Synthesis of gallium-targeting adsorbent material and method for deep gallium extraction

Abstract

This invention relates to the field of non-ferrous metal metallurgy technology, and particularly to a method for synthesizing gallium-targeted adsorption materials and a method for deep gallium extraction. The technical solution includes the following steps: dissolving hydroquinone and NaOH in acetonitrile solvent at a molar ratio of 1:10-1:1, and further adding 2-(chloromethyl)pyrrolidine, wherein the molar ratio of 2-(chloromethyl)pyrrolidine to hydroquinone is 1:1-5:1. This invention overcomes the problem of poor structural stability of traditional extractants in industrial high-acid environments, effectively increases the solvent affinity of the pyrrole column[5] aromatic functional group in acidic aqueous solution systems, facilitates the selective adsorption and separation of gallium ions in solution, and facilitates the encapsulation of target gallium ions in the cavity of the pyrrole column[5] aromatic through non-covalent interaction, thereby achieving efficient adsorption. The stable aromatic cyclic silicon-based framework ensures that it still has a good cycle life under high acid conditions.

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metal metallurgy technology, and in particular to a method for synthesizing gallium-targeted adsorption materials and deeply extracting gallium. Background Technology

[0002] Gallium is an important strategic rare and precious metal, and gallium-based semiconductors play an irreplaceable role in cutting-edge fields such as power devices, 5G communications, new displays, and military defense. Throughout the evolution of semiconductors, gallium-based compound semiconductor materials have been consistently used, such as second-generation gallium arsenide and gallium phosphide, third-generation gallium nitride, and the latest generation gallium oxide. This is because gallium-based semiconductors possess excellent semiconductor properties, especially the latest generation of semiconductor material, gallium oxide, which has a bandgap exceeding 4.9 eV, and also exhibits characteristics such as high temperature resistance, high voltage resistance, and radiation resistance, making it one of the ideal materials for manufacturing high-performance optoelectronic and power devices. With the rapid development of strategic emerging industries such as semiconductors, the demand for gallium is growing rapidly.

[0003] Gallium is a typical rare and dispersed metal, with no independent deposits in nature. It is mostly found as a byproduct of non-ferrous metal smelting, such as bauxite and sphalerite. Due to the common problems of low gallium content, high impurity content, and significant interference in non-ferrous metal smelting systems, the separation and extraction of gallium from these systems has attracted widespread attention from researchers. Chinese patent application No. 201210341651.8 discloses a composite adsorbent material for removing gallium ions from natural water bodies and its preparation method. Using sepiolite and aluminum chloride as raw materials, the gallium adsorbent material is obtained through steps such as hydrochloric acid solution modification, stirring reaction, pH adjustment, drying, and pulverization. Chinese patent application No. 202210502984.8 discloses a gallium-modified silica gel resin, its preparation method, and its application. The silica gel, solvent, silane coupling agent, and catalyst are mixed and reacted under heat to obtain the gallium-modified silica gel resin, which exhibits good adsorption selectivity for gallium and good recyclability. Chinese Patent Application No. 202210677117.8 discloses a method for preparing a chelating resin for gallium adsorption. The prepared gallium adsorption resin contains various functional groups in addition to the main framework structure, effectively enhancing the adsorption process. The saturated adsorption capacity can be maintained between 10 g / L and 15 g / L, and the desorption rate reaches over 80%. Chinese Patent Application No. 202210902839.9 discloses a chelating resin specifically for gallium adsorption and its preparation method. The prepared modified aminocarboxylic acid chelating resin can efficiently adsorb gallium while exhibiting good selectivity for vanadium impurities. Furthermore, this resin has a wide applicable pH range, achieving efficient gallium adsorption in both acidic and alkaline environments. Chinese patent application No. 201910028890.X discloses a method for preparing a gallium-adsorbing amylopectin-silica resin. The prepared resin adsorbent possesses a well-developed ordered mesoporous structure, large specific surface area, good mechanical strength and chemical stability, exhibiting high gallium adsorption capacity, good selectivity, and fast adsorption speed, demonstrating promising application prospects. Chinese patent application No. 03112341.4 discloses a gallium-specific chelating resin and its preparation method. The prepared resin, applied to gallium adsorption in Bayer mother liquor, exhibits high recovery rate and strong economic efficiency, achieving an adsorption capacity of up to 3.06 g / L in Bayer mother liquor with a gallium content of 200 mg / L. While the above adsorbent materials generally demonstrate good adsorption performance for gallium, they are difficult to achieve efficient and selective deep separation and extraction of gallium in non-ferrous metal smelting systems characterized by "low gallium and high impurities." Therefore, it is necessary to further develop novel adsorbent materials with efficient targeted adsorption capabilities for gallium, thereby achieving deep separation and recovery of gallium in complex multi-component systems. Therefore, this application proposes a method for synthesizing gallium-targeted adsorption materials and for deep gallium extraction. Summary of the Invention

