Methods for vicinal diol separation

Patent metadata

Field	Value
Publication number	US-12110267-B2
Application number	US-201917283090-A
Country	US
Kind code	B2
Filing date	Oct 7, 2019
Priority date	Oct 8, 2018
Publication date	Oct 8, 2024
Grant date	Oct 8, 2024

Abstract

The disclosure relates to methods for separating mixtures of polyols, in particular mixtures of two of more different vicinal diols having close boiling points, thus making them difficult or impossible to separate using conventional distillation techniques. The polyol mixture is reacted with an aldehyde or ketone acetalization agent to form one or more acetals as corresponding acetalization reaction products. The acetalization reaction products are more easily separable either from each other (such as via distillation) or from an unreacted vicinal diol (such as via extraction, settling, or other phase separation). After separation, hydrolysis is performed on the acetalization reaction products to recover the vicinal diols as separate, purified components. The methods provide cost-effective processes for separating different polyols originally formed in admixture.

First claim

What is claimed is:

1. A method for separating polyols, the method comprising:
feeding to a reactor:
(i) a first polyol reactant having 2 to 10 carbon atoms and comprising at least two hydroxyl groups on adjacent carbon atoms,
(ii) a second polyol reactant different from the first polyol reactant, having 2 to 10 carbon atoms, and comprising at least two hydroxyl groups on adjacent carbon atoms,
(iii) an acetalization reactant comprising at least one of an aldehyde having 1 to 10 carbon atoms and a ketone having 3 to 10 carbon atoms,
(iv) a first acetalization product comprising a reaction product between the first polyol reactant and the acetalization reactant, and
(v) optionally water;

forming in the reactor via an acid-catalyzed reaction:
(i) optionally further first acetalization product comprising a reaction product between the first polyol reactant and the acetalization reactant,
(ii) a second acetalization product comprising a reaction product between the second polyol reactant and the acetalization reactant, and
(iii) water;

separating a reactor product mixture comprising the first acetalization product, the second acetalization product, the first polyol reactant, and the water into (i) a water-immiscible product comprising the first acetalization product and the second acetalization product, and (ii) an aqueous product comprising the first polyol reactant and the water;
separating the water-immiscible product into (i) a first product comprising the first acetalization product, and (ii) a second product comprising the second acetalization product; and
hydrolyzing the second product to form the second polyol reactant from the second acetalization product.

2. The method of claim 1 , further comprising:
recycling the first product comprising the first acetalization product to the reactor.

3. A method for separating polyols, the method comprising:
feeding to a first reactor:
(i) a first polyol reactant having 2 to 10 carbon atoms and comprising at least two hydroxyl groups on adjacent carbon atoms,
(ii) a second polyol reactant different from the first polyol reactant, having 2 to 10 carbon atoms, and comprising at least two hydroxyl groups on adjacent carbon atoms,
(iii) an acetalization reactant comprising at least one of an aldehyde having 1 to 10 carbon atoms and a ketone having 3 to 10 carbon atoms,
(iv) a first acetalization product comprising a reaction product between the first polyol reactant and the acetalization reactant, and
(v) optionally water;

forming in the first reactor via an acid-catalyzed reaction;
(i) optionally further first acetalization product comprising a reaction product between the first polyol reactant and the acetalization reactant,
(ii) a second acetalization product comprising a reaction product between the second polyol reactant and the acetalization reactant, and
(iii) water;

separating a first reactor product mixture comprising the first acetalization product, the second acetalization product, the first polyol reactant, and the water into (i) a first water-immiscible product comprising the first acetalization product and the second acetalization product, and (ii) a first aqueous product comprising the first polyol reactant and the water;
separating the first water-immiscible product into (i) a first product comprising the first acetalization product, and (ii) a second product comprising the second acetalization product; and
hydrolyzing the second product to form the second polyol reactant from the second acetalization product:
feeding to a second reactor:
(i) the first product comprising the first acetalization product,
(ii) the acetalization reactant, and
(iii) the aqueous product comprising the first polyol reactant and the water;

