Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

Patent metadata

Field	Value
Publication number	US-11566332-B2
Application number	US-201314383048-A
Country	US
Kind code	B2
Filing date	Mar 5, 2013
Priority date	Mar 6, 2012
Publication date	Jan 31, 2023
Grant date	Jan 31, 2023

Abstract

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic compounds in bio-oil. The catalyst is a metal supported on a monolithic high surface area material such as activated carbon cloth. Electrocatalytic hydrogenation and/or hydrodeoxygenation stabilizes the bio-oil under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

First claim

What is claimed is:

1. A process for performing electrocatalytic hydrogenation (ECH) and optionally electrocatalytic hydrodeoxygenation (ECHDO) of an organic substrate, the process comprising:
(a) providing a reaction mixture comprising at least one of a multicomponent bio-oil and a multicomponent bio-oil fraction, which comprises a plurality of different organic reactants each comprising an aromatic CH group and being selected from the group consisting of hydroxy-substituted aromatic compounds, methoxy-substituted aromatic compounds, oligomerization products thereof, and combinations thereof;
(b) contacting the reaction mixture with a first electrode comprising a catalytic electrode composition comprising (i) a porous activated carbon cloth (ACC) support and (ii) metal catalyst particles immobilized on the ACC support, wherein:
the metal catalyst particles comprise a metal selected from the group consisting of Ru, Fe, Cu, Pt, Rh, Ir, Re, Os, Ag, Au, Co, Mo, Ga, mixtures thereof, alloys thereof, and combinations thereof;
the metal catalyst particles of the first electrode are capable of catalyzing ECH of aromatic CH groups to form corresponding CH 2 groups,
the metal catalyst particles immobilized on the ACC support are not mobile, and
the metal catalyst particles have been immobilized on the ACC support prior to contacting the ACC support with (i) the reaction mixture or (ii) one or more of water or a water-miscible solvent to which the plurality of organic reactants is added to form the reaction mixture;

(c) electrically contacting the reaction mixture with a second electrode; and
(d) applying an electrical potential between the first electrode and the second electrode to provide an electrical current therebetween and through the reaction mixture, thereby performing an ECH reaction to reduce the aromatic CH group of each of the plurality of organic reactants and to form ECH reaction products thereof each comprising a CH 2 group, wherein at least one of the plurality of organic reactants has a conversion of at least 0.8.

2. The process of claim 1 , further comprising:
(e) recovering or separating the ECH reaction products from the reaction mixture.

3. The process of claim 1 , wherein:
the reaction mixture further comprises an organic compound comprising a carbonyl carbon-oxygen double bond present in a functional group selected from the group consisting of ketone groups, aldehyde groups, carboxylic acid groups, ester groups, amide groups, enone groups, acyl halide groups, acid anhydride groups, and combinations thereof; and
applying the electrical potential further performs an ECHDO reaction to deoxygenate the carbonyl carbon-oxygen double bond.

4. The process of claim 1 , wherein the aromatic CH group is present in a functional group selected from the group consisting of benzenes, phenols, furans, pyridines, pyrazines, imidazoles, pyrazoles, oxazoles, thiophenes, naphthalenes, higher fused aromatics, and combinations thereof.

5. The process of claim 1 , wherein the reaction mixture further comprises an organic compound comprising a C═O group, and the ECH reaction further reduces the C═O group to form a corresponding ECH reaction product comprising at least one of a C—OH group and a CH 2 group.

6. The process of claim 1 , wherein the reaction mixture further comprises an organic compound comprising an ethylenic C═C group, and the ECH reaction further reduces the ethylenic C═C group to form a corresponding ECH reaction product comprising a CH—CH group.

7. The process of claim 1 , wherein the reaction mixture further comprises an organic compound comprising a C—OH group, and applying the electrical potential further performs an ECHDO reaction to deoxygenate the C—OH group to form a corresponding ECHDO reaction product comprising a CH group.

