CN117361566A - Preparation method of high-purity ammonium fluoride aqueous solution - Google Patents
Preparation method of high-purity ammonium fluoride aqueous solution Download PDFInfo
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- CN117361566A CN117361566A CN202311412488.4A CN202311412488A CN117361566A CN 117361566 A CN117361566 A CN 117361566A CN 202311412488 A CN202311412488 A CN 202311412488A CN 117361566 A CN117361566 A CN 117361566A
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- ammonium fluoride
- exchange resin
- aqueous solution
- purity
- anion exchange
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 29
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 27
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 239000012498 ultrapure water Substances 0.000 claims abstract description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000012982 microporous membrane Substances 0.000 claims abstract description 9
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 6
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 4
- 238000002161 passivation Methods 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003456 ion exchange resin Substances 0.000 abstract 1
- 229920003303 ion-exchange polymer Polymers 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/162—Ammonium fluoride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a high-purity ammonium fluoride aqueous solution, and belongs to the technical field of wet electronic chemicals. Dissolving industrial ammonium fluoride in an organic solvent, recrystallizing, drying, dissolving in high-purity water, sequentially passing through cation exchange resin and anion exchange resin to remove metal salt impurities, and then filtering by a three-stage microporous membrane to obtain a high-purity ammonium fluoride aqueous solution, wherein the cation exchange resin and the anion exchange resin are respectively soaked in 1-5wt% hydrofluoric acid and 1-5wt% sodium fluoride aqueous solution for 12-24 hours in advance for fluorination and passivation. The invention takes cheap industrial ammonium fluoride as a raw material, uses an organic solvent to recrystallize and remove most of impurities, and uses ion exchange resin to deeply remove impurities, so that the concentration of metal ions of single impurities is reduced to below 1ppb, the concentration of anions of single impurities is reduced to below 3ppm, and the UP-S level is achieved; the organic solvent and the resin can be purified or regenerated for recycling, and the overall cost is low.
Description
Technical Field
The invention belongs to the technical field of wet electronic chemicals, and particularly relates to a preparation method of a high-purity ammonium fluoride aqueous solution.
Background
With the gradual rise of the semiconductor manufacturing industry in China, the demand of the buffer oxidation etchant in China is increased year by year. The buffer oxidation etchant is mainly used in the microelectronics industry, can be used as a cleaning agent and an etchant, is commonly used for etching an oxide layer of a photoresist-free shield in the semiconductor industry, and mainly comprises hydrofluoric acid and ammonium fluoride, and is generally prepared from electronic-grade hydrofluoric acid, electronic-grade ammonium fluoride aqueous solution and additives.
The patent CN102627298A discloses a method for producing high-purity ammonium fluoride etching liquid by a liquid phase method, which comprises the steps of carrying out neutralization reaction on a high-purity HF aqueous solution with the mass percentage concentration of 49-70% and a high-purity ammonia water solution with the mass percentage concentration of 27-33% according to the mass ratio of 1:1.3-2.3, controlling the reaction temperature to be 10-50 ℃, ending the reaction when the PH value of the reaction liquid is 6-7, and filtering to remove particle impurities with the particle size of more than 0.2 microns, thereby obtaining the high-purity electronic grade ammonium fluoride etching liquid with the mass percentage concentration of 40+/-0.2%. The method has simple and easy process, but the raw materials are all high-purity materials, the price is high, and the overall cost is high.
In another patent CN103112872B, CN102557076B, industrial ammonia water is evaporated, filtered to remove impurities, and then absorbed by high-purity hydrofluoric acid, and the ammonia water is filtered and removed by molecular sieve or active carbon, so that the ammonia water is difficult to regenerate and reuse after the adsorption saturation of the filtering material, and the cost is high.
Patent CN115010098B discloses a method for efficiently preparing ultra-clean high-purity sulfuric acid, which uses industrial sodium bisulfate as a raw material, and combines the preparation of the ultra-clean high-purity sulfuric acid by sequentially exchanging complexing, recrystallizing, cation exchange resin and anion exchange resin, dehydrating, filtering by a superheated steam microporous membrane, vacuum decompression drying, decompression thermal decomposition and sulfur trioxide absorption. The sodium bisulfate is common acid salt, has no special requirement on exchange resin, has obvious difference with ammonium fluoride with stronger corrosiveness in the application, and does not form technical teaching.
