Preparation of organic phosphorus extractant and application of organic phosphorus extractant in gallium extraction

Abstract

The invention discloses preparation and gallium extraction application of an organophosphorus extractant, and belongs to the technical field of extractants, and the preparation method comprises the following steps: S1, constructing a heating system; s2, adding N-(phosphonomethyl) iminodiacetic acid and an alcohol compound, and mixing; s3, trimethylchlorosilane is added; s4, heating to obtain a crude organic phosphorus extraction agent; s5, cooling to room temperature; s6, filtering to remove residual solids, washing filtrate with water, separating liquid, and retaining an upper-layer liquid product, namely the organic phosphorus extraction agent; the organic phosphorus extraction agent prepared by the method is simple in preparation process, low in cost, free of saponification treatment, free of saponification wastewater, capable of extracting gallium ions under the acidic condition, high in extraction efficiency, good in cycle performance and capable of being recycled.

Description

Technical Field

[0001] The invention belongs to the technical field of extractants, and in particular relates to the preparation of an organic phosphorus extractant and its gallium extraction application. Background Art

[0002] Gallium is listed as a strategic metal by China, the United States, the European Union and other countries. It is a "high-tech element" of high-tech industries and is widely used in electronic communications, new energy, chips, low-melting-point alloys, military industry and other fields.

[0003] Gallium is a typical rare metal with an abundance of only 17 mg / L in the earth's crust, and most of it exists in the form of associated minerals, making the extraction of gallium ions more difficult.

[0004] At present, the methods for extracting gallium generally include ion exchange, adsorption, chemical precipitation, electrodeposition separation and solvent extraction. Among them, ion exchange, adsorption, chemical precipitation and electrodeposition separation generally have problems such as high cost, unstable separation process and slow adsorption rate during the extraction process. Therefore, solvent extraction is more widely used.

[0005] Current extractants include P204, P507, TBP and YW100, among which P204 and P507 often need to be saponified in advance. The use of saponification agents and the post-treatment of saponification wastewater will increase the application cost, and are not suitable for extracting gallium ions under high acidity. TBP usually plays an auxiliary role as a modifier in the extraction system, and the extraction efficiency is not ideal. YW100 has high water solubility and is not easy to recycle. It usually needs to be used together with P204 to reduce its water solubility.

[0006] In view of this, the preparation of organophosphorus extractants and their gallium extraction applications were designed to solve the above problems. Summary of the invention

[0007] To solve the problems raised in the above background technology. The present invention provides the preparation of an organophosphorus extractant and its gallium extraction application, which has the characteristics of simple preparation process, low cost, no need for saponification treatment, no saponification wastewater, and can also extract gallium ions under acidic conditions, with high extraction efficiency, good circulation performance, and can be recycled.

[0008] Another object of the present invention is to provide an application of an organophosphorus extractant in gallium extraction.

[0009] To achieve the above object, the present invention provides the following technical solution: the preparation of an organophosphorus extractant comprises the following steps:

[0010] S1: Build a heating system and place a pressure-resistant bottle with magnets in a sand bath;

[0011] S2: placing a set ratio of diethylene glycol phosphine and an alcohol compound in a pressure-resistant bottle, and stirring the reaction materials in the pressure-resistant bottle with a stirrer to fully mix them;

[0012] S3: Add trimethylchlorosilane in a set ratio into the pressure-resistant bottle;

[0013] S4: stirring the mixture in the pressure-resistant bottle by a stirrer, and heating the mixture in the pressure-resistant bottle by a sand bath pot, so that the mixture reacts fully, until the set reaction time is reached, and a crude organophosphorus extractant is obtained;

[0014] S5: cooling the crude organophosphorus extractant in the reaction container to room temperature;

[0015] S6: filtering the crude organophosphorus extractant cooled to room temperature to remove residual solids, then washing the filtrate with water, separating the liquids, and retaining the upper liquid product, i.e., the organophosphorus extractant.

[0016] Furthermore, in step S2, the addition ratio of diglycophosphine and alcohol compound is 1:20 according to the mass ratio, wherein the mass of the added alcohol compound is 0.384 mol.

[0017] Furthermore, in step S3, the addition ratio of trimethylchlorosilane is 6% of the volume of the alcohol compound according to the volume ratio.

[0018] Furthermore, in step S4, the heating temperature of the sand bath pot is 90°C.