8. The process of claim 1 , wherein the reaction mixture further comprises an organic compound comprising a (C═O)O group, and applying the electrical potential further performs an ECHDO reaction to deoxygenate the (C═O)O group to form a corresponding ECHDO reaction product comprising at least one of a (C═O)H group and a C—OH group.

9. The process of claim 1 , wherein the reaction mixture further comprises an organic compound comprising an ether R 1 -O-R 2 group, and applying the electrical potential further performs an ECH reaction to reduce the ether R 1 -O-R 2 group and an ECHDO reaction to deoxygenate the ether R 1 -O-R 2 group to form corresponding ECH or ECHDO reaction products comprising one or more of a R 1 H, R 2 OH, R 1 OH, and R 2 H, where R 1 and R 2 are substituents containing from 1 to 10 carbon atoms.

10. The process of claim 1 , wherein the bio-oil is a reaction product produced from fast pyrolysis of biomass.

11. The process of claim 1 , wherein the reaction mixture is free from added solvents.

12. The process of claim 1 , wherein the reaction mixture further comprises one or more of the water or the water-miscible organic solvent.

13. The process of claim 1 , wherein the reaction mixture further comprises the water, and the water is present in an amount ranging from 10 wt. % to 95 wt. % relative to the reaction mixture.

14. The process of claim 1 , wherein the reaction mixture comprises the multicomponent bio-oil fraction, the multicomponent bio-oil fraction having been obtained by extraction of bio-oil using a solvent comprising one or more of water, methanol, ethanol, diethyl ether, ethyl acetate, dichloromethane, chloroform, toluene, and hexane.

15. The process of claim 1 , wherein the plurality of different organic reactants is selected from the group consisting of phenol, guaiacol, syringol, substituted derivatives thereof, and combinations thereof.

16. The process of claim 1 , wherein the ECH reaction products comprise cyclohexanol.

17. The process of claim 1 , wherein the reaction mixture further comprises an electrolyte.

18. The process of claim 1 , wherein the second electrode comprises an electrically conductive material selected from the group consisting of Ni, Pt, carbon, lead, lead dioxide, mixtures thereof, alloys thereof, and combinations thereof.

19. The process of claim 1 , comprising performing the ECH reaction and optionally an ECHDO reaction in a divided electrochemical cell containing the reaction mixture, wherein:
(i) the second electrode is in contact with an anolyte mixture in electrical connection with the reaction mixture via an ion-exchange membrane;
(ii) the reaction mixture further comprises carboxylic acids, and
(iii) the process further comprises removing at least some of the carboxylic acids from the reaction mixture into the anolyte mixture via the ion-exchange membrane.

20. The process of claim 1 , wherein the ECH reaction products and optionally an ECHDO reaction product contains at least 80% of the carbon initially contained in the reaction mixture.

21. The process of claim 1 , wherein the first electrode is capable of catalyzing the electrocatalytic hydrogenation (ECH) and optionally the electrocatalytic hydrodeoxygenation (ECHDO).

22. The process of claim 1 , wherein the first electrode is capable of catalyzing (i) ECH of unsaturated carbon-carbon bonds in the plurality of organic reactants, optionally (ii) ECH of carbon-oxygen double bonds in the plurality of organic reactants, and optionally (iii) ECHDO of carbon-oxygen single bonds in the plurality of organic reactants.

23. The process of claim 1 , wherein:
(i) the metal catalyst particles comprise

Assignees

• Univ Michigan State

Inventors

• Saffron Christopher M
• Li Zhenglong
• Miller Dennis J
• Jackson James E

Classifications

• C25B3/00 Primary

  Electrolytic production of organic compounds · CPC title

• C25B11/051

  Electrodes formed of electrocatalysts on a substrate or carrier · CPC title

• C07D307/44

  Furfuryl alcohol · CPC title

• C07C29/132

  by reduction of an oxygen containing functional group · CPC title

• C25B11/043

  Carbon, e.g. diamond or graphene · CPC title