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CN-117342972-B - Method for preparing dihydroxypropyl hydroxylamine, reaction system and obtained product

CN117342972BCN 117342972 BCN117342972 BCN 117342972BCN-117342972-B

Abstract

A method for preparing dihydroxypropyl hydroxylamine, a reaction system and the obtained product, wherein the method comprises the following steps of S1, stirring and dissolving dihydroxypropyl amine and carboxylic acid with or without adding an organic solvent; S2, mixing the product with hydrogen peroxide solution, carrying out oxidation reaction on the hydrogen peroxide and dihydroxypropylamine, and S3, carrying out reduced pressure distillation on the obtained product, and removing the organic solvent and carboxylic acid to obtain the dihydroxypropylamine product. The method provided by the invention can prepare the dihydroxypropyl hydroxylamine compound by only one-step reaction, and has the characteristics of high reaction yield, easiness in product purification, high purity of the obtained dihydroxypropyl hydroxylamine product, and low-cost and easily available raw materials.

Inventors

  • ZHU NING
  • SUN RUI
  • XU YINMENG
  • Zou hu
  • DU PENG
  • SHI JUNJUN

Assignees

  • 中国石油化工股份有限公司
  • 中国石油化工股份有限公司石油化工科学研究院

Dates

Publication Date
20260505
Application Date
20220628

Claims (13)

  1. 1. A process for preparing dihydroxypropyl hydroxylamine comprising the steps of: s1, stirring and dissolving dihydroxypropylamine and carboxylic acid with or without an organic solvent, wherein the carboxylic acid is selected from one or more of formic acid, acetic acid, propionic acid, oxalic acid, isobutyric acid and trichloroacetic acid; s2, mixing the solution with hydrogen peroxide solution, and carrying out oxidation reaction on the hydrogen peroxide and dihydroxypropylamine; S3, carrying out reduced pressure distillation on the obtained product, and removing the organic solvent and the carboxylic acid to obtain the dihydroxypropyl hydroxylamine product.
  2. 2. The method for preparing dihydroxypropyl hydroxylamine according to claim 1, wherein in S1, the mass ratio of carboxylic acid to dihydroxypropyl amine is 5 to 50:1.
  3. 3. The method for preparing dihydroxypropyl hydroxylamine according to claim 2, wherein the mass ratio of the carboxylic acid to the dihydroxypropyl amine is 10 to 20:1.
  4. 4. A process for producing dihydroxypropyl hydroxylamine as claimed in claim 1,2 or 3, wherein the organic solvent in S1 is an alcohol, nitrile, alkane, ether or aromatic hydrocarbon organic solvent.
  5. 5. The method for preparing dihydroxypropyl hydroxylamine as claimed in claim 4, wherein the organic solvent is one or a mixture of several of aliphatic or naphthenic alcohols having 1 to 6 carbon atoms, alkanes or aromatic hydrocarbons having 5 to 9 carbon atoms, and nitriles or ethers having 2 to 6 carbon atoms.
  6. 6. The method for preparing dihydroxypropyl hydroxylamine as claimed in claim 5, wherein the organic solvent is one or more selected from the group consisting of methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol, t-amyl alcohol, cyclohexanol, cyclohexane, n-hexane, acetonitrile, diethyl ether, benzene and toluene.
  7. 7. The method for preparing dihydroxypropyl hydroxylamine as claimed in claim 4, wherein in S1, the mass ratio of the organic solvent to dihydroxypropyl amine is 0 to 25:1.
  8. 8. The method for preparing dihydroxypropyl hydroxylamine according to claim 7, wherein the mass ratio of the organic solvent to the dihydroxypropyl amine is 0 to 10:1.
  9. 9. The method for preparing dihydroxypropyl hydroxylamine according to claim 1,2 or 3, wherein in S2, the mass concentration of the hydrogen peroxide solution is 1% -70%, and the molar ratio of hydrogen peroxide to dihydroxypropyl amine is 0.5-10:1.
  10. 10. The method for preparing dihydroxypropyl hydroxylamine according to claim 9, wherein the mass concentration of the hydrogen peroxide solution is 25% -50%, and the molar ratio of hydrogen peroxide to dihydroxypropyl amine is 1-3:1.
  11. 11. The method for preparing dihydroxypropyl hydroxylamine according to claim 1,2 or 3, wherein the reaction temperature in S2 is 10 ℃ to 120 ℃ and the reaction time is 1.5h to 12h.
  12. 12. The method for producing dihydroxypropyl hydroxylamine according to claim 11, wherein the reaction temperature in S2 is 30 ℃ to 75 ℃.
  13. 13. The process for producing dihydroxypropyl hydroxylamine as claimed in claim 1,2 or 3, wherein the operation condition of the reduced pressure distillation in S3 is that the absolute pressure is 1kPa to 50kPa and the temperature is 70 ℃ to 180 ℃.

