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CN-121990893-A - Anhydrous formaldehyde alcohol solution and preparation method and application thereof

CN121990893ACN 121990893 ACN121990893 ACN 121990893ACN-121990893-A

Abstract

The invention relates to an anhydrous formaldehyde alcohol solution, a preparation method and application thereof, wherein the preparation method comprises the following steps of (1) under the action of an inorganic base catalyst, carrying out first mixing on paraformaldehyde and the alcohol solution to carry out depolymerization reaction to obtain formaldehyde alcohol solution containing inorganic base; and (2) separating the formaldehyde-alcohol solution containing the inorganic base to obtain an anhydrous formaldehyde-alcohol solution. The preparation method provided by the invention has the advantages that the process is simple, the raw materials are easy to obtain, and the preparation method is suitable for large-scale industrial application.

Inventors

  • LI CHUNSHAN
  • CHANG WEI
  • DENG SENLIN
  • CAO KAIPENG
  • LI JIE
  • WANG GANG
  • Xue Defei
  • WU YULEI

Assignees

  • 中国科学院过程工程研究所
  • 先进能源科学与技术广东省实验室

Dates

Publication Date
20260508
Application Date
20260123

Claims (10)

  1. 1. A method for preparing an anhydrous formaldehyde alcohol solution, which is characterized by comprising the following steps: (1) Under the action of an inorganic base catalyst, carrying out first mixing on paraformaldehyde and an alcohol solution to carry out depolymerization reaction, so as to obtain a formaldehyde alcohol solution containing inorganic base; (2) And separating the formaldehyde-alcohol solution containing the inorganic alkali to obtain an anhydrous formaldehyde-alcohol solution.
  2. 2. The preparation method according to claim 1, wherein the mass ratio of the paraformaldehyde to the alcohol in the alcohol solution in the first mixture is 1 (1-2.2); preferably, the alcoholic solution comprises any one or a combination of at least two of a methanol solution, an ethanol solution or an isopropanol solution.
  3. 3. The production method according to claim 1 or 2, wherein the inorganic base catalyst comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide, or magnesium hydroxide; preferably, the mass of the inorganic base catalyst is 2-8 per mill of the total mass of the paraformaldehyde and the alcohol solution.
  4. 4. The method according to any one of claims 1 to 3, wherein the depolymerization reaction is carried out at a temperature of 50 to 80 ℃; preferably, the depolymerization reaction time is 3-8 hours.
  5. 5. The method according to any one of claims 1 to 4, wherein the depolymerization reaction is carried out with stirring; preferably, the stirring speed is 300-600 rpm.
  6. 6. The method of any one of claims 1-5, wherein the separation treatment comprises rotary evaporation; Preferably, the temperature of the rotary steaming water bath is 55-90 ℃; preferably, the reflux temperature of the rotary steaming is-8 to-20 ℃; Preferably, the rotating speed of the rotary steaming is 20-45 r/min; Preferably, the spin steaming time is 1-5 h.
  7. 7. The method according to claim 6, wherein the rotary evaporation is performed under vacuum; Preferably, the vacuum degree of the rotary steaming is-0.08 to-0.1 MPa.
  8. 8. The preparation method according to any one of claims 1 to 7, characterized in that the preparation method comprises the steps of: (1) Under the action of an inorganic base catalyst, carrying out first mixing on paraformaldehyde and an alcohol solution according to the mass ratio of the paraformaldehyde to the alcohol in the alcohol solution of 1 (1-2.2) at 50-80 ℃ to carry out depolymerization reaction for 3-8 hours to obtain a formaldehyde-alcohol solution containing inorganic base; (2) And (3) carrying out rotary steaming treatment on the formaldehyde-alcohol solution containing the inorganic alkali for 1-5 hours at the vacuum degree of-0.08-0.1 MPa, wherein the water bath temperature is 55-90 ℃, the reflux temperature is-8-20 ℃, the rotating speed is 20-45 r/min, and the distillate of the rotary steaming treatment is the anhydrous formaldehyde-alcohol solution.
  9. 9. An anhydrous formaldehyde-alcohol solution prepared by the preparation method according to any one of claims 1 to 8.
  10. 10. Use of the anhydrous formaldehyde-alcohol solution according to claim 9, characterized in that the anhydrous formaldehyde-alcohol solution is used in aldol condensation reactions.

