CN115160225A - Industrial production method of electronic pure pyrazole - Google Patents
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- CN115160225A CN115160225A CN202211061745.XA CN202211061745A CN115160225A CN 115160225 A CN115160225 A CN 115160225A CN 202211061745 A CN202211061745 A CN 202211061745A CN 115160225 A CN115160225 A CN 115160225A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Abstract
The invention belongs to the field of compound preparation, and particularly relates to an industrial production method of electronic pure pyrazole. The invention uses ultrapure water and ethanol to dissolve industrial pyrazole, uses cation exchange resin and anion exchange resin to adsorb metal ions in the industrial pyrazole in series, and then carries out distillation, crystallization and centrifugation to obtain the electronic pure pyrazole product with the concentration of metal ions such as Na, mg, al, K, ca, cr, fe, cu, ni, zn and the like less than 10 ppb. The product can be used for the semiconductor process below 5 nanometers to meet the increasingly severe use requirement of electronic pure pyrazole; the method is reliable and convenient, has high distillation yield, and can be used for batch industrial production.
Description
Technical Field
The invention belongs to the field of compound preparation, and particularly relates to an industrial production method of electronic pure pyrazole.
Background
The electronic pure pyrazole can be used as a cleaning agent component for silicon chip cleaning, substrate wet cleaning and the like in the microelectronic industry such as integrated circuit and electronic element processing field due to the strong metal ion chelating effect, and is an important cleaning agent additive component at present. The cleaning and anticorrosive composition can remove etching residues on the surface of a workpiece in the manufacturing process of a semiconductor element or a display element, prevent the metal wiring containing copper or copper alloy from being deteriorated, and easily remove a preservative attached to the metal wiring before film formation in the film formation process. The key of the electronic pure pyrazole is to control the amount of metal ions contained in the pyrazole and the content of dust particles in a reagent, and for integrated circuits with small line width, a few metal ions or dust can be enough to scrap the whole circuit.
The electronic pure pyrazole used for chip manufacturing has very important influence on the yield, the electrical property and the reliability of integrated circuits. With the development of integrated circuit processes, the 32 nm semiconductor process requires half as many metal ions as there are on the product as 65 nm processes. The disclosed patents disclose that electron-pure pyrazoles having metal ion concentrations of less than 30ppb each can be used only for semiconductor processes above 12 nm, while electron-pure pyrazoles having single element metal ion concentrations of less than 10ppb each can be used for semiconductor processes below 5 nm.
At present, the method for producing the electronic pure reagent generally adopts corresponding industrial products as raw materials, and target impurities in the raw materials are removed through post-treatment and purification. The metal ion content in the industrial pyrazole sold in the market at present is higher, the requirement of silicon wafer cleaning cannot be met, and the domestic and foreign purification preparation process research is less. Therefore, it is important to develop an electron-pure pyrazole having a single element metal ion concentration of less than 10ppb each.
Pyrazole as a high boiling point chemical, the impurity content of commercially available industrial pyrazole is ppm level, while the impurity content of electronic pure pyrazole is ppb level, the production method of the electronic grade pyrazole has few domestic and foreign documents and patent reports, and the preparation methods disclosed in the prior art mainly have the following problems.
1. When complexing agent such as ethylenediamine tetraacetic acid is used for complexing, although the complexing ability is very strong, the water solubility is very poor, and the complexing agent needs to be changed into disodium salt for use, and at the moment, high-concentration sodium ions can be introduced into the system, so that difficulty is brought to subsequent purification.
2. When the traditional ion exchange resin is used for exchange, such as an acid type cation exchange resin, the N atom in pyrazole has larger electronegativity and can be exchanged into the resin, so that the column efficiency is reduced.
3. Because N atoms on the pyrazole ring are adjacent, two molecules of pyrazole can form a stable six-membered ring structure and can also form hydrogen bonds with water molecules, so that the pyrazole has high solubility in an aqueous solution, the solubility at room temperature is over 100g of pyrazole/100 g of water, when the temperature is raised to 60 ℃, the solubility is over 700g of pyrazole/100 g of water, and a large amount of water in the solution can be carried out due to the hydrogen bonding effect during condensation, so that the pyrazole and the water are difficult to separate by simple condensation.
4. The pyrazole molecules have isolated electron pairs and also have complexation effect on metal ions, so that the metal ions are complexed with the pyrazole molecules, and the separation difficulty is further improved.
