CN1189387C - High-purity hydrogen peroxide preparation - Google Patents
High-purity hydrogen peroxide preparation Download PDFInfo
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- CN1189387C CN1189387C CNB031094279A CN03109427A CN1189387C CN 1189387 C CN1189387 C CN 1189387C CN B031094279 A CNB031094279 A CN B031094279A CN 03109427 A CN03109427 A CN 03109427A CN 1189387 C CN1189387 C CN 1189387C
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- exchange resin
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Abstract
The present invention relates to a preparation method of electronic grade hydrogen dioxide with high purity. Firstly, an industrial hydrogen dioxide water solution contacts macroporous strong basic anion exchange resin; then, contacts macroporous strong acidic cation exchange resin and mixed ion exchange resin; finally, is filtered by a microfiltration membrane of which the hole diameter is less than 0.2 micrometer to prepare a hydrogen dioxide product with high purity. Colorless, tasteless and transparent liquid hydrogen dioxide products with the advantages of stable property and low impurity content can be prepared by the method. The contents of various metal ions are less than 10 ppb to conform to the international standards SEMI. C1.9 to 90 and SEMI. C7.5 to 93 of semiconductor equipment and a semiconductor material and satisfy the requirement of a wafer cleaning agent in a production technique of a semiconductor. The preparation method has the advantages of lax production technique condition, simple equipment, easy operation, easy acquirement of a raw material, low cost and high profit, and the serialization mass production can be realized.
Description
Technical field
The present invention relates to the manufacturing of electronic-grade high-purity hydrogen peroxide product, mainly be to adopt anion and cation exchange resin to remove organism, inorganic impurity in the industrial aqueous hydrogen peroxide solution, the microfiltration film is removed resin particle in small, broken bits and impurity, thereby makes the high-purity hydrogen peroxide product.The high purity hydrogen dioxide aqueous solution that this technology makes is applicable to electronic industry cleaning silicon wafer.
Background technology
High-purity hydrogen peroxide is a necessary electronics industrial chemicals in the large-scale integrated circuit production technique, and it both can be used as clean-out system, cleans silicon wafer, unicircuit etc. to make the premium insulation layer; Can be made into corrosive fluid with water, mineral acid, organism stablizer or ammoniacal liquor etc. again, to contain metallic surface on the etch for printed circuits bord, copper surface particularly; Can be used as the raw material of producing the electronic-grade high purity reagent again, as produce high-purity silicic acid etc.; Also can make the component of photoresist material stripper.High-purity hydrogen peroxide is widely used in electronics industry with its excellent capability and performance.Insulation layer with high-purity hydrogen peroxide cleaning, etched silicon chip, unicircuit can reach optimum.At present the method for domestic basic employing rectifying redilution makes, and this method is dangerous products purity but also low not only, is difficult to form the suitability for industrialized production scale.The production technology of external existing hydrogen peroxide mainly contains rectification method, reverse osmosis method, and the ion exchange resin method of purification, the silica flour absorption method, stannic oxide absorption method etc., wherein the resultant metal ionic impurity content height that obtains of rectification method also needs combine with other method; Reverse osmosis method needs compression system, and the work-ing life of film is shorter, and facility investment is big, is difficult for realizing industrialization.Absorption method is impelled decomposing hydrogen dioxide solution easily.Chinese patent CN1330035A discloses the ion exchange resin method of purification, this method complex process.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of new high-purity hydrogen peroxide, can overcome the deficiencies in the prior art, present device is simple, processing ease, and raw material is easy to get, and cost is low, and the profit height can be realized serialization scale operation.
The preparation method of high-purity hydrogen peroxide of the present invention comprises the steps:
1) industrial superoxol Continuous Flow is crossed the exchange column that is filled with bicarbonate radical type macroporous strong basic anionite-exchange resin (D296) and carry out ion-exchange; Described bicarbonate radical type D296 macroporous strong basic anionite-exchange resin is with Cl
-Type D296 macroporous strong basic anionite-exchange resin, elder generation soaked 30 minutes and drip washing with 5% sodium bicarbonate aqueous solution, and making the transition is bicarbonate radical (HCO
3 -) type D296 macroporous strong basic anionite-exchange resin, the washing lotion specific conductivity is less than 3 μ s/cm.
2) Continuous Flow is crossed and is filled with H again
+The exchange column of type D072 macropore strong acid cation exchange resin carries out ion-exchange; Described H
+Type D072 macropore strong acid cation exchange resin is with Na
+Type D072 macropore strong acid cation exchange resin elder generation soaked 30 minutes and drip washing with 5% sulphuric acid soln, and making the transition is H
+Type D072 macropore strong acid cation exchange resin, the washing lotion specific conductivity is less than 2 μ s/cm.