Description

Anhydrous formaldehyde alcohol solution and preparation method and application thereof Technical Field The invention relates to the technical field of depolymerization of paraformaldehyde, in particular to an anhydrous formaldehyde-alcohol solution, a preparation method and application thereof. Background Formaldehyde is an important organic chemical raw material, can be used as a disinfectant and a preservative, is also used for preparing various products such as phenolic resin, urea-formaldehyde resin or vinylon, and has wide application in the fields of petroleum, textile, medicine and the like. Formaldehyde is one of the trunks of downstream products of methanol, and at present, formaldehyde aqueous solution with 37-55wt% is mainly obtained by a methanol oxidation method, but the formaldehyde aqueous solution with high water content is unfavorable for water-sensitive synthesis reaction, especially in the reaction that formaldehyde participates in preparing high-performance engineering plastics and preparing unsaturated carboxylic esters such as acrylic ester by an aldol condensation method. Therefore, the preparation of anhydrous formaldehyde has become a research hot spot and has higher economic value and industrial prospect. The method for preparing anhydrous formaldehyde by catalysis comprises the steps of gasifying methanol on a fixed bed reactor, diluting with inert gas or not diluting with inert gas, reacting on a high-entropy alloy catalyst with selected element combination to generate formaldehyde, generating no water in the reaction process, and co-producing hydrogen, wherein the high-entropy alloy is one or more of TiVMnFeCoZr high-entropy alloy, tiVCrMnFeZr high-entropy alloy, tiCrMnFeNiZr high-entropy alloy, tiVCrFeNiZr high-entropy alloy, tiVZrNbHf high-entropy alloy, tiVZrNbMo high-entropy alloy, tiZrNbTa high-entropy alloy, tiCrVNb high-entropy alloy, mgTiFeCoNiZr high-entropy alloy, ALCRMNFENIW high-entropy alloy, VMNFENILA high-entropy alloy and TiVCrFeCoZr high-entropy alloy with selected element combination being determined. CN116813457A discloses a depolymerization method of paraformaldehyde, which comprises the following steps of firstly adding paraformaldehyde particles and a depolymerization catalyst accounting for 0.03% -0.05% of the mass of the paraformaldehyde particles in the bottom of a microwave reaction kettle with a stirring device, then adding silicone oil, the liquid level of which exceeds the paraformaldehyde particles, adding an alcohol solvent in the liquid level of the silicone oil and layering on the liquid level of the silicone oil, placing a stirring paddle of the stirring device below the liquid level of the silicone oil, wherein the depolymerization catalyst is copper naphthalate or copper stearate, secondly, starting stirring, heating for 3-5 min at intervals by microwaves, condensing and refluxing for 43-51 min by microwaves, standing for layering, and recovering an alcohol solvent solution by liquid separation to obtain a depolymerized formaldehyde solution. CN111217687A discloses a method for preparing anhydrous formaldehyde, wherein PtSn/SiO 2 is used as a catalyst in the preparation of the anhydrous formaldehyde, the anhydrous formaldehyde is molded, then is filled into a reaction tube and is filled into a fixed bed reactor, methanol is injected by a horizontal pump under normal pressure, inert gas is used as carrier gas, the methanol feeding ratio is 10-60vol%, the methanol feeding speed is 0.10-0.30 mL/(gcat..min), and the reaction is carried out at 350-500 ℃. CN105601487A discloses a preparation method of anhydrous formaldehyde, which comprises the following steps of taking methanol as a raw material and inert gas as a carrier, carrying out reaction in a fluidized bed reactor, filling a catalyst in a reaction tube of the reactor, placing the reactor in the reactor at a reaction temperature of 200-400 ℃, wherein the catalyst is a rare earth compound, the rare earth complex is Ln [ CH (CH 2)nR]3·xH2 O. YL; wherein Ln is a rare earth element, L is an electron donor ligand, R is phenyl, 1<x is less than or equal to 6,1 y is less than or equal to 6, and n is 3-15. CN106699536A discloses a preparation method of anhydrous formaldehyde alcohol solution, which comprises the following steps of (1) controlling the formaldehyde main content in a dilute formaldehyde aqueous solution to be more than or equal to 35%, pumping into a formaldehyde concentration device for concentration to obtain a concentrated formaldehyde aqueous solution with the formaldehyde main content to be more than or equal to 50%, pumping into a drying, polymerizing and depolymerizing integrated reactor, adding a polymerization catalyst, carrying out vacuum dehydration and drying under the conditions of 80-101kPa and 50-70 ℃ in vacuum, simultaneously carrying out polymerization reaction, controlling the reaction time to be 3-5 hours to obtain a paraformaldehyde polymer, (2) controlling the molar