Method for separation of close-boiling mixture of polyols

Patent metadata

Field	Value
Publication number	US-9926251-B2
Application number	US-201515521033-A
Country	US
Kind code	B2
Filing date	Nov 26, 2015
Priority date	Nov 28, 2014
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

This invention discloses an approach for the separation of the close-boiling mixture of polyols. The raw material is ethylene glycol containing miscellaneous polyols (such as 1,2-propylene glycol and 1,2-butanediol). Over an acid catalyst, these miscellaneous polyols, through (1) a dehydration reaction, (2) pinacol rearrangement, and (3) acetalization or ketalization reaction, are converted into aldehydes (small amounts), acetals, and ketals (trace amount), which are simultaneously and readily separated via distillation. Meanwhile, after the reaction, the mixture is further separated to obtain an ethylene glycol product at a high purity. The invention provides a technique to remove the miscellaneous polyols from ethylene glycol via liquid-phase dehydration reactions under mild conditions, with low energy consumption. In particular, this approach is markedly effective for the removal of 1,2-butanediol that is difficult to be removed via conventional techniques. The purity of the resulting ethylene glycol product is high, and value-added acetals or ketals are co-produced.

First claim

We claim:

1. A method for separating a close-boiling mixture of ethylene glycol and one or more miscellaneous polyols selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, andglycerol, the method comprising:
(a) mixing the close-boiling mixture with an acid catalyst at a temperature higher than 150° C.;
(b) performing a dehydration reaction in a reactor under at an elevated temperature;
(c) converting the miscellaneous polyols into volatile products via dehydration, acetalization, and ketalization reactions; and
(d) removing the volatile products via vaporization or distillation, thereby removing the miscellaneous polyols from the closed-boiling mixture to obtain ethylene glycol as a product.

2. The method of claim 1 , wherein said acid catalyst is selected from the group consisting of liquid Brønsted acids, solid Brønsted acids, Lewis acids, acid-site-containing oxides, acid-site-containing minerals, and combinations thereof.

3. The method of claim 1 , wherein the ethylene glycol product is further purified to remove the residual miscellaneous polyols via distillation, extraction, crystallization, adsorption, chromatography, or combinations thereof.

4. The method of claim 1 , wherein the unconverted material in the dehydration reactor contains ethylene glycol and acid catalysts;
(a) when only solid acid catalysts are used, the catalysts are removed from ethylene glycol through solid-liquid separation, evaporation or distillation; the removed solid acid is regenerated via calcination or elution or drying for the recycling of solid catalysts;
(b) when only liquid acid catalysts are used, the catalysts are removed from ethylene glycol through evaporation or distillation for the recycling of liquid catalysts; the liquid acid catalysts are neutralized with an alkali and then the product of the neutralization reaction is removed from ethylene glycol through evaporation or crystallization; and
(c) when both solid and liquid acid catalysts are used, the solid catalysts are firstly removed from ethylene glycol through solid-liquid separation; the liquid acid catalysts are removed from ethylene glycol through evaporation or distillation; or, ethylene glycol is directly separated from both solid and liquid acid catalysts via evaporation or distillation.

5. The method of claim 1 , wherein volatile products of miscellaneous polyols in the dehydration, acetalization, and ketalization reactions are vaporized, condensed, and collected; (b) the removed products include volatile oil-phase and aqueous products; (c) the oil-phase and aqueous products are then separated; (d) the oil-phase product is further separated into acetals, ketals, dioxanes, aldehydes, and ketones; apart from the removal of miscellaneous polyols, by-products of acetals, ketals, cyclic ethers, acyclic ethers, aldehydes, and ketones are co-produced; (e) the dehydration reactor itself also functions as a simple reactive distillation apparatus to remove the by-products from ethylene glycol; or, these by-products are produced and removed via multi-stage reactive distillation; or, the reaction system are refluxed in the reactor, and then the mixture is separated through decantation, extraction, adsorption, or distillation.

6. The method of claim 1 , wherein the feedstock contains 50 wt %-95 wt % ethylene glycol and 5 wt %-50 wt % of the miscellaneous polyols.

7. The method of claim 1 , wherein said acid catalyst is selected from the group consisting of H-form molecular sieves, sulfonated activated carbon, H-form resins, sulfuric acid, hydrochloric acid, and nitric acid; and said acid catalyst accounts for 0.1 wt %-15 wt % of a total weight of the dehydration reaction mixture.

8. The method of claim 1 , wherein the dehydration reaction takes place at 150-198° C. and a reaction pressure is atmospheric pressure.

9. The process of claim 1 , wherein the close-boiling mixture is synthesized from coal or biomass.

10. The method of claim 1 , wherein the solid-liquid separation is carried out in a pressure filter, a vacuum filter, a settler, or a centrifuge.

11. The method of claim 2 , wherein said acid catalyst is selected from the group consisting of H-form molecular sieves, sulfonated activated carbon, H-form resins, sulfuric acid, hydrochloric acid, and nitric acid; and said acid catalyst accounts for 0.1 wt %-15 wt % of a total weight of the dehydration reaction mixture.

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Zhang Tao
• Al Shuo
• Zheng Mingyuan
• Wang Aiqin
• Li Weizhen
• Wang Xiaodong

Classifications

• C07C1/24

  by elimination of water · CPC title

• C07C31/18

  Polyhydroxylic acyclic alcohols · CPC title

• B01D3/065

  Multiple-effect flash distillation (more than two traps) · CPC title

• C07C29/80 Primary

  by distillation · CPC title

• B01D15/08

  Selective adsorption, e.g. chromatography · CPC title