CN113636526A - Production process of ultra-clean high-purity hydrogen peroxide - Google Patents
Production process of ultra-clean high-purity hydrogen peroxide Download PDFInfo
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- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
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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
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
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Abstract
The invention discloses a production process of ultra-clean high-purity hydrogen peroxide, which relates to the technical field of chemical industry and comprises the following steps: (1) carrying out oxidation treatment on the industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence; (2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen peroxide; (3) then, performing microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane to obtain filtrate, namely high-purity hydrogen peroxide; the process of the invention can greatly improve the purity of the industrial hydrogen peroxide by treating the industrial hydrogen peroxide, thereby being better applied to a cleaning agent, a corrosive agent and a remover of photoresist of a semiconductor crystal wafer, preparing a high-grade insulating layer in the electronic industry, removing inorganic impurities in electroplating solution, having obvious effect and improving the quality of products.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a production process of ultra-clean high-purity hydrogen peroxide.
Background
Hydrogen peroxide (hydrogen peroxide) is an inorganic compound of the formula H2O 2. Pure hydrogen peroxide is light blue viscous liquid, can be mixed and dissolved with water in any proportion, is a strong oxidant, and the aqueous solution is commonly called hydrogen peroxide and is colorless transparent liquid. The water solution is suitable for medical wound disinfection, environmental disinfection and food disinfection. In general, the catalyst is decomposed slowly into water and oxygen, but the decomposition rate is extremely slow, and the reaction speed is accelerated by adding manganese dioxide or the like as a catalyst or irradiating with short-wave rays.
High-purity hydrogen peroxide is one of the essential key chemical materials in the fine processing and manufacturing process of electronic technology, and is mainly used as a cleaning agent, a corrosive agent and a photoresist remover of a semiconductor crystal wafer, a high-grade insulating layer is prepared in the electronic industry, inorganic impurities in electroplating solution are removed, and copper, copper alloy, semiconductor materials and the processing of a picture tube manufacturing process thereof and the like, and the purity of the hydrogen peroxide has very obvious influence on the yield, the electrical property and the reliability of an integrated circuit, so that how to improve the purity of the hydrogen peroxide is the technical problem to be solved at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a process for producing ultra-clean high-purity hydrogen peroxide, which has the advantage of higher purity.
The invention provides a production process of an ultra-clean high-purity hydrogen peroxide, which has the advantage of higher purity.
In order to achieve the purpose, the invention provides the following technical scheme:
a production process of ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) carrying out oxidation treatment on industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence;
(2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen oxide;
(3) and then, carrying out microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane, wherein the filtrate obtained by filtering is the high-purity hydrogen peroxide.
More preferably, the discharge of the inert gas is:
adding industrial hydrogen peroxide into a reaction kettle, and continuously introducing inert gas into the industrial hydrogen peroxide in the reaction kettle for 1-2 hours.
More preferably, the inert gas is nitrogen.
More preferably, the nitrogen flow rate is 80 to 100 mL/min.
More preferably, the oxidizing agent is oxidized by:
after the inert gas is introduced, starting to introduce ozone for 30-35min at the ozone introduction flow rate of 20-30 mL/min.
More preferably, the preparation method of the exchange resin comprises the following steps:
(1) adding AB-8 type macroporous adsorption resin into a reaction kettle, then adding paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid, adjusting the temperature to 40-50 ℃, keeping the temperature, stirring for reaction for 2 hours, then filtering, washing with absolute ethyl alcohol, drying, washing with deionized water, and drying to constant weight to obtain pretreated resin;
(2) adding the pretreatment resin into dimethyl sulfoxide to soak and swell for 9-11h, wherein the mixing mass ratio is 1: 10, soaking at the temperature of 55-60 ℃, then adding a mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid, adjusting the temperature to 75 ℃, keeping the temperature and stirring for reacting for 8-10 hours, then cleaning twice with deionized water, then sequentially cleaning 3 times with absolute ethyl alcohol and acetone, and then drying in vacuum to constant weight to obtain the product.
More preferably, the mixing weight ratio of the AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid is 50-60:6-10:1-2:4-6: 5-8;
the mass fraction of the concentrated sulfuric acid solution is 81.5 percent;
the mixing mass ratio of the pretreatment resin to the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 1: 5;
the mass fraction of the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 6.8%.
More preferably, the method for preparing the filter membrane comprises the following steps:
sequentially adding polyisophthaloyl metaphenylene diamine fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl acetamide into a reaction kettle, and then stirring for 30min to obtain a mixed solution:
and spreading the mixed solution on the surface of a glass plate, scraping the film by using a film scraping machine, standing in the air for 20s, and then soaking in deionized water for curing and film forming to obtain the glass.
More preferably, the mixture of the polyisophthaloyl metaphenylene diamine fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetamide in parts by weight is as follows: 60-68:1.2-1.6:5-8:18-20:80-100.
More preferably, the thickness of the scratch film is 150 μm.
In summary, compared with the prior art, the invention has the following beneficial effects:
the process of the invention can greatly improve the purity of the industrial hydrogen peroxide by treating the industrial hydrogen peroxide, thereby being better applied to a cleaning agent, a corrosive agent and a remover of photoresist of a semiconductor crystal wafer, preparing a high-grade insulating layer in the electronic industry, removing inorganic impurities in electroplating solution, having obvious effect and improving the quality of products.
The prepared exchange resin can exchange and adsorb metal ions in the industrial hydrogen peroxide solution with high efficiency, and the metal ions in the industrial hydrogen peroxide solution are greatly reduced by the action of Van der Waals force and adsorbate, so that the impurity pollution of the metal ions to semiconductor wafers during the treatment of the semiconductor wafers and the like is avoided, and the product quality is improved.
Because hydrogen peroxide has strong oxidizing property and weak acidity, the exchange resin prepared by the invention not only has strong oxidation resistance and stable chemical property, but also can avoid the massive decomposition of the hydrogen peroxide.
The impurities in the industrial hydrogen peroxide solution can be further removed through the prepared filtering membrane, and the purity of the hydrogen peroxide solution is improved.
Detailed Description
The present invention will be described in detail with reference to examples.
A production process of ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) carrying out oxidation treatment on industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence;
(2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen oxide;
(3) and then, carrying out microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane, wherein the filtrate obtained by filtering is the high-purity hydrogen peroxide.
The discharge of the inert gas is:
adding industrial hydrogen peroxide into a reaction kettle, and continuously introducing inert gas into the industrial hydrogen peroxide in the reaction kettle for 1-2 hours.
The inert gas is nitrogen.
The nitrogen flow rate is 80-100 mL/min.
More preferably, the oxidizing agent is oxidized by:
after the inert gas is introduced, starting to introduce ozone for 30-35min at the ozone introduction flow rate of 20-30 mL/min.
The preparation method of the exchange resin comprises the following steps:
(1) adding AB-8 type macroporous adsorption resin into a reaction kettle, then adding paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid, adjusting the temperature to 40-50 ℃, keeping the temperature, stirring for reaction for 2 hours, then filtering, washing with absolute ethyl alcohol, drying, washing with deionized water, and drying to constant weight to obtain pretreated resin;
(2) adding the pretreatment resin into dimethyl sulfoxide to soak and swell for 9-11h, wherein the mixing mass ratio is 1: 10, soaking at the temperature of 55-60 ℃, then adding a mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid, adjusting the temperature to 75 ℃, keeping the temperature and stirring for reacting for 8-10 hours, then cleaning twice with deionized water, then sequentially cleaning 3 times with absolute ethyl alcohol and acetone, and then drying in vacuum to constant weight to obtain the product.
Mixing the AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid in a weight ratio of 50-60:6-10:1-2:4-6: 5-8;
the mass fraction of the concentrated sulfuric acid solution is 81.5 percent;
the mixing mass ratio of the pretreatment resin to the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 1: 5;
the mass fraction of the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 6.8%.
The preparation method of the filter membrane comprises the following steps:
sequentially adding polyisophthaloyl metaphenylene diamine fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl acetamide into a reaction kettle, and then stirring for 30min to obtain a mixed solution:
and spreading the mixed solution on the surface of a glass plate, scraping the film by using a film scraping machine, standing in the air for 20s, and then soaking in deionized water for curing and film forming to obtain the glass.
The mixture of the polyisophthaloyl metaphenylene diamine fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetylamine in parts by weight is as follows: 60-68:1.2-1.6:5-8:18-20:80-100.
The thickness of the scratch film was 150. mu.m.
To further illustrate the present invention, the following specific examples are set forth.
Example 1:
a production process of ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) carrying out oxidation treatment on industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence;
(2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen oxide;
(3) and then, carrying out microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane, wherein the filtrate obtained by filtering is the high-purity hydrogen peroxide.
The discharge of the inert gas is:
adding industrial hydrogen peroxide into a reaction kettle, and continuously introducing inert gas into the industrial hydrogen peroxide in the reaction kettle for 1 hour.
The inert gas is nitrogen.
The nitrogen flow rate was 80 mL/min.
The oxidation of the oxidant is:
after the inert gas is introduced, starting to introduce ozone for 30min at the ozone introduction flow rate of 20 mL/min.
The preparation method of the exchange resin comprises the following steps:
(1) adding AB-8 type macroporous adsorption resin into a reaction kettle, then adding paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid, adjusting the temperature to 40 ℃, preserving heat, stirring, reacting for 2 hours, then filtering, cleaning with absolute ethyl alcohol, drying, cleaning with deionized water, and drying to constant weight to obtain pretreated resin;
(2) adding the pretreatment resin into dimethyl sulfoxide to soak and swell for 9 hours, wherein the mixing mass ratio is 1: 10, soaking at 55 ℃, then adding a mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid, adjusting the temperature to 75 ℃, carrying out heat preservation and stirring for reaction for 8 hours, then cleaning twice with deionized water, then sequentially cleaning 3 times with absolute ethyl alcohol and acetone, and then carrying out vacuum drying to constant weight to obtain the product.
Mixing AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid in a weight ratio of 50:6:1:4: 5;
the mass fraction of the concentrated sulfuric acid solution is 81.5 percent;
the mixing mass ratio of the pretreatment resin to the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 1: 5;
the mass fraction of the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 6.8%.
The preparation method of the filter membrane comprises the following steps:
sequentially adding polyisophthaloyl metaphenylene diamine fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl acetamide into a reaction kettle, and then stirring for 30min to obtain a mixed solution:
and spreading the mixed solution on the surface of a glass plate, scraping the film by using a film scraping machine, standing in the air for 20s, and then soaking in deionized water for curing and film forming to obtain the glass.
The mixture of the polyisophthaloyl metaphenylene diamine fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetylamine in parts by weight is as follows: 60:1.2:5:18:80.
The thickness of the scratch film was 150. mu.m.
Example 2
A production process of ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) carrying out oxidation treatment on industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence;
(2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen oxide;
(3) and then, carrying out microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane, wherein the filtrate obtained by filtering is the high-purity hydrogen peroxide.
The discharge of the inert gas is:
adding industrial hydrogen peroxide into a reaction kettle, and continuously introducing inert gas into the industrial hydrogen peroxide in the reaction kettle for 2 hours.
The inert gas is nitrogen.
The nitrogen flow rate was 100 mL/min.
More preferably, the oxidizing agent is oxidized by:
after the inert gas is introduced, starting to introduce ozone for 35min at the ozone introduction flow rate of 30 mL/min.
The preparation method of the exchange resin comprises the following steps:
(1) adding AB-8 type macroporous adsorption resin into a reaction kettle, then adding paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid, adjusting the temperature to 50 ℃, preserving heat, stirring, reacting for 2 hours, then filtering, cleaning with absolute ethyl alcohol, drying, cleaning with deionized water, and drying to constant weight to obtain pretreated resin;
(2) adding the pretreatment resin into dimethyl sulfoxide to soak and swell for 11h, wherein the mixing mass ratio is 1: 10, soaking at the temperature of 60 ℃, then adding a mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid, adjusting the temperature to 75 ℃, carrying out heat preservation and stirring for reaction for 10 hours, then cleaning twice with deionized water, then sequentially cleaning 3 times with absolute ethyl alcohol and acetone, and then carrying out vacuum drying to constant weight to obtain the product.
Mixing AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid in a weight ratio of 60:10:2:6: 8;
the mass fraction of the concentrated sulfuric acid solution is 81.5 percent;
the mixing mass ratio of the pretreatment resin to the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 1: 5;
the mass fraction of the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 6.8%.
The preparation method of the filter membrane comprises the following steps:
sequentially adding polyisophthaloyl metaphenylene diamine fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl acetamide into a reaction kettle, and then stirring for 30min to obtain a mixed solution:
and spreading the mixed solution on the surface of a glass plate, scraping the film by using a film scraping machine, standing in the air for 20s, and then soaking in deionized water for curing and film forming to obtain the glass.
The mixture of the polyisophthaloyl metaphenylene diamine fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetylamine in parts by weight is as follows: 68:1.6:8:20:100.
The thickness of the scratch film was 150. mu.m.
Example 3
A production process of ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) carrying out oxidation treatment on industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence;
(2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen oxide;
(3) and then, carrying out microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane, wherein the filtrate obtained by filtering is the high-purity hydrogen peroxide.
The discharge of the inert gas is:
adding industrial hydrogen peroxide into a reaction kettle, and continuously introducing inert gas into the industrial hydrogen peroxide in the reaction kettle for 1.5 hours.
The inert gas is nitrogen.
The nitrogen flow rate was 90 mL/min.
The oxidation of the oxidant is:
after the inert gas is introduced, the introduction of ozone is started, the continuous introduction time is 32min, and the ozone introduction flow rate is 26 mL/min.
The preparation method of the exchange resin comprises the following steps:
(1) adding AB-8 type macroporous adsorption resin into a reaction kettle, then adding paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid, adjusting the temperature to 45 ℃, preserving heat, stirring, reacting for 2 hours, then filtering, cleaning with absolute ethyl alcohol, drying, cleaning with deionized water, and drying to constant weight to obtain pretreated resin;
(2) adding the pretreatment resin into dimethyl sulfoxide, soaking and swelling for 10 hours, wherein the mixing mass ratio is 1: 10, soaking at the temperature of 58 ℃, then adding a mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid, adjusting the temperature to 75 ℃, keeping the temperature and stirring for reaction for 9 hours, then cleaning twice with deionized water, then sequentially cleaning 3 times with absolute ethyl alcohol and acetone, and then drying in vacuum to constant weight to obtain the product.
Mixing AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid in a weight ratio of 55:8:1.2:4.5: 7;
the mass fraction of the concentrated sulfuric acid solution is 81.5 percent;
the mixing mass ratio of the pretreatment resin to the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 1: 5;
the mass fraction of the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 6.8%.
The preparation method of the filter membrane comprises the following steps:
sequentially adding polyisophthaloyl metaphenylene diamine fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl acetamide into a reaction kettle, and then stirring for 30min to obtain a mixed solution:
and spreading the mixed solution on the surface of a glass plate, scraping the film by using a film scraping machine, standing in the air for 20s, and then soaking in deionized water for curing and film forming to obtain the glass.
The mixture of the polyisophthaloyl metaphenylene diamine fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetylamine in parts by weight is as follows: 62:1.5:6:19:90.
The thickness of the scratch film was 150. mu.m.
Example 4:
a production process of ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) carrying out oxidation treatment on industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence;
(2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen oxide;
(3) and then, carrying out microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane, wherein the filtrate obtained by filtering is the high-purity hydrogen peroxide.
The discharge of the inert gas is:
adding industrial hydrogen peroxide into a reaction kettle, and continuously introducing inert gas into the industrial hydrogen peroxide in the reaction kettle for 1 hour.
The inert gas is nitrogen.
The nitrogen flow rate was 100 mL/min.
More preferably, the oxidizing agent is oxidized by:
after the inert gas is introduced, starting to introduce ozone for 30min at the ozone introduction flow rate of 20 mL/min.
The preparation method of the exchange resin comprises the following steps:
(1) adding AB-8 type macroporous adsorption resin into a reaction kettle, then adding paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid, adjusting the temperature to 45 ℃, preserving heat, stirring, reacting for 2 hours, then filtering, cleaning with absolute ethyl alcohol, drying, cleaning with deionized water, and drying to constant weight to obtain pretreated resin;
(2) adding the pretreatment resin into dimethyl sulfoxide, soaking and swelling for 10 hours, wherein the mixing mass ratio is 1: 10, soaking at the temperature of 60 ℃, then adding a mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid, adjusting the temperature to 75 ℃, carrying out heat preservation and stirring for reaction for 8 hours, then cleaning twice with deionized water, then sequentially cleaning 3 times with absolute ethyl alcohol and acetone, and then carrying out vacuum drying to constant weight to obtain the product.
Mixing AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid in a weight ratio of 60:6:1:5: 6;
the mass fraction of the concentrated sulfuric acid solution is 81.5 percent;
the mixing mass ratio of the pretreatment resin to the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 1: 5;
the mass fraction of the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 6.8%.
The preparation method of the filter membrane comprises the following steps:
sequentially adding polyisophthaloyl metaphenylene diamine fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl acetamide into a reaction kettle, and then stirring for 30min to obtain a mixed solution:
and spreading the mixed solution on the surface of a glass plate, scraping the film by using a film scraping machine, standing in the air for 20s, and then soaking in deionized water for curing and film forming to obtain the glass.
The mixture of the polyisophthaloyl metaphenylene diamine fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetylamine in parts by weight is as follows: 60:1.6:8:18:90.
The thickness of the scratch film was 150. mu.m.
Example 5
A production process of ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) carrying out oxidation treatment on industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence;
(2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen oxide;
(3) and then, carrying out microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane, wherein the filtrate obtained by filtering is the high-purity hydrogen peroxide.
The discharge of the inert gas is:
adding industrial hydrogen peroxide into a reaction kettle, and continuously introducing inert gas into the industrial hydrogen peroxide in the reaction kettle for 2 hours.
The inert gas is nitrogen.
The nitrogen flow rate was 90 mL/min.
More preferably, the oxidizing agent is oxidized by:
after the inert gas is introduced, the introduction of ozone is started, the continuous introduction time is 35min, and the ozone introduction flow rate is 28 mL/min.
The preparation method of the exchange resin comprises the following steps:
(1) adding AB-8 type macroporous adsorption resin into a reaction kettle, then adding paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid, adjusting the temperature to 45 ℃, preserving heat, stirring, reacting for 2 hours, then filtering, cleaning with absolute ethyl alcohol, drying, cleaning with deionized water, and drying to constant weight to obtain pretreated resin;
(2) adding the pretreatment resin into dimethyl sulfoxide, soaking and swelling for 10 hours, wherein the mixing mass ratio is 1: 10, soaking at the temperature of 58 ℃, then adding a mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid, adjusting the temperature to 75 ℃, keeping the temperature and stirring for reaction for 9 hours, then cleaning twice with deionized water, then sequentially cleaning 3 times with absolute ethyl alcohol and acetone, and then drying in vacuum to constant weight to obtain the product.
Mixing AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid in a weight ratio of 55:7:1.5:4.5: 6;
the mass fraction of the concentrated sulfuric acid solution is 81.5 percent;
the mixing mass ratio of the pretreatment resin to the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 1: 5;
the mass fraction of the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 6.8%.
The preparation method of the filter membrane comprises the following steps:
sequentially adding polyisophthaloyl metaphenylene diamine fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl acetamide into a reaction kettle, and then stirring for 30min to obtain a mixed solution:
and spreading the mixed solution on the surface of a glass plate, scraping the film by using a film scraping machine, standing in the air for 20s, and then soaking in deionized water for curing and film forming to obtain the glass.
The mixture of the polyisophthaloyl metaphenylene diamine fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetylamine in parts by weight is as follows: 62:1.5:6:17:95.
The thickness of the scratch film was 150. mu.m.
Comparative example 1:
a process for producing ultra-clean high-purity hydrogen peroxide, which is different from that of example 1 in that oxidation treatment is not performed.
Comparative example 2:
the production process of ultra-clean high-purity hydrogen peroxide is different from the production process of the embodiment 1 in that the filtration treatment is not carried out by using an exchange resin.
Comparative example 3: a process for producing ultra-clean high-purity hydrogen peroxide, which is different from example 1 in that microfiltration treatment is not performed.
Test of
The total organic carbon mass fraction rho (TOC) of the industrial hydrogen peroxide is 50.21mg/L, the mass fraction is 90 percent, and the test is carried out;
TABLE 1
| ρ(TOC)mg/L | |
| Example 1 | 4.05 |
| Example 2 | 3.98 |
| Example 3 | 4.01 |
| Example 4 | 3.82 |
| Example 5 | 3.87 |
| Comparative example 1 | 10.79 |
| Comparative example 2 | 4.53 |
| Comparative example 3 | 7.85 |
As can be seen from Table 1, the high-purity hydrogen peroxide produced by the method of the invention has greatly improved purity after being treated by the process of the invention, and especially the organic carbon mass fraction in the industrial hydrogen peroxide is greatly reduced.
The metal ions in the hydrogen peroxide treated by the processes of the examples and the comparative examples are detected:
TABLE 2
| ρ(Sn)mg/L | ρ(Ni)mg/L | ρ(PO43–)mg/L | |
| Before treatment | 25 | 17 | 14 |
| Example 1 | ≤0.02 | ≤1.8 | ≤2 |
| Example 2 | ≤0.02 | ≤1.8 | ≤2 |
| Example 3 | ≤0.02 | ≤1.8 | ≤2 |
| Example 4 | ≤0.02 | ≤1.8 | ≤2 |
| Example 5 | ≤0.02 | ≤1.8 | ≤2 |
| Comparative example 1 | ≤0.03 | ≤1.9 | ≤2.2 |
| Comparative example 2 | ≤0.38 | ≤3.5 | ≤4.3 |
| Comparative example 3 | ≤0.14 | ≤2.4 | ≤2.8 |
As can be seen from Table 2, the removal rate of metal ions in the high-purity hydrogen peroxide obtained by the process treatment is greatly increased, and the metal ions in the industrial hydrogen peroxide can be removed more effectively.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (10)
1. A production process of ultra-clean high-purity hydrogen peroxide is characterized by comprising the following steps:
(1) carrying out oxidation treatment on the industrial hydrogen peroxide to obtain oxidation-treated hydrogen peroxide, wherein the oxidation treatment is divided into inert gas discharge and oxidant oxidation in sequence;
(2) filtering the obtained oxidation-treated hydrogen peroxide by using exchange resin to obtain resin-filtered hydrogen peroxide;
(3) and then, carrying out microfiltration treatment on the resin-filtered hydrogen peroxide by using a filter membrane, wherein the filtrate obtained by filtering is the high-purity hydrogen peroxide.
2. The process for producing ultra-clean high-purity hydrogen peroxide according to claim 1, wherein the inert gas is discharged as follows:
adding industrial hydrogen peroxide into a reaction kettle, and continuously introducing inert gas into the industrial hydrogen peroxide in the reaction kettle for 1-2 hours.
3. The process for producing ultra-clean high-purity hydrogen peroxide according to claim 2, wherein the inert gas is nitrogen.
4. The process for producing ultra-clean high-purity hydrogen peroxide according to claim 3, wherein the flow rate of nitrogen is 80-100 mL/min.
5. The process for producing ultra-clean high-purity hydrogen peroxide according to claim 1, wherein the oxidizing agent is oxidized by:
after the inert gas is introduced, starting to introduce ozone for 30-35min at the ozone introduction flow rate of 20-30 mL/min.
