Hydrodeoxygenation of oxygenated polymers to liquid hydrocarbons

Patent metadata

Field	Value
Publication number	US-12065618-B2
Application number	US-202117182783-A
Country	US
Kind code	B2
Filing date	Feb 23, 2021
Priority date	May 6, 2020
Publication date	Aug 20, 2024
Grant date	Aug 20, 2024

Abstract

Process are disclosed for converting plastics, and especially thermoplastic oxygenated polymers, by hydrodeoxygenation (HDO) to hydrocarbons, such as aromatic hydrocarbons including benzene, toluene, ethylbenzene, and xylene isomers. These hydrocarbons may be recovered as chemicals and/or fuels, depending on the particular chemical structures of the starting materials, including the presence of oxygen in the polymer backbones. Advantageously, using a sufficiently active catalyst, only moderate conditions, such as in terms of hydrogen partial pressure, are required, in comparison to known hydrotreating processes. This leads to the formation, with fewer non-selective side reactions, of desired liquid hydrocarbons from substantially all carbon in the oxygenated polymer, as well as water from substantially all oxygen in the oxygenated polymer. In some cases, the liquid hydrocarbons obtained are platform chemicals that can be used for a number of specialized purposes. For example, they may be converted to monomers for regenerating the oxygenated polymer or otherwise for producing a different polymer.

First claim

What is claimed is:

1. A process for the production of hydrocarbons from an oxygenated polymer, the process comprising:
partly or completely dissolving the oxygenated polymer in a solvent to produce a solvated oxygenated polymer, and, at a temperature between the melting temperature and the thermal decomposition temperature of the oxygenated polymer, filtering the solvated oxygenated polymer to separate impurities, including solids, existing under the heated, solvated condition of the oxygenated polymer; and
contacting reactant hydrogen and a feed comprising the solvated oxygenated polymer, obtained from the filtering, with a solid hydrodeoxygenation (HDO) catalyst at a hydrogen partial pressure from about 14 bar (about 200 psi) to about 35 bar (about 510 psi), to produce an HDO product comprising the hydrocarbons.

2. The process of claim 1 , wherein the reactant hydrogen comprises both fresh and recycle hydrogen.

3. The process of claim 1 , wherein the feed comprising the solvated oxygenated polymer accounts for greater than about 90 wt-% of non-gaseous components added to an HDO reactor containing the solid HDO catalyst.

4. The process of claim 1 , wherein a yield of solids from the process, based on the feed, is less than about 1 wt-%.

5. The process of claim 1 , wherein the oxygenated polymer is a bio-based thermoplastic polymer or a petroleum-based thermoplastic polymer.

6. The process of claim 1 , wherein the HDO product is provided following further deoxygenating of a partially deoxygenated intermediate.

7. The process of claim 1 , wherein the HDO product is provided following a separation from a gaseous mixture and/or aqueous product.

8. The process of claim 7 , wherein the oxygenated polymer has nitrogen and/or sulfur atoms, and wherein the gaseous mixture comprises ammonia (NH 3 ) and hydrogen sulfide (H 2 S) derived from the nitrogen and/or sulfur atoms.

9. The process of claim 1 , wherein the partly or completely dissolving the oxygenated polymer in the solvent is performed in a preparation stage.

10. The process of claim 9 , wherein the preparation stage comprises both heating the oxygenated polymer and the partly or completely dissolving the oxygenated polymer in the solvent.

11. The process of claim 10 , wherein the solvent comprises hydrocarbons or forms hydrocarbons in the process.

12. The process of claim 11 , wherein the solvent is product of crude oil refining or paper manufacturing.

13. The process of claim 1 , wherein the oxygenated polymer is polyethylene terephthalate (PET) and the hydrocarbons include para-xylene.

14. The process of claim 1 , wherein the oxygenated polymer is lignin and the hydrocarbons include gasoline boiling-range hydrocarbons and diesel boiling-range hydrocarbons.

15. The process of claim 1 , wherein the solid HDO catalyst comprises at least one Group 8 metal and at least one Group 6 metal, supported on an inorganic refractory metal oxide, a zeolite, or porous activated carbon.

16. The process of claim 1 , wherein the solid HDO catalyst is contained in an HDO reactor.

17. The process of claim 16 , wherein the HDO product is obtained from separating the HDO product from an HDO reactor effluent that is withdrawn from the HDO reactor.

18. The process of claim 17 , wherein the HDO reactor effluent comprises a partially deoxygenated intermediate and the HDO product is obtained from further deoxygenating the partially deoxygenated intermediate in a supplemental deoxygenation reactor, withdrawing a supplemental deoxygenation reactor effluent, and separating the HDO product from the supplemental deoxygenation reactor effluent.

19. The process of claim 16 , wherein the HDO reactor is a trickle bed reactor or a slurry reactor.

20. The process of claim 17 , wherein the HDO reactor effluent, from which the HDO product is obtained, is a gaseous HDO reactor effluent or a liquid HDO reactor effluent.

21. The process of claim 17 , wherein separating the HDO product comprises separation from a gaseous mixture and/or aqueous product.

22. The process of claim 21 , wherein the oxygenated polymer has nitrogen and/or sulfur atoms, and wherein the gaseous mixture comprises ammonia (NH 3 ) and hydrogen sulfide (H 2 S) derived from the nitrogen and/or sulfur atoms.

23. The process of claim 1 , wherein the solid HDO catalyst is contained in:
a trickle-bed reactor, in which flows of the reactant hydrogen and feed are downward though a fixed bed of the HDO catalyst, or a slurry reactor containing a slurry of the catalyst, into which the reactant hydrogen and feed are introduced and mixed.

24. The process of claim 17 , further comprising separating unconverted solvent from the HDO reactor effluent and recycling the unconverted solvent to a preparation stage for said partly or completely dissolving the oxygenated polymer in the solvent.

25. The process of claim 16 , wherein the oxygenated polymer is PET and the hydrocarbons include para-xylene.

26. A process for the production of an upgraded polymer from a waste oxygenated polymer having oxygen atoms in a backbone of the waste oxygenated polymer, the process comprising:
partly or completely dissolving the waste oxygenated polymer in a solvent to produce a solvated waste oxygenated polymer, and, at a temperature between the melting temperature and the thermal decomposition temperature of the waste oxygenated polymer, filtering the solvated waste oxygenated polymer to separate impurities, including solids, existing under the heated, solvated condition of the waste oxygenated polymer;
contacting reactant hydrogen and a feed comprising the solvated waste oxygenated polymer, obtained from the filtering, with a solid hydrodeoxygenation (HDO) catalyst at a hydrogen partial pressure from about 14 bar (about 200 psi) to about 35 bar (about 510 psi), to provide an HDO product comprising hydrocarbons obtained from molecular sub-units between the oxygen atoms in the backbone of the waste oxygenated polymer; and
using the hydrocarbons for the production of the upgraded polymer.

27. The process of claim 26 , wherein the waste oxygenated polymer is polyethylene terephthalate (PET), and wherein the filtering is performed at a temperature from about 250° C. to about 350° C.

28. The process of claim 26 , wherein the solvent comprises a hydrocarbon.

Assignees

• Gas Technology Inst
• Gti Energy

Inventors

• Linck Martin B
• Marker Terry
• Ortiz-Toral Pedro
• Wangerow Jim

Classifications

• C10G3/56

  suspended in the oil, e.g. slurries, ebullated beds · CPC title

• C10G2300/4012

  Pressure · CPC title

• C10G2400/30

  Aromatics · CPC title

• C10G2300/1003

  Waste materials · CPC title

• C08J2367/02

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