CN115535965A - Method for continuously removing arsenic by hydrofluoric acid - Google Patents
Method for continuously removing arsenic by hydrofluoric acid Download PDFInfo
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- CN115535965A CN115535965A CN202211252871.3A CN202211252871A CN115535965A CN 115535965 A CN115535965 A CN 115535965A CN 202211252871 A CN202211252871 A CN 202211252871A CN 115535965 A CN115535965 A CN 115535965A
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 77
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 7
- 239000012498 ultrapure water Substances 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/196—Separation; Purification by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for continuously removing arsenic by hydrofluoric acid, wherein an oxidant which is introduced into a first cooling tube pass of a low-temperature reaction module of a continuous flow reactor through a first metering pump is cooled to a first set temperature; the anhydrous hydrofluoric acid which is introduced into a second cooling tube pass of the low-temperature reaction module of the continuous flow reactor through a second metering pump is cooled to a first set temperature; the two materials which are cooled to the first set temperature are converged, and in the main tube pass of the low-temperature reaction module, after the oxidation reaction at the first set temperature, the two materials pass through the tube pass of the high-temperature reaction module of the continuous flow reactor through a pipeline; performing oxidation reaction at a second set temperature, enabling an oxidation product to enter the tower kettle through a pipeline, then removing the oxidation product through a rectifying tower to obtain hydrogen fluoride gas, and forming liquid hydrogen fluoride through a condenser; the liquid hydrogen fluoride and the ultrapure water are introduced into the blending tank together to form a hydrofluoric acid product, and the invention has the advantages of low reaction temperature, increased reaction safety and controllability of reaction conditions, and high conversion efficiency.
Description
Technical Field
The invention relates to the technical field of chemical metallurgy, in particular to a method for continuously removing arsenic by hydrofluoric acid.
Background
Hydrofluoric acid is an important chemical raw material and is commonly used for cleaning and etching integrated circuit boards.
Hydrofluoric acid is an aqueous solution of hydrogen fluoride gas. The preparation method is that ultrapure water is used for absorbing rectified anhydrous hydrogen fluoride to form aqueous solution with the mass fraction of 40%. As arsenic trifluoride contained in the hydrogen fluoride and anhydrous hydrogen fluoride are subjected to azeotropy and cannot be removed in the rectification process, and the obtained hydrofluoric acid contains arsenic impurities. The presence of arsenic impurities adversely affects the performance of the electronic device and therefore needs to be removed.
The prior arsenic removal method is a batch oxidation method. For example, patent CN101597032a adopts potassium permanganate and sodium hydroxide solution to be added into liquid hydrogen fluoride, and the mixture is subjected to rectification after standing for 0.5 to 1 hour. In patent CN100546903, potassium permanganate and hydrogen peroxide are added into a rectifying still respectively and are oxidized for 0.5 to 1 hour, and then rectification is carried out. CN108609585A, hydrogen peroxide is added into a reaction kettle to be oxidized for 3 hours and then rectified. The batch oxidation method for removing arsenic has the defects of poor reaction controllability, long time consumption and the like.
Disclosure of Invention
The invention aims to provide a method for continuously removing arsenic by hydrofluoric acid, which utilizes a tubular reactor as main reaction equipment to solve the problems of low efficiency and poor safety of intermittent oxidation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for continuously removing arsenic by hydrofluoric acid comprises the following steps: the oxidant A which is introduced into a first cooling tube pass of a low-temperature reaction module of the continuous flow reactor through a first metering pump is cooled to a first set temperature of-5-10 ℃; the anhydrous hydrofluoric acid B introduced into a second cooling tube pass of a low-temperature reaction module of the continuous flow reactor through a second metering pump is cooled to the first set temperature of minus 5-10 ℃; two materials which are cooled to the first set temperature of minus 5 ℃ to 10 ℃ are converged, and are conveyed to the tube side of the high-temperature reaction module of the continuous flow reactor through a pipeline after oxidation reaction is carried out for 5min to 10min at the first set temperature of minus 5 ℃ to 10 ℃ in the main tube side of the low-temperature reaction module; performing oxidation reaction at a second set temperature of 10-20 ℃ for 5-10min, allowing the oxidation product to enter a tower kettle through a pipeline, then passing through a rectifying tower to obtain hydrogen fluoride gas, and forming liquid hydrogen fluoride after passing through a condenser; and introducing the liquid hydrogen fluoride and the ultrapure water C into the blending tank together to form a hydrofluoric acid product D.
