CN114849667B - Gallium-adsorbed modified silica gel resin, and preparation method and application thereof - Google Patents

Gallium-adsorbed modified silica gel resin, and preparation method and application thereof Download PDF

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CN114849667B
CN114849667B CN202210502984.8A CN202210502984A CN114849667B CN 114849667 B CN114849667 B CN 114849667B CN 202210502984 A CN202210502984 A CN 202210502984A CN 114849667 B CN114849667 B CN 114849667B
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silica gel
gallium
coupling agent
silane coupling
resin
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CN114849667A (en
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谢龙
殷亮
朱刘
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First Rare Materials Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a preparation method of gallium-adsorbed modified silica gel resin, which comprises the following steps: mixing silica gel, a solvent, a silane coupling agent and a catalyst, and then heating for reaction to obtain the gallium-adsorbed modified silica gel resin. Compared with the prior art, the invention uses silica gel as a substrate raw material, has higher hardness, stable performance, rich micropore structure, high specific surface area, high purity, higher activity and higher adsorption capacity, can realize the purpose of specifically adsorbing gallium ions after being modified by the silane coupling agent, can also use acid to backwash gallium, and prolongs the service life of the resin.

Description

Gallium-adsorbed modified silica gel resin, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adsorption resins, and particularly relates to a gallium-adsorption modified silica gel resin, a preparation method and application thereof.
Background
Gallium is one of the rare metals, and the content of gallium in the crust is 0.0015%. The gallium in nature is distributed and dispersed, and is mainly in bauxite, and a small amount of gallium is in tin ore, tungsten ore and lead zinc ore, which are present in associated ores. According to the data released by the United states geological survey in 2015, the reserves of gallium in the global bauxite exceeds 100 ten thousand tons, and certain reserves of gallium resources are also reserved in the zinc ore. Although the bauxite and zinc ores contain relatively large amounts of gallium resources, the amount of gallium resources that can be developed and recovered from them is currently small.
China is one of the world gallium major countries, and according to incomplete statistics, the gallium yield of China in 2012 is 270 tons, the yield is about 330 tons, and the gallium yield accounts for about 80 percent of the global yield. The current gallium productivity of China is seriously excessive, the gallium productivity of China in 2013 is about 400-450 tons, and the gallium productivity in 2014 is about 500 tons. The national gallium consumption is about 280-300 tons in 2010, and the national gallium consumption is about 100 tons, which is about one third of the total consumption, and the national gallium consumption is increasing at a rate of 20% -30% per year. At present, the consumption field of gallium in China comprises semiconductors, photoelectric materials, solar cells, alloys, medical devices, magnetic materials and the like, wherein the semiconductor industry is the largest consumption field of gallium, and the consumption field accounts for about 80% of the total consumption.
At present, the metal gallium with the purity of 4N-5N is mainly used in the fields of solar cells, gas sensors, rare earth permanent magnet materials and the like, and the metal gallium with the purity of 6N and above is mainly used for manufacturing compound semiconductors such as gallium arsenide, gallium nitride and the like. At present, the compound semiconductor is the biggest consumption field of gallium metal in China, and accounts for about 65% of consumption. According to the measurement and calculation of the end use, about 76% of gallium in China is used in the fields of LEDs and wireless communication.
With the rapid development of the gallium industry, especially the semiconductor and solar battery industries, and the promotion of the development planning of the LED industry by the government of China, the consumption of gallium in China is still kept in a greatly increased situation. In addition, because the recovery capability of the metal gallium in China is smaller, the requirement on the metal gallium is supported by the original gallium, and the requirement on the original gallium in China market is promoted to be greatly increased. Because of the special attribute of gallium resources, the downstream terminal of the industrial chain is widely applied to strategic industries or fields such as national defense, wireless communication, new materials, new energy sources, medical treatment and the like, is not only used as one of strategic reserve mineral products in China, but also is listed in strategic or key mineral product catalogues in developed areas such as European Union, the United states, japan and the like. With the rapid development of the semiconductor, solar cell and wireless communication industry and the expansion of the application field of gallium, the requirement for gallium is expected to be greatly increased in the future. It is predicted that the global gallium resource demand in 2025 will be up to 720 tons, and the demand of China for gallium resources will be up to 370 tons, so that the recovery of gallium ions is increasingly important.