[0004] The purpose of this invention is to address the problem in the prior art that it is difficult to achieve efficient and selective deep separation and extraction of gallium in non-ferrous metal smelting systems with "low gallium and high impurity" characteristics, and to propose a method for synthesizing gallium-targeted adsorption materials and deep gallium extraction.

[0005] The technical solution of this invention: a method for synthesizing gallium-targeted adsorption materials and deeply extracting gallium, comprising the following steps:

[0006] S1. Hydroquinone and NaOH are dissolved in acetonitrile solvent at a molar ratio of 1:10-1:1. 2-(chloromethyl)pyrrolidine is then added to the solvent. The molar ratio of 2-(chloromethyl)pyrrolidine to hydroquinone is 1:1-5:1. The reaction is carried out at a constant temperature under an inert atmosphere. After the reaction is completed, the mixture is cooled to room temperature, the solvent is removed, and the product is purified to obtain intermediate product A.

[0007] S2. Dissolve intermediate product A in an appropriate amount of N,N-dimethylformamide and add an appropriate amount of NaOH. The molar ratio of intermediate product A to NaOH is 1:10-1:1. After complete dissolution, add an appropriate amount of epichlorohydrin to the reaction system and heat the reaction in an oil bath. After the reaction is completed, remove the solvent and purify to obtain intermediate product B.

[0008] S3. Mix intermediate product B with trioxymethylene in a molar ratio of 1:5-1:1, add dichloromethane to dissolve it completely, add an appropriate amount of boron trifluoride diethyl ether to the reaction system under an ice-salt bath environment, react under an inert atmosphere at room temperature, quench the residual boron trifluoride diethyl ether after the reaction is completed, remove the solvent, purify and obtain intermediate product C.

[0009] S4. Add appropriate amounts of DMF and NaOH to silanized silica powder. The liquid-solid ratio of DMF to silica powder is 5:1-50:1, and the molar ratio of NaOH to silica is 1:1-5:1. Further add appropriate amounts of intermediate product C to the mixture. The molar ratio of intermediate product C to silica is 1:1-5:1. React at a constant temperature. After the reaction is completed, the product is purified and dried to obtain the target product, gallium-targeted adsorption material.

[0010] S5. The synthesized adsorbent material is added to a low-concentration complex gallium-containing solution system with a gallium concentration of 0.001-1 g / L and a hydrogen ion concentration of 0.001-10 mol / L. The amount of adsorbent material added is 0.1-10 g / L. The reaction is carried out at a constant temperature of 20-95℃ for 1-12 hours to complete the targeted adsorption, separation and extraction of gallium.

[0011] Optionally, the isothermal reaction in step S1 is characterized by a temperature of 60-80°C and a time of 2-24 hours.

[0012] Optionally, the step S2 is characterized in that the molar ratio of epichlorohydrin to intermediate product A is 1:1-5:1, the oil bath reaction temperature is 110-150℃, and the time is 2-24h.

