CN102009957A - Method for purifying high-yield superclean high-purity hydrofluoric acid - Google Patents
Method for purifying high-yield superclean high-purity hydrofluoric acid Download PDFInfo
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- CN102009957A CN102009957A CN 201010551506 CN201010551506A CN102009957A CN 102009957 A CN102009957 A CN 102009957A CN 201010551506 CN201010551506 CN 201010551506 CN 201010551506 A CN201010551506 A CN 201010551506A CN 102009957 A CN102009957 A CN 102009957A
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Abstract
The invention relates to a method for purifying high-yield superclean high-purity hydrofluoric acid, which comprises the following process steps of: introducing industrial anhydrous hydrogen fluoride into an oxidation treater A, adding potassium permanganate solution for oxidation, introducing the liquid in the oxidation treater A into an oxidation treater B through a filter A, oxidizing by using hydrogen dioxide solution, introducing the liquid into the oxidation treater B into a rectifying tower through a filter B, and gasifying hydrogen fluoride liquid to generate purified hydrogen fluoride gas; introducing the hydrogen fluoride gas out of the rectifying tower into a cooler for cooling and filtering; injecting deionized water into an absorption tower, arranging a distribution coil at the bottom of the absorption tower, introducing the hydrogen fluoride gas out of the cooler into the distribution coil at the bottom of the absorption tower, injecting from distribution holes on the upper and lower walls of the distribution coil, and absorbing by using the deionized water to prepare a hydrofluoric acid semi-finished product; and introducing the hydrofluoric acid semi-finished product out of the absorption tower into a 0.05 mu m filter to obtain the superclean high-purity hydrofluoric acid finished product. The product prepared by the method has high purity and yield, and meets environmental protection requirement.
Description
Technical field
The present invention relates to a kind of method of purification of high yield super clean, high purified hydrofluoric acid.Belong to the electronic chemical product technical field.
Background technology
Hydrofluoric acid (hydrofluoric, HF), relative molecular weight 20.1 is colourless transparent liquid, strongly-acid; It has intensive corrodibility to metal, glass, is severe toxicity.Hydrofluoric acid density (25 ℃) is 1.13g/ml (40 weight %).And super clean, high purified hydrofluoric acid is that strongly-acid cleans, etching reagent, can be used with nitric acid, glacial acetic acid, hydrogen peroxide and ammonium hydroxide etc., is mainly used in the production of super large-scale integration Technology.
The method of purification of the hydrofluoric acid that generally adopts is at present: the rectifying purifying obtains the high-purity hydrogen fluoride of a kind of ultra-clean after adding potassium permanganate with anhydrous hydrogen fluoride for industrial use.The shortcoming of this method maximum is that the purity of hydrofluoric acid is not high, yields poorly, and the absorption tower absorptive character are poor, and the hydrofluoric acid gas that part is not fully absorbed is discharged in the air and pollutes to environment.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, a kind of product purity height is provided, output height, the method for purification of the high yield super clean, high purified hydrofluoric acid of compliance with environmental protection requirements.
The object of the present invention is achieved like this: a kind of method of purification of high yield super clean, high purified hydrofluoric acid, and the main technique of this method is as follows:
Step 1, pre-treatment
Anhydrous hydrogen fluoride for industrial use is fed oxide treatment device one, with the air in the nitrogen replacement oxide treatment device one, controlled oxidation treater one internal pressure≤0.1Mpa, add potassium permanganate solution then, stirred 10 minutes ± 5 minutes, static 20 minutes ± 5 minutes, again liquid in the oxide treatment device one is entered oxide treatment device two by strainer one, the superoxol that in oxide treatment device two, adds the 0.16-1 weight % that accounts for the anhydrous hydrogen fluoride for industrial use dosage, stirred static 20 minutes ± 5 minutes 10 minutes ± 5 minutes;
Step 2, rectifying
Liquid in the oxide treatment device two is entered rectifying tower by strainer two, be warming up to 60-80 ℃, the gasification of hydrogen fluoride liquid generates purified hydrogen fluoride gas;
Step 3, cold filtration
The purified hydrogen fluoride gas that will go out rectifying still feeds water cooler and cools off and filter, the water cooler bottom is covered with polytetrafluoroethylene packing, hydrogen fluoride gas is filtered, by cooling the hydrogen fluoride gas behind the purifying is converted to gas-liquid phase criticality, the small amount of impurities that wherein also has is separated, impurity is partly refluxed to rectifying still, and getting once more through cold filtration, purified hydrogen fluoride gas enters the absorption tower;
Step 4, absorption
Inject deionized water in the absorption tower, the bottom, absorption tower is provided with the gas distribution coil pipe, gas coil pipe is two-layer up and down, hydrogen fluoride gas after secondarily purified is fed the gas coil pipe of two layers of cloth up and down of bottom, absorption tower, absorb by deionized water again after discharging by the qi-emitting hole on the air-spreading disk tube wall and make the hydrofluoric acid work in-process;
Step 5, filtration
After filtering, the strainer that the hydrofluoric acid work in-process that go out the absorption tower feed 0.05-0.2 μ m obtains the super clean, high purified hydrofluoric acid finished product.
