Method and system embodiments for converting ethanol to para-xylene and ortho-xylene

Patent metadata

Field	Value
Publication number	US-11325873-B1
Application number	US-202117387725-A
Country	US
Kind code	B1
Filing date	Jul 28, 2021
Priority date	Jul 28, 2021
Publication date	May 10, 2022
Grant date	May 10, 2022

Abstract

Disclosed herein are embodiments of a method and system for converting ethanol to para-xylene. The method also provides a pathway to produce terephthalic acid from biomass-based feedstocks. In some embodiments, the disclosed method produces p-xylene with high selectivity over other aromatics typically produced in the conversion of ethanol to xylenes, such as m-xylene, ethyl benzene, benzene, toluene, and the like. And, in some embodiments, the method facilitates the ability to use ortho/para mixtures of methylbenzyaldehyde for preparing ortho/para xylene product mixtures that are amendable to fractionation to separate the para- and ortho-xylene products thereby providing a pure feedstock of para-xylene that can be used to form terephthalic anhydride and a pure feedstock of ortho-xylene that can be used for other purposes, such as phthalic anhydride.

First claim

We claim:

1. A method, comprising:
contacting a feed stream comprising ethanol with an oxidation catalyst under oxidation conditions to form an oxidation zone effluent stream comprising acetaldehyde;
passing the oxidation zone effluent stream to a dimerization zone and contacting the oxidation zone effluent stream with a dimerization catalyst under dimerization conditions to produce a dimerization zone effluent stream comprising 2-butenal;
passing the dimerization zone effluent stream to a cyclization zone and contacting the dimerization zone effluent stream with a cyclization catalyst under cyclization conditions to form a cyclization zone effluent stream comprising o-methylbenzaldehyde and/or p-methylbenzaldehyde; and
passing the cyclization zone effluent stream to a hydrogenation zone and contacting the cyclization zone effluent stream with a hydrogenation catalyst comprising a first Group VIII metal deposited on a support material to produce a hydrogenation zone effluent comprising a non-equilibrium mixture of xylenes.

2. The method of claim 1 , wherein the hydrogenation catalyst further comprises a second Group VIII metal, a modifier component, or a combination thereof, all deposited on the support material wherein the second Group VIII metal is not the same as the first Group VIII metal.

3. The method of claim 2 , wherein the modifier component is selected from rhenium, tin, an alkali metal, an alkali earth metal, or any combination thereof.

4. The method of claim 2 , wherein the hydrogenation catalyst comprises the modifier component and wherein the support material is carbon, the first Group VIII metal is palladium, and the modifier component is rhenium.

5. The method of claim 1 , wherein the support material is selected from carbon material, a silica, an alumina, a silica-alumina, a titania, a zirconia, a zeolite, a zinc oxide, or any combination thereof.

6. The method of claim 1 , wherein the non-equilibrium mixture of xylenes comprises m-xylene in an amount ranging from 0 wt % to less than 40 wt % of a m-xylene equilibrium concentration.

7. The method of claim 1 , wherein the non-equilibrium mixture of xylenes comprises m-xylene in an amount ranging from 0 wt % to 20 wt % of a m-xylene equilibrium concentration.

8. The method of claim 1 , wherein the non-equilibrium mixture of xylenes comprises m-xylene in an amount ranging from 0 wt % to 5 wt % of a m-xylene equilibrium concentration.

9. The method of claim 1 , wherein the non-equilibrium mixture of xylenes comprises m-xylene in an amount ranging from 0 wt % to 1 wt % of a m-xylene equilibrium concentration.

10. The method of claim 1 , wherein the ethanol is
(i) ethanol from liquid phase fermentation of cellulosic material and or sugar;
(ii) ethanol from gas phase fermentation of industrial process waste or non-waste gas, internal combustion engine exhaust fumes, syngas, direct air capture, electrolysis, CO 2 -containing gas or any combination thereof;
(iii) ethanol from a source other than cellulosic material, sugar, industrial process waste or non-waste gas, internal combustion engine exhaust fumes, gasification processes, syngas, direct air capture, electrolysis, or CO 2 -containing gas; or
(iv) ethanol from hydration of ethylene;
or any combination of (i), (ii), (iii), and/or (iv).

