阅读说明：本技术 一种电子级双氧水的制备方法 (Preparation method of electronic-grade hydrogen peroxide ) 是由 吕亮 郑小华 徐振祥 曾惠明 林锋 李建光 黄振轩 于 2021-01-07 设计创作，主要内容包括：本发明涉及双氧水制造领域,具体关于一种电子级双氧水的制备方法；本发明首先将工业双氧水通过纳米复合膜初步过滤除去机械杂质,然后经过一种有机树脂改性的介孔分子筛吸附柱,该种有机树脂改性的介孔分子筛在分子筛介孔表面原位聚合聚苯乙烯树脂,将含有两个氟代原子的苯环修饰到树脂表面,增强了表面结构的耐腐蚀性能,而且分子筛的无机结构具有超强的耐腐蚀性能,为吸附剂提供了稳定的骨架结构,保证吸附剂在强氧化环境中保持稳定,不受氧化腐蚀；完成吸附后再经过过滤,得到高纯度双氧水,本发明的高纯度双氧水中有机碳、硝酸盐的含量极低,能够满足电子行业对双氧水的质量要求。(The invention relates to the field of hydrogen peroxide preparation, in particular to a preparation method of electronic grade hydrogen peroxide; the invention firstly primarily filters industrial hydrogen peroxide through a nano composite membrane to remove mechanical impurities, and then passes through an organic resin modified mesoporous molecular sieve adsorption column, the organic resin modified mesoporous molecular sieve in-situ polymerizes polystyrene resin on the mesoporous surface of the molecular sieve, and a benzene ring containing two fluorine atoms is modified on the surface of the resin, so that the corrosion resistance of the surface structure is enhanced, and the inorganic structure of the molecular sieve has super-strong corrosion resistance, so that a stable framework structure is provided for an adsorbent, and the adsorbent is ensured to be stable in a strong oxidation environment and not corroded by oxidation; the high-purity hydrogen peroxide is obtained by filtering after adsorption is finished, and the content of organic carbon and nitrate in the high-purity hydrogen peroxide is extremely low, so that the quality requirement of the electronic industry on the hydrogen peroxide can be met.)

1. A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the antioxidant mesoporous molecular sieve comprises the following steps of performing precise filtration on industrial-grade hydrogen peroxide through a nano composite membrane, then removing organic carbon through adsorption and purification of the antioxidant mesoporous molecular sieve, and finally performing precise filtration through the nano composite membrane:

according to the mass portion, 260 portions of 180-plus phenyl ketone group mesoporous molecular sieve and 250 portions of 150-plus ethylene glycol phenyl ether are stirred and mixed for 1-5h, then 0.5-5 portions of catalyst are added, the temperature is controlled at 120-plus 150 ℃, the heat preservation reaction is carried out for 5-10h, after the reaction is finished, the filtration is carried out, 150-plus 180 portions of dichloroethane are added after the dichloroethane washes the molecular sieve, 1.2-2.4 portions of cuprous chloride are added, 0.1-0.8 portion of triphenylphosphine sodium tri-meta-sulfonate is added after the stirring and mixing are carried out uniformly, the temperature is controlled at 60-80 ℃, the stirring reaction is carried out for 6-10h, after the completion, the molecular sieve is filtered, and the molecular sieve is washed by acetone and then is washed by purified water for 2-5 times, thus obtaining the antioxidant mesoporous molecular sieve.

2. The preparation method of electronic-grade hydrogen peroxide according to claim 1, characterized by comprising the following steps: the preparation method of the phenyl ketone group mesoporous molecular sieve comprises the following steps:

according to the mass parts, soaking 200-280 parts of mesoporous molecular sieve in 300-500 parts of 10-20% hydrochloric acid solution for 1-10h, controlling the temperature of 100-150 ℃ after cleaning and drying for 1-5h, then adding the molecular sieve into 200-300 parts of organic solvent, controlling the temperature of 40-60 ℃ and slowly adding 100-200 parts of organic solution containing 60-80 parts of styrene and 2.4-4.8 parts of initiator into a reaction kettle, controlling the addition for 30-60min to be finished, continuously stirring for 30-60min, then adding the material into an autoclave, controlling the temperature of 100-130 ℃ to react for 5-10h, filtering after the reaction is finished, and washing with purified water to obtain the phenyl ketone mesoporous molecular sieve.

