Electrolyzer reactor and related methods

Patent metadata

Field	Value
Publication number	US-10633749-B2
Application number	US-201514806314-A
Country	US
Kind code	B2
Filing date	Jul 22, 2015
Priority date	Jul 23, 2014
Publication date	Apr 28, 2020
Grant date	Apr 28, 2020

Abstract

The disclosure relates to an electrolyzer reactor suitable for the reduction of organic compounds. The reactor includes a membrane electrode assembly with freestanding metallic meshes which serve both as metallic electrode structures for electron transport as well as catalytic surfaces for electron generation and organic compound reduction. Suitable organic compounds for reduction include oxygenated and/or unsaturated hydrocarbon compounds, in particular those characteristic of bio-oil (e.g., alone or a multicomponent mixtures). The reactor and related methods provide a resource- and energy-efficient approach to organic compound reduction, in particular for bio-oil mixtures which can be conveniently upgraded at or near their point of production with minimal or no transportation.

First claim

What is claimed is:

1. A method for reducing organic compounds, the method comprising:
(a) providing an electrolyzer reactor comprising:
(i) a membrane electrode assembly comprising: (A) a proton exchange membrane (PEM) having a first surface and a second surface opposing the first surface, (B) a freestanding first metallic mesh in physical contact with, but not fixedly attached to, the first PEM surface and having electrocatalytic activity for water oxidation and hydrogen ion formation, and (C) a freestanding second metallic mesh in physical contact with, but not fixedly attached to, the second PEM surface and having electrocatalytic activity for reduction of one or more organic compounds, wherein the first metallic mesh and the second metallic mesh are in electrical contact with each other via a voltage source for driving electrons therebetween, and the second metallic mesh is the only material that is in physical contact with the second PEM surface and that has electrocatalytic activity for reduction of the one or more organic compounds;
(ii) a first reaction volume in fluid communication with (A) the first metallic mesh and (B) the first PEM surface; and
(iii) a second reaction volume in fluid communication with (A) the second metallic mesh and (B) the second PEM surface

(b) applying a voltage potential to the voltage source in electrical connection with the first metallic mesh and the second metallic mesh to drive the electrons from the first metallic mesh to the second metallic mesh;
(c) supplying water to the first reaction volume, thereby oxidizing the water to form oxygen, hydrogen ions transported to the second reaction volume through the PEM, and electrons transported from the first metallic mesh to the second metallic mesh; and
(d) supplying at least one reducible organic compound to the second reaction volume, thereby reducing the organic compound with the electrons transported to the second metallic mesh.

2. The method of claim 1 , wherein the first metallic mesh and the second metallic mesh are free from catalytic materials thereon.

3. The method of claim 1 , wherein the first metallic mesh comprises a catalytic material thereon.

4. The method of claim 1 , wherein:
(i) the first reaction volume is defined by a first housing; and
(ii) the second reaction volume is defined by a second housing.

5. The method of claim 1 , wherein:
(i) the PEM is in the form of a tube, the first PEM surface being the tube interior surface and the second PEM surface being the tube exterior surface;
(ii) the PEM tube defines the first reaction volume as a tubular volume containing the first metallic mesh therein; and
(iii) the second reaction volume is defined by an outer shell as an annular volume between the outer shell and the PEM tube and containing the second metallic mesh therein.

6. The method of claim 1 , wherein
(i) the first metallic mesh comprises stainless steel; and
(ii) the second metallic mesh comprises an alloy comprising copper and nickel.

7. The method of claim 1 , wherein the second metallic mesh has electrocatalytic activity for catalyzing at least one of (i) electrocatalytic hydrogenation (ECH) of unsaturated carbon-carbon bonds in the organic compound, (ii) ECH of carbon-oxygen double bonds in the organic compound, and (iii) electrocatalytic hydrodeoxygenation (ECHDO) of carbon-oxygen single bonds in the organic compound.

