CN103086327B - Preparation method of ultra-clean high-purity hydrofluoric acid - Google Patents
Preparation method of ultra-clean high-purity hydrofluoric acid Download PDFInfo
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Abstract
The invention relates to a preparation method of ultra-clean high-purity hydrofluoric acid, which comprises the following steps: leading industrial-grade dry hydrogen fluoride used as a raw material out of a storage tank at 25-35 DEG C under the pressure of 0.08-0.12 MPa, adsorbing with a molecular sieve, filtering with a 0.01 mu m filter element, passing through a 1-2 g/L barium fluoride water solution and a 0.1-1 g/L silver fluoride water solution, absorbing with ultrapure water, adding oxydol, and keeping cyclic stirring at 20-30 DEG C for at least 1 hour; and finally, rectifying while controlling the distillation temperature at 112.5-113.5 DEG C and the reflux ratio at 2-4, and cyclically filtering the rectification fraction with a 0.1 mu m filter element, thereby obtaining the ultra-clean high-purity hydrofluoric acid. The purification route design is reasonable and ingenious; the obtained ultra-clean high-purity hydrofluoric acid satisfies the requirements for SEMIC12; and the process route is simple and convenient to operate, and can implement stable and reliable mass production of hydrofluoric acid.
Description
Technical field
The present invention relates to a kind of preparation method of super clean, high purified hydrofluoric acid, the gained high-pure hydrofluoric acid can be used for the relevant high-tech product preparation fields such as semi-conductor and TFT.
Background technology
The super-clean high-pure electronic chemical is the crucial integration starting material that super large-scale integration is made, and its purity, cleanliness factor have very important impact to yield rate, electrical property, reliability etc.The current main-stream semiconductor technology has reached 0.09～0.2 μ m, and tip has reached 22 nanometer levels.Corresponding electronic chemical product has also reached the SEMIC12 requirement.High pure electronic chemicals production technology is grasped by a few developed country such as Germany, Japan and the U.S..China only can produce elementary and intermediate electronic chemical product at present.The high pure electronic purity of chemicals is more and more higher, and value-added content of product is larger.The research and development of ultra-pure electronic chemical product and technology thereof not only have higher strategic value, and also have higher economic worth and social benefit.On July 20th, 2012, State Council printed and distributed ' State Council is about printing and distributing the notice of " 12 " national strategy new industry development program ', and the high pure electronic chemical just belongs to the electronics key foundation industry in generation information technical industry in notice.
High-pure hydrofluoric acid is semi-conductor one of electronic chemical product, is mainly used in the etching of silicon chip, the techniques such as cleaning.The main test item of current hydrofluoric acid has negatively charged ion, positively charged ion, particle.The main separating and purifying method of hydrofluoric acid has WATER-WASHING METHOD, rectification method, sequestrant, resin absorption, oxygenant arsenic removal (potassium permanganate, hydrogen peroxide, fluorine gas etc.) etc., and main focus is for removing the arsenic in hydrofluoric acid.
At present, existing more about the preparation method's of high purity hydrofluoric acid patent report, wherein, partial monopoly only provides method of purification, does not provide test result., as only having provided corresponding method of purification in patent CN1190913A, do not provide its result.Adopt the mode of hydrogen fluoride distillation and hydrofluoric acid distillation in patent CN101003361A, also do not give except concrete assay; Some patent only provides method of purification, although detected result is arranged, not concrete,, as adopting potassium permanganate, hydrogen peroxide pre-treatment in patent CN102009957A, add the rectifying mode, its test result is negatively charged ion≤30ppb, positively charged ion≤0.05ppb.In patent CN101570319A, adopt the hydrogen fluoride distillation to add the mode of hydrofluoric acid distillation, assay is negatively charged ion≤25ppb, positively charged ion≤0.03ppb.Partial monopoly provides concrete test result, but the impurity of purifying is still higher.In patent CN102320573, adopt the mode of first fluorine gas oxidation, the higher rectifying of boiling.Arsenic can be reduced to below 1ppb, but the content of the elements such as phosphorus, chlorine, sulphur still has hundreds of to one thousand ppb.In patent CN1931709A, adopt potassium permanganate to add the hydrogen peroxide pre-treatment, 35 ℃ of rectifying aftertreatments of low temperature, in its test result, same negatively charged ion is residual higher, hundreds of or even several thousand ppb.Adopt permanganate pretreatment in patent CN101597032A, high-molecular chelating agent adds the mixed bed ion system to be processed, and has only listed silicon, phosphatic result in its result, not mentioned to results such as arsenic, sulphur, chlorine.
