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CN-120987277-B - Preparation method of electronic-grade hydroxylamine aqueous solution

CN120987277BCN 120987277 BCN120987277 BCN 120987277BCN-120987277-B

Abstract

The invention discloses a preparation method of an electronic-grade hydroxylamine aqueous solution, and relates to the field of chemical preparation. Electronic grade ammonia water or organic alkali is adopted to react with electronic grade hydroxylamine salt to generate hydroxylamine aqueous solution. After the reaction, separating by a POSS nanometer blending modified membrane, and removing salt, impurities and unreacted raw materials to obtain a high-purity hydroxylamine aqueous solution. The solution was concentrated to 50% aqueous hydroxylamine using low temperature vacuum concentration techniques. The method can effectively remove metal ions and inorganic impurities, ensures that the final product has high purity and meets the electronic grade requirement.

Inventors

  • ZHOU QIANG
  • ZHOU LIYANG
  • XU BITAO
  • DUAN ZHONGGANG
  • ZHANG JUNLIANG
  • ZHANG CHAOQUN
  • XIANG WEIRONG

Assignees

  • 浙江锦华新材料股份有限公司

Dates

Publication Date
20260508
Application Date
20251023

Claims (9)

  1. 1. The preparation method of the electronic-grade hydroxylamine aqueous solution is characterized by comprising the following steps of: The reaction step is that 100-1000 parts of electronic grade ammonia water and 50-500 parts of electronic grade hydroxylamine salt are added into a reactor, the temperature is raised for reaction for 1-2 hours, and stirring is continuously carried out in the reaction process; the membrane separation step is that the solution generated by the reaction is treated by a POSS nanometer blending modified membrane at the temperature of 30-60 ℃, and the salt and unreacted raw materials are removed by membrane separation to obtain hydroxylamine aqueous solution; Concentrating the hydroxylamine water solution after membrane separation in a vacuum concentrator at 40-60 deg.c to ensure that hydroxylamine is not decomposed and concentrated to 45-60wt% hydroxylamine water solution; the POSS nanometer blending modified film is prepared by preparing blending film casting liquid through reaction of polyvinylidene fluoride, a pore-forming agent PEG400, silicon dioxide nanometer particles, hydrogen silsesquioxane and dibutyl tin dilaurate, and then carrying out phase inversion film formation.
  2. 2. The method for producing an aqueous electronic grade hydroxylamine solution as claimed in claim 1, wherein the metal ion content of the aqueous electronic grade ammonia is not more than 1ppb.
  3. 3. The method for preparing an aqueous solution of electronic grade hydroxylamine as claimed in claim 1, wherein the electronic grade hydroxylamine salt is hydroxylamine chloride, hydroxylamine sulfate or a mixture thereof.
  4. 4. The method for preparing an aqueous solution of electronic grade hydroxylamine as claimed in claim 1, wherein the temperature of the elevated reaction is 0-50 ℃.
  5. 5. The method for preparing an aqueous solution of electronic grade hydroxylamine as claimed in claim 1, wherein the stirring speed during the reaction is controlled to be 200-600rpm.
  6. 6. The preparation method of the electronic grade hydroxylamine aqueous solution of claim 1, wherein the preparation method of the POSS nanometer blending modified film is as follows in parts by mass: The preparation of the solution comprises the steps of mixing 100 parts of polyvinylidene fluoride, 200-300 parts of N, N-dimethylformamide and 10-20 parts of pore-forming agent PEG400, and stirring for 4-8 hours at 60-80 ℃ to obtain PVDF solution; Adding 5-15 parts of silicon dioxide nano particles, 1-2 parts of hydrogen silsesquioxane and 0.05-0.1 part of dibutyl tin dilaurate into the PVDF solution, and performing ultrasonic dispersion for 30-60min under the power of 200-400W to obtain a blending casting film solution; And (3) phase inversion film forming, namely casting the blending casting film into a film, and then immersing the film into a water/ethanol mixed coagulation bath for 1-2h to finish phase inversion to obtain the POSS nanometer blending modified film.
  7. 7. The method for producing an aqueous solution of electronic grade hydroxylamine as claimed in claim 1, wherein the operation pressure of the membrane separation step is controlled to be 1-5MPa.
  8. 8. The method for preparing an aqueous solution of electronic grade hydroxylamine as claimed in claim 1, wherein the vacuum concentrator is controlled to a pressure of 0.001-0.01MPa.
  9. 9. The method for preparing an electronic grade hydroxylamine aqueous solution as defined in claim 1, wherein: the concentration time is 2-6 hours.

