CN116081575B - Method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as raw material - Google Patents
Method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as raw material Download PDFInfo
- Publication number
- CN116081575B CN116081575B CN202111311111.0A CN202111311111A CN116081575B CN 116081575 B CN116081575 B CN 116081575B CN 202111311111 A CN202111311111 A CN 202111311111A CN 116081575 B CN116081575 B CN 116081575B
- Authority
- CN
- China
- Prior art keywords
- alkali metal
- hydrofluoric acid
- water
- nitric acid
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 392
- 239000002699 waste material Substances 0.000 title claims abstract description 83
- 239000007788 liquid Substances 0.000 title claims abstract description 46
- 150000007522 mineralic acids Chemical class 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 60
- 239000002994 raw material Substances 0.000 title claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910001868 water Inorganic materials 0.000 claims abstract description 78
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims abstract description 44
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 38
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims abstract description 35
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000003595 mist Substances 0.000 claims abstract description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 10
- 239000012498 ultrapure water Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 66
- -1 alkali metal salt Chemical class 0.000 claims description 56
- 229910052783 alkali metal Inorganic materials 0.000 claims description 41
- 230000008020 evaporation Effects 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 150000004673 fluoride salts Chemical class 0.000 claims description 14
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 12
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 8
- 150000002823 nitrates Chemical class 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 239000000945 filler Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229920001774 Perfluoroether Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/196—Separation; Purification by distillation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
-
- 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)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
A process for preparing electronic-class inorganic acid from waste hydrofluoric acid liquid includes such steps as adding alkali metal fluoride and alkali metal nitrate to the waste hydrofluoric acid liquid containing hydrofluoric acid, water and water, breaking the azeotropic phenomenon of hydrofluoric acid and water, and rectifying to obtain hydrogen fluoride vapour. And evaporating the nitric acid and water from the mixed solution to form a nitric acid-water mixed solution, adding alkaline earth metal nitrate into the nitric acid-water mixed solution, breaking the azeotropic phenomenon of the nitric acid and water, and rectifying and separating the nitric acid. And respectively removing mist drops containing impurities from the separated hydrogen fluoride vapor and nitric acid vapor in sequence, condensing, adding ultrapure water, and concentrating to prepare the electronic grade hydrofluoric acid and the electronic grade nitric acid which meet the purity standard required by the semiconductor industry.
Description
Technical Field
The invention relates to a method for treating waste hydrofluoric acid liquid in the electronic industry, in particular to a method for preparing electronic grade inorganic acid by taking waste hydrofluoric acid liquid as a raw material.
Background
In the current processes of high-tech electronics industry such as semiconductor and solar cells, hydrofluoric acid or a mixed acid containing hydrofluoric acid and nitric acid is used in a large amount for cleaning and etching silicon and silicon compounds, resulting in a large amount of waste hydrofluoric acid solution. The waste hydrofluoric acid liquid contains hydrofluoric acid and water or hydrofluoric acid, nitric acid and water, and if the waste hydrofluoric acid liquid is not properly treated and is directly discharged, the waste hydrofluoric acid liquid can cause resource waste and serious pollution and harm to the environment. Particularly, with the rapid development of the semiconductor industry, the use of hydrofluoric acid and nitric acid has increased, which has led to the generation of a large amount of waste hydrofluoric acid solution. Therefore, how to treat waste hydrofluoric acid liquid in the electronic industry effectively, especially to treat waste hydrofluoric acid liquid containing hydrofluoric acid, nitric acid and water, is an important subject to be solved urgently at present.
However, since the hydrofluoric acid in the waste hydrofluoric acid solution is easy to form azeotropy with water, the nitric acid is easy to form azeotropy with water, and the three-component hydrofluoric acid, nitric acid and water are also easy to form azeotropy, the existing treatment methods of the waste hydrofluoric acid solution in the electronic industry, such as a sulfuric acid method, a reduced pressure evaporation method, an ion exchange method, a solvent extraction method, an electrodialysis method and the like, cannot effectively separate the hydrofluoric acid and the nitric acid from the waste hydrofluoric acid solution, and cannot regenerate the hydrofluoric acid and the nitric acid with high purity, thereby limiting the application and economic benefits of recycling the acid.
Disclosure of Invention
The inventor aims at solving the problem that the existing electronic industry waste hydrofluoric acid liquid treatment method cannot effectively separate and recycle hydrofluoric acid and nitric acid from waste hydrofluoric acid liquid containing hydrofluoric acid, nitric acid and water, and therefore, the first aim of the invention is to provide a method for preparing electronic grade inorganic acid by taking waste hydrofluoric acid liquid as a raw material, wherein the method can realize separate and recycle of hydrofluoric acid and nitric acid and prepare high-purity electronic grade hydrofluoric acid and high-purity electronic grade nitric acid.