Patent CN111377868A, "a preparation method of electronic grade pyrazole", discloses that metal ions in industrial grade pyrazole are complexed by using an aminocarboxylic complexing agent, and then distillation is carried out, so that only electronic pure pyrazole with various metal ion concentrations of 30ppb can be obtained, and the addition of the aminocarboxylic complexing agent causes the residue of the complexing agent in subsequent purification, thereby reducing the purity.
Therefore, there is a need to develop a new pyrazole purification method, so that the content of impurities, especially metal ion impurities in the product can reach below 10ppb, and the method can be used in semiconductor processes below 5 nm to meet the increasingly stringent requirements for using electronic pure pyrazole.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of electronic pure pyrazole, which comprises the steps of dissolving industrial pyrazole in ultrapure water and ethanol, adsorbing metal ions in the industrial pyrazole in series by using cation exchange resin and anion exchange resin, and then distilling, crystallizing and centrifuging to obtain the electronic pure pyrazole product with the metal ion concentration of Na, mg, al, K, ca, cr, fe, cu, ni, zn and the like less than 10 ppb.
An industrial production method of electronic pure pyrazole, which comprises the following steps:
step 1, mixing industrial pyrazole, ethanol and high-purity water, heating, stirring and dissolving to obtain an adsorption solution;
step 2, allowing the adsorption solution obtained in the step 1 to pass through cation exchange resin and anion exchange resin which are connected in series in sequence to adsorb metal ions in the adsorption solution to obtain an electronic pure pyrazole solution, and performing distillation, crystallization and centrifugal purification to obtain an electronic pure pyrazole solid product;
and 3, regenerating and activating the cation exchange resin by using acidic liquid, and regenerating and activating the anion exchange resin by using alkaline liquid.
Preferably, the mass ratio of the industrial-grade pyrazole, the high-purity water and the ethanol added in the step 1 is 2-1: 1:1.
preferably, the mass concentration of ethanol in the adsorption solution in the step 2 is 30-35%.
Further, the resistivity of the ultrapure water in the step 1 is 18-18.25M omega cm; the resistivity of the ethanol is 18-18.25M omega cm.
Further, the temperature in the step 1 is 30-60 ℃.
Further, the cation exchange resin in the step 2 is all specification brands sold in the market at home and abroad; the anion exchange resin is all specification brands sold at home and abroad.
Preferably, the cation exchange resin in step 2 is: strong acid cation exchange resin with sulfonic acid group (-SO) 3 H) Ion exchange resins that are the primary exchange group; weakly acidic cation exchange resin prepared from carboxylic acid group (-COOH) or phosphoric acid group (-CHPO (OH) 2 ) One of the two is one or more of ion exchange resins with functional groups.
Preferably, the anion exchange resin in step 2 is: strong base anion exchange resins, the functional groups of which are of the type: type I strong basic group (-CH) 2 N(CH 3 ) 3 OH and II type strong basic groups (-CH) 2 N(CH 3 ) 2 (C 2 H 4 OH)), can dissociate OH < - >, shows strong basicity and can exchange with any anion in water; weakly basic anion exchange resin: with primary amino-CH 2 NH 2 A secondary amino group-CH 2 NHR (R represents-CH) 3 ) And tertiary amino-CH 2 NR 2 As functional groups, capable of dissociating OH in aqueous solution - But is weakly alkaline; one of the two is one or more of ion exchange resins with functional groups.
Further, the adsorption times in the step 2 are 3 to 4 times.
Preferably, the distillation in the step 2 is one or more of atmospheric distillation, vacuum distillation and rectification, and the vacuum distillation is preferred.
Preferably, the crystallization in the step 2 is one or more of concentrated crystallization, cooling crystallization and evaporation cooling crystallization.
Preferably, the centrifugation in the step 2 is one or more of a filter centrifuge, a sedimentation centrifuge and a separator.
Further, the activated and regenerated acidic liquid of the cation exchange resin in the step 3 is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid and other acidic solutions; the alkali liquid for activating and regenerating the anion exchange resin is one or a combination of more of alkali solutions such as sodium hydroxide, potassium hydroxide and the like.
Compared with the prior art, the invention has the following beneficial effects.
