Chemical recycling of polyethylene terephthalate by microwave irradiation

Patent metadata

Field	Value
Publication number	US-10508186-B2
Application number	US-201615773503-A
Country	US
Kind code	B2
Filing date	Nov 18, 2016
Priority date	Nov 20, 2015
Publication date	Dec 17, 2019
Grant date	Dec 17, 2019

Abstract

A process for chemically recycling polyethylene terephthalate (PET) which utilizes a microwave absorber to optimize glycolytic depolymerization of PET via microwave irradiation. The method of chemically degrading PET to its reactive intermediate, bis(2-hydroxyethyl) terephthalate (BHET), is carried out by: (a) combining PET with ethylene glycol and a catalytic system comprising a catalyst and a microwave absorber to produce a heterogeneous reaction mixture; and then (b) heating by microwave irradiating the reaction mixture to a temperature sufficient to produce a reaction product comprising BHET. The BHET monomer then can be purified and re-polymerized to form new, virgin PET.

First claim

What is claimed is:

1. A method of making bis(2-hydroxyethyl) terephthalate (BHET) from polyethylene terephthalate (PET), comprising:
(a) combining PET with ethylene glycol and a catalyst system to produce a heterogeneous reaction mixture, wherein the catalytic system comprises a catalyst and a microwave absorber, with the catalyst being selected from the group consisting of: zinc acetate, zinc chloride, manganese acetate, 1, 5, 7-triazabicyclo [4.4. 0] dec-5-ene (TBD), 1, 8-diazabicyclo [5. 4. 0]undec-7-ene (DBU), magnesium acetate, 4-dimethylaminopyridine (DMAP), and combinations thereof, and with the microwave absorber being selected from the group consisting of a sodium salt, lithium salt, potassium salt, calcium salt, a magnesium salt, or combination thereof; and then
(b) heating by microwave irradiation the reaction mixture to produce a reaction product comprising BHET.

2. The method of claim 1 , wherein the microwave absorber is selected from the group consisting of: sodium chloride, sodium bromide, sodium iodide, sodium fluoride, lithium chloride, potassium chloride, magnesium chloride, and calcium chloride.

3. The method of claim 1 , wherein the microwave absorber comprises sodium chloride.

4. The method of claim 1 , wherein the catalyst comprises zinc acetate.

5. The method of claim 1 , wherein the heating step (b) comprises heating by microwave irradiating the reaction mixture to a temperature greater than the boiling point of ethylene glycol.

6. The method of claim 1 , wherein the heating step (b) comprises heating by microwave irradiating the reaction mixture to a temperature of at least the melting point of the PET.

7. The method of claim 4 , wherein at least 90 percent by weight of the PET is converted to BHET.

8. The method of claim 4 , wherein not more than 10 percent by weight of the PET is converted to mono(2-hydroxyethyl) terephthalate (MHET) in the reaction product.

9. The method of claim 1 , further comprising the steps of:
(c) precipitating the BHET in the reaction product; and then
(d) separating the BHET from the reaction product to produce solid BHET and a depleted reaction product.

10. The method of claim 9 , wherein the precipitating step is carried out by cooling the reaction product to at least a first temperature less than 60° C.

11. The method of claim 9 , wherein the precipitating step (c) is carried out in stages, the stages comprising:
(i) a first stage at a first temperature to which the reaction product is cooled and during which a first portion of the BHET precipitates, followed by
(ii) a second stage at a second temperature less than the first temperature during which a second portion of the BHET precipitates.

12. The method of claim 11 , wherein the precipitating step (c) further comprises mixing said reaction product with water.

13. The method of claim 12 , wherein the separating step (d) is carried out by sedimentation, centrifugation, filtration, or a combination thereof.

14. The method of claim 9 , further comprising the steps of:
(e) distilling at least a portion of the depleted reaction product to produce a recycled ethylene glycol product and solid BHET, and then:
(f) repeating steps (c) through (d) at least once with the depleted reaction product, the recycled ethylene glycol product, or a combination thereof.

15. The method of claim 1 , wherein: the catalyst is included in the reaction mixture in an amount of from 0.01, 0.02, 0.1 or 0.2 grams per liter of ethylene glycol, up to 5, 10, 50 or 100 grams per liter of ethylene glycol; the microwave absorber is included in the reaction mixture in an amount of from 0.02, 0.04, 0.2, or 0.4 grams per liter of ethylene glycol, up to 40, 100, or 400 grams per liter of ethylene glycol; and the PET is included in the reaction mixture in an amount of from 10 or 50 grams per liter of ethylene glycol, up to 250 or 300 grams per liter of ethylene glycol.

Assignees

• Univ North Carolina Chapel Hill

Inventors

• Parrott Matthew

Classifications

• C08J2367/04

  Polyesters derived from hydroxy carboxylic acids, e.g. lactones (C08J2367/06 takes precedence) · CPC title

• C08J11/24

  containing hydroxyl groups · CPC title

• C08J11/16 Primary

  by treatment with inorganic material (C08J11/14 takes precedence) · CPC title

• C08J2367/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence) · CPC title

• C08J11/26

  containing carboxylic acid groups, their anhydrides or esters · CPC title