forming in the second reactor via an acid-catalyzed reaction:
(i) optionally the first acetalization product comprising a reaction product between the first polyol reactant and the acetalization reactant, and
(ii) the second acetalization product comprising a reaction product between the second polyol reactant and the acetalization reactant;

separating a second reactor product mixture comprising the first polyol reactant, the second acetalization product, the acetalization reactant, and the water into (i) a second water-immiscible product comprising the second acetalization product and the acetalization reactant, and (ii) a second aqueous product comprising the water; and
feeding the second water-immiscible product to the first reactor.

4. The method of claim 1 , wherein the first polyol reactant and the second polyol reactant are independently selected from the group consisting of saturated or unsaturated linear hydrocarbon polyols, branched hydrocarbon polyols, and cyclic hydrocarbon polyols.

5. The method of claim 1 , wherein the first polyol reactant and the second polyol reactant each have only two hydroxyl groups.

6. The method of claim 1 , wherein:
the first polyol reactant is 1,2-ethanediol (ethylene glycol), and
the second polyol reactant is 1,2-propanediol (propylene glycol).

7. The method of claim 1 , wherein:
the first polyol reactant is 1,2-ethanediol (ethylene glycol), and
the second polyol reactant is 1,2-butanediol.

8. The method of claim 1 , wherein the first polyol reactant and the second polyol reactant are independently selected from the group consisting of 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,2-butanediol, 1,2-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,2-hexanediol, 2,3-hexanediol, 3,4-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, and 1,2-decanediol.

9. The method of claim 1 , wherein the first polyol reactant and the second polyol reactant have boiling points that are within 10° C. of each other.

10. The method of claim 9 wherein the first acetalization product and the second acetalization product have boiling points that are more than 10° ° C. apart from each other.

11. The method of claim 1 , wherein the acetalization reactant comprises at least one of an aldehyde having 3 to 10 carbon atoms and a ketone having 4 to 10 carbon atoms.

12. The method of claim 1 , wherein the acetalization reactant is selected from the group consisting of saturated or unsaturated linear hydrocarbon aldehydes or ketones, branched hydrocarbon aldehydes or ketones, and cyclic hydrocarbon ketones.

13. The method of claim 1 , wherein the acetalization reactant is selected from the group consisting of propanal, butanal (butyraldehyde), 2-methylpropanal (isobutyraldehyde), pentanal, hexanal, heptanal, octanal, nonanal, decanal, 2-buatanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 2-octanone, 2-nonanone, 2-decanone.

14. The method of claim 1 , wherein the acetalization reactant comprises butanal (butyraldehyde).

15. The method of claim 1 , wherein the acetalization reactant has a solubility in water of up to 30 g/100 ml.

16. The method of claim 1 , wherein the first acetalization product and the second acetalization product have a solubility in water of up to 30 g/100 ml.

17. The method of claim 1 , wherein the reactor comprises a heterogeneous solid-phase acid catalyst therein for forming at least one of the first acetalization product and the second acetalization product.

18. The method of claim 1 , further comprising: feeding to the reactor a homogeneous acid catalyst for forming at least one of the first acetalization product and the second acetalization product.

19. The method of claim 1 , further comprising, after f

Assignees

• Univ Michigan State

Inventors

• Miller Dennis J
• Lira Carl T
• Peereboom Lars
• Parker Scott F
• Dionise Thomas D
• Killian William G

Classifications

• C07C29/095

  of esters of organic acids · CPC title

• C07C31/207

  1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol · CPC title

• C07C29/88

  by treatment giving rise to a chemical modification of at least one compound (chemisorption C07C29/76) · CPC title

• C07C31/202

  Ethylene glycol · CPC title

• C07C31/205

  1,3-Propanediol; 1,2-Propanediol · CPC title