[0013] Optionally, the step S3 is characterized in that the temperature of the ice-salt bath is -8 to 0°C, the molar ratio of boron trifluoride ether to intermediate product B is 1:1 to 5:1, and the reaction time is 2 to 24 h.

[0014] Optionally, the isothermal reaction in step S4 is characterized by a temperature of 20-95°C and a time of 2-24 h.

[0015] Optionally, in step S4, the liquid-solid ratio of DMF to silica powder is 10:1-40:1, the molar ratio of NaOH to silica is 2:1-4:1, and an appropriate amount of intermediate product C is further added to the mixed system, wherein the molar ratio of intermediate product C to silica is 2:1-4:1.

[0016] Optionally, in step S5, the amount of adsorbent added is 0.1-10 g / L, the reaction time is 1-12 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system is 0.001-10 mol / L, and the reaction temperature is 20-95℃.

[0017] Optionally, in step S5, the synthesized adsorbent material is added to a low-concentration complex gallium-containing solution system with a gallium concentration of 0.05-1 g / L and a hydrogen ion concentration of 0.05-10 mol / L, and the amount of adsorbent material added is 2-10 g / L.

[0018] Optionally, in step S4, the liquid-to-solid ratio of DMF to silica powder is 10:1, the molar ratio of NaOH to silica is 2:1, the molar ratio of intermediate product C to silica is 2:1, the reaction is carried out at 40°C for 8 h, and after the reaction is completed, the product is purified and dried to obtain the target product gallium-targeted adsorption material.

[0019] Optionally, in step S5, the amount of adsorbent added is 10 g / L, the reaction time is 12 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system is 10 mol / L, and the reaction temperature is 95℃.

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

[0021] The present invention relates to a method for synthesizing gallium-targeted adsorption materials and for deep gallium extraction. In terms of the functional group structure of the adsorbent, pyrrole-based columnar aromatic hydrocarbons [5] have strong structural stability. The rigid aromatic ring-constructed cyclic cavity structure has good pre-organization properties, ensuring the stability of the cavity and overcoming the problem of poor structural stability of traditional extractants in industrial high-acid environments. The ethylene oxide loaded on the upper edge can effectively overcome the problem of poor hydrophilicity of traditional columnar aromatic hydrocarbons, effectively increasing the solvent affinity of the pyrrole-based columnar aromatic hydrocarbon functional group in acidic aqueous solution systems, which facilitates the selective adsorption and separation of gallium ions in solution.

[0022] (2) In the synthesis of a gallium-targeted adsorption material and a method for deep gallium extraction of the present invention, in terms of ion-pair selective coordination, the pyrrole-based column[5]arene functional group has a cavity size suitable for coordination with gallium ions. The ethylene oxide at the upper edge can capture gallium ions through an ion-dipole mechanism and then transfer them to the π-rich cavity of the column[5]arene. The aromatic ring unit in the cavity can provide abundant strong π electrons, which facilitates the encapsulation of the target gallium ions inside the cavity of the pyrrole-based column[5]arene through non-covalent interactions, thereby achieving efficient adsorption.

[0023] (3) The present invention provides a method for synthesizing gallium-targeted adsorption materials and for deep gallium extraction, using pyrrole-based columnar aromatic hydrocarbon adsorbents[5] with stable silica as the adsorbent loading matrix. The stable aromatic cyclic silica framework ensures that it still has a good cycle life under high acid conditions.

[0024] This invention overcomes the problem of poor structural stability of traditional extractants in industrial high-acid environments, effectively increases the solvent affinity of the pyrrole column[5] aromatic functional group in acidic aqueous solution system, facilitates selective adsorption and separation of gallium ions in solution, and facilitates the encapsulation of target gallium ions in the cavity of the pyrrole column[5] aromatic through non-covalent interaction, thereby achieving efficient adsorption. The stable aromatic cyclic silicon-based framework ensures that it still has a good cycle life under high acid conditions. Detailed Implementation

[0025] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, unless otherwise specified, the following embodiments and features described therein can be combined with each other.