Disclosure of Invention
In order to overcome the defect of higher cost, the invention adopts the following technical scheme:
the invention provides a preparation method of a high-purity ammonium fluoride aqueous solution, which specifically comprises the following steps: dissolving industrial ammonium fluoride in an organic solvent, recrystallizing, drying, dissolving in high-purity water, sequentially passing through cation exchange resin and anion exchange resin to remove metal salt impurities, and filtering by a three-stage microporous membrane to obtain a high-purity ammonium fluoride aqueous solution.
The organic solvent is selected from one of methanol or acetonitrile, and the purity is more than 99.9%.
The ammonium fluoride is dissolved in an organic solvent for recrystallization, namely, the ammonium fluoride is dissolved in the organic solvent to prepare a saturated solution, the saturated solution is filtered, then 50-80% of the solvent is evaporated at 60-85 ℃, the temperature is reduced to 0-10 ℃, the ammonium fluoride is crystallized and separated out, and then the saturated solution is dissolved in the organic solvent for repeated filtration, evaporation, temperature reduction and crystallization. The drying is carried out under vacuum of-60 to-90 kPa and at a temperature of 40-70 ℃ for 4-8 hours.
Further, the organic solvent after recrystallization is reused after distillation and impurity removal.
The cation exchange resin takes porous crosslinked polystyrene as a framework, is grafted with sulfonic acid groups or iminodiacetic acid groups, preferably T-52H, T-62MP and CH-90, and can be directly purchased, wherein active groups of T-52H and T-62MP are sulfonic acid groups, and active groups of CH-90 are iminodiacetic acid groups.
The anion exchange resin takes porous crosslinked polystyrene as a framework, is grafted with quaternary amino groups, preferably A-62MP, A-107 and SL890, and can be directly purchased from commercial sources.
The aqueous ammonium fluoride solution is preferably not passed through the cationic resin and the anionic resin too rapidly, preferably in the range of 0.2 to 1.0BV/h. The resin can be regenerated after failure and then reused. The regeneration method of the cation exchange resin comprises the steps of soaking the cation exchange resin in 1-10wt% hydrochloric acid for 30-60min at the flow rate of 2-4BV/h, soaking the cation exchange resin in ultrapure water for 2-6h, wherein the content of chloride ion impurities in the soaked water is lower than 0.1ppm. The regeneration method of the anion exchange resin comprises the steps of immersing and washing the anion exchange resin for 30-60min by using 0.5-6wt% of sodium hydroxide aqueous solution, immersing and washing the anion exchange resin for 2-6h by using ultrapure water, wherein the sodium ion impurity content in the immersed and washed water is lower than 0.1ppb.
Preferably, the cation exchange resin is pre-soaked with 1-5wt% hydrofluoric acid for 12-24 hours for fluorination and passivation, and the anion exchange resin is pre-soaked with 1-5wt% sodium fluoride aqueous solution for 12-24 hours for fluorination and passivation, so as to enhance the corrosion resistance of the resin and maintain the ion exchange capability in corrosive ammonium fluoride solution.
The three-stage microporous membrane filtration is carried out by sequentially filtering through three-stage microporous membranes with pore diameters of 0.5 mu m, 0.2 mu m and 0.05 mu m under the pressure of 0.02-0.15MPa, and removing particulate impurities by using PFA and/or PTFE as filter membrane materials to obtain the high-purity ammonium fluoride aqueous solution. Through detection, the particle diameter is not less than 0.5 mu m and not more than 10pcs/ml, and meets the UP-S level requirement (GB/T30901-2014).
Common impurities in industrial ammonium fluoride include sulfate, phosphate, fluorosilicate and chloride, wherein some impurities are removed when the impurities are insoluble in an organic solvent and filtered, some impurities are dissolved in the organic solvent but have low concentration, the impurities are not separated out during crystallization, the organic solvent is recrystallized twice to remove most of the impurities, and the residual trace impurities are further removed by resin exchange twice.
The beneficial effects of the invention are as follows: the invention takes cheap industrial ammonium fluoride as a raw material, uses an organic solvent to recrystallize and remove most of impurities, and uses cation exchange resin and anion exchange resin to deeply remove impurities, so that the concentration of metal ions of single impurities is reduced to below 1ppb, the concentration of anions of single impurities is reduced to below 3ppm, and the UP-S level is achieved; the organic solvent and the resin can be purified or regenerated for recycling, and the overall cost is low.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific examples, wherein the resins used in the examples are purchased from Korea (Beijing) technology Co., ltd and Tianjin duplex technology Co., ltd, and the resins are immersed in ultrapure water until the concentration of single metal ions is below 0.1ppb and the concentration of single anions is below 0.3ppm before use.