The invention relates to a method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as a raw material, which comprises the following steps:
Step S1, adding alkali metal salt containing alkali metal fluoride and alkali metal nitrate into waste hydrofluoric acid solution containing hydrofluoric acid, nitric acid and water to destroy azeotropic phenomenon of hydrofluoric acid and water, and performing first rectification treatment in a vacuum environment to separate hydrogen fluoride vapor, wherein the distilled residue is mixed solution formed by nitric acid, water, alkali metal nitrate and alkali metal fluoride, and the dosage of the alkali metal salt ranges from 20mol% to 40mol% relative to the sum of all substances in the waste hydrofluoric acid solution and the mol% of the alkali metal salt;
Step S2, removing mist drops which contain impurities and are carried in the hydrogen fluoride vapor so as to obtain pure hydrogen fluoride vapor;
Step S3, condensing the pure hydrogen fluoride vapor and then adjusting the concentration by ultrapure water so as to prepare electronic-grade hydrofluoric acid with the concentration range of 49+/-0.5%;
Step S4, performing first evaporation treatment on the mixed solution formed by the nitric acid, water, alkali metal nitrate and alkali metal fluoride in the step S1 in a vacuum environment, thereby evaporating the nitric acid and the water from the mixed solution to form a nitric acid-water mixed solution, concentrating the alkali metal nitrate, the alkali metal fluoride and the water which is not evaporated to form an alkali metal salt concentrated solution, and introducing the alkali metal salt concentrated solution into the first rectification treatment of the step S1 for recycling;
S5, adding alkaline earth metal nitrate into the nitric acid-water mixed solution obtained in the step S4 to destroy the azeotropic phenomenon of nitric acid and water, and performing second rectification treatment in a vacuum environment to separate nitric acid vapor, wherein the distilled residue is alkaline earth metal nitrate solution formed by alkaline earth metal nitrate and water;
step S6, removing mist drops which contain impurities and are carried in the nitric acid vapor so as to obtain pure nitric acid vapor;
Step S7, condensing the pure nitric acid vapor and then adjusting the concentration by ultrapure water to obtain electronic grade nitric acid with the concentration range of 70+/-0.5 percent, and
And step S8, performing second evaporation treatment on the alkaline earth metal nitrate solution obtained in the step S5 in a vacuum environment so as to evaporate part of water in the alkaline earth metal nitrate solution and concentrate the water to form an alkaline earth metal nitrate concentrated solution, and introducing the alkaline earth metal nitrate concentrated solution into the second rectification treatment of the step S5 for recycling.
The invention relates to a method for preparing electronic grade inorganic acid by taking waste hydrofluoric acid liquid as a raw material, wherein alkali metal fluoride salt is one or more selected from lithium fluoride, potassium fluoride and cesium fluoride, alkali metal nitrate is one or more selected from lithium nitrate, potassium nitrate and cesium nitrate, and the molar ratio of the alkali metal fluoride salt to the alkali metal nitrate is in the range of 0.05-10.
In the step S1, the pressure range of the vacuum environment is 100mmHg to 500mmHg, the first rectifying treatment is carried out in a rectifying tower with a polytetrafluoroethylene lining, the temperature range of the tower bottom of the rectifying tower is 80 ℃ to 130 ℃, the temperature range of the tower top is 50 ℃ to 100 ℃ and the reflux ratio is 0.5 to 3.
In the method for preparing the electronic grade inorganic acid by using the waste hydrofluoric acid liquid as the raw material, in the step S4, the temperature range of the first evaporation treatment is 130-180 ℃.
In the method for preparing the electronic grade inorganic acid by taking the waste hydrofluoric acid solution as the raw material, in the step S5, the alkaline earth metal nitrate is one or more selected from magnesium nitrate and calcium nitrate, and the dosage of the alkaline earth metal nitrate is 40mol percent to 65mol percent relative to the sum of the alkaline earth metal nitrate, nitric acid in the nitric acid-water mixed solution and the mol of water.
In the step S5, the pressure range of the vacuum environment is 100mmHg to 500mmHg, the second rectification treatment is carried out in a rectification tower with a polytetrafluoroethylene lining, the temperature range of the tower bottom of the rectification tower is 120 ℃ to 140 ℃, the temperature range of the tower top is 70 ℃ to 100 ℃ and the reflux ratio is 0.5 to 3.
In the method for preparing the electronic grade inorganic acid by using the waste hydrofluoric acid liquid as the raw material, in the step S8, the temperature range of the second evaporation treatment is 130-180 ℃.
Further, the inventors have found that hydrofluoric acid can be efficiently separated and recovered from a waste hydrofluoric acid liquid containing hydrofluoric acid and water but no nitric acid by adding an alkali metal salt and rectifying, and therefore a second object of the present invention is to provide a method for producing an electronic grade inorganic acid from the waste hydrofluoric acid liquid as a raw material, which enables separation and recovery of hydrofluoric acid and production of high-purity electronic grade hydrofluoric acid.
The invention relates to a method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as a raw material, which comprises the following steps:
Step S1, adding alkali metal salt containing alkali metal fluoride and alkali metal nitrate into waste hydrofluoric acid solution containing hydrofluoric acid and water to break azeotropic phenomenon of hydrofluoric acid and water, and performing first rectification treatment in vacuum environment to separate hydrogen fluoride vapor, wherein the dosage range of the alkali metal salt is more than 20mol% relative to the total mol of all substances and the alkali metal salt in the waste hydrofluoric acid solution;
Step S2, removing mist drops which contain impurities and are carried in the hydrogen fluoride vapor to obtain pure hydrogen fluoride vapor, and
And S3, condensing the pure hydrogen fluoride vapor, and then adjusting the concentration by using ultrapure water, so as to prepare the electronic-grade hydrofluoric acid with the hydrofluoric acid concentration range of 49+/-0.5%.
In the method for preparing the electronic grade inorganic acid by taking the waste hydrofluoric acid solution as the raw material, in the step S1, the alkali metal fluoride salt is one or more selected from lithium fluoride, potassium fluoride and cesium fluoride, the alkali metal nitrate is one or more selected from lithium nitrate, potassium nitrate and cesium nitrate, and the molar ratio of the alkali metal fluoride salt to the alkali metal nitrate is in the range of 0.05-10.
