CN114560442A - Purification process of electronic grade hydrochloric acid - Google Patents
Purification process of electronic grade hydrochloric acid Download PDFInfo
- Publication number
- CN114560442A CN114560442A CN202210309898.5A CN202210309898A CN114560442A CN 114560442 A CN114560442 A CN 114560442A CN 202210309898 A CN202210309898 A CN 202210309898A CN 114560442 A CN114560442 A CN 114560442A
- Authority
- CN
- China
- Prior art keywords
- hydrochloric acid
- purification process
- temperature
- water pipe
- cooler
- Prior art date
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000746 purification Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000000498 cooling water Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241001550224 Apha Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000002699 waste material Substances 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
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- 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
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0712—Purification ; Separation of hydrogen chloride by distillation
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention discloses a purification process of electronic grade hydrochloric acid, which comprises the following steps: (1) introducing 32% hydrochloric acid solution and calcium chloride solution into an analytical tower, and carrying out high-temperature distillation to form gaseous hydrochloric acid; (2) sequentially passing the gaseous hydrochloric acid through concentrated sulfuric acid and a demister to reduce the water content to 5 ppm; (3) and continuously cooling the gaseous hydrochloric acid by a cooler in a circulating manner to obtain a 36% hydrochloric acid solution. The invention has large output energy consumption ratio and good product stability, and can realize continuous production.
Description
Technical Field
The invention belongs to the technical field of microelectronic chemical reagents, and particularly relates to a purification process of electronic-grade hydrochloric acid.
Background
With the rapid development of semiconductor technology, the requirement for ultra-clean and high-purity reagents is higher and higher. In the process of processing Integrated Circuits (IC), the ultra-clean high-purity reagent is mainly used for cleaning and etching the surfaces of chips and silicon wafers, and the purity and cleanliness of the ultra-clean high-purity reagent have great influence on the yield, the electrical property and the reliability of the integrated circuits.
Ultra-clean high-purity hydrochloric acid has been widely used in cleaning, drying, etc. of semiconductor and large-scale integrated circuit processing as an important microelectronic chemical. As the processing size of IC has entered submicron and deep submicron times, higher requirements are provided for ultra-clean high-purity hydrochloric acid matched with the IC, the content of particles and impurities is required to be reduced by 1-3 orders of magnitude, and the standard of SEMI C12 established by International semiconductor Equipment and Material organization is reached, wherein the content of metal cations is less than 0.1ppb, and the particle size is controlled below 0.5 μm.
At present, the ultra-clean high-purity hydrochloric acid is usually purified by using industrial-grade hydrochloric acid as a raw material in a circulating distillation and falling film absorption mode, and the defects of the ultra-clean high-purity hydrochloric acid are as follows: 1. the quality of the product, particularly the content of metal ions and the size of particle impurities in the product cannot be stably controlled; 2. crude hydrochloric acid forms an azeotrope of about 36% (the proportion of hydrogen chloride and water is constant) when heated in a tower kettle at 112 ℃, raw materials are continuously added into the tower in continuous production, residual liquid is continuously discharged, the content of hydrogen chloride in the discharged residual liquid is close to 20%, the yield is only about 60%, the discharged residual liquid causes environmental pollution, and great burden is brought to environmental protection facilities; 3. the distillation equipment adopts glass or quartz as a material and the heat supply mode determines the scale of the equipment, most enterprises produce small equipment with multiple sets, and operators have few preparations and potential hidden dangers of safe production.
Disclosure of Invention
The invention mainly solves the technical problem of providing the purification process of the electronic grade hydrochloric acid, which has large yield energy consumption ratio and good product stability and can realize continuous production.
In order to solve the technical problems, the invention adopts a technical scheme that: a purification process of electronic grade hydrochloric acid comprises the following steps:
(1) introducing 32% hydrochloric acid solution and calcium chloride solution into an analytical tower, and carrying out high-temperature distillation to form gaseous hydrochloric acid;
(2) sequentially passing the gaseous hydrochloric acid through concentrated sulfuric acid and a demister to reduce the water content to 5 ppm;
(3) and continuously cooling the gaseous hydrochloric acid by a cooler in a circulating manner to obtain a 36% hydrochloric acid solution.
Further, in the step (1), the temperature of the desorption tower is 125-130 ℃, the pressure is 1.35-1.40barg, and the gas flow rate is 0.5-0.7 m/s.
Further, in the step (1), the mixing ratio of the hydrochloric acid solution to the calcium chloride solution in percentage by weight is 3-5: 1.
further, in the step (3), the flow rate of the cooling water in the cooler is 1 to 1.5 m/s.
The cooler comprises a circulating water pipe and a cooling water pipe, wherein the water inlet temperature of the circulating water pipe is 30-35 ℃, and the water outlet temperature of the circulating water pipe is 40-45 ℃; the water inlet temperature of the cooling water pipe is-12 to-15 ℃, and the water outlet temperature is-11 to-14 ℃.
Further, the cooling water is ultrapure water.
Further, in the step (1), the concentration of the gaseous hydrochloric acid after the high-temperature distillation is 99.9%.
The invention has the beneficial effects that:
(1) according to the invention, the calcium chloride solution and the hydrochloric acid solution are mixed and then evaporated at high temperature, so that the low-concentration hydrochloric acid is effectively increased to the required concentration, the generation of waste hydrochloric acid is reduced, and the calcium chloride can be recycled;
(2) the method reduces the water content to 5ppm by carrying out concentrated sulfuric acid drying and demisting procedures on gaseous hydrochloric acid obtained by high-temperature evaporation, reduces the corrosion to pipelines, and reduces the content of trace metal impurities;
(3) the invention uses the cooler to circularly cool the gaseous hydrochloric acid to form hydrochloric acid with the concentration of 36%, thereby effectively increasing the absorption efficiency, avoiding the escape of hydrochloric acid gas and reducing the production pollution.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.
Example (b): a purification process of electronic grade hydrochloric acid comprises the following steps:
(1) introducing 32% hydrochloric acid solution and calcium chloride solution into an analytical tower, and carrying out high-temperature distillation to form gaseous hydrochloric acid;
(2) sequentially passing the gaseous hydrochloric acid through concentrated sulfuric acid and a demister to reduce the water content to 5 ppm;
(3) and continuously cooling the gaseous hydrochloric acid by a cooler in a circulating manner to obtain a 36% hydrochloric acid solution.
In the step (1), the temperature of the desorption tower is 125-130 ℃, the pressure is 1.35-1.40barg, and the gas flow rate is 0.5-0.7 m/s.
In the step (1), the mixing ratio of the hydrochloric acid solution to the calcium chloride solution in percentage by weight is 3-5: 1, preferably 4: 1.
in the step (3), the flow rate of the cooling water in the cooler is 1-1.5 m/s.
The cooler comprises a circulating water pipe and a cooling water pipe, wherein the water inlet temperature of the circulating water pipe is 30-35 ℃, and the water outlet temperature of the circulating water pipe is 40-45 ℃; the water inlet temperature of the cooling water pipe is-12 to-15 ℃, and the water outlet temperature is-11 to-14 ℃.
The cooling water is ultrapure water.
In the step (1), the concentration of the gaseous hydrochloric acid after high-temperature distillation is 99.9%.
The technical indexes of the obtained hydrochloric acid product are as follows:
| technical index | Index content |
| Concentration of | 36±0.5％ |
| Chroma (APHA) | <5 |
| Various metal impurities | ≤10ppt |
| Nitrate salt | ≤10ppb |
| Phosphate salts | ≤50ppb |
| Sulfates of sulfuric acid | ≤50ppb |
| Residue of combustion (SO)4) | ≤500ppm |
| Granule (not less than0.1um) | 1000pcs/ml |
| Particle (not less than 0.2um) | 40pcs/ml |
| Particle (not less than 0.3um) | 15pcs/ml |
| Particle (not less than 0.5um) | 5pcs/ml |
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the content of the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A purification process of electronic grade hydrochloric acid is characterized in that: the method comprises the following steps:
(1) introducing 32% hydrochloric acid solution and calcium chloride solution into an analytical tower, and carrying out high-temperature distillation to form gaseous hydrochloric acid;
(2) sequentially passing the gaseous hydrochloric acid through concentrated sulfuric acid and a demister to reduce the water content to 5 ppm;
(3) and continuously cooling the gaseous hydrochloric acid by a cooler in a circulating manner to obtain a 36% hydrochloric acid solution.
2. The process of claim 1, wherein the purification process comprises: in the step (1), the temperature of the desorption tower is 125-130 ℃, the pressure is 1.35-1.40barg, and the gas flow rate is 0.5-0.7 m/s.
3. The process of claim 1, wherein the purification process comprises: in the step (1), the mixing ratio of the hydrochloric acid solution to the calcium chloride solution in percentage by weight is 3-5: 1.
4. the process of claim 1, wherein the purification process comprises: in the step (3), the flow rate of the cooling water in the cooler is 1-1.5 m/s.
5. The process of claim 1, wherein the purification process comprises: the cooler comprises a circulating water pipe and a cooling water pipe, wherein the water inlet temperature of the circulating water pipe is 30-35 ℃, and the water outlet temperature of the circulating water pipe is 40-45 ℃; the water inlet temperature of the cooling water pipe is-12 to-15 ℃, and the water outlet temperature is-11 to-14 ℃.
6. The process of claim 4, wherein the purification process comprises: the cooling water is ultrapure water.
7. The process of claim 1, wherein the purification process comprises: in the step (1), the concentration of the gaseous hydrochloric acid after high-temperature distillation is 99.9%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210309898.5A CN114560442A (en) | 2022-03-28 | 2022-03-28 | Purification process of electronic grade hydrochloric acid |
| PCT/CN2022/140690 WO2023185124A1 (en) | 2022-03-28 | 2022-12-21 | Purification process for electronic grade hydrochloric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210309898.5A CN114560442A (en) | 2022-03-28 | 2022-03-28 | Purification process of electronic grade hydrochloric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114560442A true CN114560442A (en) | 2022-05-31 |
Family
ID=81719652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210309898.5A Pending CN114560442A (en) | 2022-03-28 | 2022-03-28 | Purification process of electronic grade hydrochloric acid |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114560442A (en) |
| WO (1) | WO2023185124A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023185124A1 (en) * | 2022-03-28 | 2023-10-05 | 联仕(昆山)化学材料有限公司 | Purification process for electronic grade hydrochloric acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285641A (en) * | 2010-06-21 | 2011-12-21 | 南通星球石墨设备有限公司 | Recycling process of waste hydrochloric acid |
| CN109678114A (en) * | 2019-02-19 | 2019-04-26 | 苏州晶瑞化学股份有限公司 | The minimizing technology of arsenic impurities in a kind of electronic grade hydrochloric acid |
| CN214399818U (en) * | 2021-01-20 | 2021-10-15 | 杭州东日节能技术有限公司 | Device for purifying hydrogen chloride by calcium chloride method containing impurity dilute hydrochloric acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO123796B (en) * | 1970-07-17 | 1972-01-17 | Norsk Hydro As | |
| 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 |
-
2022
- 2022-03-28 CN CN202210309898.5A patent/CN114560442A/en active Pending
- 2022-12-21 WO PCT/CN2022/140690 patent/WO2023185124A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285641A (en) * | 2010-06-21 | 2011-12-21 | 南通星球石墨设备有限公司 | Recycling process of waste hydrochloric acid |
| CN109678114A (en) * | 2019-02-19 | 2019-04-26 | 苏州晶瑞化学股份有限公司 | The minimizing technology of arsenic impurities in a kind of electronic grade hydrochloric acid |
| CN214399818U (en) * | 2021-01-20 | 2021-10-15 | 杭州东日节能技术有限公司 | Device for purifying hydrogen chloride by calcium chloride method containing impurity dilute hydrochloric acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023185124A1 (en) * | 2022-03-28 | 2023-10-05 | 联仕(昆山)化学材料有限公司 | Purification process for electronic grade hydrochloric acid |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023185124A1 (en) | 2023-10-05 |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
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| RJ01 | Rejection of invention patent application after publication | ||
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Application publication date: 20220531 |