Example 1
Dissolving industrial ammonium fluoride in methanol until saturation, filtering, evaporating 80% of solvent at 70 ℃, cooling to 10 ℃, standing for crystallization, dissolving in methanol, repeating the above operation, drying the obtained ammonium fluoride crystal for 8 hours at the temperature of 40 ℃ under vacuum of-90 kPa, dissolving in high-purity water to obtain 40.1wt% ammonium fluoride solution, sequentially passing through T-52H cation exchange resin and A-62MP anion exchange resin, filtering at the flow rate of 0.2BV/H, connecting three-stage microporous membrane after anion exchange resin, and obtaining high-purity ammonium fluoride aqueous solution, wherein the pore diameters are respectively 0.5um, 0.2um and 0.05um, and the pressures are respectively 0.02MPa, 0.08MPa and 0.14 MPa.
The T-52H cation exchange resin used was previously soaked with 1% hydrofluoric acid for 24 hours, and the A-62MP anion exchange resin used was previously soaked with 1% sodium fluoride aqueous solution for 24 hours.
Example 2
Dissolving industrial ammonium fluoride in methanol until saturation, filtering, evaporating 50% of solvent at 60 ℃, cooling to 0 ℃, standing for crystallization, dissolving in methanol, repeating the above operation, drying the obtained ammonium fluoride crystal for 4 hours at the temperature of 58 ℃ under vacuum of-60 kPa, dissolving in high-purity water to obtain 39.9wt% ammonium fluoride solution, sequentially passing through CH-90 cation exchange resin and SL890 anion exchange resin, filtering at the flow rate of 0.6BV/h, connecting three-stage microporous membrane after anion exchange resin, and obtaining high-purity ammonium fluoride aqueous solution with the pore diameters of 0.5um, 0.2um and 0.05um respectively and the pressures of 0.03MPa, 0.10MPa and 0.15MPa respectively.
The CH-90H cation exchange resin used was previously soaked with 5% hydrofluoric acid for 12 hours, and the SL890 anion exchange resin used was previously soaked with 5% sodium fluoride aqueous solution for 12 hours.
Example 3
Dissolving industrial ammonium fluoride in acetonitrile until saturated, filtering, evaporating 70% of solvent at 85 ℃, cooling to 5 ℃, standing for crystallization, dissolving in acetonitrile, repeating the above operation, drying the obtained ammonium fluoride crystal for 6 hours under vacuum-80 kPa and at 70 ℃, then dissolving in high-purity water to obtain 39.8wt% ammonium fluoride solution, sequentially passing through T-62MP cation exchange resin and A-107 anion exchange resin, filtering at a flow rate of 1.0BV/h, connecting three-stage microporous membrane after anion exchange resin, and obtaining high-purity ammonium fluoride aqueous solution, wherein the pore diameters are respectively 0.5um, 0.2um and 0.05um, and the pressures are respectively 0.03MPa, 0.12MPa and 0.15 MPa.
The T-62MP cation exchange resin used was previously soaked with 3% hydrofluoric acid for 18 hours, and the A-107 anion exchange resin used was previously soaked with 3% sodium fluoride aqueous solution for 18 hours.
Example 4
The resin was replaced with a resin regenerated 10 times, and the other was the same as in example 1.
The regeneration method of the T-52H cation exchange resin comprises the steps of immersing and washing with 5wt% hydrochloric acid for 60min at the flow rate of 4BV/H, immersing and washing with ultrapure water for 5H, wherein the chloride ion impurity content in the immersed and washed water is 0.01ppm; the regeneration method of the A-62MP anion exchange resin comprises the steps of soaking in 3wt% sodium hydroxide aqueous solution for 60min, the flow rate is 3BV/h, soaking in ultrapure water for 6h, and the sodium ion impurity content in the soaked water is lower than 0.02ppb.
Comparative example
The resin used was not previously fluorinated and passivated, otherwise identical to example 1. The resin has corrosion and falling phenomena in the preparation process, the blockage is serious in the subsequent microporous filtration, and the impurity content is far higher than the UP-S level index.