In the step S1, the pressure range of the vacuum environment is 100mmHg to 500mmHg, the first rectifying treatment is carried out in a rectifying tower with a polytetrafluoroethylene lining, the temperature range of the tower bottom of the rectifying tower is 80 ℃ to 130 ℃, the temperature range of the tower top is 50 ℃ to 100 ℃ and the reflux ratio is 0.5 to 3.
The method has the advantages that when the waste hydrofluoric acid liquid contains hydrofluoric acid, nitric acid and water, the method can separate out hydrogen fluoride vapor through the steps S1 to S8, particularly the step S1 breaks the azeotropic phenomenon of hydrofluoric acid and water through a specific amount of alkali metal salt, so that the first rectification treatment can separate out nitric acid vapor through the alkaline earth metal nitrate, the step S5 breaks the azeotropic phenomenon of nitric acid and water in the nitric acid-water mixed liquid, so that the second rectification treatment can separate out nitric acid vapor, and the steps S2 and S3 are matched to further prepare the hydrogen fluoride vapor into high-purity electronic grade hydrofluoric acid, and the steps S6 and S7 further prepare the nitric acid vapor into high-purity electronic grade nitric acid.
The invention has the further beneficial effects that when the waste hydrofluoric acid liquid contains hydrofluoric acid and water, the invention breaks the azeotropic phenomenon of the hydrofluoric acid and the water through the steps S1 to S3, especially through the specific dosage of the alkali metal salt in the step S1, so that the first rectification treatment can separate out the hydrogen fluoride vapor, and the hydrogen fluoride vapor is further prepared into high-purity electronic grade hydrofluoric acid by matching with the steps S2 and S3, and the high-purity electronic grade hydrofluoric acid prepared by the method is particularly suitable for the semiconductor and solar cell manufacturing process.
Detailed Description
The present invention will be described in detail below.
As used herein, the term "waste hydrofluoric acid liquid" refers generally to a waste hydrofluoric acid liquid containing hydrofluoric acid [ HF (aq) ] and water, which is produced in a process of a high-tech electronics industry such as a semiconductor industry or a photovoltaic industry. The waste hydrofluoric acid solution further comprises at least one of nitric acid [ HNO 3(aq) ] and fluosilicic acid (H 2SiF6), according to the process of producing the waste hydrofluoric acid solution. For example, waste hydrofluoric acid solutions generated during silicon wafer cleaning processes include water, about 5wt% to 35wt% hydrofluoric acid, and about 0.1wt% to 5wt% fluosilicic acid. The waste hydrofluoric acid solution generated in the polysilicon etching process comprises water, about 5wt% to 35wt% hydrofluoric acid, about 0.1wt% to 10wt% fluosilicic acid, and about 10wt% to 55wt% nitric acid.
When the waste hydrofluoric acid liquid contains hydrofluoric acid and water, the method can separate, recycle and regenerate the hydrofluoric acid from the waste hydrofluoric acid liquid to prepare high-purity electronic grade hydrofluoric acid. When the waste hydrofluoric acid liquid contains hydrofluoric acid, nitric acid and water, the method can separate and recycle the hydrofluoric acid and the nitric acid from the waste hydrofluoric acid liquid independently and regenerate the high-purity electronic grade hydrofluoric acid and the high-purity electronic grade nitric acid. Two embodiments of the method of the present invention are described in detail below.
First embodiment mode
In a first aspect of the present invention, the waste hydrofluoric acid solution includes hydrofluoric acid, nitric acid, and water. The method for preparing the electronic grade inorganic acid by taking the waste hydrofluoric acid liquid as the raw material comprises the following steps S1 to S8.
Step S1
The method comprises the steps of S1, adding alkali metal salt containing alkali metal fluoride and alkali metal nitrate into waste hydrofluoric acid liquid to destroy azeotropic phenomenon of hydrofluoric acid and water, and performing first rectification treatment in a vacuum environment to separate hydrogen fluoride vapor [ HF (g) ], wherein the distilled residue is mixed solution formed by nitric acid, water, alkali metal nitrate and alkali metal fluoride.
The alkali metal salt is capable of breaking the azeotropic phenomenon of hydrofluoric acid and water in the waste hydrofluoric acid liquid and separating hydrofluoric acid from water, and the mixed use of alkali metal fluoride and alkali metal nitrate is more effective in breaking the azeotropic phenomenon of hydrofluoric acid and water than the single use of alkali metal fluoride or single use of alkali metal nitrate, and it is also particularly noted that the azeotropic phenomenon of hydrofluoric acid and water is broken by controlling the addition ratio of the alkali metal salt, and the alkali metal salt also changes the gas-liquid balance of nitric acid and water in the waste hydrofluoric acid liquid to shift the azeotropic point, but does not break the azeotropic phenomenon of nitric acid and water, so that the first rectification treatment does not separate nitric acid vapor, and therefore hydrogen fluoride vapor can be separated alone in the step S1. More specifically, the amount of the alkali metal salt is in the range of 20mol% to 40mol% relative to the sum of all substances in the waste hydrofluoric acid solution and the mol of the alkali metal salt, the amount of the alkali metal salt is more than 20mol% and can destroy the azeotropic phenomenon of hydrofluoric acid and water, more hydrogen fluoride vapor is separated, and further the method has higher hydrofluoric acid recovery rate, and the amount of the alkali metal salt is less than 40mol% and can completely avoid the separated hydrogen fluoride vapor from entraining nitric acid vapor. In addition, the alkali metal fluoride salt and the alkali metal nitrate salt have the characteristics of high saturation solubility and difficult generation of crystallization precipitation. Preferably, the alkali metal fluoride salt is one or more selected from lithium fluoride, potassium fluoride and cesium fluoride, and the alkali metal nitrate salt is one or more selected from lithium nitrate, potassium nitrate and cesium nitrate. Preferably, the molar ratio of the alkali metal fluoride salt to the alkali metal nitrate is in the range of 0.05 to 10, so that the method has higher hydrofluoric acid recovery rate (up to more than 99 percent) and nitric acid recovery rate (up to more than 95 percent), and the prepared electronic grade hydrofluoric acid has lower nitric acid content and lower hydrofluoric acid content.