[0026] Example 1

[0027] This embodiment of a method for synthesizing gallium-targeted adsorption materials and deeply extracting gallium specifically includes the following steps:

[0028] (1) Hydroquinone and NaOH were dissolved in acetonitrile solvent, with a molar ratio of hydroquinone to NaOH of 1:10; 2-(chloromethyl)pyrrolidine was further added to the solvent, with a molar ratio of 2-(chloromethyl)pyrrolidine to hydroquinone of 1:1; the reaction was carried out at an inert atmosphere at 80°C for 2 h. After the reaction was completed, the solvent was removed and the product was purified to obtain intermediate product A.

[0029] (2) Dissolve intermediate product A in an appropriate amount of N,N-dimethylformamide and add an appropriate amount of NaOH, with a molar ratio of intermediate product A to NaOH of 1:10; after complete dissolution, add epichlorohydrin to the reaction system, with a molar ratio of epichlorohydrin to intermediate product A of 1:1; heat the reaction in an oil bath at 110°C for 2 h. After the reaction is complete, remove the solvent and purify to obtain intermediate product B.

[0030] (3) Intermediate product B and trioxymethylene were mixed at a molar ratio of 1:5, and dichloromethane was added to dissolve them completely. Boron trifluoride diethyl ether was added to the reaction system in an ice-salt bath at -8°C, with a molar ratio of boron trifluoride diethyl ether to intermediate product B of 1:1. The reaction was carried out at room temperature under an inert atmosphere for 2 h. After the reaction was completed, the residual boron trifluoride diethyl ether was quenched, the solvent was removed, and the product was purified to obtain intermediate product C.

[0031] (4) Add appropriate amounts of DMF and NaOH to silanized silica powder. The liquid-to-solid ratio of DMF to silica powder is 5:1, and the molar ratio of NaOH to silica is 1:1. Further add intermediate product C to the mixture. The molar ratio of intermediate product C to silica is 1:1. React at 20°C for 2 h. After the reaction is completed, the product is purified and dried to obtain the target product, gallium-targeted adsorption material.

[0032] (5) The synthesized adsorbent material was added to a low-concentration complex gallium-containing solution system and reacted at a constant temperature for a period of time. The amount of adsorbent material added was 0.1 g / L, the reaction time was 1 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system was 0.001 mol / L, and the reaction temperature was 20℃, so as to achieve targeted adsorption, separation and extraction of gallium.

[0033] Example 2

[0034] This embodiment of a method for synthesizing gallium-targeted adsorption materials and deeply extracting gallium specifically includes the following steps:

[0035] (1) Hydroquinone and NaOH were dissolved in acetonitrile solvent, with a molar ratio of hydroquinone to NaOH of 1:1; 2-(chloromethyl)pyrrolidine was further added to the solvent, with a molar ratio of 2-(chloromethyl)pyrrolidine to hydroquinone of 5:1; the reaction was carried out at an inert atmosphere at 60°C for 24 h. After the reaction was completed, the solvent was removed and the product was purified to obtain intermediate product A.

[0036] (2) Dissolve intermediate product A in an appropriate amount of N,N-dimethylformamide and add an appropriate amount of NaOH, with a molar ratio of intermediate product A to NaOH of 1:1; after complete dissolution, add epichlorohydrin to the reaction system, with a molar ratio of epichlorohydrin to intermediate product A of 5:1; heat the reaction in an oil bath at 150°C for 24 h. After the reaction is complete, remove the solvent and purify to obtain intermediate product B.

[0037] (3) Intermediate product B and trioxymethylene were mixed at a molar ratio of 1:1, and dichloromethane was added to dissolve them completely. Boron trifluoride diethyl ether was added to the reaction system in an ice-salt bath at 0°C, with a molar ratio of boron trifluoride diethyl ether to intermediate product B of 5:1. The reaction was carried out at room temperature under an inert atmosphere for 24 h. After the reaction was completed, the residual boron trifluoride diethyl ether was quenched, the solvent was removed, and the product was purified to obtain intermediate product C.