3) Continuous Flow is crossed and is filled with bicarbonate radical type D296 macroporous strong basic anionite-exchange resin and H then
+The mixture iron exchange resin of type D072 macropore strong acid cation exchange resin carries out ion-exchange, and the volume ratio of described anionite-exchange resin and described Zeo-karb is 1: 1-2.
Above-mentioned ion-exchange condition is: with 12Hr
-1Reduced superficial velocity, 0 ℃-25 ℃ of ion-exchange temperatures, preferred ion-exchange temperature is controlled at 5-10 ℃.Described ion exchange column intermediate ion exchange resin loading height is 10: 1 with the column diameter ratio.
Above-mentioned industrial hydrogen peroxide is the aqueous solution of 32%-35%.
The invention enables chlorion, phosphate anion and sulfate ion not to be higher than 200ppb, nitrate ion is not higher than 400ppb, and cation impurity levels is not higher than 10ppb.The aqueous hydrogen peroxide solution that the present invention obtains filters through 0.2 μ m polyvinylidene fluoride microporous filtering film, can make the product that satisfies semiconductor devices and material international standard SEMIC19-90 and SEMIC75-93.
Product of the present invention is colourless, tasteless, transparent liquid, stable performance, foreign matter content is low, meet semiconductor devices and material international standard SEMIC19-90 and SEMIC75-93, can satisfy the requirement of wafer clean-out system in the production process of semiconductor, solve the domestic high-purity hydrogen peroxide product problem of dependence on import all the time.
Manufacturing condition of the present invention is not harsh, and equipment is simple, processing ease, and raw material is easy to get, and cost is low, and the profit height can be realized serialization scale operation.
Embodiment
Embodiment 1:
With 35% industrial superoxol (impurity wherein sees Table 1) with 12Hr
-1The reduced superficial velocity Continuous Flow cross the exchange column that is filled with bicarbonate radical type D296 anionite-exchange resin, the exchange temperature be controlled at 5 ℃; Again with 12Hr
-1The reduced superficial velocity Continuous Flow cross and be filled with H
+The exchange column of type D072 Zeo-karb, the exchange temperature is controlled at 5 ℃; Then with 12Hr
-1The superficial velocity Continuous Flow cross and be filled with bicarbonate radical type D296 anionite-exchange resin and H
+The exchange column of the mixture iron exchange resin of type D072 Zeo-karb (volume ratio of anionite-exchange resin and Zeo-karb is 1: 1), the exchange temperature is controlled at 5 ℃.
In the anion regeneration post, carry out the regeneration of anionite-exchange resin, carry out the regeneration of Zeo-karb in the positively charged ion actifier column, mixture iron exchange resin in purification column after purifying, with pressurized air blowback layering, and then squeeze into respectively in the yin, yang ion actifier column, together regenerate with anion and cation exchange resin in the independent actifier column, actifier column is different with the purifying exchange column of aqueous hydrogen peroxide solution.
Use the D072 storng-acid cation exchange resin (Na that regenerated
+Type D072 macropore strong acid cation exchange resin, Chemical Plant of Nankai Univ. produces), the Zeo-karb regenerator is 5% sulphuric acid soln.The regeneration of Zeo-karb is in the actifier column of Zeo-karb, with regenerator with 2Hr
-1Reduced superficial velocity SV and after the BV of 0.65L/L-R flows through actifier column, stop to flow of regenerator, soaked 30 minutes, regenerator is bled off, continuation is passed through this actifier column with identical SV and BV with regenerator, is 10 times of Zeo-karb volume until regenerant consumption.Pure water is with 12Hr then
-1Reduced superficial velocity and the BV of 0.25L/L-R be downward through actifier column, upwards flow through actifier column with identical SV and BV again, until the washing lotion specific conductivity less than 2 μ s/cm.
Use the D296 strongly basic anion exchange resin (Cl that regenerated
-Type D296 macroporous strong basic anionite-exchange resin, Chemical Plant of Nankai Univ. produces), the anionite-exchange resin regenerator is 5% sodium hydrogen carbonate solution.The regeneration of anionite-exchange resin is in the actifier column of anionite-exchange resin, with regenerator with 2Hr
-1Reduced superficial velocity SV and after the BV of 0.65L/L-R flows through actifier column, stop to flow of regenerator, soaked 30 minutes, regenerator is bled off, continuation is passed through this actifier column with identical SV and BV with regenerator, is 10 times of Zeo-karb volume until regenerant consumption.Pure water is with 12Hr then
-1Reduced superficial velocity and the BV of 0.25L/L-R be downward through actifier column, upwards flow through actifier column with identical SV and BV again, until the washing lotion specific conductivity less than 3 μ s/cm.