Preferably, the pressure of the vacuum environment is 100mmHg to 500mmHg, the first rectification treatment is performed in a rectification tower with a polytetrafluoroethylene lining, the temperature of the tower bottom of the rectification tower is 80 ℃ to 130 ℃, the temperature of the tower top is 50 ℃ to 100 ℃, and the reflux ratio is 0.5 to 3. Wherein the reflux ratio is in the range of 0.5 to 3, and hydrogen fluoride vapor with higher purity can be separated. It is worth mentioning that by adding the alkali metal salt, the first rectification treatment can be performed in a low tower bottom temperature range and a low tower top temperature range, so that the effects of saving energy and reducing corrosion of the rectification tower are achieved.
If the waste hydrofluoric acid solution further contains fluosilicic acid, the step S1 further comprises adding sodium hydroxide to the waste hydrofluoric acid solution to convert fluosilicic acid into sodium fluosilicate before adding the alkali metal salt, and removing the sodium fluosilicate through filtration treatment.
Step S2
And S2, removing mist drops which contain impurities and are entrained in the hydrogen fluoride vapor to obtain pure hydrogen fluoride vapor.
Wherein the droplets are removed by passing the hydrogen fluoride vapor through a multiple demister apparatus comprising at least two demisters connected in series, each demister comprising more than one packing unit. The packing unit is provided with a bearing frame and packing filled in the bearing frame. The material of the bearing frame is at least one selected from perfluoro alkoxy vinyl ether copolymer (PFA) and modified polytetrafluoroethylene (M-PTFE). The filler is made of a material selected from perfluoroalkoxy vinyl ether copolymer or modified polytetrafluoroethylene. The filler material of the filler units in each demister can be the same or different. The filler is in a wire mesh shape or a 3D honeycomb shape, and the specific surface area of the filler ranges from 200m 2/m3 to 2000m 2/m3.
Step S3
And S3, condensing the pure hydrogen fluoride vapor, and then adjusting the concentration by using ultrapure water, so as to prepare the electronic-grade hydrofluoric acid with the hydrofluoric acid concentration range of 49+/-0.5%.
Step S4
Step S4, performing a first evaporation treatment on the mixed solution formed by the nitric acid, the water, the alkali metal nitrate and the alkali metal fluoride in the step S1 in a vacuum environment, thereby evaporating the nitric acid and the water from the mixed solution to form a nitric acid-water mixed solution, and concentrating the alkali metal nitrate, the alkali metal fluoride and the water which is not evaporated to form an alkali metal salt concentrated solution.
Preferably, the temperature of the first evaporation treatment is in the range of 130 ℃ to 180 ℃, and the first evaporation treatment is performed in a vacuum evaporation kettle with a polytetrafluoroethylene lining. Wherein the temperature of the first evaporation treatment is in the range of 130 ℃ to 180 ℃ so that the alkali metal salt concentrated solution has high concentration, thereby being beneficial to the transportation of the alkali metal salt concentrated solution in equipment and pipelines.
In the step S4, the alkali metal salt concentrated solution is recovered and introduced into the first rectification treatment of the step S1 for recycling. More specifically, the alkali metal salt concentrated solution recovered in step S4 is used in the next step S1 to break the azeotropic phenomenon between hydrofluoric acid and water, and since a relatively large amount of alkali metal nitrate and alkali metal fluoride are used in the actual implementation of the method of the present invention, a relatively large amount of alkali metal salt concentrated solution is relatively generated, the alkali metal salt concentrated solution is recovered and recycled, so that the method not only avoids deriving the waste of the secondary process, but also is more energy-saving and environment-friendly.
Step S5
And S5, adding alkaline earth metal nitrate into the nitric acid-water mixed solution obtained in the step S4 to destroy the azeotropic phenomenon of nitric acid and water, and performing second rectification treatment in a vacuum environment to separate nitric acid vapor [ NO 3(g) ], wherein the distilled residue is alkaline earth metal nitrate solution formed by alkaline earth metal nitrate and water.
The nitric acid and water in the nitric acid-water mixed solution obtained in the step S4 still have an azeotropic point, and the azeotropic phenomenon of the nitric acid and water in the nitric acid-water mixed solution can be broken by adding the alkaline earth metal nitrate in the step S5, so that the nitric acid and water can be separated, and therefore the nitric acid vapor can be separated from the nitric acid-water mixed solution in the step S5, and the alkaline earth metal nitrate solution is formed by the water and the alkaline earth metal nitrate. Preferably, the alkaline earth metal nitrate is one or more selected from magnesium nitrate and calcium nitrate. Preferably, the amount of the alkaline earth metal nitrate ranges from 40mol% to 65mol% relative to the sum of the alkaline earth metal nitrate, the nitric acid and water in the nitric acid-water mixed solution, more nitric acid vapor can be separated from the alkaline earth metal nitrate more than 40mol% so that the method has higher nitric acid recovery rate, and the amount of the alkaline earth metal nitrate less than 65mol% can prevent the alkaline earth metal nitrate from generating crystallization due to the too high concentration of the alkaline earth metal nitrate so as to block a pipeline of equipment.