To sum up, although more about the preparation method's of high purity hydrofluoric acid patent report, according to the method for these reports, or do not reach SEMI C12 standard, or can't reach and stablize in batches the preparation level.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides a kind of stably manufactured in batches to reach the method for the super clean, high purified hydrofluoric acid of SEMIC12 requirement.
For solving the problems of the technologies described above, the present invention takes following technical scheme:
A kind of preparation method of super clean, high purified hydrofluoric acid, in weight content, in described super clean, high purified hydrofluoric acid, individual event anionic impurity content≤50ppb, individual event metals content impurity≤0.1ppb,＞0.2 μ m granule density≤100/ml, described method is take technical grade dry state hydrogen fluoride as raw material, the following step that comprises successively and carry out continuously:
(1), raw material dry state hydrogen fluoride is derived under 25 ℃ ~ 35 ℃ of temperature and pressure 0.08 ~ 0.12Mpa from storage tank;
(2), make the hydrogen fluoride gas of derivation successively by molecular sieve adsorption, 0.01 μ m filter element filtering, the barium fluoride aqueous solution of 1 ~ 2g/L and the silver fluoride aqueous solution of 0.1 ~ 1g/L, afterwards, absorb to such an extent that set the aqueous hydrogen fluoride solution of concentration with the ultrapure water that resistivity surpasses 18M Ω, and interpolation hydrogen peroxide, obtaining content of hydrogen peroxide is the mixing solutions of 0.01wt% ~ 0.1wt%, remain under 20 ℃ ~ 30 ℃ circulation stirring at least 1 hour;
(3), control 112.5 ℃ ~ 113.5 ℃ of distillation temperatures, reflux ratio 2 ~ 4, aqueous hydrogen fluoride solution is carried out rectifying, the rectifying cut, through 0.1 μ m filter core circulating filtration, obtains described super clean, high purified hydrofluoric acid.
According to further scheme of the present invention:
In step (1), the derivation speed of hydrogen fluoride gas is preferably for example 160 ~ 240kg/h.Hydrogen fluoride gas is derived with a more rational speed, be conducive to avoid or reduce impurity and derive with hydrogen fluoride gas.
In step (2), molecular sieve is 5A type molecular sieve, is used for removing at least part of organic gas.In an embodiment, the diameter of molecular sieve is 1.5 ~ 2mm.
In step (2), the described barium fluoride aqueous solution, the silver fluoride aqueous solution are by analytical pure or above preparation of raw material.To reduce the content of S, P, As, B, Cl, Si etc. in hydrogen fluoride gas by the purpose of the barium fluoride aqueous solution and the silver fluoride aqueous solution successively with hydrogen fluoride.In the barium fluoride aqueous solution and the silver fluoride aqueous solution, control the amount of cation impurity less than 100pb, to be advisable, anionic impurity is less than 500ppb, to be advisable, and TOC is to be advisable less than 1ppm.
In step (2), it is fixed that the concentration of aqueous hydrogen fluoride solution can be come according to the application requiring of product, and described setting concentration namely refers to the concentration of requirement.Generally speaking, the concentration of aqueous hydrogen fluoride solution is between 35wt% ~ 60wt%.
In step (2), the hydrogen peroxide of interpolation be preferably the UP level and more than, wherein cation impurity levels is less than 10ppb, anionic impurity content is less than 500ppb, the concentration of hydrogen peroxide is generally 30wt% ~ 50wt%.Add hydrogen peroxide, make the mixing solutions of aqueous hydrogen fluoride solution and hydrogen peroxide keep at a certain temperature specified time, can effectively remove impurity A s, and can not introduce new impurity simultaneously.
In step (2), the time that described circulation stirring carries out is generally 1 ~ 3 hour.