1. The method can greatly reduce the concentration of metal ions, and the used high-purity water and ethanol are used for dissolving pyrazole, so that the separation and distillation are convenient; cation exchange resin and anion exchange resin are used for absorbing metal ions in industrial pyrazole in series, so that the produced electronic pure pyrazole has higher purity and lower content of various metal ions.
2. The preparation method can be used for obtaining the electron pure pyrazole with the metal ion concentrations of Na, mg, al, K, ca, cr, fe, cu, ni, zn and the like less than 10ppb, and meets the increasingly severe requirements of the electron pure pyrazole; the method is reliable and convenient, has high distillation yield, and can be used for batch industrial production.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
An industrial production method of electronic pure pyrazole specifically comprises the following steps:
step 1, mixing industrial pyrazole, ethanol and high-purity water, heating, stirring and dissolving to obtain an adsorption solution;
step 2, enabling the adsorption solution obtained in the step 1 to pass through cation exchange resin and anion exchange resin which are connected in series in sequence to adsorb metal ions in the adsorption solution to obtain an electronic pure pyrazole solution, and carrying out distillation, crystallization and centrifugal purification to obtain an electronic pure pyrazole solid product;
and 3, regenerating and activating the cation exchange resin by using acidic liquid, and regenerating and activating the anion exchange resin by using alkaline liquid.
Preferably, the mass ratio of the industrial-grade pyrazole, the high-purity water and the ethanol added in the step 1 is 2-1: 1:1.
preferably, the mass concentration of ethanol in the adsorption solution in the step 2 is 30-35%.
Further, the resistivity of the ultrapure water in the step 1 is 18-18.25M omega cm; the resistivity of the ethanol is 18-18.25M omega cm.
Further, the temperature in the step 1 is 30-60 ℃.
Further, the cation exchange resin in the step 2 is all specifications and brands sold in the market at home and abroad; the anion exchange resin is all specification brands sold at home and abroad.
Preferably, the cation exchange resin in step 2 is: strong acid cation exchange resin with sulfonic acid group (-SO) 3 H) Ion exchange resins that are the primary exchange group; weakly acidic cation exchange resin prepared from carboxylic acid group (-COOH) or phosphoric acid group (-CHPO (OH) 2 ) One of the two is one or more of ion exchange resin with functional group.
Preferably, the anion exchange resin in step 2 is: strong base anion exchange resins, the functional groups of which are of the type: type I strong basic group (-CH) 2 N(CH 3 ) 3 OH and II type strong basic groups (-CH) 2 N(CH 3 ) 2 (C 2 H 4 OH)), can dissociate OH < - >, shows strong basicity and can exchange with any anion in water; weakly basic anion exchange resin: with primary amino-CH 2 NH 2 A secondary amino group-CH 2 NHR (R represents-CH) 3 ) And tertiary amino-CH 2 NR 2 As functional groups, capable of dissociating OH in aqueous solution - But is weakly alkaline. One of the two is one or more of ion exchange resins with functional groups.
Further, the adsorption times in the step 2 are 3 to 4 times.
Preferably, the distillation in the step 2 is one or more of atmospheric distillation, vacuum distillation and rectification, and preferably vacuum distillation.
Preferably, the crystallization in the step 2 is one or more of concentrated crystallization, cooling crystallization and evaporation cooling crystallization.
Preferably, the centrifugation in the step 2 is one or more of a filter centrifuge, a sedimentation centrifuge and a separator.
Further, the activated and regenerated acidic liquid of the cation exchange resin in the step 3 is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid and other acidic solutions; the activated and regenerated alkaline liquid of the anion exchange resin is one or a combination of more of alkaline solutions such as sodium hydroxide, potassium hydroxide and the like.
In the following examples, "industrial-grade pyrazole" is a commercially available industrial pyrazole, wherein the metal ion content is shown in Table 1.
Example 1.
Step 1, mixing 1kg of industrial pyrazole, 0.5kg of ethanol and 0.5kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, connecting a cation exchange resin (D001) column and an anion exchange resin (D201) column in series, adsorbing the mixture for three times through the columns, distilling the adsorption solution under reduced pressure, removing components such as moisture, ethanol and the like to obtain a purified pyrazole product, wherein the final pyrazole yield is 91%.
Example 2.
Step 1, mixing 200kg of industrial pyrazole, 200kg of ethanol and 200kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, connecting a cation exchange resin (D001) column and an anion exchange resin (D201) column in series, adsorbing the mixture for three times by the columns, distilling the adsorption solution under reduced pressure, removing components such as moisture, ethanol and the like, and obtaining a purified pyrazole product, wherein the final pyrazole yield is 90%.