Preferably, the pressure of the vacuum environment is 100mmHg to 500mmHg, the second rectification treatment is performed in a rectification tower with a polytetrafluoroethylene lining, the temperature of the tower bottom of the rectification tower is 120 ℃ to 140 ℃, the temperature of the tower top is 70 ℃ to 100 ℃ and the reflux ratio is 0.5 to 3, wherein the reflux ratio is 0.5 to 3, and nitric acid vapor with higher purity can be separated.
Step S6
And S6, removing mist drops which contain impurities and are entrained in the nitric acid vapor so as to obtain pure nitric acid vapor. The nitric acid vapor is passed through a multiple demisting device to remove the droplets, wherein the multiple demisting device is as described above and will not be described herein.
Step S7
And S7, condensing the pure nitric acid vapor, and then adjusting the concentration by using ultrapure water to obtain the electronic grade nitric acid with the nitric acid concentration range of 70+/-0.5%.
Step S8
And S8, carrying out second evaporation treatment on the alkaline earth metal nitrate solution obtained in the step S5, and evaporating part of water in the alkaline earth metal nitrate solution to concentrate the water to form an alkaline earth metal nitrate concentrated solution. Wherein the temperature of the second evaporation treatment is in the range of 130 ℃ to 180 ℃, and the second evaporation treatment is performed in a vacuum evaporation kettle with a polytetrafluoroethylene lining.
In the step S8, the alkaline earth metal nitrate concentrated solution is recovered and introduced into the second rectification treatment of the step S5 for recycling. More specifically, the alkaline earth metal nitrate concentrated solution recovered in step S8 is used in the next step S5 to break the azeotropic phenomenon between nitric acid and water, and since a relatively large amount of alkaline earth metal nitrate is used in the actual implementation of the method of the present invention, a relatively large amount of alkaline earth metal nitrate concentrated solution is relatively produced, the alkaline earth metal nitrate concentrated solution is recovered and recycled, so that the secondary process waste is avoided, and the method is more energy-saving and environment-friendly.
Second mode of implementation
In a second embodiment of the present invention, the waste hydrofluoric acid solution contains hydrofluoric acid and water, and the method for preparing electronic grade inorganic acid by using the waste hydrofluoric acid solution as raw material of the present invention comprises the following steps S1 to S3.
Step S1
And S1, adding alkali metal salt containing alkali metal fluoride and alkali metal nitrate into the waste hydrofluoric acid liquid to destroy azeotropic phenomenon of hydrofluoric acid and water, and performing first rectification treatment in a vacuum environment to separate hydrogen fluoride vapor, wherein the distilled residue is mixed solution formed by nitric acid, water, alkali metal nitrate and alkali metal fluoride.
The alkali metal salt can destroy the azeotropic phenomenon of hydrofluoric acid and water in the waste hydrofluoric acid liquid so as to separate the hydrofluoric acid from the water, and compared with the alkali metal fluoride salt or the alkali metal nitrate which are singly used, the mixed use of the alkali metal fluoride salt and the alkali metal nitrate has better effect of destroying the azeotropic phenomenon of the hydrofluoric acid and the water. Preferably, the alkali metal fluoride salt is one or more selected from lithium fluoride, potassium fluoride and cesium fluoride, and the alkali metal nitrate salt is one or more selected from lithium nitrate, potassium nitrate and cesium nitrate. Preferably, the alkali metal salt is used in an amount in the range of 20mol% or more, relative to the sum of the moles of all the substances in the waste hydrofluoric acid solution and the alkali metal salt, to separate out more of the hydrogen fluoride vapor and thereby to give the process of the present invention a higher hydrofluoric acid recovery rate, and more preferably, the alkali metal salt is used in an amount in the range of 20mol% to 40mol%. Preferably, the molar ratio of the alkali metal fluoride to the alkali metal nitrate is in the range of 0.05 to 10, enabling the process of the invention to have a higher recovery of hydrofluoric acid.
Preferably, the pressure of the vacuum environment is 100mmHg to 500mmHg, the first rectification treatment is performed in a rectification tower with a polytetrafluoroethylene lining, the temperature of the tower bottom of the rectification tower is 80 ℃ to 130 ℃, the temperature of the tower top is 50 ℃ to 100 ℃ and the reflux ratio is 0.5 to 3, wherein the reflux ratio is 0.5 to 3, and the hydrogen fluoride vapor with higher purity can be separated.
If the waste hydrofluoric acid solution further contains fluosilicic acid, the step S1 further comprises adding sodium hydroxide to the waste hydrofluoric acid solution to convert fluosilicic acid into sodium fluosilicate before adding the alkali metal salt, and removing the sodium fluosilicate through filtration treatment.
Step S2
And S2, removing mist drops which contain impurities and are entrained in the hydrogen fluoride vapor to obtain pure hydrogen fluoride vapor.
Wherein the droplets are removed by passing the hydrogen fluoride vapor through a multiple demister apparatus comprising at least two demisters connected in series, each demister comprising more than one packing unit. The packing unit is provided with a bearing frame and packing filled in the bearing frame. The material of the bearing frame is at least one selected from perfluoro alkoxy vinyl ether copolymer (PFA) and modified polytetrafluoroethylene (M-PTFE). The filler is made of a material selected from perfluoroalkoxy vinyl ether copolymer or modified polytetrafluoroethylene. The filler material of the filler units in each demister can be the same or different. The filler is in a wire mesh shape or a 3D honeycomb shape, and the specific surface area of the filler ranges from 200m 2/m3 to 2000m 2/m3.