3. The preparation method of electronic-grade hydrogen peroxide according to claim 1, characterized by comprising the following steps: the catalyst is ferric chloride or stannic chloride or zinc chloride.

4. The preparation method of electronic-grade hydrogen peroxide according to claim 2, characterized by comprising the following steps: the particle size of the mesoporous molecular sieve is 0.6-1.2 mm.

5. The preparation method of electronic-grade hydrogen peroxide according to claim 2, characterized by comprising the following steps: the organic solvent is acetone or tetrahydrofuran.

6. The preparation method of electronic-grade hydrogen peroxide according to claim 1, characterized by comprising the following steps: the nano composite membrane is a polysulfone nano composite membrane.

7. The preparation method of electronic-grade hydrogen peroxide according to claim 2, characterized by comprising the following steps: the initiator is azobisisobutyronitrile or azobisisoheptonitrile.

Technical Field

The invention relates to the field of hydrogen peroxide preparation, in particular to a preparation method of electronic grade hydrogen peroxide.

Background

A small amount of anthraquinone organic matters are generated in the process of producing hydrogen peroxide by an anthraquinone method, the content of the anthraquinone organic matters is increased along with the increase of the operation time of the device, and the organic carbon concentration is higher and higher sometimes along with the extension of the operation time of the device. The organic carbon in hydrogen peroxide can seriously affect the quality of the product,

CN111252740A provides a new method for hydrogen peroxide purification, which comprises a hydrogen peroxide raw material, a replacement liquid A, a desorption liquid, a replacement liquid B and a hydrogen peroxide finished product, wherein the hydrogen peroxide raw material, the replacement liquid A, the desorption liquid overhead replacement liquid feeding pipe, the desorption liquid feeding pipe, the replacement liquid B and the hydrogen peroxide finished product replacement feeding pipe respectively enter into corresponding resin columns, and then are discharged from a hydrogen peroxide finished product discharging pipe, a replacement liquid A discharging pipe, a desorption liquid overhead replacement liquid discharging pipe, a desorption liquid discharging pipe, a replacement liquid B discharging pipe and a finished product replacement hydrogen peroxide discharging pipe, so that the whole process is completed. The method adopts a multi-way conversion valve system, and the production cost can be reduced by 30-50%.

CN209065420U discloses a purification system for working solution in hydrogen peroxide production, which comprises a flash tank, a primary vacuum condenser, a secondary vacuum condenser, a water separator and a vacuum pumping system, wherein a feed inlet of the flash tank is arranged in the middle of the top end of a tank body, the feed inlet is connected with the middle of a distributor through an inverted bell-mouthed diffusion tube barrel, a wire mesh packing layer is arranged on the distributor, and a second distributor is arranged below the distributor; the gas phase outlet of the flash tank is connected with a first-stage vacuum condenser, the liquid phase outlet is connected to a working liquid cooler through an electric valve, the first-stage vacuum condenser, a second-stage vacuum condenser are connected, a water separator and a vacuum pumping system are sequentially connected in sequence, and the lower end of the water separator and a drainage pipeline of the vacuum pumping system are converged and connected to a water recovery container. The utility model discloses a purification system of working solution in hydrogen peroxide solution production, safe and reliable, energy consumption greatly reduced utilizes respectively after working solution, solvent steam, water are retrieved the separation, is favorable to energy-concerving and environment-protective.