[0038] (4) Add appropriate amounts of DMF and NaOH to silanized silica powder. The liquid-to-solid ratio of DMF to silica powder is 50:1, and the molar ratio of NaOH to silica is 5:1. Further add intermediate product C to the mixture. The molar ratio of intermediate product C to silica is 5:1. React at 95℃ for 24 h. After the reaction is completed, the product is purified and dried to obtain the target product, gallium-targeted adsorption material.

[0039] (5) The synthesized adsorbent material was added to a low-concentration complex gallium-containing solution system and reacted at a constant temperature for a period of time. The amount of adsorbent material added was 10 g / L, the reaction time was 12 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system was 10 mol / L, and the reaction temperature was 95℃, so as to achieve targeted adsorption, separation and extraction of gallium.

[0040] Example 3

[0041] This embodiment of a method for synthesizing gallium-targeted adsorption materials and deeply extracting gallium specifically includes the following steps:

[0042] (1) Hydroquinone and NaOH were dissolved in acetonitrile solvent, with a molar ratio of hydroquinone to NaOH of 1:7; 2-(chloromethyl)pyrrolidine was further added to the solvent, with a molar ratio of 2-(chloromethyl)pyrrolidine to hydroquinone of 2:1; the reaction was carried out at an inert atmosphere of 65°C for 8 h. After the reaction was completed, the solvent was removed and the product was purified to obtain intermediate product A.

[0043] (2) Dissolve intermediate product A in an appropriate amount of N,N-dimethylformamide and add an appropriate amount of NaOH, with a molar ratio of intermediate product A to NaOH of 1:7; after complete dissolution, add epichlorohydrin to the reaction system, with a molar ratio of epichlorohydrin to intermediate product A of 2:1; heat the reaction in an oil bath at 120°C for 8 h. After the reaction is complete, remove the solvent and purify to obtain intermediate product B.

[0044] (3) Intermediate product B and trioxymethylene were mixed at a molar ratio of 1:2, and dichloromethane was added to dissolve them completely. Boron trifluoride diethyl ether was added to the reaction system in an ice-salt bath at -6°C, with a molar ratio of boron trifluoride diethyl ether to intermediate product B of 2:1. The reaction was carried out at room temperature under an inert atmosphere for 8 h. After the reaction was completed, the residual boron trifluoride diethyl ether was quenched, the solvent was removed, and the product was purified to obtain intermediate product C.

[0045] (4) Add appropriate amounts of DMF and NaOH to silanized silica powder. The liquid-to-solid ratio of DMF to silica powder is 10:1, and the molar ratio of NaOH to silica is 2:1. Further add intermediate product C to the mixture. The molar ratio of intermediate product C to silica is 2:1. React at 40℃ for 8 h. After the reaction is completed, the product is purified and dried to obtain the target product, gallium-targeted adsorption material.

[0046] (5) The synthesized adsorbent material was added to a low-concentration complex gallium-containing solution system and reacted at a constant temperature for a period of time. The amount of adsorbent material added was 2 g / L, the reaction time was 3 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system was 2 mol / L, and the reaction temperature was 40℃, so as to achieve targeted adsorption, separation and extraction of gallium.

[0047] Example 4

[0048] This embodiment of a method for synthesizing gallium-targeted adsorption materials and deeply extracting gallium specifically includes the following steps:

[0049] (1) Hydroquinone and NaOH were dissolved in acetonitrile solvent, with a molar ratio of hydroquinone to NaOH of 1:5; 2-(chloromethyl)pyrrolidine was further added to the solvent, with a molar ratio of 2-(chloromethyl)pyrrolidine to hydroquinone of 3:1; the reaction was carried out at an inert atmosphere of 70°C for 12 h. After the reaction was completed, the solvent was removed and the product was purified to obtain intermediate product A.