The inventive method is utilized twice effective cooperation that oxidation unit makes full use of oxidant potassium permanganate and hydrogen peroxide, with sulfurous gas in the anhydrous hydrogen fluoride for industrial use and arsenous fluoride impurity exhaustive oxidation, sulfurous gas and arsenous fluoride separate impurities have been strengthened, make and be difficult to evaporable impurity and in rectifying, do not taken out of and stockpile and at the bottom of still, get rid of in addition, like this, not only improve the purity of product but also realized environmental protection production.In the bottom, absorption tower the gas distribution coil pipe is set, and adopt two-layerly to be arranged in parallel up and down, change the present gas distribution coil pipe that utilizes the bottom, absorption tower into and discharge gas, improved the uniform absorption degree on absorption tower and strengthened assimilated efficiency greatly, output increases 3 times, and absorbs fully near 100%.
In sum, the inventive method following advantage of having compared with present preparation technology:
1, by the effect of potassium permanganate and twice oxidation of hydrogen peroxide and the cooling and the filteration of water cooler, thoroughly solve impurity such as trivalent arsenic and be difficult for removing this difficult problem, thereby product purity is improved greatly, make the super clean, high purified hydrofluoric acid of making reach semi-conductor SEMI-C12 standard, satisfy the manufacturing of super large-scale integration fully.Specific targets are as follows: granularity 0.3 μ m≤100, purity: negatively charged ion≤30ppb, positively charged ion≤0.05ppb.
2, the absorption tower can absorb the high-purity hydrogen fluoride gas of the later ultra-clean of the purifying that is distillated fully fully, in the bottom, absorption tower the gas distribution coil pipe is set, and adopt and two-layerly be arranged in parallel up and down, make gas distribution more even, when improving assimilated efficiency, also improved output greatly, the hydrogen fluoride gas of having avoided part fully not absorbed simultaneously is leaked in the air, pollutes to environment, meets the environmental protection and energy saving requirement.
Embodiment
Embodiment 1:
The 330kg anhydrous hydrogen fluoride for industrial use feeds oxide treatment device one in the raw material tank, with the air in the nitrogen replacement oxide treatment device one, controlled oxidation treater one internal pressure≤0.1Mpa, add the 0.6kg potassium permanganate solution then, stirred 10 minutes, static 20 minutes, again liquid in the oxide treatment device one is entered oxide treatment device two by strainer one, the superoxol that in oxide treatment device two, adds 4kg 30 weight %, stirred 10 minutes, and static 20 minutes, again liquid in the oxide treatment device two was entered rectifying tower by strainer two, be warming up to 60 ℃ then, the gasification of hydrogen fluoride liquid generates purified hydrogen fluoride gas; The purified hydrogen fluoride gas that will go out rectifying still feeds water cooler and carries out cold filtration, by cooling the hydrogen fluoride gas behind the purifying is converted to gas-liquid phase criticality, the small amount of impurities that wherein also has is separated, impurity is partly refluxed to rectifying still, and getting once more through cold filtration, purified hydrogen fluoride gas enters the absorption tower.Inject deionized water in the absorption tower, the bottom, absorption tower is provided with the gas distribution coil pipe, and the hydrogen fluoride gas that will go out water cooler feeds the gas distribution coil pipe of bottom, absorption tower, makes the hydrofluoric acid work in-process by being absorbed by deionized water after the ejection on the air-spreading disk tube wall again; The strainer that the hydrofluoric acid work in-process that go out the absorption tower feed 0.05 μ m obtains 570kg49%(wt after filtering in hundred grades of environment purifications (granularity 0.5 μ m be controlled at≤100)) the super clean, high purified hydrofluoric acid finished product.Detected result: granularity 0.3 μ m≤100, purity: negatively charged ion≤30ppb, positively charged ion≤0.05ppb.
Embodiment 2:
The 220kg anhydrous hydrogen fluoride for industrial use feeds oxide treatment device one in the raw material tank, with the air in the nitrogen replacement oxide treatment device one, controlled oxidation treater one internal pressure≤0.1Mpa, add the 0.5kg potassium permanganate solution then, stirred 10 minutes, static 20 minutes, again liquid in the oxide treatment device one is entered oxide treatment device two by strainer one, the superoxol that in oxide treatment device two, adds 2.7kg 30 weight %, stirred 10 minutes, and static 20 minutes, again liquid in the oxide treatment device two was entered rectifying tower by strainer two, be warming up to 80 ℃ then, the gasification of hydrogen fluoride liquid generates purified hydrogen fluoride gas; The purified hydrogen fluoride gas that will go out rectifying still feeds water cooler and cools off and filter, by cooling the hydrogen fluoride gas behind the purifying is converted to gas-liquid phase criticality, the small amount of impurities that wherein also has is separated, impurity is partly refluxed to rectifying still, and getting once more through cold filtration, purified hydrogen fluoride gas enters the absorption tower; Inject deionized water in the absorption tower, the bottom, absorption tower is provided with the gas distribution coil pipe, and the hydrogen fluoride gas that will go out water cooler feeds the two layers of cloth gas coil pipe of bottom, absorption tower, makes the hydrofluoric acid work in-process by being absorbed by deionized water after the ejection on the two layers of cloth gas coil pipe tube wall again; The strainer that the hydrofluoric acid work in-process that go out the absorption tower feed 0.05 μ m obtains 415kg40%(wt after filtering in hundred grades of environment purifications (granularity 0.5 μ m be controlled at≤100)) the super clean, high purified hydrofluoric acid finished product.Detected result: granularity 0.3 μ m≤100, purity: negatively charged ion≤30ppb, positively charged ion≤0.05ppb.
Claims (1)
1. the method for purification of a high yield super clean, high purified hydrofluoric acid is characterized in that the main technique of this method is as follows:
Step 1, pre-treatment
Anhydrous hydrogen fluoride for industrial use is fed oxide treatment device one, with the air in the nitrogen replacement oxide treatment device one, controlled oxidation treater one internal pressure≤0.1Mpa, add potassium permanganate solution then, stirred 10 minutes ± 5 minutes, static 20 minutes ± 5 minutes, again liquid in the oxide treatment device one is entered oxide treatment device two by strainer one, the superoxol that in oxide treatment device two, adds the 0.16-1 weight % that accounts for the anhydrous hydrogen fluoride for industrial use dosage, stirred static 20 minutes ± 5 minutes 10 minutes ± 5 minutes;
Step 2, rectifying
Liquid in the oxide treatment device two is entered rectifying tower by strainer two, be warming up to 60-80 ℃, the gasification of hydrogen fluoride liquid generates purified hydrogen fluoride gas;
Step 3, cold filtration
The purified hydrogen fluoride gas that will go out rectifying still feeds water cooler and cools off and filter, the water cooler bottom is covered with polytetrafluoroethylene packing, hydrogen fluoride gas is filtered, by cooling the hydrogen fluoride gas behind the purifying is converted to gas-liquid phase criticality, the small amount of impurities that wherein also has is separated, impurity is partly refluxed to rectifying still, and getting once more through cold filtration, purified hydrogen fluoride gas enters the absorption tower;