Step S3
And S3, condensing the pure hydrogen fluoride vapor, and then adjusting the concentration by using ultrapure water to obtain the electronic-grade hydrofluoric acid with the hydrofluoric acid concentration range of 49+/-0.5%.
In the second embodiment, the mixed solution obtained in the step S1 may be recovered for recycling after being concentrated by evaporation.
The invention will be further illustrated with reference to the following examples, but it should be understood that the examples are for illustrative purposes only and should not be construed as limiting the practice of the invention.
Examples 1 to 3
In examples 1 and 2, the steps S1 to S8 of the first embodiment were performed to produce electronic grade hydrofluoric acid and electronic grade nitric acid, and in example 3, the steps S1 to S3 of the second embodiment were performed to produce electronic grade hydrofluoric acid. The composition and the feed amount of the waste hydrofluoric acid solutions, the molar ratio of sodium hydroxide to fluorosilicic acid in step S1, the hydrofluoric acid recovery rate, and the nitric acid recovery rate in examples 1 to 3 are shown in table 1. The results of the total analysis of the electronic grade hydrofluoric acid produced in examples 1 to 3 are shown in Table 2, and the results of the total analysis of the electronic grade nitric acid produced in examples 1 to 2 are shown in Table 3.
The composition of the waste hydrofluoric acid liquid is measured by an automatic titrator and an ultraviolet-visible light spectrospectrometer.
Hydrofluoric acid recovery = (HF concentration of electronic grade hydrofluoric acid x volume of electronic grade hydrofluoric acid)/(HF concentration of waste hydrofluoric acid liquid x waste hydrofluoric acid liquid volume).
Nitric acid recovery = (HNO 3 concentration of electronic grade nitric acid x volume of electronic grade nitric acid)/(HNO 3 concentration of waste hydrofluoric acid liquid x volume of waste hydrofluoric acid liquid).
The full-quantity analysis of the electronic grade hydrofluoric acid is according to a SEMIC-0618 standard analysis method, the full-quantity analysis of the electronic grade nitric acid is according to a SEMIC-0708 standard analysis method, metal ion content is respectively measured by utilizing an inductively coupled plasma mass spectrometer for analysis, chloride ion content is measured by utilizing a turbidimeter for analysis, nitrate ion content and phosphate ion content are measured by utilizing an ultraviolet-visible light spectroscope for analysis, sulfate ion content is measured by utilizing an ion chromatograph, and hydrofluoric acid content, nitric acid content, firing residue content, fluosilicic acid content and reducing substance content are measured by utilizing an automatic titration instrument for analysis.
TABLE 1
Note that the non-volatile acid includes sulfuric acid.
Referring to table 1, the nitric acid recovery rate of examples 1 to 2 is greater than 95% and the hydrofluoric acid recovery rate is greater than 99%, illustrating that examples 1 to 2 can effectively recover nitric acid and hydrofluoric acid from the waste hydrofluoric acid solution by performing the steps S1 to S7.
The recovery rate of hydrofluoric acid of example 3 is greater than 99.5%, indicating that example 3 can effectively recover hydrofluoric acid from the waste hydrofluoric acid solution by performing steps S1 to S3.
TABLE 2
TABLE 3 Table 3
Referring to the full analysis results of tables 2 and 3, the electronic grade hydrofluoric acid prepared in examples 1 to 2 meets the purity standard of the electronic grade hydrofluoric acid required by the semiconductor industry, and the prepared electronic grade nitric acid meets the purity standard of the electronic grade nitric acid required by the semiconductor industry, which means that examples 1 to 2 can effectively recover and regenerate hydrofluoric acid from waste hydrofluoric acid solution to prepare electronic grade hydrofluoric acid and nitric acid to prepare electronic grade nitric acid by performing steps S1 to S7, and the prepared electronic grade hydrofluoric acid and electronic grade nitric acid are particularly suitable for use in the high-tech electronic industry processes such as semiconductor processes and solar cell processes.
Referring to the full analysis results of table 2, the electronic grade hydrofluoric acid prepared in example 3 meets the purity standard of the electronic grade hydrofluoric acid required by the semiconductor industry, which means that the electronic grade hydrofluoric acid can be effectively recovered and regenerated from the waste hydrofluoric acid solution by performing steps S1 to S3 in example 3, and the prepared electronic grade hydrofluoric acid is particularly suitable for use in the high-tech electronic industry processes such as semiconductor process and solar cell process.
In summary, the method of the invention prepares electronic grade hydrofluoric acid and electronic grade nitric acid by using waste hydrofluoric acid liquid generated in the process of the high-tech electronic industry as raw materials, and not only the specifications of the prepared electronic grade hydrofluoric acid and electronic grade nitric acid meet the purity standard required by the semiconductor industry, but also the green circulation of the waste hydrofluoric acid liquid is realized, and the contribution to waste reduction and environmental protection is very remarkable. Therefore, the object of the present invention can be achieved.
However, that the invention is not limited to the specific embodiments described herein, but is to be accorded the full scope consistent with the claims and the description so as to cover all such modifications and equivalent structures.