[0050] (2) Dissolve intermediate product A in an appropriate amount of N,N-dimethylformamide and add an appropriate amount of NaOH, with a molar ratio of intermediate product A to NaOH of 1:5; after complete dissolution, add epichlorohydrin to the reaction system, with a molar ratio of epichlorohydrin to intermediate product A of 3:1; heat the reaction in an oil bath at 130°C for 12 h. After the reaction is complete, remove the solvent and purify to obtain intermediate product B.

[0051] (3) Intermediate product B and trioxymethylene were mixed at a molar ratio of 1:3, and dichloromethane was added to dissolve them completely. Boron trifluoride diethyl ether was added to the reaction system in an ice-salt bath at -4°C, with a molar ratio of boron trifluoride diethyl ether to intermediate product B of 3:1; the reaction was carried out at room temperature under an inert atmosphere for 12 h. After the reaction was completed, the residual boron trifluoride diethyl ether was quenched, the solvent was removed, and the product was purified to obtain intermediate product C.

[0052] (4) Add appropriate amounts of DMF and NaOH to silanized silica powder. The liquid-to-solid ratio of DMF to silica powder is 20:1, and the molar ratio of NaOH to silica is 3:1. Further add intermediate product C to the mixture. The molar ratio of intermediate product C to silica is 3:1. React at 55°C for 12 h. After the reaction is completed, the product is purified and dried to obtain the target product, gallium-targeted adsorption material.

[0053] (5) The synthesized adsorbent material was added to a low-concentration complex gallium-containing solution system and reacted at a constant temperature for a period of time. The amount of adsorbent material added was 5 g / L, the reaction time was 6 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system was 5 mol / L, and the reaction temperature was 55℃, so as to achieve targeted adsorption, separation and extraction of gallium.

[0054] Example 5

[0055] This embodiment of a method for synthesizing gallium-targeted adsorption materials and deeply extracting gallium specifically includes the following steps:

[0056] (1) Hydroquinone and NaOH were dissolved in acetonitrile solvent, with a molar ratio of hydroquinone to NaOH of 1:3; 2-(chloromethyl)pyrrolidine was further added to the solvent, with a molar ratio of 2-(chloromethyl)pyrrolidine to hydroquinone of 4:1; the reaction was carried out at an inert atmosphere of 75°C for 18 h. After the reaction was completed, the solvent was removed and the product was purified to obtain intermediate product A.

[0057] (2) Dissolve intermediate product A in an appropriate amount of N,N-dimethylformamide and add an appropriate amount of NaOH, with a molar ratio of intermediate product A to NaOH of 1:3; after complete dissolution, add epichlorohydrin to the reaction system, with a molar ratio of epichlorohydrin to intermediate product A of 4:1; heat the reaction in an oil bath at 140℃ for 18 h. After the reaction is completed, remove the solvent and purify to obtain intermediate product B.

[0058] (3) Intermediate product B and trioxymethylene were mixed at a molar ratio of 1:4, and dichloromethane was added to dissolve them completely. Boron trifluoride diethyl ether was added to the reaction system in an ice-salt bath at -2°C, with a molar ratio of boron trifluoride diethyl ether to intermediate product B of 4:1. The reaction was carried out at room temperature under an inert atmosphere for 18 h. After the reaction was completed, the residual boron trifluoride diethyl ether was quenched, the solvent was removed, and the product was purified to obtain intermediate product C.

[0059] (4) Add appropriate amounts of DMF and NaOH to silanized silica powder. The liquid-to-solid ratio of DMF to silica powder is 40:1, and the molar ratio of NaOH to silica is 4:1. Further add intermediate product C to the mixture. The molar ratio of intermediate product C to silica is 4:1. React at 80℃ for 18 h. After the reaction is completed, the product is purified and dried to obtain the target product, gallium-targeted adsorption material.

[0060] (5) The synthesized adsorbent material was added to a low-concentration complex gallium-containing solution system and reacted at a constant temperature for a period of time. The amount of adsorbent material added was 8 g / L, the reaction time was 10 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system was 8 mol / L, and the reaction temperature was 80℃, so as to achieve targeted adsorption, separation and extraction of gallium.