Step 4, absorption
Inject deionized water in the absorption tower, the bottom, absorption tower is provided with the gas distribution coil pipe, gas coil pipe is two-layer up and down, hydrogen fluoride gas after secondarily purified is fed the gas coil pipe of two layers of cloth up and down of bottom, absorption tower, absorb by deionized water again after discharging by the qi-emitting hole on the air-spreading disk tube wall and make the hydrofluoric acid work in-process;
Step 5, filtration
After filtering, the strainer that the hydrofluoric acid work in-process that go out the absorption tower feed 0.05-0.2 μ m obtains the super clean, high purified hydrofluoric acid finished product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174233A (en) * | 2015-09-25 | 2015-12-23 | 江阴润玛电子材料股份有限公司 | Ultra-clean high-purity sulfuric acid production method |
| CN107720698A (en) * | 2017-11-03 | 2018-02-23 | 深圳市纯水号水处理科技有限公司 | A kind of hydrofluoric acid recovery process |
| CN107934915A (en) * | 2017-12-29 | 2018-04-20 | 云南瓮福云天化氟化工科技有限公司 | The purification method of impurity in-kind of anhydrous hydrogen fluoride production process |
| CN112978680A (en) * | 2021-04-28 | 2021-06-18 | 联仕(昆山)化学材料有限公司 | Production process and production device of electronic-grade hydrofluoric acid |
| CN115535965A (en) * | 2022-10-13 | 2022-12-30 | 云南氟磷电子科技有限公司 | Method for continuously removing arsenic by hydrofluoric acid |
| CN115636429A (en) * | 2022-12-07 | 2023-01-24 | 山东立中新能源材料有限公司 | Preparation process of lithium hexafluorophosphate |
| CN116873870A (en) * | 2023-09-08 | 2023-10-13 | 上海联风气体有限公司 | Method for recovering and refining hydrofluoric acid from solution containing hydrofluoric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101125639A (en) * | 2007-08-06 | 2008-02-20 | 江阴市润玛电子材料有限公司 | Method for purifying ultra-pure hydrofluoric acid |
| CN201280430Y (en) * | 2008-09-18 | 2009-07-29 | 江阴市润玛电子材料有限公司 | Purification apparatus for ultra-pure hydrofluoric acid |
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- 2010-11-20 CN CN 201010551506 patent/CN102009957A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125639A (en) * | 2007-08-06 | 2008-02-20 | 江阴市润玛电子材料有限公司 | Method for purifying ultra-pure hydrofluoric acid |
| CN201280430Y (en) * | 2008-09-18 | 2009-07-29 | 江阴市润玛电子材料有限公司 | Purification apparatus for ultra-pure hydrofluoric acid |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174233A (en) * | 2015-09-25 | 2015-12-23 | 江阴润玛电子材料股份有限公司 | Ultra-clean high-purity sulfuric acid production method |
| CN107720698A (en) * | 2017-11-03 | 2018-02-23 | 深圳市纯水号水处理科技有限公司 | A kind of hydrofluoric acid recovery process |
| CN107934915A (en) * | 2017-12-29 | 2018-04-20 | 云南瓮福云天化氟化工科技有限公司 | The purification method of impurity in-kind of anhydrous hydrogen fluoride production process |
| CN112978680A (en) * | 2021-04-28 | 2021-06-18 | 联仕(昆山)化学材料有限公司 | Production process and production device of electronic-grade hydrofluoric acid |
| CN115535965A (en) * | 2022-10-13 | 2022-12-30 | 云南氟磷电子科技有限公司 | Method for continuously removing arsenic by hydrofluoric acid |
| CN115636429A (en) * | 2022-12-07 | 2023-01-24 | 山东立中新能源材料有限公司 | Preparation process of lithium hexafluorophosphate |
| CN116873870A (en) * | 2023-09-08 | 2023-10-13 | 上海联风气体有限公司 | Method for recovering and refining hydrofluoric acid from solution containing hydrofluoric acid |
| CN116873870B (en) * | 2023-09-08 | 2023-11-24 | 上海联风气体有限公司 | Method for recovering and refining hydrofluoric acid from solution containing hydrofluoric acid |
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Application publication date: 20110413 |