[0019] The prepared organophosphorus extractant is used in extracting gallium ions.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The organic phosphorus extractant prepared by the present invention has a simple preparation process and low cost, does not require saponification treatment, does not generate saponification wastewater, can also extract gallium ions under acidic conditions, has high extraction efficiency, has good circulation performance, and can be recycled. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Characterization diagram of the organophosphorus extractant prepared by the present invention;

[0023] Figure 2 The single factor and saturation capacity experimental results of the organic phosphorus extractant prepared by the present invention for extracting gallium ions;

[0024] Figure 3 This is a diagram showing the results of stripping and recycling experiments of the organophosphorus extractant prepared in the present invention. DETAILED DESCRIPTION

[0025] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] The present invention provides the following technical solution: the preparation of an organophosphorus extractant comprises the following steps:

[0027] S1: Build a heating system and place a pressure-resistant bottle with magnets in a sand bath;

[0028] S2: placing a set ratio of diethylene glycol phosphine and an alcohol compound in a pressure-resistant bottle, and stirring the reaction materials in the pressure-resistant bottle with a stirrer to fully mix them;

[0029] S3: Add trimethylchlorosilane in a set ratio into the pressure-resistant bottle;

[0030] S4: stirring the mixture in the pressure-resistant bottle by a stirrer, and heating the mixture in the pressure-resistant bottle by a sand bath pot, so that the mixture reacts fully, until the set reaction time is reached, and a crude organophosphorus extractant is obtained;

[0031] S5: cooling the crude organophosphorus extractant in the reaction container to room temperature;

[0032] S6: filtering the crude organophosphorus extractant cooled to room temperature to remove residual solids, then washing the filtrate with water, separating the liquids, and retaining the upper liquid product, i.e., the organophosphorus extractant.

[0033] The reaction expression is:

[0034]

[0035] Where: R1 is C4-C 12 The alkyl group in the above formula is C4-C 12 At least one of the alcohol compounds.

[0036] Specifically, in step S2, the addition ratio of diglycophosphine and the alcohol compound is 1:20 in terms of mass ratio, wherein the mass of the added alcohol compound is 0.384 mol.

[0037] Specifically, in step S3, the addition ratio of trimethylchlorosilane is 6% of the volume of the alcohol compound according to the volume ratio.

[0038] Specifically, in step S4, the heating temperature of the sand bath pot is 90°C.

[0039] Application of the prepared organophosphorus extractant in extracting gallium ions.

[0040] See attached Figure 1 , the characterization diagram generated by measuring the organophosphorus extractant by infrared spectrometer, Figure 1 It can be seen that the C=O peak in the infrared product moves, indicating the transformation of the carboxyl group to the ester group. The esterification reaction between glyphosate and the alcohol compound is successful. The glyphosate is transformed from a water-soluble powder to a water-insoluble liquid, and the extractant is successfully prepared.

[0041] See attached Figure 2 , single factor and saturation capacity experiments on the extraction of gallium ions by organophosphorus extractants were conducted. A 100 mg / L gallium solution was prepared and subjected to single factor experiments on pH, phase ratio and time. Figure 2 It can be seen that within 15 minutes, the single-stage extraction rate of gallium by the extractant under acidic conditions can reach 93%, and the saturation capacity is ≈6 g / L, which has the effect of efficiently extracting gallium ions.

[0042] See attached Figure 3 , stripping and recycling experiments were conducted on organophosphorus extractants. Figure 3 It can be seen that after 5 cycles, the extraction rate still reaches more than 93%, which has the effect of recycling.

[0043] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. Preparation of an organophosphorus extractant, characterized in that: The following steps are involved: S1: Build a heating system and place a pressure-resistant bottle with magnets in a sand bath; S2: placing a set ratio of diethylene glycol phosphine and an alcohol compound in a pressure-resistant bottle, and stirring the reaction materials in the pressure-resistant bottle with a stirrer to fully mix them; S3: Add trimethylchlorosilane in a set ratio into the pressure-resistant bottle; S4: stirring the mixture in the pressure-resistant bottle by a stirrer, and heating the mixture in the pressure-resistant bottle by a sand bath pot, so that the mixture reacts fully, until the set reaction time is reached, and a crude organophosphorus extractant is obtained; S5: cooling the crude organophosphorus extractant in the reaction container to room temperature; S6: filtering the crude organophosphorus extractant cooled to room temperature to remove residual solids, then washing the filtrate with water, separating the liquids, and retaining the upper liquid product, i.e., the organophosphorus extractant.

2. The preparation of the organophosphorus extractant according to claim 1, characterized in that: In the step S2, the addition ratio of diglycophosphine and alcohol compound is 1:20 according to the mass ratio, wherein the mass of the added alcohol compound is 0.384 mol.

3. The preparation of the organophosphorus extractant according to claim 1, characterized in that: In the step S3, the addition ratio of trimethylchlorosilane is 6% of the volume of the alcohol compound according to the volume ratio.

4. The preparation of the organophosphorus extractant according to claim 1, characterized in that: In step S4, the heating temperature of the sand bath pot is 90°C.

5. Use of the organophosphorus extractant prepared according to any one of claims 1 to 4 in extracting gallium ions.

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