Description

Method for preparing dihydroxypropyl hydroxylamine, reaction system and obtained product Technical Field The invention relates to the technical field of organic synthesis. In particular to a preparation method of dihydroxypropyl hydroxylamine compound. Background Dihydroxypropylhydroxylamine is an important fine chemical, often abbreviated as HPHA, and is widely used in the field of styrene polymerization inhibition due to its excellent polymerization inhibition effect on olefins. In addition, the catalyst has strong reducibility and can be used as an antioxidant, a boiler scale remover and the like. The prior dihydroxypropyl hydroxylamine synthesis method has few reports, and CN106957240A discloses a method for preparing the hydroxypropyl hydroxylamine, which comprises the steps of firstly adopting substituted hydroxylamine to react with alkali liquor to generate free alkyl hydroxylamine, and then adding propylene oxide into the solution to generate dihydroxypropyl hydroxylamine. The free hydroxylamine formed in the first step is unstable and needs to be carried out in an ice-water bath. And the reaction of hydroxylamine salt and alkali liquor gives off a large amount of heat, so that the decomposition of hydroxylamine may be caused and the yield is reduced. The reaction temperature of propylene oxide needs to be about 20 ℃, and the temperature needs to be increased, so that a certain hydroxylamine loss can be caused. US6028225A discloses a method for directly synthesizing dihydroxypropyl hydroxylamine by using free hydroxylamine and propylene oxide, wherein the raw materials used in the method are not stable enough, are easy to decompose and are inconvenient to store. CN112159333a discloses an improved method, that is, propylene oxide and hydroxylamine salt are added into solvent in advance to be mixed uniformly, then alkali solution is added dropwise, two steps of reaction can be completed once, free hydroxylamine is avoided to be generated and decomposed, the production safety and the product yield are improved, but the neutralization process of hydroxylamine hydrochloride and alkali inevitably generates hydrochloride, which is difficult to separate from raw materials, and can cause discharge of salt-containing wastewater. The raw materials used in the method are hydroxylamine salts or hydroxylamine, the cost is high, the product purification steps are more, and a plurality of steps such as extraction, distillation and the like are needed. Therefore, providing a method for preparing dihydroxypropyl hydroxylamine with low cost, high yield and easy product separation has become a problem to be solved in the field. Disclosure of Invention The invention aims to provide a novel method for preparing dihydroxypropyl hydroxylamine and a reaction system. In a first aspect, the present invention provides a process for preparing dihydroxypropyl hydroxylamine comprising the steps of: s1, stirring and dissolving dihydroxypropylamine and carboxylic acid with or without an organic solvent; s2, mixing the solution with hydrogen peroxide solution, and carrying out oxidation reaction on the hydrogen peroxide and dihydroxypropylamine; S3, carrying out reduced pressure distillation on the obtained product, and removing the organic solvent and the carboxylic acid to obtain the dihydroxypropyl hydroxylamine product. In a second aspect, the reaction system for preparing dihydroxypropyl hydroxylamine provided by the invention comprises a reaction kettle, a buffer tank and a reduced pressure distillation tower which are sequentially communicated, wherein the bottom of the buffer tank is communicated with a feed inlet of the reduced pressure distillation tower through a material pump, and the reaction material is dihydroxypropyl amine, carboxylic acid and hydrogen peroxide, and contains or does not contain an organic solvent. In a third aspect, the dihydroxypropyl hydroxylamine product prepared by the method is provided. The method for preparing dihydroxypropyl hydroxylamine, the reaction system and the obtained product have the beneficial effects that: The preparation method provided by the invention has the advantages that the reaction yield is high, the product purification is easy, the purity of the obtained dihydroxypropyl hydroxylamine product is high, and the raw materials are cheap and easy to obtain. The reaction system for preparing dihydroxypropyl hydroxylamine provided by the invention is suitable for the method provided by the invention, and can be continuously operated to obtain dihydroxypropyl hydroxylamine products. Drawings Fig. 1 is a schematic flow chart of a continuous reaction system for preparing dihydroxypropyl hydroxylamine. Wherein: 1-reaction kettle, 2-buffer tank, 3-vacuum distillation tower, 4-material pump, 5-valve, 6-recovered solvent, 7-dihydroxypropyl hydroxylamine product, 8, 9, 10-pipeline. Detailed Description The following will describe the technical scheme of the present invention in detail a