CN114849667A - Modified silica gel resin for adsorbing gallium, preparation method and application thereof - Google Patents
Modified silica gel resin for adsorbing gallium, preparation method and application thereof Download PDFInfo
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- CN114849667A CN114849667A CN202210502984.8A CN202210502984A CN114849667A CN 114849667 A CN114849667 A CN 114849667A CN 202210502984 A CN202210502984 A CN 202210502984A CN 114849667 A CN114849667 A CN 114849667A
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- silica gel
- gallium
- adsorbing
- coupling agent
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 87
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000011347 resin Substances 0.000 title claims abstract description 62
- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000741 silica gel Substances 0.000 claims abstract description 62
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 62
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- -1 gallium ions Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009854 hydrometallurgy Methods 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 238000009997 thermal pre-treatment Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000005498 polishing Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000013595 supernatant sample Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000011001 backwashing Methods 0.000 description 4
- 229910001570 bauxite Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229910000154 gallium phosphate Inorganic materials 0.000 description 3
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229940007392 tylan Drugs 0.000 description 2
- WBPYTXDJUQJLPQ-VMXQISHHSA-N tylosin Chemical compound O([C@@H]1[C@@H](C)O[C@H]([C@@H]([C@H]1N(C)C)O)O[C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)CO[C@H]1[C@@H]([C@H](OC)[C@H](O)[C@@H](C)O1)OC)CC)[C@H]1C[C@@](C)(O)[C@@H](O)[C@H](C)O1 WBPYTXDJUQJLPQ-VMXQISHHSA-N 0.000 description 2
- 235000019375 tylosin Nutrition 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 208000022345 tetraamelia syndrome Diseases 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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 modified silica gel resin for adsorbing gallium, which comprises the following steps: mixing silica gel, a solvent, a silane coupling agent and a catalyst, and heating for reaction to obtain the gallium-adsorbing modified silica gel resin. Compared with the prior art, the invention takes the silica gel as the substrate raw material, has higher hardness, stable performance, rich microporous 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
Technical Field
The invention belongs to the technical field of adsorption resin, and particularly relates to modified silica gel resin for adsorbing gallium, and a preparation method and application thereof.
Background
Gallium is one of the rare earth metals, and the content of gallium in the earth crust is 0.0015%. Gallium in nature is distributed relatively dispersedly, mostly exists in associated ores, mainly exists in bauxite, and exists in small amount in tin ore, tungsten ore and lead-zinc ore. According to the data published by the American geological survey 2015, the reserves of gallium in global bauxite exceed 100 million tons, and a certain reserve of gallium resources exist in zinc ore. Although the amount of gallium resources contained in bauxite and zinc ore is relatively large, the amount of gallium resources that can be developed and recovered from bauxite and zinc ore is small at present.
China is one of the gallium major producing countries in the world, and according to incomplete statistics, the yield of gallium in China in 2012 is 270 tons, the capacity is about 330 tons, and the yield accounts for about 80% of the global yield. At present, the gallium productivity in China is seriously surplus, the gallium productivity in China is about 400-450 tons in 2013, and the gallium productivity in 2014 is about 500 tons. China is also a main gallium consuming country and an imported country, the global gallium consumption is about 280-300 tons in 2010, the gallium consumption is about 100 tons in China, which accounts for about one third of the total consumption, and the gallium consumption in China is increasing at a rate of 20-30% per year. At present, the consumption fields of metal gallium in China comprise semiconductors, photoelectric materials, solar cells, alloys, medical instruments, magnetic materials and the like, wherein the semiconductor industry becomes the largest consumption field of gallium and accounts for about 80% of the total consumption.
At present, metal gallium with purity of 4N-5N is mainly used in the fields of solar cells, gas sensors, rare earth permanent magnet materials and the like, and metal gallium with purity of 6N or more is mainly used for manufacturing compound semiconductors such as gallium arsenide, gallium nitride and the like. At present, the compound semiconductor is the largest consumption field of metal gallium in China, and accounts for about 65% of consumption. According to the measurement and calculation of the final application, about 76% of metal gallium in China is used in the fields of LEDs and wireless communication.