Anion and cation exchange resin after the above-mentioned regeneration is together squeezed in separately the purification column with pure water respectively.The volume ratio of anion and cation exchange resin is 1: 1 in the mixing column.
By behind each ion exchange column, with 18.0M Ω pure water dilution effusive aqueous hydrogen peroxide solution from last mixed type ion exchange resin column, making aqueous hydrogen peroxide solution concentration is 30-32% at aqueous hydrogen peroxide solution.
The plasma emission spectroscopy ICP-900 (N+M) that produces with graphite furnace atomic absorption spectrometry and U.S. T, J, A company measures the concentration of impurity metal ion in the gained purifying aqueous hydrogen peroxide solution, and experimental result sees Table 2.
The concentration of metal ion and acid ion impurity in the table 1 raw material aqueous hydrogen peroxide solution
| Impurity title (metal ion) | Na | K | Ca | Fe | Al | Mg | Cu | Pb |
| Analytical value (ppb) | 1530 | 796 | 685 | 432 | 265 | 68 | 85 | 105 |
| Impurity title (acid ion) | SO 4 2- | Cl - | NO 3 - | PO 4 3- | ||||
| Analytical value (ppm) | 365 | 208 | 186 | 336 |
The concentration of impurity metal ion in the aqueous hydrogen peroxide solution behind table 2 purifying
| The impurity title | Analytical value (ppb) | The impurity title | Analytical value (ppb) | The impurity title | Analytical value (ppb) |
| Ag | 4 | Cr | 2 | Mo | 5 |
| Al | 10 | Co | 5 | Ni | 5 |
| As | 5 | Cu | 2 | Na | 10 |
| Au | 5 | Fe | 2 | Pt | 5 |
| B | 10 | Ga | 5 | Sr | 2 |
| Ba | 2 | Ge | 10 | Tl | 2 |
| Be | 10 | K | 10 | Sn | 5 |
| Bi | 10 | Li | 5 | Ti | 5 |
| Ca | 5 | Mg | 2 | V | 5 |
| Cd | 2 | Mn | 2 | Zn | 5 |
Embodiment 2:
With 35% industrial superoxol with 12Hr
-1The reduced superficial velocity Continuous Flow cross the exchange column that is filled with bicarbonate radical type anionite-exchange resin, the exchange temperature be controlled at 10 ℃; Again with 12Hr
-1The reduced superficial velocity Continuous Flow cross and be filled with H
+The exchange column of type Zeo-karb, the exchange temperature is controlled at 10 ℃; Then with 12Hr
-1The superficial velocity Continuous Flow cross and be filled with bicarbonate radical type anionite-exchange resin and H
+The exchange column of the mixture iron exchange resin of type Zeo-karb (volume ratio of anionite-exchange resin and Zeo-karb is 1: 2), the exchange temperature is controlled at 10 ℃.
The raw material aqueous hydrogen peroxide solution contacted with various ion exchange resin and carry out purifying, various metal ion contents following (table 3, table 4) in the aqueous hydrogen peroxide solution of gained with method identical in the example 1:
The concentration of impurity metal ion in the aqueous hydrogen peroxide solution behind table 3 purifying
| The impurity title | Analytical value (ppb) | The impurity title | Analytical value (ppb) | The impurity title | Analytical value (ppb) |
| Ag | ＜2 | Cr | ＜2 | Mn | 3 |
| Al | ＜3 | Co | 5 | Mo | ＜10 |
| As | ＜5 | Cu | ＜2 | Ni | 8 |
| B | ＜2 | Fe | 2 | Na | 10 |
| Ba | 2 | K | 10 | Sr | 2 |
| Be | 1 | Li | ＜10 | Sn | ＜5 |
| Ca | 1 | Mg | 2 | Ti | 2 |
| Cd | 5 |
The concentration of acid ion impurity in the aqueous hydrogen peroxide solution behind table 4 purifying
| The impurity title | SO 4 2- | Cl - | NO 3 - | PO 4 3- |
| Analytical value (ppb) | 185 | 147 | 103 | 33 |
Claims (7)
1, a kind of preparation method of high-purity hydrogen peroxide is characterized in that it comprises the steps:
1) industrial superoxol Continuous Flow is crossed the exchange column that is filled with bicarbonate radical type macroporous strong basic anionite-exchange resin and carried out ion-exchange;
2) cross with Continuous Flow again and be filled with H
+The exchange column of type macropore strong acid cation exchange resin carries out ion-exchange;
3) Continuous Flow is crossed and is filled with bicarbonate radical type macroporous strong basic anionite-exchange resin and H then
+The mixture iron exchange resin of type macropore strong acid cation exchange resin carries out ion-exchange, and the volume ratio of described anionite-exchange resin and described Zeo-karb is 1: 1-2.