CN106178592B discloses a safety control system and a safety control method for hydrogen peroxide adsorption and purification, wherein a resin bed layer is arranged in an adsorption tank, a plurality of temperature detectors are arranged in the adsorption tank, the temperature detectors are in communication connection with a temperature alarm, and the temperature alarm is in communication connection with a temperature interlocking device; an emergency cooling water pipeline is arranged on the upper portion of the adsorption tank, a first control valve is arranged on the emergency cooling water pipeline, a hydrogen peroxide returning pipeline is arranged on the lower portion of the adsorption tank, a second control valve is arranged on the hydrogen peroxide returning pipeline, and the first control valve and the second control valve are in communication connection with a temperature interlocking device. Pressure monitoring is arranged at the top, the bottom and the middle part of the adsorption tank, and an alarm is given when the pressure is ultrahigh; an emergency cooling water pipeline is arranged, the cooling water is desalted water, when the temperature interlocking device is started, the third control valve is closed, the first control valve and the second control valve are opened, desalted water is injected into the third control valve, and the third control valve and the second control valve are discharged out of the device as soon as possible, so that the adsorption tank is prevented from exploding under the limit condition, and the overall safety of the anthraquinone method hydrogen peroxide production process is effectively guaranteed.

The purification of hydrogen peroxide is currently a rectification method which is widely applied in industry. However, in the rectification method, because the gas-liquid separation is incomplete and the mist liquid is carried, volatile organic matters enter a rectification system along with hydrogen peroxide steam, the purity is not very high generally, and particularly the organic matters are easy to volatilize and enter the rectification system.

Disclosure of Invention

In order to solve the problems, the invention provides a preparation method of electronic-grade hydrogen peroxide.

A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the antioxidant mesoporous molecular sieve comprises the following steps:

according to the mass portion, 260 portions of 180-plus phenyl ketone group mesoporous molecular sieve and 250 portions of 150-plus ethylene glycol phenyl ether are stirred and mixed for 1-5h, then 0.5-5 portions of catalyst are added, the temperature is controlled at 120-plus 150 ℃, the heat preservation reaction is carried out for 5-10h, after the reaction is finished, the filtration is carried out, 150-plus 180 portions of dichloroethane are added after the dichloroethane washes the molecular sieve, 1.2-2.4 portions of cuprous chloride are added, 0.1-0.8 portion of triphenylphosphine sodium tri-meta-sulfonate is added after the stirring and mixing are carried out uniformly, the temperature is controlled at 60-80 ℃, the stirring reaction is carried out for 6-10h, after the completion, the molecular sieve is filtered, and the molecular sieve is washed by acetone and then is washed by purified water for 2-5 times, thus obtaining the antioxidant mesoporous molecular sieve.

The preparation method of the phenyl ketone group mesoporous molecular sieve comprises the following steps:

controlling the temperature of 20-25 parts of mesoporous molecular sieve and 0.3-1.6 parts of vinyl triethoxysilane, reacting for 30-100min at 60-68 ℃, then adding 1-5 parts of 1- (4-vinyl-phenyl) -ethanone, 0.5-1.0 part of tetramethyldisilane, 0.01-0.05 part of chloroplatinic acid and 100 parts of DMF, uniformly mixing in a reaction kettle, then heating to 70-80 ℃, reacting for 1-4h, filtering, washing and drying to obtain the phenyl ketone group mesoporous molecular sieve.

The mesoporous molecular sieve is firstly reacted with vinyl triethoxysilane to obtain a vinyl mesoporous molecular sieve, and then the vinyl mesoporous molecular sieve is subjected to a hydrogen peroxide addition reaction with 1- (4-vinyl-phenyl) -ethanone and tetramethyldisilane, and a partial equation of the molecular sieve is shown as follows:

the catalyst is ferric chloride or stannic chloride or zinc chloride.

The particle size of the mesoporous molecular sieve is 0.6-1.2 mm.

The organic solvent is acetone or tetrahydrofuran.

The nano composite membrane is a polysulfone nano composite membrane.

The initiator is azobisisobutyronitrile or azobisisoheptonitrile.