8. The method of claim 1 , wherein the second metallic mesh has electrocatalytic activity for reduction of one or more organic compounds comprising one or more functional groups selected from the group consisting of carbonyl carbon-oxygen double bonds, aromatic double bonds, ethylenic carbon-carbon double bonds, acetylenic carbon-carbon triple bonds, hydroxyl carbon-oxygen single bonds, ether carbon-oxygen single bonds, and combinations thereof.

9. The method of claim 1 , wherein the first metallic mesh comprises at least one metal component having electrocatalytic activity for reduction of the one or more organic compounds.

10. The method of claim 1 , wherein the first metallic mesh and the second metallic mesh each comprise the same metal.

11. The method of claim 1 , wherein the proton exchange membrane (PEM) comprises a perfluorocarbon sulfonate polymer.

12. The method of claim 1 , wherein the water supplied to the first reaction volume comprises an electrolyte.

13. The method of claim 1 , further comprising supplying water to the second reaction volume.

14. The method of claim 1 , wherein the second reaction volume is free from added electrolytes.

15. The method of claim 1 , wherein the at least one reducible organic compound supplied to the second reaction volume comprises one or more functional groups selected from the group consisting of carbonyl carbon-oxygen double bonds, aromatic double bonds, ethylenic carbon-carbon double bonds, acetylenic carbon-carbon triple bonds, hydroxyl carbon-oxygen single bonds, ether carbon-oxygen single bonds, and combinations thereof.

16. The method of claim 1 , comprising supplying a plurality of reducible organic compounds to the second reaction volume, thereby reducing the plurality of organic compounds with the electrons transported to the second metallic mesh, the plurality of organic compounds being selected from the group consisting of a multicomponent bio-oil, a multicomponent bio-oil fraction, a plurality of bio-oil components, and combinations thereof;
wherein the reduced plurality of organic compounds reaction product comprises an upgraded bio-oil product.

17. The method of claim 1 , wherein:
the at least one reducible organic compound supplied in part (d) comprises a plurality of bio-oil pyrolysis products selected from the group consisting of acetol, hydroxyacetaldehyde, glyoxal, formaldehyde, acetic acid, phenol, guaiacol, syringol, levoglucosan, furfural, glucose, xylose, substituted derivatives thereof, and combinations thereof; and
part (d) comprises reducing the plurality of bio-oil pyrolysis products with the electrons transported to the second metallic mesh.

18. The method of claim 1 , wherein the reduced at least one organic compound reaction product comprises one or more of ethylene glycol, propylene glycol, cyclohexanol, furfuryl alcohol, and methanol.

19. The method of claim 1 , wherein:
the at least one reducible organic compound supplied in part (d) comprises a plurality of lignin depolymerization products selected from the group consisting of phenolic methoxylated monomers, phenolic methoxylated oligomers having 2-10 phenolic residues, and combinations thereof resulting from depolymerization of lignin-containing biomass; and
part (d) comprises reducing the plurality of lignin depolymerization products with the electrons transported to the second metallic mesh.

20. The method of claim 1 , further comprising: (e) recovering or separating the organic compound resulting from reduction in part (d) from the second reaction volume.

21. The method of claim 1 , further comprising: (e) recovering or separating hydrogen gas generated during organic compound reduction from the second reaction volume and feeding the hydrogen gas to a biomass fast pyrolysis reactor.

22. The method of claim 1 , wherein part (d) comprises reducing the organic compound at a temperature ranging from 0° C. to 100° C. and at a pressure ranging from 0.8 atm to 1.2 atm.

23. The method of claim 1 , wherein:
the first metallic mesh is not hot-pressed to the first PEM surface with

Assignees

• Univ Michigan State

Inventors

• Jackson James E
• Lam Chun Ho
• Saffron Christopher M
• Miller Dennis J

Classifications

• C25B9/08

  Chemistry & Metallurgy · mapped topic

• C25B3/04 Primary

  Chemistry & Metallurgy · mapped topic

• C25B11/03

  perforated or foraminous · CPC title

• C25B9/015

  Cylindrical cells · CPC title

• C25B3/25 Primary

  Reduction · CPC title