With the rapid development of the gallium industry, particularly the semiconductor and solar cell industry, and the promotion of the government of China on the development and planning of the LED industry, the consumption of gallium in China still keeps a great growth situation. In addition, because the recovery capacity of gallium metal in China is low, the demand of gallium metal is supported by native gallium, and the demand of the national market for the native gallium is greatly increased. Due to the specific attribute of gallium resources, downstream terminals of the industrial chain are widely applied to strategic industries or fields such as national defense, wireless communication, new materials, new energy, medical treatment and the like, are taken as one of strategic reserve minerals in China, and are listed in strategic or key mineral catalogues in developed areas such as European Union, America, Japan and the like. With the rapid development of semiconductors, solar cells and wireless communication industries and the expansion of gallium application fields and the influence of new crown epidemic situations on global social economy, the demand for gallium is expected to increase greatly in the future. The recovery of gallium ions is becoming increasingly important as global demand for gallium resources is predicted to reach 720 tons in 2025, and the demand for gallium resources in China also reaches 370 tons.
The gallium-adsorbing resin in the market is mainly a resin produced by Xian blue Xiao corporation, for example, the resin LSC-600 is mainly used for adsorbing gallium in alkaline solution, the resin LSC-900 is mainly used for adsorbing gallium in acid solution, the LSC-760 is mainly used for extracting gallium from Bayer mother liquor with high vanadium content, and the like, and the products occupy a large market of gallium resins at home and abroad. The lead company is a relatively large domestic scattered metal company, secondary resource recovery of scattered metals accounts for a relatively large proportion in the company industrial chain, in recent years, gallium is a relatively popular product raw material in scattered metals, the price of gallium is increased year by year in the field of semiconductors and solar thin films as day, if the gallium resource can be efficiently recovered, the development of the company is of great significance, even if the company is dedicated to the research and development of scattered metal recovery for many years, partial gallium-containing waste materials still exist and are difficult to treat due to high cost, the gallium resource is lost, gallium in semiconductor gallium arsenide polishing waste water cannot be separated out, the resource loss is caused, the LSC-600 resin produced by blue-day company is used for treatment, the resin is swelled, broken and discolored after being soaked in the waste water, and the cost of blue-day resin is high, in addition, the recovery of gallium from the polishing wastewater cannot be solved in terms of effect, and new gallium resin is required for recovery.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a gallium-adsorbing modified silica gel resin with good adsorption efficiency and stability, and a preparation method and an application thereof.
The invention provides a preparation method of modified silica gel resin for adsorbing gallium, which comprises the following steps:
mixing silica gel, a solvent, a silane coupling agent and a catalyst, and heating for reaction to obtain the gallium-adsorbing 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 and the solvent are mixed in a container provided with a water separator and a condensation pipe; the silane coupling agent and the catalyst are sequentially added into the system after heating pretreatment in a dropwise manner; after the catalyst is added, the temperature is raised to 80-90 ℃ until the amount of distillate is not increased any more, and the heating reaction is carried out.
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, azobisisobutyronitrile, benzoyl peroxide and tert-butyl peroxide.
Preferably, the mass of the silane coupling agent is 20-40% of that of the silica gel; the mass of the catalyst is 0.1-1% of that of the 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; and a silane coupling agent is coupled on the silica gel.
The invention also provides application of the modified silica gel resin for adsorbing gallium 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 modified silica gel resin for adsorbing gallium, 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-adsorption modified silica gel resin. Compared with the prior art, the invention takes the silica gel as the substrate raw material, has higher hardness, stable performance, rich microporous 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 showing the mechanism of coupling silica gel with the silane coupling agent of the present invention;
FIG. 2 is an infrared spectrum of the pretreated silica gel and modified silica gel resin in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of modified silica gel resin for adsorbing gallium, which comprises the following steps: mixing silica gel, a solvent, a silane coupling agent and a catalyst, and heating for reaction to obtain the gallium-adsorbing modified silica gel resin.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
In the present invention, it is preferable that the silica gel is mixed with the solvent and then heated for pretreatment; the silica gel and the solvent are preferably mixed in a container provided with a water separator and a condensation pipe; 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 further preferably 60-70 min; the drying temperature is preferably 90-100 ℃; the drying time is preferably 6-10 hours, and more preferably 8-9 hours. The solvent is a solvent well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of xylene, water, methanol, ethanol, toluene, o-xylene, m-xylene, p-xylene, and ethylene glycol are preferable; the ratio of silica gel to solvent is preferably 100 g: (150-500) mL, more preferably 100 g: (150-400) mL, 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 further 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 has a general formula of RSiX 3 Wherein R represents a reactive functional group having affinity or reactivity with a polymer molecule, such as oxy, mercapto, vinyl, epoxy, amide, aminopropyl, etc., and X represents a hydrolyzable alkoxy group, such as halogen, alkoxy, acyloxy, etc.; in the present invention, the silane coupling agent is preferably aminopropyltrimethoxysilane; the mass of the silane coupling agent is 20-40% of that of the 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, azobisisobutyronitrile, 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 a system after heating pretreatment in a dropwise manner; the silane coupling agent and the catalyst are preferably added within 0.5-2 h, more preferably within 0.8-1.5 h, and even more preferably within 1-1.2 h.