The invention relates to a preparation method of electronic grade hydrogen peroxide, firstly removing mechanical impurities in industrial hydrogen peroxide by preliminary filtration of a nano composite membrane, then leading the hydrogen peroxide to pass through a mesoporous molecular sieve modified by organic resin, leading the mesoporous molecular sieve modified by the organic resin to firstly react with vinyl triethoxysilane in the mesoporous molecular sieve to obtain a vinyl mesoporous molecular sieve, then leading the vinyl mesoporous molecular sieve to have a hydrogen peroxide addition reaction with 1- (4-vinyl-phenyl) -ethanone and tetramethyl disilane, then leading the vinyl mesoporous molecular sieve to react with ethylene glycol phenyl ether and triphenylphosphine sodium tri-m-sulfonate, leading benzene rings containing silane to be modified to the surface of resin, enhancing the corrosion resistance of a surface structure, leading the inorganic structure of the molecular sieve to have super-strong corrosion resistance, providing a stable framework structure for an adsorbent, ensuring that the adsorbent is kept stable in a strong oxidation environment, the coating is not corroded by oxidation; the hydrogen peroxide with high quality and high purity is obtained by filtering after adsorption is finished, and the content of organic carbon and nitrate in the hydrogen peroxide with high purity is extremely low, so that the quality requirement of the electronic industry on the hydrogen peroxide can be met.

Drawings

FIG. 1 is a Fourier infrared spectrum of a sample of the antioxidant mesoporous molecular sieve prepared in example 2:

at 1454/1430/1375cm^-1An absorption peak of benzene ring at 1728cm^-1The stretching absorption peak of carbonyl exists nearby, which shows that the phenyl ketone group mesoporous molecular sieve participates in the reaction; at 1175cm^-1An antisymmetric telescopic absorption peak of ether bond at 3337cm^-1A stretching absorption peak of hydroxyl exists nearby, so that the ethylene glycol phenyl ether participates in the reaction; at 1265cm^-1A telescopic absorption peak of sulfonate ions exists nearby, which indicates that triphenylphosphine sodium tri-meta-sulfonate participates in the reaction.

Detailed Description

The invention is further illustrated by the following specific examples:

example 1

A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the antioxidant mesoporous molecular sieve comprises the following steps:

stirring and mixing 180kg of phenyl ketone group mesoporous molecular sieve and 150kg of ethylene glycol phenyl ether for 1 hour, then adding 0.5kg of anhydrous ferric chloride, controlling the temperature to 120 ℃, preserving the temperature for reaction for 5 hours, filtering after the reaction is finished, adding 150kg of dichloroethane and 1.5kg of cuprous chloride after the dichloroethane washes the molecular sieve, stirring and mixing uniformly, adding 0.1kg of triphenylphosphine sodium tri-meta-sulfonate, controlling the temperature to 65 ℃, stirring and reacting for 8 hours, filtering the molecular sieve after the reaction is finished, washing with acetone, and then washing with purified water for 3 times to obtain the antioxidant mesoporous molecular sieve.

The preparation method of the phenyl ketone group mesoporous molecular sieve comprises the following steps:

20kg of mesoporous molecular sieve and 0.3kg of vinyl triethoxysilane are reacted for 30min at the temperature of 60 ℃, 1kg of 1- (4-vinyl-phenyl) -ethanone, 0.5kg of tetramethyldisilane, 0.01kg of chloroplatinic acid and 100kg of DMF are added and evenly mixed in a reaction kettle, then the temperature is raised to 70 ℃, the reaction is carried out for 1h, and the phenyl ketone group mesoporous molecular sieve is obtained after filtering, washing and drying.

The mesoporous molecular sieve has the model of MCM-41 and the particle size of 0.6 mm.

The organic solvent is acetone.

The nano composite membrane is a polysulfone nano composite membrane.

The initiator is azobisisobutyronitrile.

Example 2

A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the antioxidant mesoporous molecular sieve comprises the following steps:

stirring and mixing 220kg of phenyl ketone group mesoporous molecular sieve and 200kg of ethylene glycol phenyl ether for 3h, then adding 2.5kg of stannic chloride, controlling the temperature to 130 ℃, preserving the heat for reaction for 8h, filtering after the reaction is finished, adding 160kg of dichloroethane after the dichloroethane washes the molecular sieve, adding 1.6kg of cuprous chloride, stirring and mixing uniformly, adding 0.5kg of triphenylphosphine sodium tri-meta-sulfonate, controlling the temperature to 70 ℃, stirring and reacting for 6h, filtering the molecular sieve after the reaction is finished, washing with acetone, and then washing with purified water for 3 times to obtain the antioxidant mesoporous molecular sieve.