As a further improvement of the invention, the oxidant is at least one of ozone, hydrogen peroxide and potassium permanganate.
The invention has the beneficial effects that:
the method for converting trivalent arsenic into pentavalent arsenic has the advantages of low reaction temperature, short reaction time, high reaction mass transfer efficiency and heat exchange efficiency due to the adoption of the continuous flow reactor which has obvious pressure drop and large heat exchange area, and the reaction is easier to control because reaction materials do not need to be mixed in advance.
Drawings
FIG. 1 is a reaction scheme of the present invention.
Detailed Description
The invention is further elucidated with reference to the drawing.
Example 1
A method for continuously removing arsenic by hydrofluoric acid comprises the following steps: the oxidant A (ozone) which is introduced into a first cooling tube pass 10 of a low-temperature reaction module 1 of a continuous flow reactor 7 through a first metering pump 8 is cooled to a first set temperature of-5 ℃; the anhydrous hydrofluoric acid B which is introduced into a second cooling tube pass 11 of the low-temperature reaction module 1 of the continuous flow reactor 7 through a second metering pump 9 is cooled to the first set temperature of minus 5 ℃; two materials which are cooled to the first set temperature of minus 5 ℃ are converged, and in the main tube side 12 of the low-temperature reaction module 1, after oxidation reaction is carried out for 5min at the first set temperature of minus 5 ℃, the materials pass through the tube side of the high-temperature reaction module 2 of the continuous flow reactor 7 through a pipeline; performing oxidation reaction at a second set temperature of 20 ℃ for 10min, enabling an oxidation product to enter a tower kettle 3 through a pipeline, then passing through a rectifying tower 4 to obtain hydrogen fluoride gas, and forming liquid hydrogen fluoride after passing through a condenser 5; and introducing the liquid hydrogen fluoride and the ultrapure water C into the blending tank 6 together to form a hydrofluoric acid product D. The concentration of trivalent arsenic at the inlet of the low-temperature reaction module 1 is 158ppm, the concentration of trivalent arsenic at the inlet of the high-temperature reaction module 2 is 82ppm, and the concentration of trivalent arsenic at the outlet of the high-temperature module 2 is 0.01ppb.
Example 2
A method for continuously removing arsenic by hydrofluoric acid comprises the following steps: an oxidant A (30 mass percent aqueous hydrogen peroxide) which is introduced into a first cooling tube pass 10 of a low-temperature reaction module 1 of a continuous flow reactor 7 through a first metering pump 8 is cooled to a first set temperature of 10 ℃; the anhydrous hydrofluoric acid which is introduced into a second cooling tube pass 11 of the low-temperature reaction module 1 of the continuous flow reactor 7 through a second metering pump 9 is cooled to a first set temperature of 10 ℃; two materials which are cooled to the first set temperature of 10 ℃ are converged, and in the main tube side 12 of the low-temperature reaction module 1, after oxidation reaction is carried out for 10min at the first set temperature of 10 ℃, the materials pass through the tube side of the high-temperature reaction module 2 of the continuous flow reactor 7 through a pipeline; carrying out oxidation reaction at a second set temperature of 15 ℃ for 5min, enabling an oxidation product to enter a tower kettle 3 through a pipeline, then passing through a rectifying tower 4 to obtain hydrogen fluoride gas, and forming liquid hydrogen fluoride after passing through a condenser 5; and introducing the liquid hydrogen fluoride and the ultrapure water C into the blending tank 6 together to form a hydrofluoric acid product D. The concentration of trivalent arsenic at the inlet of the low-temperature reaction module 1 is 158ppm, the concentration of trivalent arsenic at the inlet of the high-temperature reaction module 2 is 76ppm, and the concentration of trivalent arsenic at the outlet of the high-temperature module 2 is 0.01ppb.