The results of the product measurements obtained in examples 1-4 are shown in the following table:
note that: ND is undetected.
Claims (10)
1. A preparation method of high-purity ammonium fluoride aqueous solution is characterized in that industrial ammonium fluoride is dissolved in an organic solvent for recrystallization and drying, and then dissolved in high-purity water to obtain ammonium fluoride aqueous solution, and the ammonium fluoride aqueous solution sequentially passes through cation exchange resin and anion exchange resin to remove metal salt impurities; then filtering by using a three-stage microporous membrane to prepare a high-purity ammonium fluoride aqueous solution; the cation exchange resin and the anion exchange resin are soaked in 1-5wt% hydrofluoric acid and 1-5wt% sodium fluoride water solution for 12-24h respectively in advance for fluorination and passivation.
2. The method for preparing a high purity ammonium fluoride aqueous solution according to claim 1, wherein the cation exchange resin is grafted with sulfonic acid groups or iminodiacetic acid groups by using porous crosslinked polystyrene as a skeleton.
3. The method for preparing high purity ammonium fluoride aqueous solution according to claim 2, wherein the cation exchange resin is T-52H, T-62MP, CH-90.
4. The method for preparing a high-purity ammonium fluoride aqueous solution according to claim 1, wherein the anion exchange resin is grafted with quaternary amine groups by taking porous crosslinked polystyrene as a framework.
5. The method for producing a high purity aqueous ammonium fluoride solution according to claim 4, wherein the anion exchange resin is A-62MP, A-107, SL890.
6. The method for producing a high purity aqueous ammonium fluoride solution according to any one of claims 1 to 5, wherein the aqueous ammonium fluoride solution is passed through the cation exchange resin and the anion exchange resin at a rate of 0.2 to 1.0BV/h.
7. The method for preparing high purity aqueous ammonium fluoride solution according to claim 1, wherein the cation exchange resin and the anion exchange resin are regenerated after being deactivated and then reused, and the method for regenerating the cation exchange resin comprises the steps of: immersing and washing with 1-10wt% hydrochloric acid for 30-60min at a flow rate of 2-4BV/h, immersing and washing with ultrapure water for 2-6h, wherein the chloride ion impurity content in the immersed and washed water is lower than 0.1ppm; the anion exchange resin regeneration method comprises the following steps: immersing and washing with 0.5-6wt% sodium hydroxide aqueous solution for 30-60min at a flow rate of 2-4BV/h, immersing and washing with ultrapure water for 2-6h, wherein the sodium ion impurity content in the immersed and washed water is lower than 0.1ppb.
8. The method for preparing high purity ammonium fluoride aqueous solution according to claim 1, wherein the organic solvent is one selected from methanol and acetonitrile, and the purity is more than 99.9%.
9. The method for producing a high purity ammonium fluoride aqueous solution according to claim 1, wherein the recrystallization is: dissolving ammonium fluoride in an organic solvent to prepare a saturated solution, filtering, evaporating 50-80% of the solvent at 60-85 ℃, cooling to 0-10 ℃, crystallizing and separating out ammonium fluoride, dissolving in the organic solvent, and repeating the steps of filtering, evaporating, cooling and crystallizing once; the drying is carried out under vacuum of-60 to-90 kPa and at a temperature of 40-70 ℃ for 4-8 hours.
10. The method for preparing high-purity ammonium fluoride aqueous solution according to claim 1, wherein the tertiary microporous membrane filtration is carried out by sequentially passing through tertiary microporous membranes with pore diameters of 0.5 μm, 0.2 μm and 0.05 μm, the pressure is 0.02-0.15MPa, and the membrane material is PFA and/or PTFE.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311412488.4A CN117361566A (en) | 2023-10-27 | 2023-10-27 | Preparation method of high-purity ammonium fluoride aqueous solution |
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|---|---|---|---|
| CN202311412488.4A CN117361566A (en) | 2023-10-27 | 2023-10-27 | Preparation method of high-purity ammonium fluoride aqueous solution |
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| CN117361566A true CN117361566A (en) | 2024-01-09 |
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| CN202311412488.4A Pending CN117361566A (en) | 2023-10-27 | 2023-10-27 | Preparation method of high-purity ammonium fluoride aqueous solution |
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