Example 3.
Step 1, mixing 200kg of industrial pyrazole, 200kg of ethanol and 200kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, connecting a cation exchange resin (D001) column and an anion exchange resin (D201) column in series, adsorbing the mixture for four times through the columns, distilling the adsorption solution under reduced pressure, removing components such as moisture, ethanol and the like to obtain a purified pyrazole product, wherein the final pyrazole yield is 90%.
Comparative example 1.
Step 1, mixing 1kg of industrial pyrazole, 1kg of ethanol and 1kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, passing the mixture through a cation exchange resin (D001) column once, distilling the adsorption solution under reduced pressure, removing components such as water, ethanol and the like, and obtaining a purified pyrazole product, wherein the final pyrazole yield is 92%.
Comparative example 2.
Step 1, mixing 1kg of industrial pyrazole, 0.5kg of ethanol and 0.5kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, passing the mixture through a cation exchange resin (D001) column once, distilling the adsorption solution under reduced pressure, removing components such as water, ethanol and the like to obtain a purified pyrazole product, wherein the final pyrazole yield is 95%.
Comparative example 3.
Step 1, mixing 1kg of industrial pyrazole, 1kg of ethanol and 1kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, passing the mixture through an anion exchange resin (D201) column once, distilling the adsorption solution under reduced pressure, removing components such as water, ethanol and the like, and obtaining a purified pyrazole product, wherein the final pyrazole yield is 92%.
Comparative example 4.
Step 1, mixing 1kg of industrial pyrazole, 0.5kg of ethanol and 0.5kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, passing the mixture through a cation exchange resin (D101) column twice, distilling the adsorption solution under reduced pressure, removing components such as water, ethanol and the like to obtain a purified pyrazole product, wherein the final pyrazole yield is 95%.
Comparative example 5.
Step 1, mixing 1kg of industrial pyrazole, 1kg of ethanol and 1kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, passing the mixture through an anion resin (D201) column twice, distilling the adsorption solution under reduced pressure, removing components such as water, ethanol and the like, and obtaining a purified pyrazole product, wherein the final pyrazole yield is 95%.
Comparative example 6.
Step 1, mixing 1kg of industrial pyrazole, 0.5kg of ethanol and 0.5kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, connecting a cation exchange resin (D001) column and an anion exchange resin (D201) column in series, adsorbing the mixture once through the columns, distilling the adsorption solution under reduced pressure, removing components such as moisture, ethanol and the like to obtain a purified pyrazole product, wherein the final pyrazole yield is 95%.
Comparative example 7.
Step 1, mixing 1kg of industrial pyrazole, 1kg of ethanol and 1kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, connecting a cation exchange resin (D001) column and an anion exchange resin (D201) column in series, adsorbing the mixture once through the columns, distilling the adsorption solution under reduced pressure, removing components such as moisture, ethanol and the like to obtain a purified pyrazole product, wherein the final pyrazole yield is 93%.
Comparative example 8.
Step 1, mixing 1kg of industrial pyrazole, 0.5kg of ethanol and 0.5kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, connecting a cation exchange resin (D001) column and an anion exchange resin (D201) column in series, adsorbing the mixture twice through the columns, distilling the adsorption solution under reduced pressure, removing components such as moisture, ethanol and the like, and obtaining a purified pyrazole product, wherein the final pyrazole yield is 92%.
Comparative example 9.
Step 1, mixing 1kg of industrial pyrazole, 1kg of ethanol and 1kg of high-purity water, heating to 40 ℃, and stirring for dissolving;
and 2, connecting a cation exchange resin (D001) column and an anion exchange resin (D201) column in series, adsorbing the mixture twice through the columns, distilling the adsorption solution under reduced pressure, removing components such as moisture, ethanol and the like to obtain a purified pyrazole product, wherein the final pyrazole yield is 90%.
The pyrazole products after purification were obtained by the methods of the above examples and comparative examples, and the contents of metal ions in the products obtained in the respective examples were measured, and the results are shown in table 1.
TABLE 1 concentration of metal ions in the product (. Mu.g/kg).
Remarking: ND means not detected; the detection limit of the method is 0.1 mu g/kg;1 μ g/kg = 1ppb.