Example 3
A method for continuously removing arsenic by hydrofluoric acid comprises the following steps: an oxidant A (5 mass percent potassium permanganate aqueous solution) which is introduced into a first cooling tube pass 10 of a low-temperature reaction module 1 of a continuous flow reactor 7 through a first metering pump 8 is cooled to a first set temperature of 5 ℃; the anhydrous hydrofluoric acid which is introduced into a second cooling tube pass 11 of the low-temperature reaction module 1 of the continuous flow reactor 7 through a second metering pump 9 is cooled to a first set temperature of 5 ℃; two materials which are cooled to the first set temperature of 5 ℃ are converged, and are oxidized and reacted for 10min at the first set temperature of 5 ℃ in the main tube side 12 of the low-temperature reaction module 1, and then pass through the tube side of the high-temperature reaction module 2 of the continuous flow reactor 7 through a pipeline; carrying out oxidation reaction for 5min at a second set temperature of 10 ℃; the oxidation product enters a tower kettle 3 through a pipeline, then passes through a rectifying tower 4 to obtain hydrogen fluoride gas, and forms liquid hydrogen fluoride after passing through a condenser 5; and introducing the liquid hydrogen fluoride and the ultrapure water C into the blending tank 6 together to form a hydrofluoric acid product D. And (3) detection results: the arsenic content is less than or equal to 0.02ppb. The concentration of trivalent arsenic at the inlet of the low-temperature reaction module 1 is 158ppm, the concentration of trivalent arsenic at the inlet of the high-temperature reaction module 2 is 80ppm, and the concentration of trivalent arsenic at the outlet of the high-temperature reaction module 2 is 0.02ppb. The continuous flow reactor is commercially available, for example, from corning corporation as a G1, G2, G3 or G4 continuous flow reactor.
The invention adopts the continuous flow reactor to purify hydrofluoric acid containing trivalent arsenic to remove arsenic, the main structure of the continuous flow reactor is a conveying pipe with a jacket, reaction liquid is conveyed inside, temperature control protection liquid is conveyed outside, the whole reaction has strong controllability, the low-temperature reaction module 1 and the high-temperature reaction module 2 are connected in series to operate, the whole reaction is smooth, because the content of trivalent arsenic in the low-temperature reaction module 1 is higher, the content of oxidant is also higher, and the whole reaction belongs to exothermic reaction, the low-temperature tubular reactor is adopted to carry out mixing reaction under the condition of higher concentration of the trivalent arsenic and the oxidant, the controllability is strong, the trivalent arsenic can be removed by about 30 percent after the reaction module 1 under normal conditions, and simultaneously, the trivalent arsenic and the oxidant can form good mixing effect through a series of mixing reactions.
The whole reaction is relatively violent in the high-temperature reaction module 2, most of trivalent arsenic is removed in the high-temperature reaction module 2, the trivalent arsenic forms refractory salt of pentavalent arsenic under the strong oxidation of an oxidant, and the refractory salt of pentavalent arsenic is remained in the mixed solution and is removed from the bottom of the rectifying tower 4 when the trivalent arsenic passes through the rectifying tower 4.
Claims (2)
1. A method for continuously removing arsenic by hydrofluoric acid comprises the following steps: the oxidant A which is introduced into a first cooling tube pass of a low-temperature reaction module of the continuous flow reactor through a first metering pump is cooled to a first set temperature of-5-10 ℃; the anhydrous hydrofluoric acid B introduced into a second cooling tube pass of a low-temperature reaction module of the continuous flow reactor through a second metering pump is cooled to the first set temperature of minus 5-10 ℃; two materials which are cooled to the first set temperature of minus 5 ℃ to 10 ℃ are converged, and are conveyed to the tube side of the high-temperature reaction module of the continuous flow reactor through a pipeline after oxidation reaction is carried out for 5min to 10min at the first set temperature of minus 5 ℃ to 10 ℃ in the main tube side of the low-temperature reaction module; performing oxidation reaction at a second set temperature of 10-20 ℃ for 5-10min, allowing the oxidation product to enter a tower kettle through a pipeline, then passing through a rectifying tower to obtain hydrogen fluoride gas, and forming liquid hydrogen fluoride after passing through a condenser; and introducing the liquid hydrogen fluoride and the ultrapure water C into the blending tank together to form a hydrofluoric acid product D.