After the catalyst is dripped, preferably heating to 80-90 ℃ until the amount of distillate is not increased any more, and heating for reaction; the heating reaction temperature is preferably 90-110 ℃, more preferably 95-105 ℃, and further preferably 100 ℃; the heating reaction time is preferably 1-4 h, more preferably 2-4 h, and still more preferably 3-4 h.
After heating reaction, preferably washing and drying to obtain modified silica gel resin for absorbing gallium; the washing is preferably carried out by sequentially adopting an alcohol solvent and water; the above-mentionedThe alcohol solvent is preferably methanol; the drying temperature is preferably 90-100 ℃; the drying is preferably to constant weight. The silane coupling agent is coupled to the surface of the silica gel through a heating reaction, and during coupling, the silane coupling agent RSiX is firstly used 3 The X radical water in the inorganic powder forms silanol which then reacts with hydroxyl on the surface of inorganic powder silica gel particles to form hydrogen bonds and is condensed into-SiO-M covalent bonds (M represents the surface of the inorganic powder particles). Meanwhile, silanol of each molecule of silane is mutually associated and oligomerized to form a film with a net structure to cover the surfaces of the powder particles, so that the surfaces of the inorganic powder are organized. Taking the 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, stable performance, abundant 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, and can also use acid to backwash gallium, thereby prolonging 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; and a silane coupling agent is coupled on the silica gel. The silica gel and the silane coupling agent are the same as described above, and are not described herein again. The saturated adsorption capacity of the modified silica gel resin for adsorbing gallium to 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 modified silica gel resin for adsorbing gallium prepared by the preparation method in adsorbing gallium ions in a gallium-containing solution.
Preferably, the gallium-containing solution is a neutral or weakly acidic 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 50ppm or more.
Backwashing the gallium-adsorbing modified resin after adsorbing gallium ions by preferably using dilute hydrochloric acid or dilute sulfuric acid so as to collect gallium ions; the mass concentration of the dilute hydrochloric acid or dilute sulfuric acid is preferably 5 to 10%, and more preferably 6 to 8%.
In order to further illustrate the present invention, the following describes in detail a modified silica gel resin for adsorbing gallium, a preparation method and an application thereof provided by the present invention with reference to examples.
The reagents used in the following examples are all commercially available; the reagent used in the examples 3-aminopropyltrimethoxysilane, 13822-56-5, Ron's reagent; xylene, 1330-20-7 tetam; azobisisobutyronitrile, 78-67-1 tylan; column chromatography silica gel, Qingdao sea silica gel; methanol 67-56-1 tylan.
Example 1
Pretreating silica gel, putting 100g of column chromatography silica gel (100 meshes) into 200ml of water, stirring and washing for 1h, filtering, spreading the silica gel in a glass vessel, putting the glass vessel into a drying box, drying for 8h at 90-100 ℃, taking out for later use, pouring 230ml of dimethylbenzene into a 1L three-neck flask by using a measuring cylinder, pouring 100g of pretreated silica gel into the three-neck flask, putting the three-neck flask into an oil bath, heating to 50 ℃, connecting a water separator, connecting a reflux condenser tube, starting stirring, weighing 26.7g of aminopropyltrimethoxysilane, pouring into a constant pressure funnel, slowly dripping into the three-neck flask, dripping 0.3g of tert-butyl hydroperoxide, heating to 90 ℃, distilling off colorless solution in the water separator until no distillate is heated to 100 ℃, preserving heat and stirring for 4h, cooling, performing suction filtration, sequentially using methanol and water for washing, spreading the silica gel on the glass vessel after washing, and (3) drying the mixture in a drying oven at 90-100 ℃ to constant weight to obtain the modified silica gel resin product.
The pretreated silica gel and the modified silica gel resin are analyzed by infrared spectroscopy, and an infrared spectrum of the pretreated silica gel and the modified silica gel resin is obtained as shown in figure 2, wherein the upper figure is the pretreated silica gel, and the lower figure is the modified silica gel resin.