According to the present invention, also in step (3), the leachable metallic impurity mass concentration of adoption of innovation is carried out described rectifying less than the high purity graphite still kettle of 10ppb.During rectifying, the temperature of cooling water general control is at 4 ~ 8 ℃, and distillation speed can be for example 500 ± 100L/H., by this rectification step, further reduce for example Na of impurity cationic contained in hydrogen fluoride, K, Ca etc.
In step (3), the time of circulating filtration is generally 2 ~ 3 hours.
Due to the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The present invention is take technical grade hydrogen fluoride as raw material, and the integrated use multiple means is purified to hydrogen fluoride, and the purification highway route design is rationally ingenious, the final high purity hydrofluoric acid that obtains to reach the SEMIC12 requirement.In addition, operational path of the present invention is simple, and is easy to operate, can realize the batch production that hydrofluoric acid is reliable and stable.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the invention is not restricted to following examples.
Embodiment 1
A kind of preparation method of super clean, high purified hydrofluoric acid, the following step that it comprises successively and carries out continuously:
(1), raw material dry state hydrogen fluoride is derived from storage tank under 25 ℃ ~ 30 ℃ of temperature and pressure 0.1 ~ 0.12Mpa, derivation speed is 160 ~ 170kg/h.
(2), making the hydrogen fluoride gas of derivation is 5A type molecular sieve adsorption, the 0.01 μ m filter element filtering of 1.5 ~ 2mm successively by diameter;
(3), make hydrogen fluoride gas successively the barium fluoride aqueous solution by 1.5g/L is housed volume tank and the volume tank of the silver fluoride aqueous solution of 0.5g/L is housed, in volume tank, liquid level maintains 800 ± 100L, reduce the content of S in hydrogen fluoride gas, P, As, B, Cl, Si etc. by gas washing, hydrogen fluoride gas is derived from volume tank speed is 165 ± 5kg/h.
(4), the hydrogen fluoride gas that surpasses the ultrapure water absorption derivation of 18M Ω with resistivity, obtain the aqueous hydrogen fluoride solution of 40wt%, adding concentration is the UP grade hydrogen peroxide of 35wt%, and obtaining content of hydrogen peroxide is the mixing solutions of 0.05wt%, remain under 20 ℃ ~ 30 ℃ circulation stirring 1 hour;
(3), with the aqueous hydrogen fluoride solution of step (4) with the high rectifying of boiling of high purity graphite still kettle, control 112.5 ~ 113.5 ℃ of distillation temperatures, reflux ratio 3,4 ~ 8 ℃ of temperature of cooling water, distillation speed 500L/H, obtain the rectifying cut through 0.1 μ m filter core circulating filtration 2 ~ 3 hours, obtain super clean, high purified hydrofluoric acid.
Embodiment 2
A kind of preparation method of super clean, high purified hydrofluoric acid, the following step that it comprises successively and carries out continuously:
(1), raw material dry state hydrogen fluoride is derived from storage tank under 30 ℃ ~ 35 ℃ of temperature and pressure 0.08 ~ 0.1Mpa, derivation speed is 200 ~ 220kg/h.
(2), making the hydrogen fluoride gas of derivation is 5A type molecular sieve adsorption, the 0.01 μ m filter element filtering of 1.5 ~ 2mm successively by diameter;
(3), make hydrogen fluoride gas successively the barium fluoride aqueous solution by 1.2g/L is housed volume tank and the volume tank of the silver fluoride aqueous solution of 0.2g/L is housed, in volume tank, liquid level maintains 800 ± 100L, reduce the content of S in hydrogen fluoride gas, P, As, B, Cl, Si etc. by gas washing, hydrogen fluoride gas is derived from volume tank speed is 210 ± 10kg/h.
(4), the hydrogen fluoride gas that surpasses the ultrapure water absorption derivation of 18M Ω with resistivity, obtain the aqueous hydrogen fluoride solution of 49.0wt%, adding concentration is the UP grade hydrogen peroxide of 35wt%, and obtaining content of hydrogen peroxide is the mixing solutions of 0.1wt%, remain under 20 ℃ ~ 30 ℃ circulation stirring 3 hours;
(3), with the aqueous hydrogen fluoride solution of step (4) with the high rectifying of boiling of high purity graphite still kettle, control 112.5 ~ 113.5 ℃ of distillation temperatures, reflux ratio 2.5,4 ~ 8 ℃ of temperature of cooling water, distillation speed 500L/H, obtain the rectifying cut through 0.1 μ m filter core circulating filtration 2 ~ 3 hours, obtain super clean, high purified hydrofluoric acid.
