CN119191228B - Method for removing arsenic element in electronic grade hydrochloric acid - Google Patents
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- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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Abstract
本发明涉及一种去除电子级盐酸中砷元素的方法；本发明将工业级盐酸，通过精馏分离，产生气态氯化氢，依次通过活性炭吸附塔、耐酸分子筛吸附塔、氧化锆吸附塔，吸附后进入含高纯水的暂存槽；暂存槽的氯化氢调配成质量浓度为28‑32%的盐酸进入精馏塔，精馏后的气态氯化氢进入调配槽；调配槽的气态氯化氢调配成质量浓度为36‑37%盐酸进入成品槽，成品槽中的盐酸通过多级过滤得到电子级盐酸；本发明的耐酸分子筛吸附塔采用改性Y型分子筛，通过Γ‑环氧丙氧(基)丙基三甲氧基硅烷、Y型分子筛、氨基三甲叉磷酸、双‑(2‑甲基烯丙基)环辛‑1,5‑二烯钌反应制得；本发明制备的电子级盐酸，杂质含量低，砷元素去除率高。The invention relates to a method for removing arsenic in electronic-grade hydrochloric acid. The method comprises the following steps: separating industrial-grade hydrochloric acid through rectification to generate gaseous hydrogen chloride, which is sequentially passed through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower and a zirconium oxide adsorption tower, and then enters a temporary storage tank containing high-purity water after adsorption; the hydrogen chloride in the temporary storage tank is prepared into hydrochloric acid with a mass concentration of 28-32% and enters the rectification tower, and the gaseous hydrogen chloride after rectification enters the preparation tank; the gaseous hydrogen chloride in the preparation tank is prepared into hydrochloric acid with a mass concentration of 36-37% and enters a finished product tank, and the hydrochloric acid in the finished product tank is filtered in multiple stages to obtain electronic-grade hydrochloric acid; the acid-resistant molecular sieve adsorption tower adopts a modified Y-type molecular sieve, and is prepared by reacting Γ-glycidoxypropyltrimethoxysilane, a Y-type molecular sieve, aminotri(methylenephosphoric acid) and bis(2-methylallyl)cyclooctane-1,5-dieneruthenium; the electronic-grade hydrochloric acid prepared by the method has low impurity content and high arsenic removal rate.
Description
Technical Field
The invention relates to the technical field of electronic grade hydrochloric acid, in particular to a method for removing arsenic element in electronic grade hydrochloric acid.
Background
Arsenic in hydrochloric acid exists in the forms of trivalent AsCl 3 and trivalent H 3AsO3, but the boiling points of AsCl 3 and 28-32% hydrochloric acid solution are relatively close, and trivalent arsenic ions are difficult to remove by a common rectification method.
The adsorption method is to remove impurity ions by using the attraction of the adsorbent to the impurity elements, and can effectively adsorb the impurity ions from the gas or the liquid, and the adsorbent comprises kaolinite, lignin, carbon nanotubes, graphene, metal oxide, silica gel and the like. However, in order to effectively remove arsenic element in hydrochloric acid, it is difficult to achieve an optimal separation effect by only one adsorbent.
Chinese patent CN108609584A discloses a production process of electronic grade hydrochloric acid, and relates to the technical field of chemical industry. The invention provides a production process of electronic grade hydrochloric acid, which comprises the steps of placing industrial grade hydrochloric acid in a reaction kettle, adding hydrazine hydrate into the reaction kettle, stirring and mixing until complete reaction, introducing all the reacted materials into a deacidification tower, maintaining negative pressure in the deacidification tower, introducing air into the deacidification tower to carry out bubbling stirring and blowing desorption on the solution to obtain escape gas and tower bottom liquid, compressing the escape gas desorbed in the deacidification tower by a compressor, and enabling the compressed escape gas to enter an acid washing tower for acid washing to obtain the electronic grade hydrochloric acid, wherein non-condensable gas returns to the bottom of the deacidification tower for bubbling circulation, and maintaining the negative pressure in the acid washing tower.
Chinese patent CN117585644A relates to the technical field of high-purity hydrochloric acid, and particularly discloses a preparation method of electronic grade hydrochloric acid. A preparation method of electronic grade hydrochloric acid comprises the following specific steps of S1, sequentially carrying out primary filtration and pretreatment on industrial grade hydrochloric acid to obtain primary hydrochloric acid, S2, conveying the primary hydrochloric acid to a rectifying tower to obtain gas-phase hydrogen chloride, then carrying out dehydration and demisting treatment on the gas-phase hydrogen chloride by concentrated sulfuric acid, reducing the moisture in the gas-phase hydrogen chloride, and then carrying out condensation treatment to obtain a hydrochloric acid semi-finished product, S3, circularly absorbing hydrogen chloride tail gas by using ultrapure water by using the hydrochloric acid semi-finished product, and finally carrying out secondary filtration and impurity removal purification to obtain the electronic grade hydrochloric acid, wherein the pretreatment is carried out on the industrial grade hydrochloric acid by using a reducing agent.
Chinese patent CN109761196A provides a production method of electronic grade hydrochloric acid, which sequentially comprises the following steps of 1, feeding synthesized hydrogen chloride gas into an adsorption tower to remove free chlorine, 2, adopting a reagent grade hydrochloric acid solvent, feeding the hydrogen chloride gas into a washing tower from an upper inlet of the washing tower to wash and adsorb the hydrogen chloride gas so as to remove soluble impurities, 3, condensing the washed hydrogen chloride gas through a first stage and a second stage, feeding the hydrogen chloride gas into a demister to remove water mist in the hydrogen chloride gas so as to obtain high-purity hydrogen chloride gas, 4, absorbing the high-purity hydrogen chloride gas through a first-stage falling film absorber, a second-stage falling film absorber and a tail gas absorber, and then obtaining a finished product through a hydrochloric acid cooler, 5, adopting ultrapure water for absorption, 6, feeding the finished product obtained in the step 4 into a finished product storage tank, and removing particle impurities through ultrafiltration so as to obtain the electronic grade hydrochloric acid.
The electronic grade hydrochloric acid prepared by the above patent and the prior art, wherein free chlorine, arsenic element and other impurities are still to be further reduced.
Disclosure of Invention
In order to solve the problems, the invention provides a method for removing arsenic element in electronic grade hydrochloric acid, which comprises the following operation steps:
s1, rectifying and separating industrial grade hydrochloric acid with the mass concentration of 25-30% to generate gaseous hydrogen chloride, wherein the gaseous hydrogen chloride enters a temporary storage tank containing high-purity water after passing through an active carbon adsorption tower, an acid-resistant molecular sieve adsorption tower and a zirconia adsorption tower in sequence;
s2, preparing hydrochloric acid with the mass concentration of 28-32% by using the hydrogen chloride entering the temporary storage tank, rectifying the hydrochloric acid, and enabling the rectified gaseous hydrogen chloride to enter the preparation tank;
And S3, preparing gaseous hydrogen chloride entering a preparation tank into hydrochloric acid with the mass concentration of 36-37% into a finished product tank, and performing multistage filtration on the hydrochloric acid in the finished product tank to obtain electronic grade hydrochloric acid.
The adsorption temperature of S1 is 25-35 ℃, and the adsorption time is 10-60min.
The rectification temperature of the S2 is 105-120 ℃.
The acid-resistant molecular sieve adsorption tower adopts a modified Y-type molecular sieve, and the preparation method comprises the following steps:
a1, stirring and mixing 2-5 parts of gamma-glycidoxy (propyl) trimethoxy silane, 100-150 parts of Y-type molecular sieve and 1000-1300 parts of solvent at normal temperature;
A2, adding 9-18 parts of aminotrimethylene phosphoric acid and 0.003-0.03 part of bis- (2-methallyl) cycloocta-1, 5-diene ruthenium, adjusting the pH to be 9 by using triethylamine, reacting, filtering, washing to be neutral, and drying to obtain the modified Y-type molecular sieve.
The solvent of A1 is DMF.
The stirring time of the A1 is 90-120min.
The reaction temperature of the A2 is 80-90 ℃ and the reaction time is 24-48 hours.
The preparation method of the zirconia particles in the zirconia adsorption tower comprises the following steps:
10-16 parts of high-purity ZrCl 4 is added into a reaction kettle, 10-32 parts of oxygen and 10-32 parts of hydrogen are introduced, and the mixture is heated for reaction, so that zirconia particles are obtained.
The heating reaction temperature is 300-700 ℃ and the reaction time is 2-6h.
The diameter of the zirconia particles is 6-10 microns, the specific surface area is 320-400m 2/g, and the porosity is 0.12-0.20cm 3/g.
Reaction mechanism
And (3) condensation reaction is carried out on the gamma-glycidoxy (radical) propyl trimethoxy silane and hydroxyl on the surface of the Y-type molecular sieve to generate the epoxy Y-type molecular sieve. This step is critical because it provides an active site for the subsequent ring opening reaction.
The epoxy Y-type molecular sieve is subjected to ring opening reaction with the amino group of the amino trimethophosphate to form a stable chemical bond. This process enables the effective grafting of the trimetaphosphate onto the molecular sieve surface.
The bis- (2-methallyl) cycloocta-1, 5-diene ruthenium and amino trimethophosphate undergo amino-allyl addition reaction, so that the structure of the molecular sieve surface is further stabilized, and a ruthenium diene complex is introduced. The modified Y-type molecular sieve has stronger adsorption capacity and selectivity.
Technical effects
Compared with the prior art, the method for removing the arsenic element in the electronic grade hydrochloric acid has the following remarkable effects:
1. The zirconia is a weak acid oxide, has stable chemical property, has enough stability in acid solution, has good adsorption effect on arsenic (III) and arsenic (V), adopts zirconia particles, combines active carbon and acid-resistant molecular sieve, and can remove arsenic element in hydrochloric acid;
2. In order to prevent impurities brought by an adsorbent in the adsorption tower from entering products, the adsorbed hydrogen chloride is further absorbed by high-purity water to prepare hydrochloric acid with the concentration of 28-32%, the impurities brought by the adsorption tower are dissolved in the high-purity water, and the high-purity hydrogen chloride is further obtained by rectification;
3. the method can effectively remove impurities in the industrial hydrochloric acid through rectification, and can effectively remove arsenic impurities in the hydrochloric acid by combining activated carbon, a molecular sieve and a technique of adsorbing arsenic impurities in the hydrochloric acid by zirconia, wherein mesoporous zirconia is used as an adsorbent;
4. the combination of the trimetaphosphate and the ruthenium dioxide complex greatly improves the adsorption capacity of the Y-type molecular sieve to arsenic. This is because the trimetaphosphate has multiple functional groups and can form stable complexes with arsenic, and the introduction of the ruthenium dicyclopentadiene complex further enhances this stability.
The modified Y-type molecular sieve not only can remove arsenic element in the electronic grade hydrochloric acid efficiently, but also can maintain the high purity of the hydrochloric acid. This is because no other impurity ions are introduced throughout the process, which is critical to the production of electronic grade products.
The continuous stable production capacity of this technology is also one of its important advantages. The electronic grade hydrochloric acid treated by the method can meet strict industrial standards, and meanwhile, the production efficiency and the stability of the product quality are ensured.
In conclusion, the ruthenium complex modified Y-type molecular sieve has excellent performance and technical effect in removing arsenic element in electronic grade hydrochloric acid. The method not only can effectively convert and fix arsenic element, but also can maintain high purity of hydrochloric acid and continuity of production, which has important significance for production of electronic grade products.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is made with reference to examples and comparative examples:
detection was performed with reference to Q/GR101-2024 electronic grade hydrochloric acid.
Example 1
A method for removing arsenic element in electronic grade hydrochloric acid comprises the following operation steps:
s1, rectifying and separating industrial grade hydrochloric acid with the mass concentration of 25% to generate gaseous hydrogen chloride, wherein the gaseous hydrogen chloride enters a temporary storage tank containing high-purity water after passing through an active carbon adsorption tower, an acid-resistant molecular sieve adsorption tower and a zirconia adsorption tower in sequence;
S2, preparing hydrochloric acid with the mass concentration of 28% by using the hydrogen chloride entering the temporary storage tank, rectifying the hydrochloric acid in a rectifying tower, and enabling the rectified gaseous hydrogen chloride to enter the preparation tank;
and S3, preparing gaseous hydrogen chloride entering a preparation tank into hydrochloric acid with the mass concentration of 36% into a finished product tank, and performing multistage filtration on the hydrochloric acid in the finished product tank to obtain electronic grade hydrochloric acid.
The adsorption temperature of S1 is 25 ℃, and the adsorption time is 10min.
The rectification temperature of the S2 is 105 ℃.
The acid-resistant molecular sieve adsorption tower adopts a modified Y-type molecular sieve, and the preparation method comprises the following steps:
a1, mixing 2g of gamma-glycidoxy (propyl) trimethoxy silane, 100gY g of molecular sieve and 1000g of solvent at normal temperature;
A2, adding 9g of aminotrimethylene phosphoric acid, 0.003g of bis- (2-methylallyl) cycloocta-1, 5-diene ruthenium, regulating the pH to be 9 by using triethylamine, reacting, filtering, washing to be neutral, and drying to obtain the modified Y-type molecular sieve.
The solvent of A1 is DMF.
The stirring time of A1 is 90min.
The reaction temperature of the A2 is 80 ℃ and the reaction time is 24 hours.
The preparation method of the zirconia particles in the zirconia adsorption tower comprises the following steps:
10g of high-purity ZrCl 4 is added into a reaction kettle, 10g of oxygen and 10g of hydrogen are introduced, and the mixture is heated for reaction, so that zirconia particles are obtained.
The heating reaction temperature is 300 ℃, and the reaction time is 2 hours.
The diameter of the zirconia particles is 6 microns, the specific surface area is 320m 2/g, and the porosity is 0.12cm 3/g.
Example 2
A method for removing arsenic element in electronic grade hydrochloric acid comprises the following operation steps:
s1, rectifying and separating industrial grade hydrochloric acid with the mass concentration of 28% to generate gaseous hydrogen chloride, wherein the gaseous hydrogen chloride enters a temporary storage tank containing high-purity water after passing through an active carbon adsorption tower, an acid-resistant molecular sieve adsorption tower and a zirconia adsorption tower in sequence;
s2, preparing hydrochloric acid with the mass concentration of 30% by using the hydrogen chloride entering the temporary storage tank, rectifying the hydrochloric acid in a rectifying tower, and enabling the rectified gaseous hydrogen chloride to enter the preparation tank;
and S3, preparing gaseous hydrogen chloride entering a preparation tank into hydrochloric acid with the mass concentration of 36% into a finished product tank, and performing multistage filtration on the hydrochloric acid in the finished product tank to obtain electronic grade hydrochloric acid.
The adsorption temperature of S1 is 28 ℃, and the adsorption time is 30min.
The rectification temperature of the S2 is 110 ℃.
The acid-resistant molecular sieve adsorption tower adopts a modified Y-type molecular sieve, and the preparation method comprises the following steps:
A1, mixing 3g of gamma-glycidoxy (propyl) trimethoxy silane, 110gY g of molecular sieve and 1100g of solvent at normal temperature;
a2, adding 12g of aminotrimethylene phosphoric acid, 0.01g of bis- (2-methylallyl) cycloocta-1, 5-diene ruthenium, regulating the pH to be 9 by using triethylamine, reacting, filtering, washing to be neutral, and drying to obtain the modified Y-type molecular sieve.
The solvent of A1 is DMF.
The stirring time of A1 is 100min.
The reaction temperature of A2 is 85 ℃ and the reaction time is 30 hours.
The preparation method of the zirconia particles in the zirconia adsorption tower comprises the following steps:
12g of high-purity ZrCl 4 is added into a reaction kettle, 16g of oxygen and 16g of hydrogen are introduced, and the mixture is heated for reaction, so that zirconia particles are obtained.
The heating reaction temperature is 400 ℃, and the reaction time is 3 hours.
The diameter of the zirconia particles is 7 microns, the specific surface area is 360m 2/g, and the porosity is 0.16cm 3/g.
Example 3
A method for removing arsenic element in electronic grade hydrochloric acid comprises the following operation steps:
s1, rectifying and separating industrial grade hydrochloric acid with the mass concentration of 28% to generate gaseous hydrogen chloride, wherein the gaseous hydrogen chloride enters a temporary storage tank containing high-purity water after passing through an active carbon adsorption tower, an acid-resistant molecular sieve adsorption tower and a zirconia adsorption tower in sequence;
s2, preparing hydrochloric acid with the mass concentration of 30% by using the hydrogen chloride entering the temporary storage tank, rectifying the hydrochloric acid in a rectifying tower, and enabling the rectified gaseous hydrogen chloride to enter the preparation tank;
and S3, preparing gaseous hydrogen chloride entering the preparation tank into hydrochloric acid with the mass concentration of 37% into a finished product tank, and performing multistage filtration on the hydrochloric acid in the finished product tank to obtain electronic grade hydrochloric acid.
The adsorption temperature of S1 is 32 ℃, and the adsorption time is 50min.
The rectification temperature of the S2 is 115 ℃.
The acid-resistant molecular sieve adsorption tower adopts a modified Y-type molecular sieve, and the preparation method comprises the following steps:
a1, mixing 4g of gamma-glycidoxy (propyl) trimethoxy silane, 140gY g of molecular sieve and 1200g of solvent at normal temperature;
a2, adding 16g of aminotrimethylene phosphoric acid, 0.02g of bis- (2-methylallyl) cycloocta-1, 5-diene ruthenium, regulating the pH to be 9 by using triethylamine, reacting, filtering, washing to be neutral, and drying to obtain the modified Y-type molecular sieve.
The solvent of A1 is DMF.
The stirring time of A1 is 110min.
The reaction temperature of A2 is 85 ℃ and the reaction time is 40 hours.
The preparation method of the zirconia particles in the zirconia adsorption tower comprises the following steps:
14g of high-purity ZrCl 4 is added into a reaction kettle, 28g of oxygen and 28g of hydrogen are introduced, and the mixture is heated for reaction, so that zirconia particles are obtained.
The heating reaction temperature is 600 ℃, and the reaction time is 5 hours.
The diameter of the zirconia particles is 9 microns, the specific surface area is 380m 2/g, and the porosity is 0.18cm 3/g.
Example 4
A method for removing arsenic element in electronic grade hydrochloric acid comprises the following operation steps:
s1, separating industrial grade hydrochloric acid with the mass concentration of 30% by rectification to generate gaseous hydrogen chloride, enabling the gaseous hydrogen chloride to enter a temporary storage tank containing high-purity water after passing through an active carbon adsorption tower, an acid-resistant molecular sieve adsorption tower and a zirconia adsorption tower in sequence;
S2, preparing hydrochloric acid with the mass concentration of 32% by using the hydrogen chloride entering the temporary storage tank, rectifying the hydrochloric acid, and enabling the rectified gaseous hydrogen chloride to enter the preparation tank;
and S3, preparing gaseous hydrogen chloride entering the preparation tank into hydrochloric acid with the mass concentration of 37% into a finished product tank, and performing multistage filtration on the hydrochloric acid in the finished product tank to obtain electronic grade hydrochloric acid.
The adsorption temperature of S1 is 35 ℃, and the adsorption time is 60min.
The rectification temperature of the S2 is 120 ℃.
The acid-resistant molecular sieve adsorption tower adopts a modified Y-type molecular sieve, and the preparation method comprises the following steps:
a1, mixing 5g of gamma-glycidoxy (propyl) trimethoxy silane, 150gY g of molecular sieve and 1300g of solvent at normal temperature;
A2, adding 18g of aminotrimethylene phosphoric acid, 0.03g of bis- (2-methylallyl) cycloocta-1, 5-diene ruthenium, regulating the pH to be 9 by using triethylamine, reacting, filtering, washing to be neutral, and drying to obtain the modified Y-type molecular sieve.
The solvent of A1 is DMF.
The stirring time of A1 is 120min.
The reaction temperature of the A2 is 90 ℃ and the reaction time is 48 hours.
The preparation method of the zirconia particles in the zirconia adsorption tower comprises the following steps:
16g of high-purity ZrCl 4 was added to the reactor, and 32g of oxygen and 32g of hydrogen were introduced and heated to react, thereby obtaining zirconia particles.
The heating reaction temperature is 700 ℃, and the reaction time is 6 hours.
The diameter of the zirconia particles is 10 microns, the specific surface area is 400m 2/g, and the porosity is 0.20cm 3/g.
Comparative example 1
The modification of the Y-type molecular sieve was not performed, and the same as in example 1 was conducted.
Comparative example 2
The procedure of example 1 was repeated except that no amino trimethoprim was added.
Comparative example 3
Bis- (2-methylallyl) cycloocta-1, 5-diene ruthenium was not added, otherwise as in example 1.
| Mg/μg/L | Al/μg/L | Zn/μg/L | Ca/μg/L | Mn/μg/L | Fe/μg/L | As/μg/L | |
| Example 1 | 0.007 | 0.007 | 0.007 | 0.009 | 0.008 | 0.009 | 0.006 |
| Example 2 | 0.006 | 0.006 | 0.006 | 0.008 | 0.007 | 0.008 | 0.005 |
| Example 3 | 0.006 | 0.005 | 0.005 | 0.007 | 0.006 | 0.007 | 0.003 |
| Example 4 | 0.005 | 0.005 | 0.004 | 0.006 | 0.006 | 0.007 | 0.002 |
| Comparative example 1 | 0.29 | 0.28 | 0.27 | 0.30 | 0.32 | 0.31 | 0.26 |
| Comparative example 2 | 0.17 | 0.16 | 0.16 | 0.18 | 0.21 | 0.20 | 0.16 |
| Comparative example 3 | 0.15 | 0.14 | 0.15 | 0.16 | 0.19 | 0.17 | 0.14 |
Through the data analysis of the above examples and comparative examples, the electronic grade hydrochloric acid prepared by the invention has low impurity content and high arsenic element removal rate. The contents of metal impurity elements in the hydrochloric acid prepared in the above examples and comparative examples were obtained by AGILENT ICP-MS8900 test, the test working parameters were that the power was 1.5KW, the air pressure was 0.7MPa, the hydrogen gas was 0.05MPa, the helium gas was 0.05MPa, the carrier gas flow rate was 0.75L/min, the compensating gas flow rate was 0.41L/min, the sampling depth was 8mm, and the ultra-pure water was Millipore water. The tuning mode is conventional, the sample injection pipeline is placed into tuning liquid, and after the sample injection pipeline is stabilized for 15 seconds, the signal value cps of the element with the mass number of 7Li is larger than 4000. Test method standard addition method.
The present invention is not limited in any way by the above-described preferred embodiments, but is not limited to the above-described preferred embodiments, and any person skilled in the art will appreciate that the present invention can be embodied in the form of a program for carrying out the method of the present invention, while the above disclosure is directed to equivalent embodiments capable of being modified or altered in some ways, it is apparent that any modifications, equivalent variations and alterations made to the above embodiments according to the technical principles of the present invention fall within the scope of the present invention.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624050A (en) * | 2020-12-16 | 2021-04-09 | 浙江天采云集科技股份有限公司 | FTrPSA separation and purification method for HCl gas containing low-concentration HF through deep defluorination and drying |
| CN114655928A (en) * | 2022-02-25 | 2022-06-24 | 江苏捷创新材料有限责任公司 | Preparation method of electronic-grade hydrochloric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100317113B1 (en) * | 1999-03-03 | 2002-01-18 | 박대치 | The method of purifying hydrogen chloride |
| CN102398895B (en) * | 2010-09-16 | 2014-09-24 | 上海化学试剂研究所 | A kind of production method of ultrapure electronic grade chemical reagent |
| CN104353440A (en) * | 2014-11-28 | 2015-02-18 | 南京信息工程大学 | Biomass resin based inorganic nano-oxide composite adsorbent and preparation method and application thereof |
| CN109678114B (en) * | 2019-02-19 | 2021-04-02 | 苏州晶瑞化学股份有限公司 | Method for removing arsenic impurity in electronic grade hydrochloric acid |
| CN111960384B (en) * | 2020-08-26 | 2022-04-12 | 浙江凯圣氟化学有限公司 | Method for removing free chlorine in hydrochloric acid |
| KR20230058221A (en) * | 2021-10-22 | 2023-05-03 | 효성화학 주식회사 | Methode for preparing high-purity hydrogen chloride |
| CN114560442A (en) * | 2022-03-28 | 2022-05-31 | 联仕(昆山)化学材料有限公司 | Purification process of electronic grade hydrochloric acid |
| CN117585644A (en) * | 2023-11-07 | 2024-02-23 | 江苏省化工设计院有限公司 | Preparation method of electronic grade hydrochloric acid |
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| CN112624050A (en) * | 2020-12-16 | 2021-04-09 | 浙江天采云集科技股份有限公司 | FTrPSA separation and purification method for HCl gas containing low-concentration HF through deep defluorination and drying |
| CN114655928A (en) * | 2022-02-25 | 2022-06-24 | 江苏捷创新材料有限责任公司 | Preparation method of electronic-grade hydrochloric acid |
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