11. The method of claim 10 , wherein the industrial process is selected from ferrous metal products manufacturing, steel mill manufacturing, non-ferrous products manufacturing, petroleum refining, electric power production, carbon black production, paper and pulp production, ammonia production, methanol production, coke manufacturing, petrochemical production, carbohydrate fermentation, cellulosic fermentation, cement making, aerobic digestion, anerobic digestion, catalytic processes, natural gas extraction, oil extraction or any combination thereof; and/or wherein the syngas is from coal gasification, refinery residues gasification, petroleum coke gasification, biomass gasification, lignocellulosic material gasification, waste wood gasification, black liquor gasification, natural gas reforming, municipal solid or liquid waste gasification, refuse derived fuel gasification, sewerage or sewerage sludge gasification, sludge from waste water treatment gasification and/or industrial solid waste gasification or any combination thereof.

12. The method of claim 1 , wherein:
(i) the conversion of acetaldehyde in the dimerization zone provides 15 wt % to 65 wt % of a product reaction mixture comprising 2-butenal;
(ii) the selectivity of acetaldehyde to 2-butenal in the dimerization zone ranges from 57 wt % to 91 wt %;
(iii) the conversion of 2-butenal in the cyclization zone provides 70 wt % to 95 wt % of a product reaction mixture comprising o-methylbenzaldehyde and p-methylbenzaldehyde;
(iv) the selectivity of 2-butenal to o-methylbenzaldehyde and p-methylbenzaldehyde in the cyclization zone ranges from 50 wt % to 95 wt %; or
(v) any combination of (i), (ii), (iii), and/or (iv).

13. The method of claim 1 , further comprising passing the hydrogenation zone effluent to a fractionation zone and separating a stream comprising o-xylene from (i) a stream comprising p-xylene or (ii) a stream comprising p-xylene and m-xylene.

14. The method of claim 13 , wherein (i) the stream comprising p-xylene or (ii) the stream comprising p-xylene and m-xylene comprises a minimum amount of p-xylene, wherein the minimum amount of p-xylene ranges from a minimum of at least 65 wt % to a minimum of at least 85 wt %.

15. The method of claim 13 , further comprising (i) drying the stream comprising the o-xylene; (ii) reacting the o-xylene in the stream comprising o-xylene under reaction conditions to form phthalic anhydride; or both (i) and (ii).

16. The method of claim 15 , further comprising drying the hydrogenation zone effluent prior to passing it to the fractionation zone, and/or drying the stream comprising the o-xylene.

17. The method of claim 13 , further comprising passing (i) the stream comprising p-xylene or (ii) the stream comprising p-xylene and m-xylene to a crystallizer and recovering a purified p-xylene stream comprising at least 99.5 wt % p-xylene.

18. The method of claim 17 , wherein the purified p-xylene stream comprises at least 99.8 wt % p-xylene.

19. The method of claim 17 , further comprising reacting at least a portion of the p-xylene from the purified p-xylene stream under reaction conditions to form terephthalic acid.

20. The method of claim 19 , further comprising reacting at least a portion of the terephthalic acid with ethylene glycol under reaction conditions to form polyethylene terephthalate.

21. The method of claim 20 , further comprising forming the polyethylene terephthalate into one or more products.

22. The method of claim 1 , further comprising one or more separation and/or recycling steps, wherein the recycling steps are selected from
(i) recycling at least a portion of the oxidation zone effluent stream to the oxidation zone until a predetermined target concentration of acetaldehyde in the oxidation zone effluent stream is achieved;
(ii) recycling at least a portion of the dimerization zone effluent stream to the dimerization zone until a predetermined target concentration of 2-butenal in the dimerization zone effluent stream is achieved;
(iii) recycling at least a portion of the cyclization zone effluent stream to the cyclization zone until a predetermined target concentration of o-methylbenzaldehyde and/or p-methylbe

Assignees

• Battelle Memorial Institute
• Lanzatech Inc

Inventors

• Ramasamy Karthikeyan K
• Guo Mond
• Rosin Richard Russell
• Kocal Joseph Anthony

Classifications

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C2523/44

  Palladium · CPC title

• C07C2529/44

  Noble metals · CPC title

• C07C2521/18

  Carbon · CPC title

• C07C2521/04

  Alumina · CPC title