2. The method for continuous arsenic removal by hydrofluoric acid according to claim 1, wherein: the oxidant is at least one of ozone, hydrogen peroxide and potassium permanganate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211252871.3A CN115535965A (en) | 2022-10-13 | 2022-10-13 | Method for continuously removing arsenic by hydrofluoric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211252871.3A CN115535965A (en) | 2022-10-13 | 2022-10-13 | Method for continuously removing arsenic by hydrofluoric acid |
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| CN115535965A true CN115535965A (en) | 2022-12-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202211252871.3A Pending CN115535965A (en) | 2022-10-13 | 2022-10-13 | Method for continuously removing arsenic by hydrofluoric acid |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032621A (en) * | 1975-11-24 | 1977-06-28 | E. I. Du Pont De Nemours And Company | Preparation of hydrogen fluoride with low levels of arsenic, iron and sulfite |
| US4083941A (en) * | 1977-04-18 | 1978-04-11 | E. I. Du Pont De Nemours And Company | Purification of anhydrous hydrogen fluoride |
| US4756899A (en) * | 1987-02-12 | 1988-07-12 | Allied-Signal Inc. | Manufacture of high purity low arsenic anhydrous hydrogen fluoride |
| US4954330A (en) * | 1989-11-30 | 1990-09-04 | E. I. Dupont De Nemours And Company | Process for purifying hydrogen fluoride |
| WO1997018158A1 (en) * | 1995-11-13 | 1997-05-22 | Alliedsignal Inc. | Manufacture of very low arsenic hydrogen fluoride |
| CN102009957A (en) * | 2010-11-20 | 2011-04-13 | 江阴市润玛电子材料有限公司 | Method for purifying high-yield superclean high-purity hydrofluoric acid |
| CN103864018A (en) * | 2014-03-05 | 2014-06-18 | 福建省邵武市永飞化工有限公司 | Method for removing arsenic from industrial hydrofluoric acid |
| CN103991847A (en) * | 2013-02-18 | 2014-08-20 | 福建省邵武市永晶化工有限公司 | Preparation method for electron-grade hydrofluoric acid |
| KR20150049389A (en) * | 2013-10-30 | 2015-05-08 | 램테크놀러지 주식회사 | Method of purifying hydrogen fluoride |
| CN111393284A (en) * | 2020-04-18 | 2020-07-10 | 云南正邦科技有限公司 | Method for continuously preparing carboxylic acid by oxidizing primary alcohol |
| CN112897467A (en) * | 2021-03-18 | 2021-06-04 | 福建省建阳金石氟业有限公司 | Production method of electronic-grade hydrofluoric acid |
-
2022
- 2022-10-13 CN CN202211252871.3A patent/CN115535965A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032621A (en) * | 1975-11-24 | 1977-06-28 | E. I. Du Pont De Nemours And Company | Preparation of hydrogen fluoride with low levels of arsenic, iron and sulfite |
| US4083941A (en) * | 1977-04-18 | 1978-04-11 | E. I. Du Pont De Nemours And Company | Purification of anhydrous hydrogen fluoride |
| US4756899A (en) * | 1987-02-12 | 1988-07-12 | Allied-Signal Inc. | Manufacture of high purity low arsenic anhydrous hydrogen fluoride |
| US4954330A (en) * | 1989-11-30 | 1990-09-04 | E. I. Dupont De Nemours And Company | Process for purifying hydrogen fluoride |
| WO1997018158A1 (en) * | 1995-11-13 | 1997-05-22 | Alliedsignal Inc. | Manufacture of very low arsenic hydrogen fluoride |
| CN102009957A (en) * | 2010-11-20 | 2011-04-13 | 江阴市润玛电子材料有限公司 | Method for purifying high-yield superclean high-purity hydrofluoric acid |
| CN103991847A (en) * | 2013-02-18 | 2014-08-20 | 福建省邵武市永晶化工有限公司 | Preparation method for electron-grade hydrofluoric acid |
| KR20150049389A (en) * | 2013-10-30 | 2015-05-08 | 램테크놀러지 주식회사 | Method of purifying hydrogen fluoride |
| CN103864018A (en) * | 2014-03-05 | 2014-06-18 | 福建省邵武市永飞化工有限公司 | Method for removing arsenic from industrial hydrofluoric acid |
| CN111393284A (en) * | 2020-04-18 | 2020-07-10 | 云南正邦科技有限公司 | Method for continuously preparing carboxylic acid by oxidizing primary alcohol |
| CN112897467A (en) * | 2021-03-18 | 2021-06-04 | 福建省建阳金石氟业有限公司 | Production method of electronic-grade hydrofluoric acid |
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Application publication date: 20221230 |