Embodiment 3
A kind of preparation method of super clean, high purified hydrofluoric acid, the following step that it comprises successively and carries out continuously:
(1), raw material dry state hydrogen fluoride is derived from storage tank under 25 ℃ ~ 35 ℃ of temperature and pressure 0.08 ~ 0.12Mpa, derivation speed is 240kg/h.
(2), making the hydrogen fluoride gas of derivation is 5A type molecular sieve adsorption, the 0.01 μ m filter element filtering of 1.5 ~ 2mm successively by diameter;
(3), make hydrogen fluoride gas successively the barium fluoride aqueous solution by 1g/L is housed volume tank and the volume tank of the silver fluoride aqueous solution of 0.8g/L is housed, in volume tank, liquid level maintains 800 ± 100L, reduce the content of S in hydrogen fluoride gas, P, As, B, Cl, Si etc. by gas washing, hydrogen fluoride gas is derived from volume tank speed is 240kg/h.
(4), the hydrogen fluoride gas that surpasses the ultrapure water absorption derivation of 18M Ω with resistivity, obtain the aqueous hydrogen fluoride solution of 55wt%, adding concentration is the UP grade hydrogen peroxide of 35wt%, and obtaining content of hydrogen peroxide is the mixing solutions of 0.08wt%, remain under 20 ℃ ~ 30 ℃ circulation stirring 2 hours;
(3), with the aqueous hydrogen fluoride solution of step (4) with the high rectifying of boiling of high purity graphite still kettle, control 112.5 ~ 113.5 ℃ of distillation temperatures, reflux ratio 3.5,4 ~ 8 ℃ of temperature of cooling water, distillation speed 500L/H, obtain the rectifying cut through 0.1 μ m filter core circulating filtration 2 ~ 3 hours, obtain super clean, high purified hydrofluoric acid.
Embodiment 4
A kind of preparation method of super clean, high purified hydrofluoric acid, the following step that it comprises successively and carries out continuously:
(1), raw material dry state hydrogen fluoride is derived from storage tank under 25 ℃ ~ 35 ℃ of temperature and pressure 0.08 ~ 0.12Mpa, derivation speed is 200kg/h.
(2), making the hydrogen fluoride gas of derivation is 5A type molecular sieve adsorption, the 0.01 μ m filter element filtering of 1.5 ~ 2mm successively by diameter;
(3), make hydrogen fluoride gas successively the barium fluoride aqueous solution by 2g/L is housed volume tank and the volume tank of the silver fluoride aqueous solution of 1g/L is housed, in volume tank, liquid level maintains 800 ± 100L, reduce the content of S in hydrogen fluoride gas, P, As, B, Cl, Si etc. by gas washing, hydrogen fluoride gas is derived from volume tank speed is 200kg/h.
(4), the hydrogen fluoride gas that surpasses the ultrapure water absorption derivation of 18M Ω with resistivity, obtain the aqueous hydrogen fluoride solution of 40wt%, adding concentration is the UP grade hydrogen peroxide of 35wt%, and obtaining content of hydrogen peroxide is the mixing solutions of 0.02wt%, remain under 25 ℃ ~ 30 ℃ circulation stirring 3 hours;
(3), with the aqueous hydrogen fluoride solution of step (4) with the high rectifying of boiling of high purity graphite still kettle, control 112.5 ~ 113.5 ℃ of distillation temperatures, reflux ratio 3,4 ~ 8 ℃ of temperature of cooling water, distillation speed 500L/H, obtain the rectifying cut through 0.1 μ m filter core circulating filtration 2 ~ 3 hours, obtain super clean, high purified hydrofluoric acid.
Embodiment 5
A kind of preparation method of super clean, high purified hydrofluoric acid, the following step that it comprises successively and carries out continuously:
(1), raw material dry state hydrogen fluoride is derived from storage tank under 25 ℃ ~ 35 ℃ of temperature and pressure 0.08 ~ 0.12Mpa, derivation speed is 200kg/h.
