated, filtered and washed to obtain indium hydroxide, the yield of indium is 95%, and the purity of indium is 99.999%.

Claims

1. Use of an amino group-containing neutral phosphine extractant of general formula I for the extraction separation of gallium from a feed solution containing gallium and indium: （I） wherein, R1 and R2 are each independently selected from C6~C 14 alkyl; R3 and R4 are each independently selected from hydrogen, C1~C8 alkyl, C3~C 10 Alicyclic alkyl groups and C6~C 10 Aryl; R5 and R6 are each independently selected from C4~C 16 alkyl, wherein the feed solution is a hydrochloric acid solution containing gallium and indium in trivalent ionic form.

2. The use according to claim 1, wherein, R1and R2are each independently selected from the group consisting of C7-Ci8alkyl; and / or 12 alkyl; and / or R3and R4are each independently selected from the group consisting of hydrogen, Ci-C6alkyl, C3-C8cycloalkyl and C6-C8aryl; and / or R5and R6are each independently selected from C5-Ci2alkyl. 12 alkyl.

3. The use according to claim 1, wherein, R1and R2are each independently selected from C8-C32alkyl; and / or 12 alkyl; and / or R3and R4are each independently selected from the group consisting of hydrogen, Ci-C6alkyl, C3-C8cycloalkyl and C6-C8aryl; and / or R5 and R6 are each independently selected from C6~C 10 alkyl.

4. The use according to claim 3, wherein, R5and R6are each independently selected from the group consisting of C6-C8alkyl.

5. The use according to claim 1, wherein, R1and R2are identical alkyl groups; and / or R1and R2have a total number of carbon atoms which is an integer between 14 and 24; and / or R3and R4are each independently selected from the group consisting of hydrogen, Ci-C4alkyl, C3-C6cycloalkyl and C6-C8aryl; and / or R3and R4have a total number of carbon atoms which is an integer between 0 and 12; and / or R5and R6are identical C6-C8alkyl groups; and / or R5and R6have a total number of carbon atoms which is an integer between 10 and 24; and / or R1, R2, R3, R4, R5and R6have a total number of carbon atoms which is 30-48.

6. The use according to claim 5, wherein, R1and R2are the same C8-C 12 alkyl; and / or R1and R2have a total number of carbon atoms which is an integer between 16 and 24; and / or R3and R4are each independently selected from the group consisting of hydrogen, methyl, ethyl, cyclohexyl and phenyl; and / or R3and R4have a total number of carbon atoms which is an integer between 0 and 7; and / or R5and R6have a total number of carbon atoms which is an integer between 12 and 20; and / or R1, R2, R3, R4, R5and R6have a total number of carbon atoms which is 30-42.

7. The use according to claim 5, wherein, R3is selected from the group consisting of hydrogen, Ci-C4alkyl, C3-C6cycloalkyl and C6-C8aryl; R4is selected from the group consisting of hydrogen, Ci-C4alkyl; and / or R1, R2, R3, R4, R5and R6have a total number of carbon atoms which is 32-40.

8. The use according to claim 5, wherein, R3is selected from the group consisting of hydrogen, methyl, ethyl, cyclohexyl and phenyl; R4is selected from the group consisting of hydrogen, methyl, ethyl.

9. The use according to claim 1, wherein, the amino group-containing neutral phosphine extractant of general formula I is one or more selected from the group consisting of N,N'-di(2-ethylhexyl)aminomethylphosphonic acid di(2- ethylhexyl) ester, N,N'-di(2-ethylhexyl)aminomethylphosphonic acid didodecyl ester, 1-(N,N'- di(2-ethylhexyl)amino)-1-ethylphosphonic acid di(2-ethylhexyl) ester, 1-(N,N'-di(2- ethylhexyl)amino)-1-ethylpropylphosphonic acid di(2-ethylhexyl) ester, 1-(N,N'-dihexylamino)-1- phenylmethylphosphonic acid di(2-ethylhexyl) ester, 1-(N,N'-di(2-ethylhexyl)amino)-1- cyclohexylmethylphosphonic acid di(2-ethylhexyl) ester, 1-(N,N'-di(2-ethylhexyl)amino)-1- methylethylphosphonic acid di(2-ethylhexyl) ester.

10. A process for the extraction of gallium from a gallium and indium containing feed solution, said process comprising the step of using the amino group containing neutral phosphine extractant as claimed in any one of claims 1 to 9 to extract gallium from a gallium and indium containing feed solution to extract gallium; wherein, the feed solution is a hydrochloric acid solution containing gallium and indium in trivalent ionic form.