Claims (10)
1. A method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as a raw material, which is characterized by comprising the following steps:
Step S1, adding alkali metal fluoride and alkali metal nitrate to waste hydrofluoric acid solution containing hydrofluoric acid, nitric acid and water to break azeotropic phenomenon of hydrofluoric acid and water, and performing first rectification treatment in vacuum environment to separate hydrogen fluoride vapor, wherein the distilled residue is mixed solution formed by nitric acid, water, alkali metal nitrate and alkali metal fluoride, and the dosage of the alkali metal salt ranges from 20mol% to 40mol% relative to the sum of all substances in the waste hydrofluoric acid solution and the alkali metal salt;
Step S2, removing mist drops which contain impurities and are carried in the hydrogen fluoride vapor so as to obtain pure hydrogen fluoride vapor;
Step S3, condensing the pure hydrogen fluoride vapor and then adjusting the concentration by ultrapure water so as to prepare electronic-grade hydrofluoric acid with the concentration range of 49+/-0.5%;
Step S4, performing first evaporation treatment on the mixed solution formed by the nitric acid, water, alkali metal nitrate and alkali metal fluoride in the step S1 in a vacuum environment, thereby evaporating the nitric acid and the water from the mixed solution to form a nitric acid-water mixed solution, concentrating the alkali metal nitrate, the alkali metal fluoride and the water which is not evaporated to form an alkali metal salt concentrated solution, and introducing the alkali metal salt concentrated solution into the first rectification treatment of the step S1 for recycling;
S5, adding alkaline earth metal nitrate into the nitric acid-water mixed solution obtained in the step S4 to destroy the azeotropic phenomenon of nitric acid and water, and performing second rectification treatment in a vacuum environment to separate nitric acid vapor, wherein the distilled residue is alkaline earth metal nitrate solution formed by alkaline earth metal nitrate and water;
step S6, removing mist drops which contain impurities and are carried in the nitric acid vapor so as to obtain pure nitric acid vapor;
Step S7, condensing the pure nitric acid vapor and then adjusting the concentration by ultrapure water to obtain electronic grade nitric acid with the concentration range of 70+/-0.5 percent, and
And step S8, performing second evaporation treatment on the alkaline earth metal nitrate solution obtained in the step S5 to evaporate part of water in the alkaline earth metal nitrate solution so as to concentrate the alkaline earth metal nitrate solution to form an alkaline earth metal nitrate concentrated solution, and introducing the alkaline earth metal nitrate concentrated solution into the second rectification treatment of the step S5 for recycling.
2. The method according to claim 1, wherein in the step S1, the alkali metal fluoride salt is one or more selected from the group consisting of lithium fluoride, potassium fluoride and cesium fluoride, the alkali metal nitrate salt is one or more selected from the group consisting of lithium nitrate, potassium nitrate and cesium nitrate, and a molar ratio of the alkali metal fluoride salt to the alkali metal nitrate salt is in a range of 0.05 to 10.
3. The method according to claim 1, wherein in the step S1, the vacuum environment is 100mmHg to 500mmHg, the first rectification treatment is performed in a rectification column with a polytetrafluoroethylene lining, and the temperature of the bottom of the rectification column is 80 ℃ to 130 ℃, the temperature of the top of the column is 50 ℃ to 100 ℃, and the reflux ratio is 0.5 to 3.
4. The method for producing an electronic grade inorganic acid from a waste hydrofluoric acid solution as claimed in claim 1, wherein in the step S4, the temperature of the first evaporation treatment is 130 ℃ to 180 ℃.
5. The method according to claim 1, wherein in the step S5, the alkaline earth metal nitrate is one or more selected from magnesium nitrate and calcium nitrate, and the alkaline earth metal nitrate is used in an amount ranging from 40mol% to 65mol% with respect to the sum of the alkaline earth metal nitrate, the nitric acid in the nitric acid-water mixture, and the water.
6. The method according to claim 1, wherein in the step S5, the vacuum environment is 100mmHg to 500mmHg, the second rectification treatment is performed in a rectification column with a polytetrafluoroethylene lining, and the temperature of the bottom of the rectification column is 120 ℃ to 140 ℃, the temperature of the top of the column is 70 ℃ to 100 ℃, and the reflux ratio is 0.5 to 3.
7. The method for producing an electronic grade inorganic acid from a waste hydrofluoric acid solution as claimed in claim 1, wherein in the step S8, the temperature of the second evaporation treatment is 130 ℃ to 180 ℃.
8. A method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as raw material comprises the following steps:
Step S1, adding alkali metal salt containing alkali metal fluoride and alkali metal nitrate into waste hydrofluoric acid solution containing hydrofluoric acid and water to break azeotropic phenomenon of hydrofluoric acid and water, and performing first rectification treatment in vacuum environment to separate hydrogen fluoride vapor, wherein the dosage range of the alkali metal salt is more than 20mol% relative to the total mol of all substances and the alkali metal salt in the waste hydrofluoric acid solution;
Step S2, removing mist drops which contain impurities and are carried in the hydrogen fluoride vapor to obtain pure hydrogen fluoride vapor, and
And S3, condensing the pure hydrogen fluoride vapor, and then adjusting the concentration by using ultrapure water, so as to prepare the electronic-grade hydrofluoric acid with the hydrofluoric acid concentration range of 49+/-0.5%.
9. The method according to claim 8, wherein in the step S1, the alkali metal fluoride salt is one or more selected from the group consisting of lithium fluoride, potassium fluoride and cesium fluoride, the alkali metal nitrate salt is one or more selected from the group consisting of lithium nitrate, potassium nitrate and cesium nitrate, and a molar ratio of the alkali metal fluoride salt to the alkali metal nitrate salt is in a range of 0.05 to 10.