2. Instrument information: ICP-MS Perkin Elmer Nexion 300D.
As seen from table 1, the concentration of metal ions was greatly reduced in the product obtained using the preparation method of the example of the present invention, as compared to the comparative example. Compared with the raw material industrial grade pyrazole, the products obtained in the comparative examples 1, 2, 3, 4 and 5 have the advantages that the concentration of metal ions is reduced, but the reduction range is not obvious, and the content of sodium, calcium and iron ions is still over 1000 ppb; and the total concentration of ions in the product is still higher, so that the requirement of electronic pure pyrazole is not met.
Comparative examples 6 to 9 the cationic resin column and the anionic resin column were connected in series, and the mixture was passed through the columns 1 to 2 times, and the single element metal ions were reduced, but not reduced to less than 10 ppb.
Examples 1 and 2 connect cation exchange resin column and anion exchange resin column in series, the mixture passes through column three times, the single element metal ion is reduced below 10ppb, example 3 connects cation exchange resin column and anion exchange resin column in series, the mixture passes through column four times, the single element metal ion is reduced below 7.1ppb, and only sodium, magnesium and calcium are detected, the concentration of single element Na, mg, al, K, ca, cr, fe, cu, ni, zn and other metal ion in pyrazole is less than 10ppb, which satisfies the requirement of electronic pure pyrazole.
Meanwhile, as can be seen from the embodiments 1 to 3 of the invention, the yield of pyrazole product is 90% or more on the basis of greatly reducing the content of single-element metal ions in the product. The preparation method of the invention has the advantages that the loss of the raw material pyrazole in the intermediate link is less, thereby having the basis of large-scale production.
In conclusion, the electronic pure pyrazole product obtained by the preparation method has the concentration of metal ions such as single elements Na, mg, al, K, ca, cr, fe, cu, ni, zn and the like which is less than 10ppb, completely meets the requirement of an electronic-grade reagent on the ion concentration, can be applied to the field of high-end integrated circuits, and can be used for semiconductor processes below 5 nanometers. All purification means of the invention can be conveniently applied to large-scale industrial production, the yield of the final product is high, and the invention can be applied to batch production.
It should be understood that the embodiments of the present invention have been described in terms of preferred embodiments, and not by way of limitation, and that those skilled in the art can readily devise many variations and modifications of the disclosed embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. An industrial production method of electronic pure pyrazole is characterized by comprising the following steps:
step 1, mixing industrial pyrazole, ethanol and high-purity water, heating, stirring and dissolving to obtain an adsorption solution;
step 2, enabling the adsorption solution obtained in the step 1 to pass through cation exchange resin and anion exchange resin which are connected in series in sequence to adsorb metal ions in the adsorption solution to obtain an electronic pure pyrazole solution, and carrying out distillation, crystallization and centrifugal purification to obtain an electronic pure pyrazole solid product;
and 3, regenerating and activating the cation exchange resin by using acidic liquid, and regenerating and activating the anion exchange resin by using alkaline liquid.
2. The industrial production method of electronically pure pyrazole according to claim 1, wherein the mass ratio of the industrial-grade pyrazole, the high purity water and the ethanol added in step 1 is 2 to 1:1:1.
3. the industrial production method of electronically pure pyrazole according to claim 1, wherein the mass concentration of ethanol in the adsorption solution of step 2 is from 30% to 35%.
4. The industrial production method of electronically pure pyrazole according to claim 1, wherein said ultrapure water in said step 1 has a resistivity of from 18 to 18.25 Μ Ω cm; the resistivity of the ethanol is 18-18.25M omega cm.
5. The process for the industrial production of electronically pure pyrazoles according to claim 1, in which the temperature in step 1 is from 30 to 60 ℃.
6. The process for the industrial production of electronically pure pyrazoles according to claim 1 in which the cation exchange resin in step 2 is: strong acid cation exchange resin with sulfonic acid group (-SO) 3 H) Ion exchange resins that are the primary exchange group; weakly acidic cation exchange resin prepared from carboxylic acid group (-COOH) or phosphoric acid group (-CHPO (OH) 2 ) One of the two is one or more of ion exchange resins with functional groups.