11. The method according to claim 10, wherein, The method for extracting and separating gallium is carried out by using a solvent extraction method, and the method comprises the following steps: mixing a neutral phosphine extraction system containing the amino-containing neutral phosphine extractant according to any one of claims 1-9 with a gallium and indium-containing feed liquid to carry out extraction, so as to obtain a gallium-containing extraction liquid and an indium-containing raffinate; or The method for extracting and separating gallium is carried out by using a solid-liquid extraction method, and the method comprises the following steps: contacting a solid separation material prepared by using the amino-containing neutral phosphine extractant according to any one of claims 1-9 with a gallium and indium-containing feed liquid to carry out solid-liquid extraction, so as to obtain a gallium-containing solid separation material and an indium-containing raffinate.

12. The method of claim 11, wherein, In the solvent extraction method, The neutral phosphine extraction system comprises the amino-containing neutral phosphine extractant, an optional auxiliary extractant, an optional phase modifier and a diluent.

13. The method according to claim 12, wherein, The auxiliary extractant is selected from phosphorus or phosphine extractants of the following general formula V: （V） wherein, Z is O or S; R7is selected from the group consisting of hydrogen, CrC 16 alkyl, CrC 16 alkoxy, -SH and -NH2substituted with at least one substituent selected from the group consisting of CrC 16 alkyl; R8 and R9 are each independently selected from C4~C 12 Alkyl, C4~C 12 Alkyl groups and those selected from C4~C 12 -NH2 is substituted by at least one substituent in the alkyl group; The phase modifier is one or more selected from C4-C 10 one or more of an alkanol and tributyl phosphate; The diluent is selected from the group consisting of: C5to C 16 alkanes; aviation kerosene; sulfonated kerosene, liquid paraffin; C5to C 16 cycloalkanes; C6to C 10 aromatics.

14. The method according to claim 13, wherein, R7is selected from the group consisting of hydrogen, CrC 12 alkyl, CrC 12 alkoxy, -SH and -NH2substituted with at least one substituent selected from the group consisting of C4-C 12 alkyl, C4-C 10 alkoxy and -NH2substituted with at least one substituent selected from the group consisting of C4-C 10 alkyl, C4-C 10 alkoxy and -NH2substituted with at least one substituent selected from the group consisting of C4-C The phase modifier is one or more selected from the group consisting of n-octanol, iso-octanol, 2-methylheptanol, a mixed alcohol obtained by mixing the above three alcohols in any ratio, and tributyl phosphate; and / or said C5to C12 16 alkanes are selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane; and / or The liquid paraffin is a 250-400 ℃ light lubricating oil fraction; and / or said C5to C12cycloalkyl is selected from the group consisting of cyclopentane, C1to C4alkyl substituted cyclopentane, cyclohexane, C1to C4alkyl substituted cyclohexane, decalin; and / or 16 cycloalkyl is selected from the group consisting of cyclopentane, C1to C4alkyl substituted cyclopentane, cyclohexane, C1to C4alkyl substituted cyclohexane, decalin; and / or The C6~C 10 Aromatic hydrocarbons are selected from benzene, toluene, and xylene.

15. The method according to claim 13, wherein, In general formula V, R7is selected from the group consisting of C1-C 10 alkyl and C1-C 10 alkoxy; and / or R8and R9are each independently selected from the group consisting of C4-C 10 alkyl and C4-C 10 alkoxy; and / or The phase modifier is a mixed alcohol obtained by mixing n-octanol, iso-octanol and 2-methylheptanol in any ratio, or 2-methylheptanol; and / or The diluent is one or more selected from the group consisting of aviation kerosene, sulfonated kerosene, heptane and xylene.

16. The method of claim 12, wherein, The auxiliary extractant is selected from the group consisting of neutral phosphorus or phosphine extractants, acidic phosphorus or phosphine extractants, neutral phosphamide extractants, and mixed extractants obtained by mixing the above extractants in any ratio.

17. The method according to claim 16, wherein, The neutral phosphorus or phosphine extractant is selected from the group consisting of linear trialkyl phosphine oxide Cyanex 923, branched trialkyl phosphine oxide Cyanex 925, trioctyl phosphine oxide TOPO, dimethylheptyl methylphosphonate, di(-2-ethylhexyl) 2-ethylhexylphosphonate, tributyl phosphate; The acidic phosphorus or phosphine extractant is selected from the group consisting of di(2,4,4-trimethylpentyl) dithiophosphonic acid, di(2,4,4-trimethylpentyl) thiophosphonic acid, di(2-ethylhexyl) phosphoric acid, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, di(2,4,4-trimethylpentyl) phosphonic acid, di(2-ethylhexyl) phosphonic acid; The neutral phosphamide extractant is selected from the group consisting of triisooctyl phosphamide, diisooctyl-isooctyloxy phosphamide, isooctyl-diisooctyloxy phosphamide, tri(diisobutyl) phosphamide, di(diisobutyl)-isooctyloxy phosphamide, tridecyl phosphamide and dihexyl-decyloxy phosphamide.

18. The method of claim 12, wherein, In the amino-containing neutral phosphine extraction system, the volume ratio of the amino-containing neutral phosphine extractant, the optional auxiliary extractant, the optional phase modifier and the diluent is as follows: amino-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = 1-60: 0-40: 0-20: 40-110.

19. The method of claim 18, wherein, Amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = 10-40: 0-20: 0-20: 50-100.

20. The method of claim 18, wherein, Amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = 15-35: 0-15: 0-15: 55-90.

21. The method of claim 18, wherein, Amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = 15-35: 3-15: 0: 55-90, or amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = 15-35: 0: 3-15: 55-90, or amino group-containing neutral phosphine extractant: auxiliary extractant: phase modifier: diluent = 15-35: 0: 0: 55-90.

22. The method according to claim 12, wherein, the volume ratio of the neutral phosphine extraction system to the feed solution is 0.1-20: 1; and / or the extraction is carried out in 1-20 stages; and / or the extraction is carried out in countercurrent extraction mode.

23. The method according to claim 22, wherein, the volume ratio of the neutral phosphine extraction system to the feed solution is 0.5-10: 1; and / or the extraction is carried out in 1-10 stages.

24. The method of claim 11, wherein, The solvent extraction method further comprises the step of stripping the gallium in the gallium-containing extract solution with a stripping agent to obtain a gallium-containing stripping product.

25. The method according to claim 24, wherein, the stripping is carried out in 1-10 stages; and / or the volume ratio of the gallium-containing extract solution to the stripping agent is 0.1-10: 1; and / or the stripping is carried out in countercurrent stripping mode; and / or in the solvent extraction method, the extraction and stripping are carried out in a series of separatory funnels, mixer-settler extraction tanks or centrifugal extractors; and / or the extraction and stripping are carried out intermittently or continuously.

26. The method according to claim 25, wherein, the stripping is carried out in 2-6 stages; and / or the volume ratio of the gallium-containing extract solution to the stripping agent is 0.5-5: 1; and / or in the solvent extraction method, the extraction and stripping are carried out in mixer-settler extraction tanks or centrifugal extractors; and / or the extraction and stripping are carried out continuously.

27. The method of claim 11, wherein, In the solid-liquid extraction method, the solid separation material is selected from the group consisting of a resin loaded with an amine group-containing neutral phosphine extractant, porous silica spheres, diatomite; the content of gallium in the indium-containing raffinate is not more than 1 mg / L.

28. The method of claim 27, wherein, In the solid-liquid extraction method, the solid separation material is a chelating resin; the content of gallium in the indium-containing raffinate is not more than 0.1 mg / L.

29. The method of claim 11, wherein, The solid-liquid extraction method further comprises the step of stripping the gallium in the gallium-containing solid separation material with a stripping agent to obtain a gallium-containing stripping product.

30. The method according to claim 24 or 29, wherein, the stripping agent is selected from the group consisting of an acid solution; and / or the molar concentration of hydrogen ions in the stripping agent is 1 x 10 -8 ~ 6 mol / L; and / or the method further comprises the step of recovering gallium from the gallium-containing stripping product.

31. The method according to claim 30, wherein, the stripping agent is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid or a mixed solution of the above acids in any proportion; and / or the molar concentration of hydrogen ions in the stripping agent is 0.01-5 mol / L.

32. The method of claim 10, wherein, the method further comprises a step of treating the indium-containing raffinate to recover indium; and / or the concentration of gallium and the concentration of indium in the feed solution are each independently 0.0001-2 mol / L; and / or the hydrochloric acid concentration of the feed solution is 0.1-6 mol / L; and / or the molar ratio of indium to gallium in the feed solution is 500:1-1:

500.

33. The method of claim 32, wherein, the hydrochloric acid concentration of the feed solution is 1-5 mol / L; and / or the molar concentration of indium in the feed solution is not less than the molar concentration of gallium.

34. The method of claim 33, wherein, the molar ratio of indium to gallium in the feed solution is 1:1-100:1.

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