10. The method according to claim 8, wherein in the step S1, the vacuum environment is 100mmHg to 500mmHg, the first rectification treatment is performed in a rectification column with a polytetrafluoroethylene lining, and the temperature of the bottom of the rectification column is 80 ℃ to 130 ℃, the temperature of the top of the column is 50 ℃ to 100 ℃, and the reflux ratio is 0.5 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111311111.0A CN116081575B (en) | 2021-11-08 | 2021-11-08 | Method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111311111.0A CN116081575B (en) | 2021-11-08 | 2021-11-08 | Method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116081575A CN116081575A (en) | 2023-05-09 |
| CN116081575B true CN116081575B (en) | 2025-02-18 |
Family
ID=86201205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111311111.0A Active CN116081575B (en) | 2021-11-08 | 2021-11-08 | Method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116081575B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261349A (en) * | 2014-09-02 | 2015-01-07 | 中国科学院过程工程研究所 | Process method of recovering hydrofluoric acid and nitric acid from electronic waste acid |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5119564B2 (en) * | 2001-09-05 | 2013-01-16 | ダイキン工業株式会社 | Method for recovering hydrogen fluoride |
| JP4147408B2 (en) * | 2002-11-28 | 2008-09-10 | 株式会社ササクラ | Hydrofluoric acid wastewater treatment method and apparatus |
| JP2007275830A (en) * | 2006-04-11 | 2007-10-25 | Hideki Yamamoto | Method for recovering nitric acid from acetic acid-nitric acid-phosphoric acid mixed acid waste liquid |
| JP6728731B2 (en) * | 2016-02-04 | 2020-07-22 | 三菱ケミカル株式会社 | Method for recovering hydrofluoric acid and nitric acid |
| CN205699506U (en) * | 2016-05-17 | 2016-11-23 | 常州泰特环境设备工程有限公司 | A kind of electronics acid pickle electron-level phosphoric acid recycling and processing device |
| CN110844885A (en) * | 2019-09-06 | 2020-02-28 | 浙江东氟塑料科技有限公司 | Method for recovering and regenerating hydrofluoric acid from waste liquid |
| CN111620306B (en) * | 2020-05-29 | 2021-12-31 | 盛隆资源再生（无锡）有限公司 | Mixed acid separation and recovery processing method |
| CN112028022A (en) * | 2020-09-18 | 2020-12-04 | 宣城亨泰电子化学材料有限公司 | Pretreatment method for preparing electronic-grade high-purity hydrofluoric acid |
-
2021
- 2021-11-08 CN CN202111311111.0A patent/CN116081575B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261349A (en) * | 2014-09-02 | 2015-01-07 | 中国科学院过程工程研究所 | Process method of recovering hydrofluoric acid and nitric acid from electronic waste acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116081575A (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7922876B2 (en) | Method for processing an etching mixture which is formed during the production of highly pure silicon | |
| CN101787537B (en) | Method for recovering waste nitric-hydrofluoric acid from stainless steel annealing-pickling by micro- and negative-pressure evaporation and crystallization processes | |
| CN103848426B (en) | Vacuum falling film method of evaporation is utilized to concentrate the method for silicofluoric acid | |
| JP2008189484A (en) | Method and apparatus for separating and recovering acid components from waste liquid containing hydrofluoric acid and silicohydrofluoric acid | |
| CN212050528U (en) | High-efficient purification system of hydrogen fluoride | |
| TWI540098B (en) | Production method of fluoride gas | |
| CN112607707A (en) | Separation and purification method of FTrPSA refined from industrial-grade high-concentration HF into electronic grade | |
| CN111170320B (en) | Device and method for recycling waste acid solution for polycrystalline silicon texturing | |
| CN110092523B (en) | Method for treating fluorine-containing, ammonia nitrogen-containing and phosphorus-containing wastewater | |
| CN105417556B (en) | Preparation method of ammonium bifluoride | |
| CN107117753A (en) | A kind of method that silicon solar cell making herbs into wool devil liquor recovery is utilized | |
| CN114735652A (en) | Preparation and purification method of electronic-grade hydrofluoric acid | |
| RU2393113C2 (en) | Silicon tetrafluoride synthesis method and device for realising said method | |
| CN116081575B (en) | Method for preparing electronic grade inorganic acid by using waste hydrofluoric acid liquid as raw material | |
| CN112957758A (en) | Method for recovering high-purity nitric acid and hydrofluoric acid from etching waste acid | |
| TWI782757B (en) | Method for preparing electronic grade inorganic acid with waste hydrofluoric acid liquid as raw material | |
| CN112661115B (en) | Separation and purification method for deep dehydration and impurity removal of FTrPSA refined by anhydrous HF produced by fluorite method | |
| CN113336247A (en) | Method for recycling waste aluminum etching liquid | |
| CN111017931A (en) | Method for concentrating fluosilicic acid by high-temperature dilute sulfuric acid | |
| CN108103585B (en) | A kind of processing method of fine-hair maring using monocrystalline silicon slice waste liquid | |
| CN112744788B (en) | Separation and purification method for deep dehydration and impurity removal of FTrPSA refined by anhydrous HF (hydrogen fluoride) produced by fluosilicic acid method | |
| CN113955720A (en) | Method and device for preparing hydrogen fluoride from BOE waste liquid | |
| CN219585937U (en) | BOE waste liquid recycling treatment system | |
| JPH09271785A (en) | Treatment of fluorine containing waste water | |
| CN114369013B (en) | Method for recovering propylene glycol methyl ether from water-containing waste liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |