CN113636526B - Production process of ultra-clean high-purity hydrogen peroxide - Google Patents
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- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
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- C—CHEMISTRY; METALLURGY
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- 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) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment comprises the steps of discharging inert gas and oxidizing an oxidant in sequence; (2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain resin filtered hydrogen peroxide; (3) Then the resin filtered hydrogen peroxide is subjected to microfiltration treatment by adopting a filter membrane, and the filtrate obtained by filtration is the high-purity hydrogen peroxide; the process of the invention is used for treating industrial hydrogen peroxide, which can greatly improve the purity of the industrial hydrogen peroxide, thereby being better applied to cleaning agents for semiconductor crystal plates, corrosive agents and photoresist removers, and the electronic industry prepares a high-grade insulating layer, removes inorganic impurities in electroplating solution, has remarkable effect and improves 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 H2O2. Pure hydrogen peroxide is light blue viscous liquid, can be mixed with water in any proportion, is a strong oxidant, and the aqueous solution is commonly called hydrogen peroxide and is colorless transparent liquid. The aqueous solution is suitable for medical wound disinfection, environment disinfection and food disinfection. In general, the catalyst is slowly decomposed into water and oxygen, but the decomposition speed is extremely low, and the method for accelerating the reaction speed is to add a catalyst, such as manganese dioxide, or irradiate with short-wave rays.
The high-purity hydrogen peroxide is one of the essential basic chemical materials in the micro-machining and manufacturing process of electronic technology, is mainly used as a cleaning agent for semiconductor crystal chips, a corrosive agent and a photoresist remover, is used for preparing an advanced insulating layer and removing inorganic impurities in electroplating liquid in the electronic industry, and is used for treating copper, copper alloy, semiconductor materials and kinescope manufacturing processes thereof, and the like, and the purity of the hydrogen peroxide has very obvious influence on the yield, the electrical performance 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 currently.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a production process of ultra-clean high-purity hydrogen peroxide, which has the advantage of higher purity.
The invention provides a production process of ultra-clean high-purity hydrogen peroxide, which has the advantage of higher purity.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the production process of the ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment is sequentially divided into the discharge of inert gas and the oxidation of oxidant;
(2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain filtered hydrogen oxide;
(3) And then the resin is used for filtering the hydrogen peroxide, and a filtering membrane is used for carrying out microfiltration treatment, and the filtrate obtained by filtration is the high-purity hydrogen peroxide.
Further 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.
Further preferably, the inert gas is nitrogen.
It is further preferred that the nitrogen flow rate is 80-100mL/min.
Further preferably, the oxidizing agent is oxidized as:
after the end of the inert gas, ozone is introduced, the continuous introduction time is 30-35min, and the ozone introduction flow rate is 20-30mL/min.
Further 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, regulating the temperature to 40-50 ℃, carrying out heat preservation and stirring reaction for 2 hours, then filtering, cleaning by adopting absolute ethyl alcohol, drying, cleaning by adopting deionized water, and drying to constant weight to obtain pretreated resin;
(2) Adding the pretreatment resin into dimethyl sulfoxide for soaking and swelling for 9-11h, wherein the mixing mass ratio is 1:10, soaking at 55-60 ℃, then adding iminodiacetic acid and benzenesulfonic acid mixed water solution, adjusting the temperature to 75 ℃, keeping the temperature, stirring and reacting for 8-10 hours, then washing twice with deionized water, washing 3 times with absolute ethyl alcohol and acetone in sequence, and then drying in vacuum to constant weight.
Further preferably, the AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid are mixed according to the 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%;
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%.
Further preferably, the filtration membrane preparation method comprises the following steps:
sequentially adding the poly (m-phenylene isophthalamide) fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl formamide into a reaction kettle, and stirring for 30min to obtain a mixed solution:
spreading the mixed solution on the surface of a glass plate, then adopting a film scraping machine to scrape a film, standing for 20s in air, and then immersing in deionized water to solidify and form a film.
Still more preferably, the mixed weight parts of the poly m-phenylene isophthalamide fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethylacetamide are as follows: 60-68:1.2-1.6:5-8:18-20:80-100.
Further preferably, the scratch film has a thickness of 150 μm.
In summary, compared with the prior art, the invention has the following beneficial effects:
the process of the invention is used for treating industrial hydrogen peroxide, which can greatly improve the purity of the industrial hydrogen peroxide, thereby being better applied to cleaning agents for semiconductor crystal plates, corrosive agents and photoresist removers, and having obvious effect on preparing high-grade insulating layers and removing inorganic impurities in electroplating liquid by the electronic industry 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 van der Waals force and adsorbate act to greatly reduce the metal ions in the industrial hydrogen peroxide solution, so that the impurity pollution of 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 has strong oxidation resistance and stable chemical property, and can avoid causing massive decomposition of hydrogen peroxide.
The prepared filtering membrane can further remove impurities in the industrial hydrogen peroxide solution, and improve the purity of the hydrogen peroxide solution.
Detailed Description
The present invention will be described in detail with reference to examples.
The production process of the ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment is sequentially divided into the discharge of inert gas and the oxidation of oxidant;
(2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain filtered hydrogen oxide;
(3) And then the resin is used for filtering the hydrogen peroxide, and a filtering membrane is used for carrying out microfiltration treatment, and the filtrate obtained by filtration is the high-purity hydrogen peroxide.
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.
The inert gas is nitrogen.
The flow rate of nitrogen is 80-100mL/min.
Further preferably, the oxidizing agent is oxidized as:
after the end of the inert gas, ozone is introduced, the continuous introduction time is 30-35min, and the ozone introduction flow rate is 20-30mL/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, regulating the temperature to 40-50 ℃, carrying out heat preservation and stirring reaction for 2 hours, then filtering, cleaning by adopting absolute ethyl alcohol, drying, cleaning by adopting deionized water, and drying to constant weight to obtain pretreated resin;
(2) Adding the pretreatment resin into dimethyl sulfoxide for soaking and swelling for 9-11h, wherein the mixing mass ratio is 1:10, soaking at 55-60 ℃, then adding iminodiacetic acid and benzenesulfonic acid mixed water solution, adjusting the temperature to 75 ℃, keeping the temperature, stirring and reacting for 8-10 hours, then washing twice with deionized water, washing 3 times with absolute ethyl alcohol and acetone in sequence, and then drying in vacuum to constant weight.
AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid are mixed according to the 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%;
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 filtering membrane comprises the following steps:
sequentially adding the poly (m-phenylene isophthalamide) fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl formamide into a reaction kettle, and stirring for 30min to obtain a mixed solution:
spreading the mixed solution on the surface of a glass plate, then adopting a film scraping machine to scrape a film, standing for 20s in air, and then immersing in deionized water to solidify and form a film.
The mixture weight ratio of the poly (m-phenylene isophthalamide) fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethyl acetamide is as follows: 60-68:1.2-1.6:5-8:18-20:80-100.
The scratch film thickness was 150 microns.
In order to further illustrate the invention, the following are specific examples.
Example 1:
the production process of the ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment is sequentially divided into the discharge of inert gas and the oxidation of oxidant;
(2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain filtered hydrogen oxide;
(3) And then the resin is used for filtering the hydrogen peroxide, and a filtering membrane is used for carrying out microfiltration treatment, and the filtrate obtained by filtration is the high-purity hydrogen peroxide.
The inert gas is discharged as follows:
industrial hydrogen peroxide is added into the reaction kettle, and then inert gas is continuously introduced into the industrial hydrogen peroxide in the reaction kettle for 1 hour.
The inert gas is nitrogen.
The nitrogen flow rate was 80mL/min.
The oxidation of the oxidizing agent is:
after the end of the inert gas, ozone is started to be introduced, the continuous introduction time is 30min, and the ozone introduction flow rate is 20mL/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, regulating the temperature to 40 ℃, carrying out heat preservation and stirring reaction for 2 hours, then filtering, cleaning by adopting absolute ethyl alcohol, drying, cleaning by adopting deionized water, and drying to constant weight to obtain pretreated resin;
(2) Adding the pretreatment resin into dimethyl sulfoxide, soaking and swelling for 9h, wherein the mixing mass ratio is 1:10, soaking at 55 ℃, then adding iminodiacetic acid and benzenesulfonic acid mixed water solution, adjusting the temperature to 75 ℃, preserving heat, stirring and reacting for 8 hours, then washing twice with deionized water, washing 3 times with absolute ethyl alcohol and acetone in sequence, and then drying in vacuum to constant weight.
AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid are mixed according to the weight ratio of 50:6:1:4:5;
the mass fraction of the concentrated sulfuric acid solution is 81.5%;
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 filtering membrane comprises the following steps:
sequentially adding the poly (m-phenylene isophthalamide) fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl formamide into a reaction kettle, and stirring for 30min to obtain a mixed solution:
spreading the mixed solution on the surface of a glass plate, then adopting a film scraping machine to scrape a film, standing for 20s in air, and then immersing in deionized water to solidify and form a film.
The mixture weight ratio of the poly (m-phenylene isophthalamide) fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethyl acetamide is as follows: 60:1.2:5:18:80.
The scratch film thickness was 150 microns.
Example 2
The production process of the ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment is sequentially divided into the discharge of inert gas and the oxidation of oxidant;
(2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain filtered hydrogen oxide;
(3) And then the resin is used for filtering the hydrogen peroxide, and a filtering membrane is used for carrying out microfiltration treatment, and the filtrate obtained by filtration is the high-purity hydrogen peroxide.
The inert gas is discharged as follows:
and adding industrial hydrogen peroxide into the reaction kettle, and then 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 100mL/min.
Further preferably, the oxidizing agent is oxidized as:
after the end of the inert gas, ozone is started to be introduced, the continuous introduction time is 35min, and the ozone introduction flow rate is 30mL/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, regulating the temperature to 50 ℃, carrying out heat preservation and stirring reaction for 2 hours, then filtering, cleaning by adopting absolute ethyl alcohol, drying, cleaning by adopting deionized water, and drying to constant weight to obtain pretreated resin;
(2) Adding the pretreatment resin into dimethyl sulfoxide, soaking and swelling for 11h, wherein the mixing mass ratio is 1:10, soaking at 60 ℃, then adding iminodiacetic acid and benzenesulfonic acid mixed water solution, adjusting the temperature to 75 ℃, keeping the temperature, stirring and reacting for 10 hours, then washing twice with deionized water, washing 3 times with absolute ethyl alcohol and acetone in sequence, and then drying in vacuum to constant weight.
AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid are mixed according to the weight ratio of 60:10:2:6:8;
the mass fraction of the concentrated sulfuric acid solution is 81.5%;
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 filtering membrane comprises the following steps:
sequentially adding the poly (m-phenylene isophthalamide) fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl formamide into a reaction kettle, and stirring for 30min to obtain a mixed solution:
spreading the mixed solution on the surface of a glass plate, then adopting a film scraping machine to scrape a film, standing for 20s in air, and then immersing in deionized water to solidify and form a film.
The mixture weight ratio of the poly (m-phenylene isophthalamide) fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethyl acetamide is as follows: 68:1.6:8:20:100.
The scratch film thickness was 150 microns.
Example 3
The production process of the ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment is sequentially divided into the discharge of inert gas and the oxidation of oxidant;
(2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain filtered hydrogen oxide;
(3) And then the resin is used for filtering the hydrogen peroxide, and a filtering membrane is used for carrying out microfiltration treatment, and the filtrate obtained by filtration is the high-purity hydrogen peroxide.
The inert gas is discharged as follows:
industrial hydrogen peroxide is added into the reaction kettle, and then inert gas is continuously introduced into the industrial hydrogen peroxide in the reaction kettle for 1.5 hours.
The inert gas is nitrogen.
The nitrogen flow rate was 90mL/min.
The oxidation of the oxidizing agent is:
after the end of the inert gas, ozone is started to be introduced, the continuous introduction time is 32min, and the ozone introduction flow rate is 26mL/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, regulating the temperature to 45 ℃, carrying out heat preservation and stirring reaction for 2 hours, then filtering, cleaning by adopting absolute ethyl alcohol, drying, cleaning by adopting 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 58 ℃, then adding iminodiacetic acid and benzenesulfonic acid mixed water solution, adjusting the temperature to 75 ℃, keeping the temperature, stirring and reacting for 9 hours, then washing twice with deionized water, washing 3 times with absolute ethyl alcohol and acetone in sequence, and then drying in vacuum to constant weight.
AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid are mixed according to the weight ratio of 55:8:1.2:4.5:7;
the mass fraction of the concentrated sulfuric acid solution is 81.5%;
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 filtering membrane comprises the following steps:
sequentially adding the poly (m-phenylene isophthalamide) fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl formamide into a reaction kettle, and stirring for 30min to obtain a mixed solution:
spreading the mixed solution on the surface of a glass plate, then adopting a film scraping machine to scrape a film, standing for 20s in air, and then immersing in deionized water to solidify and form a film.
The mixture weight ratio of the poly (m-phenylene isophthalamide) fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethyl acetamide is as follows: 62:1.5:6:19:90.
The scratch film thickness was 150 microns.
Example 4:
the production process of the ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment is sequentially divided into the discharge of inert gas and the oxidation of oxidant;
(2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain filtered hydrogen oxide;
(3) And then the resin is used for filtering the hydrogen peroxide, and a filtering membrane is used for carrying out microfiltration treatment, and the filtrate obtained by filtration is the high-purity hydrogen peroxide.
The inert gas is discharged as follows:
industrial hydrogen peroxide is added into the reaction kettle, and then inert gas is continuously introduced into the industrial hydrogen peroxide in the reaction kettle for 1 hour.
The inert gas is nitrogen.
The nitrogen flow rate was 100mL/min.
Further preferably, the oxidizing agent is oxidized as:
after the end of the inert gas, ozone is started to be introduced, the continuous introduction time is 30min, and the ozone introduction flow rate is 20mL/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, regulating the temperature to 45 ℃, carrying out heat preservation and stirring reaction for 2 hours, then filtering, cleaning by adopting absolute ethyl alcohol, drying, cleaning by adopting 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 60 ℃, then adding iminodiacetic acid and benzenesulfonic acid mixed water solution, adjusting the temperature to 75 ℃, preserving heat, stirring and reacting for 8 hours, then washing twice with deionized water, washing 3 times with absolute ethyl alcohol and acetone in sequence, and then drying in vacuum to constant weight.
AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid are mixed according to the weight ratio of 60:6:1:5:6;
the mass fraction of the concentrated sulfuric acid solution is 81.5%;
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 filtering membrane comprises the following steps:
sequentially adding the poly (m-phenylene isophthalamide) fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl formamide into a reaction kettle, and stirring for 30min to obtain a mixed solution:
spreading the mixed solution on the surface of a glass plate, then adopting a film scraping machine to scrape a film, standing for 20s in air, and then immersing in deionized water to solidify and form a film.
The mixture weight ratio of the poly (m-phenylene isophthalamide) fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethyl acetamide is as follows: 60:1.6:8:18:90.
The scratch film thickness was 150 microns.
Example 5
The production process of the ultra-clean high-purity hydrogen peroxide comprises the following steps:
(1) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment is sequentially divided into the discharge of inert gas and the oxidation of oxidant;
(2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain filtered hydrogen oxide;
(3) And then the resin is used for filtering the hydrogen peroxide, and a filtering membrane is used for carrying out microfiltration treatment, and the filtrate obtained by filtration is the high-purity hydrogen peroxide.
The inert gas is discharged as follows:
and adding industrial hydrogen peroxide into the reaction kettle, and then 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 90mL/min.
Further preferably, the oxidizing agent is oxidized as:
after the end of the inert gas, ozone is started to be introduced, the continuous introduction time is 35min, and the ozone introduction flow rate is 28mL/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, regulating the temperature to 45 ℃, carrying out heat preservation and stirring reaction for 2 hours, then filtering, cleaning by adopting absolute ethyl alcohol, drying, cleaning by adopting 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 58 ℃, then adding iminodiacetic acid and benzenesulfonic acid mixed water solution, adjusting the temperature to 75 ℃, keeping the temperature, stirring and reacting for 9 hours, then washing twice with deionized water, washing 3 times with absolute ethyl alcohol and acetone in sequence, and then drying in vacuum to constant weight.
AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid are mixed according to the weight ratio of 55:7:1.5:4.5:6;
the mass fraction of the concentrated sulfuric acid solution is 81.5%;
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 filtering membrane comprises the following steps:
sequentially adding the poly (m-phenylene isophthalamide) fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethyl formamide into a reaction kettle, and stirring for 30min to obtain a mixed solution:
spreading the mixed solution on the surface of a glass plate, then adopting a film scraping machine to scrape a film, standing for 20s in air, and then immersing in deionized water to solidify and form a film.
The mixture weight ratio of the poly (m-phenylene isophthalamide) fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethyl acetamide is as follows: 62:1.5:6:17:95.
The scratch film thickness was 150 microns.
Comparative example 1:
the production process of ultra-clean high-purity hydrogen peroxide is different from that of example 1 in that the oxidation treatment is not performed.
Comparative example 2:
the production process of ultra-clean high-purity hydrogen peroxide is different from that of example 1 in that the filtration treatment is not performed by using an exchange resin.
Comparative example 3: the production process of ultra-clean high-purity hydrogen peroxide is different from that of example 1 in that no microfiltration treatment is performed.
Test
The industrial hydrogen peroxide has total organic carbon mass fraction rho (TOC) of 50.21mg/L and mass fraction of 90 percent, and is tested;
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 present invention has a greatly improved purity, and in particular, the mass fraction of organic carbon in industrial hydrogen peroxide is greatly reduced.
Metal ions in hydrogen peroxide treated by the process of the examples and the comparative examples were detected:
TABLE 2
| ρ(Sn)mg/L | ρ(Ni)mg/L | ρ(PO4 3– )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 metal ion removal rate of the high-purity hydrogen peroxide obtained by the process treatment of the invention is greatly increased, and the metal ions in the industrial hydrogen peroxide can be removed more efficiently.
The embodiments of the present invention are all preferred embodiments of the present invention, and are not intended to limit the scope of the present invention in this way, therefore: all equivalent changes in structure, shape and principle of the invention should be covered in the scope of protection of the invention.
Claims (1)
1. The production process of the ultra-clean high-purity hydrogen peroxide is characterized by comprising the following steps of:
(1) Oxidizing industrial hydrogen peroxide to obtain oxidized hydrogen peroxide, wherein the oxidizing treatment comprises the steps of discharging inert gas and oxidizing an oxidant in sequence;
(2) Filtering the obtained oxidized hydrogen peroxide by adopting exchange resin to obtain resin filtered hydrogen peroxide;
(3) Then the resin filtered hydrogen peroxide is subjected to microfiltration treatment by adopting a filter membrane, and the filtrate obtained by filtration is the high-purity hydrogen peroxide;
the discharge of the inert gas is 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;
the inert gas is nitrogen;
the flow rate of the nitrogen is 80-100mL/min;
the oxidation of the oxidant is as follows:
after the end of the inert gas, starting to introduce ozone, wherein the continuous time of the ozone is 30-35min, and the ozone introducing flow rate is 20-30mL/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 ℃, carrying out heat preservation and stirring reaction for 2 hours, then filtering, cleaning by using absolute ethyl alcohol, drying, cleaning by using deionized water, and drying to constant weight to obtain pretreated resin;
(2) Adding the pretreatment resin into dimethyl sulfoxide for soaking and swelling for 9-11h, wherein the mixing mass ratio is 1:10, soaking at 55-60 ℃, then adding iminodiacetic acid and benzenesulfonic acid mixed water solution, adjusting the temperature to 75 ℃, carrying out heat preservation and stirring reaction for 8-10 hours, then washing twice with deionized water, washing 3 times with absolute ethyl alcohol and acetone in sequence, and then carrying out vacuum drying to constant weight to obtain the product;
the AB-8 type macroporous adsorption resin, paraformaldehyde, titanium chloride, concentrated sulfuric acid and glacial acetic acid are mixed according to the 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%;
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 filtering membrane comprises the following steps:
sequentially adding the poly (m-phenylene isophthalamide) fiber, lithium chloride, polyvinylpyrrolidone, polyethylene glycol and N-N dimethylacetamide into a reaction kettle, and stirring for 30min to obtain a mixed solution:
spreading the mixed solution on the surface of a glass plate, then adopting a film scraping machine to scrape a film, standing for 20s in air, and then immersing in deionized water to cure and form a film;
the mixed weight parts of the poly (m-phenylene isophthalamide) fiber, the lithium chloride, the polyvinylpyrrolidone, the polyethylene glycol and the N-N dimethylacetamide are as follows: 60-68:1.2-1.6:5-8:18-20:80-100;
the scratch film thickness was 150 microns.
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| JP3791709B2 (en) * | 1996-07-09 | 2006-06-28 | 三菱化学株式会社 | Oxidation resistant anion exchange resin and method for purifying oxidizing aqueous solution |
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