(2), making the hydrogen fluoride gas of derivation is 5A type molecular sieve adsorption, the 0.01 μ m filter element filtering of 1.5 ~ 2mm successively by diameter;
(3), make hydrogen fluoride gas successively the barium fluoride aqueous solution by 1g/L is housed volume tank and the volume tank of the silver fluoride aqueous solution of 0.5g/L is housed, in volume tank, liquid level maintains 800 ± 100L, reduce the content of S in hydrogen fluoride gas, P, As, B, Cl, Si etc. by gas washing, hydrogen fluoride gas is derived from volume tank speed is 200kg/h.
(4), the hydrogen fluoride gas that surpasses the ultrapure water absorption derivation of 18M Ω with resistivity, obtain the aqueous hydrogen fluoride solution of 40wt%, adding concentration is the hydrogen peroxide of 35wt%, and obtaining content of hydrogen peroxide is the mixing solutions of 0.02wt%, remain under 25 ℃ ~ 30 ℃ circulation stirring 3 hours;
(3), with the aqueous hydrogen fluoride solution of step (4) with the high rectifying of boiling of high purity graphite still kettle, control 112.5 ~ 113.5 ℃ of distillation temperatures, reflux ratio 3,4 ~ 8 ℃ of temperature of cooling water, distillation speed 500L/H, obtain the rectifying cut through 0.1 μ m filter core circulating filtration 2 ~ 3 hours, obtain super clean, high purified hydrofluoric acid.
Impurity component in the super clean, high purified hydrofluoric acid of embodiment 1 ~ 5 preparation is detected, and result is referring to table 1.As seen from Table 1, in the super clean, high purified hydrofluoric acid of the inventive method preparation, the individual event cation impurity levels is little below 0.05ppb, and most of cation impurity levels are below 0.01ppb, and particularly the content of As is reduced to 0.001ppb.In super clean, high purified hydrofluoric acid, anionic impurity also obtains extraordinary control, the highest 20ppb that is no more than, and therefore, gained super clean, high purified hydrofluoric acid of the present invention reaches the SEMIC12 requirement fully.
The detected result of the super clean, high purified hydrofluoric acid of table 1 embodiment 1 ~ 5
| Impurity component | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| CL | ppb | 1.3 | 0.6 | 0.9 | 0.4 | 3.6 |
| NO 3 | ppb | 0.2 | 0.6 | 0.8 | 0.6 | 0.7 |
| PO 4 | ppb | 10.1 | 8 | 10.2 | 18.2 | 7.2 |
| SO 4 | ppb | 4.3 | 4.6 | 4.4 | 5.4 | 4.2 |
| H 2SiF 6 | ppb | 16000 | 18000 | 13000 | 19500 | 17000 |
| Sodium (Na) | ppb | 0.007 | 0.003 | 0.005 | 0.011 | 0.001 |
| Magnesium (Mg) | ppb | 0.001 | 0.002 | 0.002 | 0.004 | 0.009 |
| Aluminium (Al) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.011 |
| Potassium (K) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.010 |
| Calcium (Ca) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.004 |
| Titanium (Ti) | ppb | 0.007 | 0.001 | 0.008 | 0.004 | 0.039 |
| Vanadium (V) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.010 |
| Chromium (Cr) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Manganese (Mn) | ppb | 0.001 | 0.001 | 0.001 | 0.020 | 0.001 |
| Iron (Fe) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Nickel (Ni) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Cobalt (Co) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Copper (Cu) | ppb | 0.001 | 0.001 | 0.001 | 0.004 | 0.001 |
| Zinc (Zn) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Gallium (Ga) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Germanium (Ge) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Arsenic (As) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Strontium (Sr) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Zirconium (Zr) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.002 |
| Niobium (Nb) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Molybdenum (Mo) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Silver (Ag) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Cadmium (Cd) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Tin (Sn) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Antimony (Sb) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Barium (Ba) | ppb | 0.002 | 0.002 | 0.003 | 0.003 | 0.003 |
| Tantalum (Ta) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Plumbous (Pb) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| Bismuth (Bi) | ppb | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
Above the present invention is described in detail; its purpose is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (7)