The gallium-absorbing resin on the market is mainly resin produced by Xiean blue dawn company, for example, resin LSC-600 is mainly used for absorbing gallium in alkaline solution, resin LSC-900 is mainly used for absorbing gallium in acid solution, LSC-760 is mainly used for extracting gallium from Bayer mother liquor with higher vanadium content, and the like, and the products occupy a large number of markets of gallium resins at home and abroad. The lead company is a larger scattered metal company in China, the secondary resource recovery of the scattered metal also occupies a larger proportion in the industrial chain of the company, in recent years, gallium is a popular product raw material in the scattered metal, the price of gallium is increased year by year in the fields of semiconductors and solar energy films, if the gallium resource can be efficiently recovered, the lead company has great significance for the development of the company, even if the company is responsible for the recovery and research of the scattered metal, part of gallium-containing waste is still difficult to treat because of higher cost, the loss of the gallium resource is caused, the gallium in the semiconductor gallium arsenide polishing wastewater cannot be separated, the resource loss is caused, the LSC-600 resin produced by the blue dawn company is used for treatment, the resin swells, breaks and changes color after being soaked in the wastewater, the cost of Lan Xiao resin is high, and the problem of gallium recovery of the polishing wastewater cannot be solved from the effect point of view, and new gallium resin is needed for recovery.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a gallium-adsorbing modified silica gel resin with better adsorption efficiency and stability, and a preparation method and application thereof.
The invention provides a preparation method of gallium-adsorbed modified silica gel resin, which comprises the following steps:
mixing silica gel, a solvent, a silane coupling agent and a catalyst, and then heating for reaction to obtain the gallium-adsorbed modified silica gel resin.
Preferably, the silica gel is mixed with the solvent and then heated for pretreatment, and then the silane coupling agent and the catalyst are added.
Preferably, the temperature of the heating pretreatment is 40-60 ℃; the heating pretreatment time is 30-90 min.
Preferably, the temperature of the heating reaction is 90-110 ℃; the heating reaction time is 1-4 h.
Preferably, the silica gel is mixed with the solvent in a container provided with a water separator and a condenser tube; the silane coupling agent and the catalyst are sequentially added into the system after the heating pretreatment in a dropwise manner; after the catalyst is added dropwise, the temperature is raised to 80-90 ℃ until the distillate amount is not increased, and the reaction is heated.
Preferably, the solvent is selected from one or more of xylene, water, methanol, ethanol, toluene, o-xylene, m-xylene, p-xylene and ethylene glycol; the silane coupling agent is selected from aminopropyl trimethoxy silane; the catalyst is selected from one or more of tert-butyl hydroperoxide, azodiisobutyronitrile, benzoyl peroxide and tert-butyl peroxide.
Preferably, the mass of the silane coupling agent is 20% -40% of the mass of the silica gel; the mass of the catalyst is 0.1% -1% of that of silica gel.
The invention also provides the gallium-adsorbing modified silica gel resin prepared by the preparation method, which takes silica gel as a substrate; the silica gel is coupled with a silane coupling agent.
The invention also provides application of the gallium-adsorbing modified silica gel resin prepared by the preparation method in adsorbing gallium ions in a gallium-containing solution.
Preferably, the gallium-containing solution is derived from hydrometallurgy.
The invention provides a preparation method of gallium-adsorbed modified silica gel resin, which comprises the following steps: mixing silica gel, a solvent, a silane coupling agent and a catalyst, and then heating for reaction to obtain the gallium-adsorbed modified silica gel resin. Compared with the prior art, the invention uses silica gel as a substrate raw material, has higher hardness, stable performance, rich micropore structure, high specific surface area, high purity, higher activity and higher adsorption capacity, can realize the purpose of specifically adsorbing gallium ions after being modified by the silane coupling agent, can also use acid to backwash gallium, and prolongs the service life of the resin.
Drawings
FIG. 1 is a schematic diagram of the mechanism of the silane coupling agent coupling silica gel of the present invention;
FIG. 2 is an infrared spectrum of the pretreated silica gel and the modified silica gel resin in example 1 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of gallium-adsorbed modified silica gel resin, which comprises the following steps: mixing silica gel, a solvent, a silane coupling agent and a catalyst, and then heating for reaction to obtain the gallium-adsorbed modified silica gel resin.
The source of all the raw materials is not particularly limited and is commercially available.
In the present invention, it is preferable to mix silica gel with a solvent and then heat-pretreat it; the silica gel is preferably mixed with the solvent in a container provided with a water separator and a condenser tube; the silica gel is preferably column chromatography silica gel; the mesh number of the silica gel is preferably 100-200 meshes; in the present invention, the silica gel is preferably washed, dried and then mixed with a solvent; the washing is preferably with water; the washing time is preferably 30-90 min, more preferably 40-80 min, and still more preferably 60-70 min; the drying temperature is preferably 90-100 ℃; the drying time is preferably 6 to 10 hours, more preferably 8 to 9 hours. The solvent is a solvent well known to those skilled in the art, and is not particularly limited, and one or more of xylene, water, methanol, ethanol, toluene, o-xylene, m-xylene, p-xylene and ethylene glycol are preferable in the present invention; the ratio of silica gel to solvent is preferably 100 g: (150-500) mL, more preferably 100 g: (150-400 mL), and more preferably 100 g: (200-300) mL, more preferably 100 g: (200-250) mL, most preferably 100 g:230 mL; the temperature of the heating pretreatment is preferably 40-60 ℃, more preferably 45-55 ℃, and still more preferably 50 ℃; the time of the heating pretreatment is preferably 30-90 min, more preferably 50-80 min, and still more preferably 60-70 min.
Then adding a silane coupling agent and a catalyst; the silane coupling agent is a low molecular organosilicon compound with a special structure, and the general formula is RSiX 3 Wherein R represents a reactive functional group having affinity or reactivity with the polymer molecule, such as an oxy group, a mercapto group, a vinyl group, an epoxy group, an amide group, an aminopropyl group, etc., and X represents an alkoxy group capable of hydrolysis, such as a halogen, an alkoxy group, an acyloxy groupEtc.; in the present invention, the silane coupling agent is preferably aminopropyl trimethoxysilane; the mass of the silane coupling agent is 20% -40% of that of silica gel, more preferably 22% -35%, still more preferably 24% -30%, still more preferably 26% -28%, and most preferably 26.7%; the catalyst is preferably one or more of tert-butyl hydroperoxide, azodiisobutyronitrile, benzoyl peroxide and tert-butyl peroxide; the mass of the catalyst is preferably 0.1% -1%, more preferably 0.2% -0.8%, still more preferably 0.2% -0.6%, still more preferably 0.2% -0.4% and most preferably 0.3% of the mass of the silica gel; in the invention, the silane coupling agent and the catalyst are sequentially added into the system after the heating pretreatment in a dropwise manner; the silane coupling agent and the catalyst are preferably added dropwise within 0.5-2 h, more preferably within 0.8-1.5 h, and still more preferably within 1-1.2 h.
After the catalyst is added dropwise, preferably heating to 80-90 ℃ until the distillate amount is not increased, and heating for reaction; the temperature of the heating reaction is preferably 90-110 ℃, more preferably 95-105 ℃ and still more preferably 100 ℃; the heating reaction time is preferably 1 to 4 hours, more preferably 2 to 4 hours, and still more preferably 3 to 4 hours.
After the heating reaction, preferably washing and drying to obtain the gallium-adsorbed modified silica gel resin; the washing is preferably performed sequentially with an alcohol solvent and water; the alcohol solvent is preferably methanol; the drying temperature is preferably 90-100 ℃; the drying is preferably to constant weight. The invention couples the silane coupling agent to the surface of silica gel through heating reaction, and when coupling is carried out, the silane coupling agent RSiX is firstly used 3 The X-group water in (2) forms silanol, then reacts with hydroxyl groups on the surfaces of inorganic powder silica gel particles to form hydrogen bonds and is condensed into-SiO-M covalent bonds (M represents the surfaces of inorganic powder particles). Meanwhile, silanol of each molecule of the silane is mutually associated and oligomerized to form a film with a net structure to cover the surface of the powder particles, so that the surface of the inorganic powder is organized. Taking an X amino group as an example, the coupling mechanism is shown in FIG. 1.
The invention takes silica gel as a substrate raw material, has higher hardness and stable performance, has rich micropore structure, high specific surface area, high purity, higher activity and higher adsorption capacity, can realize the purpose of specifically adsorbing gallium ions after being modified by a silane coupling agent, can also use acid to backwash gallium, and prolongs the service life of the resin.
The invention also provides the gallium-adsorbing modified silica gel resin prepared by the preparation method, which takes silica gel as a substrate; the silica gel is coupled with a silane coupling agent. The silica gel and the silane coupling agent are the same as those described above, and are not described in detail herein. The saturated adsorption capacity of the gallium-adsorbed modified silica gel resin on gallium ions is preferably 5 g/L-10 g/L, and more preferably 6 g/L-8 g/L.
The invention also provides application of the gallium-adsorbing modified silica gel resin prepared by the preparation method in adsorbing gallium ions in a gallium-containing solution.
Preferably, the gallium-containing solution is preferably a neutral or weak acid solution, and more preferably has a pH value of 1.5-7.5; further preferably, the gallium-containing solution is derived from hydrometallurgy.
In the present invention, the concentration of gallium ions in the gallium-containing solution is preferably 50 ppm or more.
The gallium-ion-adsorbed gallium-modified resin after adsorbing gallium ions is preferably backwashed by using dilute hydrochloric acid or dilute sulfuric acid, so that the gallium ions can be collected; the mass concentration of the dilute hydrochloric acid or the dilute sulfuric acid is preferably 5% -10%, more preferably 6% -8%.
In order to further illustrate the present invention, the following describes in detail a gallium-adsorbing modified silica gel resin, a preparation method and application thereof according to examples.
The reagents used in the examples below are all commercially available; the reagent 3-aminopropyl trimethoxysilane, 13822-56-5, ron reagent used in the examples; xylene, 1330-20-7 tetan; azobisisobutyronitrile, 78-67-1 tetan; column chromatography silica gel, qingdao ocean silica gel; methanol 67-56-1 tetan.
Example 1
Pretreating silica gel, namely placing 100 g column chromatography silica gel (100 meshes) in 200 ml water, stirring and washing 1h, filtering, spreading the silica gel in a glass vessel, placing in a drying oven, drying for 8 hours at 90-100 ℃, taking out for later use, taking 230 ml xylene out of a dosage cylinder, pouring the 230 ml xylene into a 1L three-neck flask, pouring the 100 g pretreated silica gel into the three-neck flask, placing the three-neck flask into an oil bath, heating to 50 ℃, connecting a water separator, connecting a reflux condenser, starting stirring, weighing 26.7 g aminopropyl trimethoxysilane, pouring into a constant pressure funnel, slowly dripping into the three-neck flask, dripping 0.3 g tertiary butyl hydroperoxide after dripping, heating to 90 ℃, distilling colorless solution in the water separator until no distillate is heated to 100 ℃, preserving heat, stirring 4 h, cooling, washing with methanol and water sequentially, washing, placing the silica gel on glass, placing into the drying oven, and drying to constant weight, thus obtaining a modified silica gel product.
The pretreated silica gel and the modified silica gel resin are analyzed by utilizing infrared spectrum, and the obtained infrared spectrum is shown in figure 2, wherein the upper graph is the pretreated silica gel, and the lower graph is the modified silica gel resin.
Example 2
Taking 1.5 g of the modified silica gel resin synthesized in example 1, placing the modified silica gel resin in a dry beaker, pouring 50 ml of gallium phosphate wastewater (pH 1.5~2.5;Fe:1688ppm,Ga:238ppm,Zn:740ppm,Al:417ppm, si:97 ppm) generated in a certain recovery workshop into the beaker, stirring the wastewater with a mechanical stirrer at a rotating speed of 200 r/min, stirring the wastewater for 4 hours, carrying out suction filtration on the silica gel and the solution, washing the silica gel with a small amount of water, transferring the filtrate and the washing water into a 250 ml volumetric flask, sampling to measure the gallium concentration to be <1 ppm, backwashing the modified silica gel with 6-8% diluted hydrochloric acid 10 ml, and analyzing the components of the obtained backwashing liquid to obtain the backwashing liquid, wherein the backwashing liquid contains Fe:21 ppm, ga:867 ppm, zn:11 ppm, al:14ppm, si:150 ppm.
Example 3
Placing 10 g modified silica gel resin into a drying beaker, pouring gallium arsenide wastewater (pH value 6.5~7.5;As:70 ppm,Ga:70 ppm,K:60 ppm,Na:1112 ppm,P:276 ppm,S:176 ppm,Si:1442 ppm) generated in a semiconductor workshop of 100 ml into the beaker, detecting that the gallium concentration is 70 ppm, stirring by using a mechanical stirrer, stirring at a rotating speed of 200 r/min for 1 hour, suction filtering, detecting filtrate to obtain Ga concentration of <1 ppm, backwashing the modified silica gel by using 6-8% dilute hydrochloric acid 20 ml, and analyzing the components of the obtained backwashing liquid to obtain the content of As in the backwashing liquid: 5ppm, ga:310 ppm, K:10 ppm, na:20 ppm, P:15 ppm, S:10 ppm, si:150 ppm.
Example 4
Placing 100 g modified silica gel resin into a drying beaker, pouring polishing wastewater (pH 6.5~7.5;As:72 ppm,Ga:72 ppm, si:98 ppm) generated in a gallium arsenide wafer workshop of 1L into the beaker, detecting that the gallium concentration is 72 ppm and the arsenic concentration is 72 ppm, stirring by using a mechanical stirrer at the rotating speed of 200 r/min, stirring for 1 hour, layering the solution after standing, supernatant and suspension, and taking supernatant for detection to obtain As:67 ppm, ga: after washing the silica gel resin with the supernatant, draining, the resin was put into the polishing wastewater of the second cup 1L, stirred for 1h, and the delamination was also achieved, as after supernatant sampling and detection: 62 ppm, ga: after washing the silica gel resin with the supernatant, draining, the resin was put into polishing wastewater of third cup 1L, stirred for 1h, and the delamination was also achieved, as after supernatant sampling and detection: 63 ppm, ga: after washing the silica gel resin with the supernatant, draining, putting the resin into a fourth cup of 1L polishing wastewater, stirring for 1h, and likewise layering, sampling the supernatant, and detecting As:62 ppm, ga:1 ppm, after washing the silica gel resin with the supernatant, pumping out, putting the resin into the polishing wastewater of a fifth cup 1L, stirring 1h, and likewise achieving delamination, sampling and detecting As by the supernatant: 63 ppm, ga:1 ppm, after washing the silica gel resin with the supernatant, pumping out, putting the resin into the polishing wastewater of a sixth cup 1L, stirring for 1h, and likewise layering, sampling and detecting As by the supernatant: 63 ppm, ga:1 ppm, after washing the silica gel resin with the supernatant, pumping out, putting the resin into polishing wastewater of a seventh cup 1L, stirring for 1h, and likewise layering, sampling and detecting As by the supernatant: 63 ppm, ga: 3ppm, after washing the silica gel resin with supernatant, pumping out, putting the resin into polishing wastewater of eighth cup 1L, stirring for 1h, and likewise layering, sampling and detecting As by supernatant: 68 ppm, ga: 2ppm, washing the silica gel resin with supernatant, draining, adding the resin into polishing wastewater of a ninth cup 1L, stirring for 1h, layering, sampling the supernatant, and detecting As:70 ppm, ga: 3ppm, through calculation, 9 times of adsorption co-adsorption gallium 648 mg, and 100 g modified silica gel can be used for preliminary calculation, the saturated adsorption effect of the product reaches 6 g/L, and the adsorption level of the commercial product is reached.
