SU504754A1 - Method for producing ethylene glycol acetates - Google Patents

Description

The process for the preparation of glycol acetate is carried out as follows.

Ethylene is added to a solution containing acetic acid, a palladium (II) salt and a solution of the CCP in acetic acid. After the recovery of the CCP (as judged by the color change of the solution), the supply of ethylene is stopped, pure oxygen is supplied. The process is carried out at a temperature higher than 20-60 ° C and a pressure of 1-0 atm.

Example 1

50 ml of acetic acid, 11 ml of 0, ZM HPC-6 in acetic acid, 2 ml of sulfuric acid, 7 ml of 0.1 M Pd (NO3) 2 are loaded into the reactor with stirring. The temperature of the experiment is 18 ° C, p 1 atm.

The initial concentration of acetic acid is 15 mol / L.

Pure ethylene is fed to the solution. The ethylene concentration in the solution is constant and is 6-10 mol / L. The reaction rate is judged by the rate of ethylene absorption. The average rate of glycol acetate formation is 0.58 mol of C2P4 / L solution per hour.

4 cycles are carried out (cycle is alternating supply of oxygen and ethylene). Total absorbed 0.6 liters of ethylene. The solution with the restored form HCP-6 is treated with oxygen. The transition of the oxidized GCP to the reduced state is judged by the color of the solution (the oxidized form of the GCP has a dark red color and the reduced color is green).

Chromatographic analysis indicates that the main product is ethylene glycol diacetate (99%). The total process time is 1 hour. There is a small amount of ethylene glycol monoacetate ().

Example 2. 30 ml of acetic acid, the total concentration of 11.5 mol / l, 10 ml of O, 3 MH HPA-8 in acetic acid, 1.5 ml of 0.5 M RB (KoS) 2 and 4 ml of HNOS . atm Pure ethylene is added to the solution. Its center is 6-10 mol / l. The solution with the restored form of the HCOC is treated with oxygen. Conduct b cycles.

Total absorbed 1.5 liters of ethylene. Medium (the rate of glycol acetate formation is 1.03 mol of solution per hour. The average oxygen absorption rate is 0.8 mol of O2 / L solution per hour. In total 0.66 L of oxygen is absorbed. The products of the reaction were ethylene glycol monoacetate (30%) , ethylene glycol diacetate (60%) and acetic aldehyde (10%). The total process time is 1.5 hours.

Froze

30 ml of acetic acid, 8 ml of 0, 3 M HPA-4 in acetic acid, total concentration 13 mol / l, 0.2 ml of H2SO4, 0.11 g of Pd (OAc) 2 and 0.5 g are loaded into the solution with stirring.

LiOAc. The temperature of the experiment is 18 ° C, atm. Pure ethylene is served. After recovery of HPA-4, the contact solution is treated with oxygen. Spend 4 cycles. The average ethylene absorption rate is 0.3 mol.

S2P4 / L solution per hour. Total absorbed 0.3 liters of ethylene. The average rate of oxygen uptake is 0.2 mol 02 / l solution per hour. Absorbed 0.22 liters of oxygen. Chromatographic analysis showed that the product consists of

ethylene glycol monoacetate (30%), ethylene glycol diacetate (35%), ethylidene diacetate (18%), ethylene glycol (9%) and acetaldehyde (12%). The total process time is 1.5 hours.

Formula and 3 optics

The method of producing ethylene glycol acetates by the oxidation of ethylene with oxygen in acetic acid solution in the presence of divalent palladium salts and a reversible oxidizing agent at a temperature not exceeding 60 ° C and a pressure of 1 -

10 atm, characterized in that, for the purpose of the upron, of the process and ensuring its explosion-base, the sodium salt of the phosphorus-molybdenum-vanadium heteropolyacid is used as a reversible oxidant, followed by oxidation of the heteropolyacid reduced in the process by oxygen.