Description

Preparation method of electronic-grade hydroxylamine aqueous solution Technical Field The invention relates to the field of chemical preparation, in particular to a preparation method of an electronic-grade hydroxylamine aqueous solution. Background Hydroxylamine (NH 2 OH) is an important chemical intermediate and is widely used in the fields of high precision tips such as pharmacy, electronics, metallurgy, etc. Particularly in semiconductor manufacturing, hydroxylamine is used as a cleaning and etching liquid, and its purity is required to be extremely high, so that the demand for electronic grade hydroxylamine is increasing. Electronic grade hydroxylamine has a low impurity content and requires that any impurities or byproducts that may affect the purity of the product be avoided from being introduced during the production process. In order to meet the requirement, it is important to develop an efficient and environment-friendly preparation method. The traditional hydroxylamine preparation method mainly comprises a hydrolysis method, an oxidation method, an ammonification method and the like. Hydrolysis method the earliest hydroxylamine preparation method is to generate hydroxylamine through hydrolysis reaction, generally uses amino compound to react with hydrogen peroxide or sodium chloride, and the reaction is simpler, but the method has obvious limitation in obtaining high-purity hydroxylamine, generates more byproducts and has lower purity, and cannot meet the requirements of high-end application. Oxidation, an oxidation method is a method which is common in the current industrial production, and ammonia gas is oxidized by using an oxidizing agent such as hydrogen peroxide to generate hydroxylamine. Although this method can give hydroxylamine of higher purity, since the reaction process generates a large amount of oxidized byproducts such as hydrogen peroxide residues, an additional treatment step is required to remove these byproducts. The ammonification method is mainly used for converting other amino compounds into hydroxylamine through ammonification reaction, generally requires high-temperature and high-pressure conditions, and requires a complex separation process, so that equipment investment and energy consumption are high, and the purity of the final product is difficult to ensure. Although the traditional method can synthesize hydroxylamine, the problems of harsh reaction conditions, more impurities, low reaction efficiency and the like generally exist, and the requirement of high-purity electronic-grade hydroxylamine cannot be met. Electronic grade hydroxylamine is widely used in the fields of semiconductors, electro-optical display devices, integrated circuits, and other precision manufacturing. With the continued development of electronics, the refinement of manufacturing processes requires highly pure chemicals, in particular gases and solutions for use in etching processes, which are extremely high in purity. In order to avoid any impurities affecting the circuit or material properties, the electronic grade hydroxylamine must ensure extremely low impurity levels. In addition, in these applications, hydroxylamine often needs to react with other chemicals (e.g., fluorides, peroxides, etc.) to form specific chemicals, so it is important to control the impurity type and concentration of hydroxylamine, especially the content of inorganic impurities such as heavy metals and salts. Disclosure of Invention The invention provides a new preparation method of electronic-grade hydroxylamine aqueous solution, which can obviously improve the purity of a final product while ensuring high reaction efficiency by optimizing the reaction conditions of ammonia water or organic alkali and electronic-grade hydroxylamine salt and introducing high-efficiency membrane separation and low-temperature concentration technology. The technical proposal is as follows: the preparation method of the electronic-grade hydroxylamine aqueous solution comprises the following steps of: The reaction step is that 100-1000 parts of electronic grade ammonia water and 50-500 parts of electronic grade hydroxylamine salt are added into a reactor, the temperature is raised for reaction for 1-2 hours, and stirring is continuously carried out in the reaction process; the membrane separation step is that the solution generated by the reaction is treated by a POSS nanometer blending modified membrane at the temperature of 30-60 ℃, and the salt and unreacted raw materials are removed by membrane separation to obtain hydroxylamine aqueous solution; And concentrating the hydroxylamine water solution after membrane separation in a vacuum concentrator at 40-60 deg.c to ensure that hydroxylamine is not decomposed and concentrated into hydroxylamine water solution of 45-60 wt%. In some embodiments of the invention, the electronic grade aqueous ammonia metal ion content is no greater than 1ppb. In some embodiments of the invention, the electroni