The preparation method of the phenyl ketone group mesoporous molecular sieve comprises the following steps:

controlling the temperature of 22kg of mesoporous molecular sieve and 0.5kg of vinyl triethoxysilane, reacting for 70min at 63 ℃, then adding 3kg of 1- (4-vinyl-phenyl) -ethanone, 0.6kg of tetramethyldisilane, 0.03kg of chloroplatinic acid and 110kg of DMF, uniformly mixing in a reaction kettle, then heating to 75 ℃, reacting for 2h, filtering, washing and drying to obtain the phenyl ketone group mesoporous molecular sieve.

The model of the mesoporous molecular sieve is KIT-6, and the particle size is 0.9 mm.

The organic solvent is tetrahydrofuran.

The nano composite membrane is a polysulfone nano composite membrane.

The initiator is azobisisoheptonitrile.

Example 3

A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the antioxidant mesoporous molecular sieve comprises the following steps:

mixing 260kg of phenyl ketone group mesoporous molecular sieve and 250kg of ethylene glycol phenyl ether under stirring for 5h, then adding 5kg of anhydrous zinc chloride, controlling the temperature to be 150 ℃, preserving the temperature for reaction for 10h, after the reaction is finished, filtering, adding 180kg of dichloroethane after the dichloroethane washes the molecular sieve, adding 2.4kg of cuprous chloride, stirring and mixing uniformly, adding 0.8kg of triphenylphosphine sodium tri-meta-sulfonate, controlling the temperature to be 80 ℃, stirring and reacting for 12h, after the reaction is finished, filtering the molecular sieve, washing with acetone, and then washing with purified water for 5 times to obtain the antioxidant mesoporous molecular sieve.

The preparation method of the phenyl ketone group mesoporous molecular sieve comprises the following steps:

reacting 25kg of mesoporous molecular sieve and 1.6kg of vinyl triethoxysilane at the temperature of 68 ℃ for 100min, then adding 5kg of 1- (4-vinyl-phenyl) -ethanone, 1.0kg of tetramethyldisilane, 0.05kg of chloroplatinic acid and 120kg of DMF, uniformly mixing in a reaction kettle, then heating to 80 ℃, reacting for 4h, filtering, washing and drying to obtain the phenyl ketone group mesoporous molecular sieve.

The type of the mesoporous molecular sieve is SBA-2, and the particle size is 1.2 mm.

The organic solvent is tetrahydrofuran.

The nano composite membrane is a polysulfone nano composite membrane.

The initiator is azobisisoheptonitrile.

Comparative example 1

A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the phenyl ketone-based mesoporous molecular sieve comprises the following steps:

controlling the temperature of 20-25kg of mesoporous molecular sieve and 0.3-1.6kg of vinyl triethoxysilane, reacting for 30-100min at 60-68 ℃, then adding 1-5kg of 1- (4-vinyl-phenyl) -ethanone, 0.5-1.0kg of tetramethyldisilane, 0.01-0.05kg of chloroplatinic acid and 100kg of DMF, uniformly mixing in a reaction kettle, then heating to 70-80 ℃, reacting for 1-4h, filtering, washing and drying to obtain the phenyl ketone group mesoporous molecular sieve.

The mesoporous molecular sieve has the model of MCM-41 and the particle size of 0.6 mm.

The organic solvent is acetone.

The nano composite membrane is a polysulfone nano composite membrane.

The initiator is azobisisobutyronitrile.

Comparative example 2

A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the antioxidant mesoporous molecular sieve comprises the following steps:

stirring and mixing 180kg of phenyl ketone group mesoporous molecular sieve and 150kg of ethylene glycol phenyl ether for 1h, then adding 0.5kg of catalyst, controlling the temperature to 120 ℃, preserving the temperature for 5h, after the reaction is finished, filtering, adding 150kg of dichloroethane after the dichloroethane washes the molecular sieve, adding, stirring and mixing uniformly, controlling the temperature to 60 ℃, stirring and reacting for 6h, after the reaction is finished, filtering the molecular sieve, washing with acetone and then washing with purified water for 2 times, thus obtaining the antioxidant mesoporous molecular sieve.