Comparative example 1
Pouring 230 ml dimethylbenzene into a 1L three-neck flask by using a measuring cylinder, pouring 100 g pretreated (pretreatment: washing silica gel by using water and drying) silica gel into the three-neck flask, placing the three-neck flask into an oil bath, heating to 50 ℃, connecting a water knockout vessel, connecting a reflux condenser pipe, starting stirring, weighing 26.7 g trimercapto-propyl trimethoxysilane, pouring into a constant pressure funnel, slowly dripping into the three-neck flask, dripping 0.3 g tertiary butyl hydroperoxide, heating to 90 ℃, cooling, carrying out suction filtration, washing by using methanol and water in sequence, spreading the silica gel on a glass dish, placing the silica gel into a drying box, drying to constant weight at 90-100 ℃, and testing the obtained modified silica gel by using gallium phosphate wastewater (pH value 1.5-2.5; fe:168 ppm, ga:238ppm, zn:740ppm, al:417ppm, si:97 ppm) with the components of Fe:1679ppm, ga:230ppm, zn:737ppm, al:412ppm, si:100ppm, indicating that the modified silica gel obtained in comparative example 1 has little absorption effect on gallium.
Comparative example 2
Pouring 230 ml dimethylbenzene into a 1L three-neck flask by using a measuring cylinder, pouring 100 g pretreated (pretreatment: washing silica gel with water and drying) silica gel into the three-neck flask, placing the three-neck flask into an oil bath, heating to 50 ℃, connecting a water knockout vessel, connecting a reflux condenser pipe, starting stirring, weighing 26.7 g vinyltrimethoxysilane, pouring into a constant pressure funnel, slowly dripping into the three-neck flask, dripping 0.3 g tertiary butyl hydroperoxide, heating to 90 ℃, cooling to perform suction filtration, washing with methanol and water in sequence, spreading the silica gel on a glass dish, placing the silica gel into a drying oven at 90-100 ℃ and drying to constant weight, and testing the obtained modified silica gel by using gallium phosphate wastewater (pH value is 1.5-2.5; fe:168 ppm, ga:238ppm, zn:740ppm, al:417ppm, si:97 ppm) to obtain Fe in the adsorbed wastewater: 1675ppm, ga:232ppm, zn: holding capacity of 730 ppm, al:416ppm, si:103ppm, indicating that the modified silica gel obtained in comparative example 2 had little adsorption effect on gallium adsorption.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The preparation method of the gallium-adsorbed modified silica gel resin is characterized by comprising the following steps of:
mixing silica gel, a solvent, a silane coupling agent and a catalyst, and then heating for reaction to obtain gallium-adsorbed modified silica gel resin;
firstly mixing silica gel with a solvent, then heating for pretreatment, and then adding a silane coupling agent and a catalyst;
the solvent is selected from one or more of dimethylbenzene, water, methanol, ethanol, methylbenzene and glycol; the silane coupling agent is selected from aminopropyl trimethoxy silane; the catalyst is selected from one or more of azodiisobutyronitrile, benzoyl peroxide and tert-butyl peroxide;
the mass of the silane coupling agent is 20% -40% of that of silica gel; the mass of the catalyst is 0.1% -1% of that of silica gel.
2. The method according to claim 1, wherein the temperature of the heating pretreatment is 40 ℃ to 60 ℃; the heating pretreatment time is 30-90 min.
3. The method according to claim 1, wherein the temperature of the heating reaction is 90 ℃ to 110 ℃; the heating reaction time is 1-4 h.
4. The preparation method according to claim 1, wherein the silica gel is mixed with a solvent in a container provided with a water separator and a condenser tube; the silane coupling agent and the catalyst are sequentially added into the system after the heating pretreatment in a dropwise manner; after the catalyst is added dropwise, the temperature is raised to 80-90 ℃ until the distillate amount is not increased, and the reaction is heated.
5. The gallium-adsorbed modified silica gel resin prepared by the preparation method of any one of claims 1 to 4, which is characterized in that silica gel is used as a substrate; the silica gel is coupled with a silane coupling agent.
6. The use of the gallium-adsorbing modified silica gel resin prepared by the preparation method of any one of claims 1-4 for adsorbing gallium ions in a gallium-containing solution.
7. The use according to claim 6, wherein the gallium-containing solution is derived from hydrometallurgy.
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