1. the preparation method of a super clean, high purified hydrofluoric acid, it is characterized in that: in weight content, in described super clean, high purified hydrofluoric acid, individual event anionic impurity content≤50ppb, individual event metals content impurity≤0.1ppb,＞0.2 μ m granule density≤100/ml, described method is take technical grade dry state hydrogen fluoride as raw material, the following step that comprises successively and carry out continuously:
(1), raw material dry state hydrogen fluoride is derived under 25 ℃ ~ 35 ℃ of temperature and pressure 0.08 ~ 0.12Mpa from storage tank;
(2), make the hydrogen fluoride gas of derivation pass through successively molecular sieve adsorption, 0.01 μ m filter element filtering, the barium fluoride aqueous solution of 1 ~ 2g/L and the silver fluoride aqueous solution of 0.1 ~ 1g/L, afterwards, absorb to such an extent that set the aqueous hydrogen fluoride solution of concentration with the ultrapure water that resistivity surpasses 18M Ω, and interpolation hydrogen peroxide, the acquisition content of hydrogen peroxide is the mixing solutions of 0.01 wt% ~ 0.1wt%, remain under 20 ℃ ~ 30 ℃, circulation stirring at least 1 hour, wherein: the described barium fluoride aqueous solution, the silver fluoride aqueous solution is by analytical pure or above preparation of raw material, in weight content, in described hydrogen peroxide, every cation impurity levels is less than 10ppb, anionic impurity content is less than 500ppb, molecular sieve adsorption is used for removing at least partly the organic gas impurity that hydrogen fluoride gas contains,
(3), control 112.5 ℃ ~ 113.5 ℃ of distillation temperatures, reflux ratio 2 ~ 4, aqueous hydrogen fluoride solution is carried out rectifying, the rectifying cut is through 0.1 μ m filter core circulating filtration, obtain described super clean, high purified hydrofluoric acid, wherein utilize leachable metallic impurity mass concentration to carry out described rectifying less than the high purity graphite still kettle of 10ppb.
2. the preparation method of super clean, high purified hydrofluoric acid according to claim 1, it is characterized in that: in step (2), described setting concentration is 35wt% ~ 60wt%.
3. the preparation method of super clean, high purified hydrofluoric acid according to claim 1 and 2, it is characterized in that: in step (2), the concentration of the hydrogen peroxide that adds is 30wt % ~ 50wt%.
4. the preparation method of super clean, high purified hydrofluoric acid according to claim 1, it is characterized in that: in step (2), the time that described circulation stirring carries out is 1 ~ 3 hour.
5. the preparation method of super clean, high purified hydrofluoric acid according to claim 1, it is characterized in that: in step (2), described molecular sieve is 5A type molecular sieve.
6. the preparation method of super clean, high purified hydrofluoric acid according to claim 1, it is characterized in that: in step (3), the time of circulating filtration is 2 ~ 3 hours.
7. the preparation method of super clean, high purified hydrofluoric acid according to claim 1, it is characterized in that: in step (1), the derivation speed of hydrogen fluoride gas is 160 ~ 240kg/h.
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| CN104973573B (en) * | 2015-06-18 | 2017-03-29 | 多氟多化工股份有限公司 | A kind of preparation method of the preparation method and high-pure hydrofluoric acid of high-purity hydrogen fluoride |
| 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 |
| CN108975274B (en) * | 2018-10-17 | 2019-12-27 | 杨松 | Preparation electronic level hydrogen fluoride oxidation reaction unit |
| CN110127616B (en) * | 2019-04-17 | 2021-05-04 | 苏州汉谱埃文材料科技有限公司 | Purification process of ultrapure acid liquid |
| CN116654872B (en) * | 2023-06-26 | 2024-02-02 | 江苏省化工设计院有限公司 | Preparation method of electronic grade hydrofluoric acid |
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| CN1931709A (en) * | 2006-10-09 | 2007-03-21 | 殷福华 | Prepn process of high purity hydrofluoric acid |
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| CN102092684A (en) * | 2011-01-06 | 2011-06-15 | 苏州晶瑞化学有限公司 | Method for preparing electronic grade ultrahigh purity hydrofluoric acid |
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| US4954330A (en) * | 1989-11-30 | 1990-09-04 | E. I. Dupont De Nemours And Company | Process for purifying hydrogen fluoride |
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