2,, it is characterized in that described ion-exchange condition is: with 12Hr according to the preparation method of the described high-purity hydrogen peroxide of claim 1
-1Reduced superficial velocity, 0 ℃-25 ℃ of ion-exchange temperatures.
3,, it is characterized in that described ion-exchange temperature is controlled at 5-10 ℃ according to the preparation method of the described high-purity hydrogen peroxide of claim 2.
4,, it is characterized in that described bicarbonate radical type macroporous strong basic anionite-exchange resin is with Cl according to the preparation method of the described high-purity hydrogen peroxide of claim 1
-Type macroporous strong basic anionite-exchange resin elder generation soaked 30 minutes and drip washing with 5% sodium bicarbonate aqueous solution, and making the transition is bicarbonate radical type macroporous strong basic anionite-exchange resin, and the washing lotion specific conductivity is less than 3 μ s/cm.
5,, it is characterized in that described H according to the preparation method of the described high-purity hydrogen peroxide of claim 1
+Type macropore strong acid cation exchange resin is with Na
+Type macropore strong acid cation exchange resin elder generation soaked 30 minutes and drip washing with 5% sulphuric acid soln, and making the transition is H
+Type macropore strong acid cation exchange resin, the washing lotion specific conductivity is less than 2 μ s/cm.
6,, it is characterized in that described industrial hydrogen peroxide is the aqueous solution of 32%-35% according to the preparation method of the described high-purity hydrogen peroxide of claim 1.
7,, it is characterized in that described ion exchange column intermediate ion exchange resin loading height is 10: 1 with the column diameter ratio according to the preparation method of the described high-purity hydrogen peroxide of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031094279A CN1189387C (en) | 2003-04-10 | 2003-04-10 | High-purity hydrogen peroxide preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031094279A CN1189387C (en) | 2003-04-10 | 2003-04-10 | High-purity hydrogen peroxide preparation |
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|---|---|
| CN1439600A CN1439600A (en) | 2003-09-03 |
| CN1189387C true CN1189387C (en) | 2005-02-16 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8715613B2 (en) | 2010-12-02 | 2014-05-06 | Shanghai Chemical Reagent Research Institute | Method for producing of ultra-clean and high-purity aqueous hydrogen peroxide solution |
| CN109205572A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | A method of purifying hydrogen peroxide |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420625C (en) * | 2006-08-18 | 2008-09-24 | 上海华谊微电子化学品有限公司 | Process for preparation of ultrapure hydrogen peroxide |
| CN102556976A (en) * | 2010-12-08 | 2012-07-11 | 上海华谊微电子材料有限公司 | Method for continuous production of ultrapure hydrogen peroxide |
| CN106185831B (en) * | 2016-07-12 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of adsorption tanks for dioxygen water purification process |
| JP2018127383A (en) * | 2017-02-09 | 2018-08-16 | 栗田工業株式会社 | Manufacturing apparatus for ammonia aqueous solution and process for manufacturing ammonia aqueous solution |
| CN110451460A (en) * | 2018-05-07 | 2019-11-15 | 中国石油化工股份有限公司 | The recovery method of hydrogen peroxide oxidation raffinate |
| CN109941967A (en) * | 2019-04-24 | 2019-06-28 | 广州市天夫美新材料科技有限公司 | The production technology of One-step production super-clean high-purity microelectronics grade hydrogen peroxide |
| CN112062096B (en) * | 2020-08-31 | 2022-08-23 | 北京化工大学 | Production device and production method of electronic-grade hydrogen peroxide aqueous solution |
-
2003
- 2003-04-10 CN CNB031094279A patent/CN1189387C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8715613B2 (en) | 2010-12-02 | 2014-05-06 | Shanghai Chemical Reagent Research Institute | Method for producing of ultra-clean and high-purity aqueous hydrogen peroxide solution |
| CN109205572A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | A method of purifying hydrogen peroxide |
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| CN1439600A (en) | 2003-09-03 |
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