Example 2
Taking 1.5g of the modified silica gel resin synthesized in example 1, placing the modified silica gel resin in a dry beaker, pouring 50ml of gallium phosphate wastewater (pH value is 1.5-2.5; Fe: 1688ppm, Ga: 238ppm, Zn: 740ppm, Al: 417ppm, Si: 97ppm) generated in a certain recovery workshop into the beaker, stirring the wastewater by using a mechanical stirrer at the rotating speed of 200r/min for 4 hours, performing suction filtration on the silica gel and the solution, washing the silica gel by using a small amount of water, transferring all filtrate and washing water into a 250ml volumetric flask, sampling to obtain the gallium concentration of less than 1ppm, performing backwashing on the modified silica gel by using 10ml of 6-8% diluted hydrochloric acid, and analyzing the components of the obtained backwashing liquid to obtain a backwashing liquid containing Fe: 21ppm, Ga: 867ppm, Zn: 11ppm, Al: 14ppm, Si: 150 ppm.
Example 3
10g of modified silica gel resin is placed in a drying beaker, 100ml of gallium arsenide wastewater (pH value is 6.5-7.5; As: 70ppm, Ga: 70ppm, K: 60ppm, Na: 1112ppm, P: 276ppm, S: 176ppm, Si: 1442ppm) generated in a certain semiconductor workshop is poured into the beaker, and after detection, the gallium concentration is 70ppm, the modified silica gel is stirred by using a mechanical stirrer, the rotating speed is 200r/min, the stirring is carried out for 1 hour, the filtration is carried out, the filtrate is detected, the Ga concentration is less than 1ppm, the modified silica gel is backwashed by using 20ml of dilute hydrochloric acid with the concentration of 6-8%, and the component of the obtained backwash liquid is analyzed, so that the backwash liquid contains As: 5ppm, Ga: 310ppm, K: 10ppm, Na: 20ppm, P: 15ppm, S: 10ppm, Si: 150 ppm.
Example 4
Placing 100g of modified silica gel resin into a dry beaker, pouring into the beaker, detecting that 1L of polishing wastewater (pH value is 6.5-7.5; As: 72ppm, Ga: 72ppm and Si: 98ppm) generated in a gallium arsenide wafer workshop has the gallium concentration of 72ppm and the arsenic concentration of 72ppm, stirring by using a mechanical stirrer at the rotating speed of 200r/min for 1 hour, standing, layering the solution, taking supernatant, and detecting to obtain As: 67ppm, Ga: <1ppm, after will rinsing silica gel resin with the supernatant, take out futilely, throw the resin into the polishing waste water of second cup 1L, stir 1h, reach the layering equally, As after the supernatant sample test: 62ppm, Ga: <1ppm, after rinsing silica gel resin with the supernatant, take out futilely, throw the resin into the polishing waste water of third cup 1L, stir 1h, reach the layering equally, As after supernatant sample test: 63ppm, Ga: <1ppm, after rinsing silica gel resin with the supernatant, take out futilely, throw the resin into the polishing waste water of fourth cup 1L, stir 1h, reach the layering equally, As after supernatant sample test: 62ppm, Ga: 1ppm, after rinsing silica gel resin with the supernatant, take out futilely, throw the resin into the polishing waste water of the fifth cup 1L, stir 1h, reach the layering equally, As after supernatant sample test: 63ppm, Ga: 1ppm, after rinsing silica gel resin with the supernatant, take out futilely, throw the resin into the polishing waste water of the sixth cup 1L, stir 1h, reach the layering equally, As after supernatant sample test: 63ppm, Ga: 1ppm, after washing silica gel resin with the supernatant, draining, throwing the resin into a seventh cup of 1L polishing wastewater, stirring for 1h, achieving layering in the same way, sampling and detecting the supernatant As: 63ppm, Ga: 3ppm, after rinsing silica gel resin with the supernatant, take out futilely, throw the resin into the polishing waste water of the eighth cup 1L, stir 1h, reach the layering equally, As after supernatant sample test: 68ppm, Ga: 2ppm, after washing the silica gel resin with the supernatant, draining, putting the resin into the 1L polishing wastewater of the ninth cup, stirring for 1h, and similarly achieving layering, As after sampling and detecting the supernatant: 70ppm, Ga: 3ppm, through calculation, 9 times of adsorption co-adsorbs 648mg of gallium, and 100g of modified silica gel is used, so that the primary calculation can be carried out, the saturated adsorption effect of the product reaches 6g/L, and the adsorption level of a commercial product is reached.