[0061] The gallium ion concentrations before and after adsorption in Examples 1-5 were determined by ICP-MS, and the results are shown in the following table:

[0062] Table 1. ICP-MS detection data from Examples 1-5

[0063] Testing items <![CDATA[Stock solution Ga 3+ Concentration (mg / L)]]> <![CDATA[Residual liquid Ga 3+ concentration (mg / L)]]> Gallium adsorption capacity (mg / g) Example 1 38.20 0.53 376.70 Example 2 730.20 3.60 363.30 Example 3 635.00 0.60 371.20 Example 4 359.10 0.50 358.60 Example 5 728.30 1.10 363.60

[0064] Table 2. Performance parameters of gallium selective recognition adsorption materials:

[0065] physical form White microspheres Particle size 0.5-0.65mm Moisture content ＜1% stability Stable to acid and alkaline aqueous solutions Wet apparent density 462 g / L Operating temperature range 0～125℃

[0066] Referring to Tables 1-2, the data from the above embodiments demonstrate that this invention achieves targeted adsorption and separation of gallium through aptamer functionalization, exhibiting high selectivity and higher extraction efficiency, making it an environmentally friendly gallium extraction technology. Furthermore, by flexibly modifying the aptamer sequence, gallium extraction technologies for various complex systems can be rapidly developed.

[0067] The present invention relates to a method for synthesizing gallium-targeted adsorption materials and for deep gallium extraction. In terms of the functional group structure of the adsorbent, pyrrole-based columnar aromatic hydrocarbons [5] have strong structural stability. The rigid aromatic ring-constructed cyclic cavity structure has good pre-organization properties, ensuring the stability of the cavity and overcoming the problem of poor structural stability of traditional extractants in industrial high-acid environments. The ethylene oxide loaded on the upper edge can effectively overcome the problem of poor hydrophilicity of traditional columnar aromatic hydrocarbons, effectively increasing the solvent affinity of the pyrrole-based columnar aromatic hydrocarbon functional group in acidic aqueous solution systems, which facilitates the selective adsorption and separation of gallium ions in solution.

[0068] In terms of ion-pair selective coordination, the pyrrole-based columnar aromatic functional group [5] has a cavity size suitable for coordination with gallium ions. The ethylene oxide alkyl group at the top edge can capture gallium ions via an ion-dipole mechanism and then transfer them to the π-rich cavity of the columnar aromatic [5]. The aromatic ring unit inside the cavity can provide abundant strong π electrons, which facilitates the encapsulation of the target gallium ions inside the cavity of the pyrrole-based columnar aromatic [5] through non-covalent interactions, thereby achieving efficient adsorption.

[0069] Furthermore, using pyrrole-based column[5] aromatic adsorbents with stable silica as the adsorbent support matrix, the stable aromatic cyclic silica framework ensures that it still has a good cycle life under high acidity conditions.

[0070] The above specific embodiments are merely several optional embodiments of the present invention. Based on the technical solutions of the present invention and the relevant teachings of the above embodiments, those skilled in the art can make various alternative improvements and combinations to the above specific embodiments.

Claims

1. A method for synthesizing a gallium-targeted adsorption material, characterized in that, Includes the following steps: S1. Hydroquinone and NaOH are dissolved in acetonitrile solvent at a molar ratio of 1:10-1:

1. 2-(chloromethyl)pyrrolidine is then added to the solvent. The molar ratio of 2-(chloromethyl)pyrrolidine to hydroquinone is 1:1-5:

1. The reaction is carried out at a constant temperature under an inert atmosphere. After the reaction is completed, the mixture is cooled to room temperature, the solvent is removed, and the product is purified to obtain intermediate product A. S2. Dissolve intermediate product A in an appropriate amount of N,N-dimethylformamide and add an appropriate amount of NaOH. The molar ratio of intermediate product A to NaOH is 1:10-1:

1. After complete dissolution, add an appropriate amount of epichlorohydrin to the reaction system and heat the reaction in an oil bath. After the reaction is completed, remove the solvent and purify to obtain intermediate product B. S3. Mix intermediate product B with trioxymethylene in a molar ratio of 1:5-1:1, add dichloromethane to dissolve it completely, add an appropriate amount of boron trifluoride diethyl ether to the reaction system under an ice-salt bath environment, react under an inert atmosphere at room temperature, quench the residual boron trifluoride diethyl ether after the reaction is completed, remove the solvent, purify and obtain intermediate product C. S4. Add appropriate amounts of DMF and NaOH to silanized silica powder. The liquid-solid ratio of DMF to silica powder is 5:1-50:1, and the molar ratio of NaOH to silica is 1:1-5:

1. Further add appropriate amounts of intermediate product C to the mixture. The molar ratio of intermediate product C to silica is 1:1-5:

1. React at a constant temperature. After the reaction is completed, the product is purified and dried to obtain the target product, gallium-targeted adsorption material.

2. The method for synthesizing a gallium-targeted adsorption material according to claim 1, characterized in that, In step S1, the isothermal reaction temperature is 60-80℃ and the time is 2-24h.

3. The method for synthesizing a gallium-targeted adsorption material according to claim 1, characterized in that, In step S2, the molar ratio of epichlorohydrin to intermediate product A is 1:1-5:1, the oil bath reaction temperature is 110-150℃, and the time is 2-24h.

4. The method for synthesizing a gallium-targeted adsorption material according to claim 1, characterized in that, In step S3, the temperature of the ice-salt bath is -8 to 0°C, the molar ratio of boron trifluoride ether to intermediate product B is 1:1 to 5:1, and the reaction time is 2 to 24 h.

5. The method for synthesizing a gallium-targeted adsorption material according to claim 1, characterized in that, In step S4, the isothermal reaction temperature is 20-95℃ and the time is 2-24 h.

6. The method for synthesizing a gallium-targeted adsorption material according to claim 1, characterized in that, In step S4, the liquid-solid ratio of DMF to silica powder is 10:1-40:1, the molar ratio of NaOH to silica is 2:1-4:1, and an appropriate amount of intermediate product C is further added to the mixed system, with the molar ratio of intermediate product C to silica being 2:1-4:

1.

7. The method for synthesizing a gallium-targeted adsorption material according to claim 1, characterized in that, In step S4, the liquid-to-solid ratio of DMF to silica powder is 10:1, the molar ratio of NaOH to silica is 2:1, the molar ratio of intermediate product C to silica is 2:1, and the reaction is carried out at 40°C for 8 hours. After the reaction is completed, the product is purified and dried to obtain the target product, gallium-targeted adsorption material.

8. A method for deep gallium extraction, characterized in that, The gallium-targeted adsorption material prepared by the method of claim 1 includes the following steps: S5. The synthesized adsorbent material is added to a low-concentration complex gallium-containing solution system with a gallium concentration of 0.001-1 g / L and a hydrogen ion concentration of 0.001-10 mol / L. The amount of adsorbent material added is 0.1-10 g / L. The reaction is carried out at a constant temperature of 20-95℃ for 1-12 hours to complete the targeted adsorption, separation and extraction of gallium.

9. A method for deep gallium extraction according to claim 8, characterized in that, In step S5, the amount of adsorbent added is 0.1-10 g / L, the reaction time is 1-12 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system is 0.001-10 mol / L, and the reaction temperature is 20-95℃.

10. The method for deep gallium extraction according to claim 8, wherein in step S5, the synthesized adsorbent material is added to a low-concentration complex gallium-containing solution system with a gallium concentration of 0.05-1 g / L and a hydrogen ion concentration of 0.05-10 mol / L, and the amount of adsorbent material added is 2-10 g / L; In step S5, the amount of adsorbent added is 10 g / L, the reaction time is 12 h, the hydrogen ion concentration in the low-concentration complex gallium-containing solution system is 10 mol / L, and the reaction temperature is 95℃.