6. The process for producing ultra-clean high-purity hydrogen peroxide according to claim 1, wherein the exchange resin is prepared by the following steps:
(1) adding AB-8 type macroporous adsorption resin into a reaction kettle, then adding paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid, adjusting the temperature to 40-50 ℃, preserving heat, stirring for reaction for 2 hours, then filtering, cleaning with absolute ethyl alcohol, drying, cleaning with deionized water, and drying to constant weight to obtain pretreated resin;
(2) adding the pretreatment resin into dimethyl sulfoxide to soak and swell for 9-11h, wherein the mixing mass ratio is 1: 10, soaking at 55-60 ℃, then adding a mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid, adjusting the temperature to 75 ℃, keeping the temperature and stirring for reacting for 8-10 hours, then cleaning twice with deionized water, then sequentially cleaning 3 times with absolute ethyl alcohol and acetone, and then carrying out vacuum drying to constant weight to obtain the product.
7. The production process of ultra-clean high-purity hydrogen peroxide according to claim 6, wherein the weight ratio of the AB-8 type macroporous adsorbent resin to paraformaldehyde to titanium chloride to concentrated sulfuric acid to glacial acetic acid is 50-60:6-10:1-2:4-6: 5-8;
the mass fraction of the concentrated sulfuric acid solution is 81.5 percent;
the mixing mass ratio of the pretreatment resin to the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 1: 5;
the mass fraction of the mixed aqueous solution of iminodiacetic acid and benzenesulfonic acid is 6.8%.
8. The production process of ultra-clean high-purity hydrogen peroxide as claimed in claim 1, wherein the preparation method of the filtering membrane is as follows:
sequentially adding polyisophthaloyl metaphenylene diamine fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethylacetamide into a reaction kettle, and then stirring for 30min to obtain a mixed solution:
and spreading the mixed solution on the surface of a glass plate, scraping the film by using a film scraping machine, standing in the air for 20s, and then soaking in deionized water for curing and film forming to obtain the glass.
9. The process for producing ultra-clean high-purity hydrogen peroxide according to claim 8, wherein the polyisophthaloyl metaphenylene diamine fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetamide are mixed according to the weight ratio: 60-68:1.2-1.6:5-8:18-20:80-100.
10. The process for producing ultra-clean high-purity hydrogen peroxide according to claim 8, wherein the thickness of the scraped film is 150 μm.
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| US4028284A (en) * | 1973-01-23 | 1977-06-07 | Unitika Ltd. | Phenolic chelate resin |
| JPH0971404A (en) * | 1995-09-04 | 1997-03-18 | Mitsubishi Gas Chem Co Inc | Purification of hydrogen peroxide |
| JPH09100106A (en) * | 1995-10-02 | 1997-04-15 | Mitsubishi Gas Chem Co Inc | Removing method of organic impurity in hydrogen peroxide |
| JPH1015402A (en) * | 1996-07-09 | 1998-01-20 | Mitsubishi Chem Corp | Oxidation-resistant anion-exchange resin and method for refining oxidative aqueous solution |
| CN111921386A (en) * | 2020-09-08 | 2020-11-13 | 北京理工大学 | Preparation method of polyisophthaloyl metaphenylene diamine ultrafiltration membrane |
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| US4028284A (en) * | 1973-01-23 | 1977-06-07 | Unitika Ltd. | Phenolic chelate resin |
| JPH0971404A (en) * | 1995-09-04 | 1997-03-18 | Mitsubishi Gas Chem Co Inc | Purification of hydrogen peroxide |
| JPH09100106A (en) * | 1995-10-02 | 1997-04-15 | Mitsubishi Gas Chem Co Inc | Removing method of organic impurity in hydrogen peroxide |
| JPH1015402A (en) * | 1996-07-09 | 1998-01-20 | Mitsubishi Chem Corp | Oxidation-resistant anion-exchange resin and method for refining oxidative aqueous solution |
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