7. The process for the industrial production of electronically pure pyrazoles according to claim 1 in which the anion exchange resin in step 2 is: the functional groups of the strong base anion exchange resin and the strong base cation exchange resin are as follows: type I strong basic group (-CH) 2 N(CH 3 ) 3 OH and II type strong basic groups (-CH) 2 N(CH 3 ) 2 (C 2 H 4 OH)), can be dissociated in water to generate OH < - >, has strong basicity and can exchange with any anion; weakly basic anion exchange resin: with primary amino-CH 2 NH 2 A secondary amino group-CH 2 NHR (R represents-CH) 3 ) And a tertiary amino group-CH 2 NR 2 As functional groups, capable of dissociating OH in aqueous solution - But is weakly alkaline; one of the two is one or more of ion exchange resin with functional group.
8. The process for industrially producing an electronically pure pyrazole according to claim 1, wherein the number of times of adsorption in the step 2 is from 3 to 4 times.
9. The method for industrially producing electronically pure pyrazole according to claim 1 wherein the distillation in step 2 is one or more selected from the group consisting of atmospheric distillation, vacuum distillation and rectification; the crystallization is one or more of concentrated crystallization, cooling crystallization and evaporation cooling crystallization; the centrifugation is one or a combination of a filtering centrifuge, a sedimentation centrifuge and a separator.
10. The industrial process for producing electronically pure pyrazoles according to claim 1, wherein the acidic liquid for activating and regenerating the cation exchange resin in step 3 is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and the like; the alkali liquid for activating and regenerating the anion exchange resin is one or a combination of more of alkali solutions such as sodium hydroxide, potassium hydroxide and the like.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11180704A (en) * | 1997-12-19 | 1999-07-06 | Ube Ind Ltd | Production of aqueous high-purity hydrogen peroxide solution |
| CN1330035A (en) * | 2000-06-21 | 2002-01-09 | 三德化学工业株式会社 | Method for producing purified aqueous hydrogen peroxide solution |
| CN101973871A (en) * | 2010-09-01 | 2011-02-16 | 日照金禾生化集团股份有限公司 | Electronic grade citric acid and production method thereof |
| CN101993386A (en) * | 2010-11-03 | 2011-03-30 | 天津大学 | Method for preparing electronic-grade N, N-dimethylformamide by ion exchange resin method |
| CN102001986A (en) * | 2010-12-23 | 2011-04-06 | 上海化学试剂研究所 | Method for improving quality of industrial N-methylpyrrolidone |
| CN111377868A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | Preparation method of electronic-grade pyrazole |
| CN112642498A (en) * | 2020-08-08 | 2021-04-13 | 华东理工大学 | Electronic grade pyrazole aqueous solution and preparation method thereof |
| CN113429329A (en) * | 2021-07-06 | 2021-09-24 | 镇江润晶高纯化工科技股份有限公司 | Purification method of semiconductor grade N-methyl pyrrolidone |
| CN113443639A (en) * | 2021-06-25 | 2021-09-28 | 江阴润玛电子材料股份有限公司 | Preparation process of electronic-grade potassium hydroxide |
-
2022
- 2022-09-01 CN CN202211061745.XA patent/CN115160225A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11180704A (en) * | 1997-12-19 | 1999-07-06 | Ube Ind Ltd | Production of aqueous high-purity hydrogen peroxide solution |
| CN1330035A (en) * | 2000-06-21 | 2002-01-09 | 三德化学工业株式会社 | Method for producing purified aqueous hydrogen peroxide solution |
| CN101973871A (en) * | 2010-09-01 | 2011-02-16 | 日照金禾生化集团股份有限公司 | Electronic grade citric acid and production method thereof |
| CN101993386A (en) * | 2010-11-03 | 2011-03-30 | 天津大学 | Method for preparing electronic-grade N, N-dimethylformamide by ion exchange resin method |
| CN102001986A (en) * | 2010-12-23 | 2011-04-06 | 上海化学试剂研究所 | Method for improving quality of industrial N-methylpyrrolidone |
| CN111377868A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | Preparation method of electronic-grade pyrazole |
| CN112642498A (en) * | 2020-08-08 | 2021-04-13 | 华东理工大学 | Electronic grade pyrazole aqueous solution and preparation method thereof |
| CN113443639A (en) * | 2021-06-25 | 2021-09-28 | 江阴润玛电子材料股份有限公司 | Preparation process of electronic-grade potassium hydroxide |
| CN113429329A (en) * | 2021-07-06 | 2021-09-24 | 镇江润晶高纯化工科技股份有限公司 | Purification method of semiconductor grade N-methyl pyrrolidone |
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