Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

Patent metadata

Field	Value
Publication number	US-9951431-B2
Application number	US-201314061460-A
Country	US
Kind code	B2
Filing date	Oct 23, 2013
Priority date	Oct 24, 2012
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as 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 reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates 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 at least one of electrocatalytic hydrogenation (ECH) and electrocatalytic hydrodeoxygenation (ECHDO) of an organic substrate, the process comprising:
(a) providing a reaction mixture comprising (i) water in an amount of at least 25 wt. % relative to the reaction mixture and (ii) an organic reactant 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;
(b) contacting the reaction mixture with a first electrode and a catalytic composition comprising a skeletal metal catalyst capable of catalyzing at least one of electrocatalytic hydrogenation (ECH) and electrocatalytic hydrodeoxygenation (ECHDO);
(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 at least one of an ECH reaction and an ECHDO reaction to reduce or deoxygenate at least one of the functional groups of the organic reactant and to form at least one of (i) an ECH reaction product thereof and (ii) an ECHDO reaction product thereof;
wherein the reaction mixture has a pH value ranging from 4 to 11 when applying the electrical potential to form the reaction product,
wherein the reaction mixture is free from added water-miscible organic solvents,
wherein the reaction mixture comprises a plurality of the organic reactants, the plurality being selected from the group consisting of a multicomponent bio-oil, a multicomponent bio-oil fraction, a plurality of bio-oil components, a multicomponent lignin depolymerization product, a multicomponent lignin depolymerization product fraction, a plurality of lignin depolymerization product components, and combinations thereof, and
wherein the organic reactant has a conversion of at least 80% as a result the at least one of the ECH reaction and the ECHDO reaction in part (d).

2. The process of claim 1 , wherein the reaction mixture has an initial pH value ranging from 4 to 10 and is maintained in the range from 4 to 10 during the application of the electrical potential to form the reaction product.

3. The process of claim 1 , wherein the reaction mixture further comprises a pH buffer to maintain the pH value of the reaction mixture in a selected range during the application of the electrical potential to form the reaction product.

4. The process of claim 1 , wherein the metal of the skeletal metal catalyst comprises at least one of Ni and a Ni-containing alloy.

5. The process of claim 1 , wherein the skeletal metal catalyst comprises an alkaline leaching product of an alloy comprising (i) aluminum and (ii) nickel as the metal of the skeletal metal catalyst.

6. The process of claim 1 , wherein the skeletal metal catalyst has a microporous structure with a specific BET surface area ranging from 5 m 2 /g to 100 m 2 /g.

7. The process of claim 1 , wherein the catalytic composition is immobilized on the first electrode.

8. The process of claim 7 , wherein the catalyst composition comprises an alkaline leaching product of a composite material comprising (i) a metal matrix and (ii) an alloy comprising (A) aluminum and (B) the metal of the skeletal metal catalyst.

9. The process of claim 1 , wherein the catalyst composition is capable of catalyzing at least one of (i) ECH of unsaturated carbon-carbon bonds in an organic substrate, (ii) ECH of carbon-oxygen double bonds in an organic substrate, and (iii) ECHDO of carbon-oxygen single bonds in an organic substrate.

10. The process of claim 1 , wherein the organic reactant comprises the aromatic double bonds and at least 80% of the aromatic double bonds are hydrogenated via ECH in the ECH reaction product.

11. The process of claim 1 , wherein the organic reactant comprises the ether carbon-oxygen single bonds and at least 80% of the ether carbon-oxygen single bonds are cleaved via ECHDO in the ECHDO reaction product.

12. The process of claim 1 , wherein the aromatic double bonds are present and 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.

13. The process of claim 1 , wherein the functional group comprises an aromatic CH group, and the corresponding ECH reaction product comprises a CH 2 group.

14. The process of claim 1 , wherein the functional group comprises an ether R 1 —O—R 2 group, and the corresponding ECH or ECHDO reaction products comprise 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.

15. The process of claim 1 , wherein:
(i) the functional group comprises an ether R 1 —O—R 2 group,
(ii) the corresponding ECH or ECHDO reaction products comprise one or more of a R 1 H, R 2 OH, R 1 OH, and R 2 H,
(iii) R 1 is a substituted or unsubstituted aromatic or heteroaromatic substituent containing 3 to 20 carbon atoms, and
(iv) R 2 is a substituted or unsubstituted alkyl substituent containing from 1 to 10 carbon atoms.

16. The process of claim 1 , wherein:
(i) the functional group comprises an ether R 1 —O—R 2 group,
(ii) the corresponding ECH or ECHDO reaction products comprise one or more of R 1 *H and R 2 OH,
(iii) R 1 is a substituted or unsubstituted aromatic or heteroaromatic substituent containing 3 to 20 carbon atoms,
(iv) R 1 * is a hydrogenated analog of R 1 , and
(v) R 2 is a substituted or unsubstituted alkyl substituent containing from 1 to 10 carbon atoms.

17. The process of claim 1 , wherein the reaction mixture comprises a plurality of the organic reactants, the plurality 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.

18. The process of claim 1 , wherein the reaction mixture comprises a plurality of the organic reactants, the plurality being selected from the group consisting of a multicomponent lignin depolymerization product, a multicomponent lignin depolymerization product fraction, a plurality of lignin depolymerization product components, and combinations thereof.

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

20. The process of claim 1 , comprising performing the ECH or ECHDO reaction at a temperature ranging from 0° C. to 100° C. and at a pressure ranging from 0.8 atm to 1.2 atm.

21. The process of claim 1 , wherein the reaction mixture further comprises a surfactant.

22. The process of claim 1 , wherein the second electrode comprises cobalt(III) phosphate.

23. A process for performing at least one of electrocatalytic hydrogenation (ECH) and electrocatalytic hydrodeoxygenation (ECHDO) of an organic substrate, the process comprising:
(a) providing a reaction mixture comprising (i) water in an amount of at least 15 wt. % relative to the reaction mixture and (ii) a plurality of organic reactants, wherein:
the plurality of organic reactants is selected from the group consisting of a multicomponent bio-oil, a multicomponent bio-oil frac

Assignees

• Univ Michigan State

Inventors

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

Classifications

• C25B11/0415

  Chemistry & Metallurgy · mapped topic

• C25B3/04 Primary

  Chemistry & Metallurgy · mapped topic

• C25B11/0442

  Chemistry & Metallurgy · mapped topic

• C25B9/00 Primary

  Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features · CPC title

• C25B11/057

  consisting of a single element or compound · CPC title