Comparative example 1
230ml of dimethylbenzene is taken by a measuring cylinder and poured into a 1L three-neck flask, 100g of pretreated (pretreatment: washing the silica gel by water and drying) silica gel is poured into the three-neck flask, the three-neck flask is put into an oil bath, the temperature is raised to 50 ℃, a water separator is connected, a reflux condenser tube is connected, stirring is started, 26.7g of trimercaptopropyl trimethoxy silane is weighed, poured into a constant pressure funnel, slowly dripped into the three-neck flask, 0.3g of tert-butyl hydroperoxide is dripped after dripping is finished, the temperature is raised to 90 ℃, cooling and suction filtration are carried out, methanol is sequentially used, washing, spreading the silica gel on a glass dish after cleaning, putting the glass dish into a drying oven to be dried at 90-100 ℃ to constant weight, and testing the obtained modified silica gel by using gallium phosphate wastewater (the pH value is 1.5-2.5; Fe: 1688ppm, Ga: 238ppm, Zn: 740ppm, Al: 417ppm and Si: 97ppm), wherein the components in the adsorbed wastewater are Fe: 1679ppm, Ga: 230ppm, Zn: 737ppm, Al: 412ppm, Si: 100ppm, indicating that the modified silica gel obtained in comparative example 1 has little effect on absorbing gallium.
Comparative example 2
Pouring 230ml of dimethylbenzene into a 1L three-mouth flask by using a measuring cylinder, pouring 100g of pretreated (pretreatment: washing silica gel with water and drying) silica gel into the three-mouth flask, putting the three-mouth flask into an oil bath, heating to 50 ℃, connecting a water separator, connecting a reflux condenser tube, stirring, weighing 26.7g of vinyltrimethoxysilane, pouring into a constant-pressure funnel, slowly dripping into the three-mouth flask, dripping 0.3g of tert-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 after cleaning, putting into a drying box, drying to constant weight at 90-100 ℃, testing the obtained modified silica gel by using gallium phosphate wastewater (pH value is 1.5-2.5; Fe: 1688ppm, Ga: 238ppm, Zn: 740ppm, Al: 417ppm and Si: 97ppm), and adsorbing the Fe in the wastewater: 1675ppm, Ga: 232ppm, Zn: 735ppm, Al: 416ppm, Si: 103ppm, indicating that the modified silica gel obtained in comparative example 2 has almost no adsorption effect on gallium.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of modified silica gel resin for adsorbing gallium is characterized by comprising the following steps:
mixing silica gel, a solvent, a silane coupling agent and a catalyst, and heating for reaction to obtain the gallium-adsorbing modified silica gel resin.
2. The method according to claim 1, wherein the silica gel is mixed with a solvent and then heated for pretreatment, and then the silane coupling agent and the catalyst are added.
3. The method of claim 2, wherein the temperature of the thermal pretreatment is 40 ℃ to 60 ℃; the heating pretreatment time is 30-90 min.
4. The preparation method according to claim 2, wherein the temperature of the heating reaction is 90 ℃ to 110 ℃; the heating reaction time is 1-4 h.
5. The production method according to claim 2, wherein the silica gel is mixed with the solvent in a vessel provided with a water separator and a condensation pipe; the silane coupling agent and the catalyst are sequentially added into the system after heating pretreatment in a dropwise manner; after the catalyst is added, the temperature is raised to 80-90 ℃ until the amount of distillate is not increased any more, and the heating reaction is carried out.
6. The method according to claim 1, wherein 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, azobisisobutyronitrile, benzoyl peroxide and tert-butyl peroxide.
7. The preparation method according to claim 1, wherein 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 the silica gel.
8. The gallium-adsorbing modified silica gel resin prepared by the preparation method of any one of claims 1 to 7, which is characterized in that silica gel is used as a substrate; and a silane coupling agent is coupled on the silica gel.
9. The use of the modified silica gel resin adsorbing gallium prepared by the preparation method of any one of claims 1 to 7 for adsorbing gallium ions in a gallium-containing solution.
10. Use according to claim 9, wherein the gallium-containing solution originates from hydrometallurgy.
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| CN115558153A (en) * | 2022-09-28 | 2023-01-03 | 苏州泰吉诺新材料科技有限公司 | Liquid metal chemical anti-overflow foam and preparation method thereof |
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