The preparation method of the phenyl ketone group mesoporous molecular sieve comprises the following steps:

20kg of mesoporous molecular sieve and 0.3kg of vinyl triethoxysilane are reacted for 30min at the temperature of 60 ℃, then 1kg of 1- (4-vinyl-phenyl) -ethanone, 0.5kg of tetramethyldisilane, 0.01kg of chloroplatinic acid and 100kg of DMF are added and uniformly mixed in a reaction kettle, then the temperature is raised to 70 ℃, the reaction is carried out for 1h, and the phenyl ketone group mesoporous molecular sieve is obtained after filtering, washing and drying.

The catalyst is ferric chloride.

The mesoporous molecular sieve has the model of MCM-41 and the particle size of 0.6 mm.

The organic solvent is acetone.

The nano composite membrane is a polysulfone nano composite membrane.

The initiator is azobisisobutyronitrile.

Comparative example 3

A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the antioxidant mesoporous molecular sieve comprises the following steps:

stirring and mixing 180kg of silane modified mesoporous molecular sieve and 150kg of ethylene glycol phenyl ether for 1h, then adding 0.5kg of catalyst, controlling the temperature to 120 ℃, preserving the heat for 5h, after the reaction is finished, filtering, adding 150kg of dichloroethane after the dichloroethane washes the molecular sieve, adding 1.2kg of cuprous chloride, stirring and mixing uniformly, adding 0.1kg of triphenylphosphine sodium tri-meta-sulfonate, controlling the temperature to 60 ℃, stirring and reacting for 6h, after the reaction is finished, filtering the molecular sieve, washing with acetone, and washing with purified water for 2 times to obtain the antioxidant mesoporous molecular sieve.

The preparation method of the silane modified mesoporous molecular sieve comprises the following steps:

20kg of mesoporous molecular sieve and 0.3kg of vinyl triethoxysilane are reacted for 30min at the temperature of 60 ℃, then 0.5kg of tetramethyldisilane, 0.01kg of chloroplatinic acid and 100kg of DMF are added and mixed uniformly in a reaction kettle, then the temperature is raised to 70 ℃, the reaction is carried out for 1h, and the silane modified mesoporous molecular sieve is obtained after filtration, washing and drying.

The catalyst is ferric chloride.

The mesoporous molecular sieve has the model of MCM-41 and the particle size of 0.6 mm.

The organic solvent is acetone.

The nano composite membrane is a polysulfone nano composite membrane.

The initiator is azobisisobutyronitrile.

Comparative example 4

A preparation method of electronic grade hydrogen peroxide comprises the following specific scheme:

the preparation method is characterized in that the preparation method of the mesoporous molecular sieve comprises the following steps:

the catalyst is ferric chloride.

The mesoporous molecular sieve has the model of MCM-41 and the particle size of 0.6 mm.

The organic solvent is acetone.

The nano composite membrane is a polysulfone nano composite membrane.

The initiator is azobisisobutyronitrile.

35% technical hydrogen peroxide solution was used for 8h according to the method in the example^-1The empty tower speed of (2) and 100L of exchange columns, and the exchange temperature is controlled to be 20 ℃; the method for testing the total carbon content and the nitrate content in the hydrogen peroxide is tested according to the method in GB 1616-2003 industrial hydrogen peroxide, and the organic carbon purification rate before and after treatment is calculated, wherein the total carbon content in the hydrogen peroxide before treatment is 320ppm, and the nitrate content is 350 ppm.

The nitrate content and the total carbon removal rate after treatment of the hydrogen peroxide solutions of the above examples and comparative examples are shown in the following table:

	nitrate content (ppm)	Total carbon removal (%)
			Example 1	12	99.9
Example 2	18	99.7
			Example 3	20	99.5
Comparative example 1	147	79.3
			Comparative example 2	96	90.9
Comparative example 3	91	90.1
			Comparative example 4	228	62.7