System and method of dehydrogenative coupling

Patent metadata

Field	Value
Publication number	US-11097243-B2
Application number	US-201916670243-A
Country	US
Kind code	B2
Filing date	Oct 31, 2019
Priority date	May 5, 2012
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

Embodiments include a system that may include a reactor including a reaction zone and a gas release zone separated by a selectively permeable membrane, wherein the selectively permeable membrane permits hydrogen to pass through the membrane and substantially blocks a substrate and its dehydrogenative coupling product from passing through the membrane. Embodiments further include a method of producing a dehydrogenative coupling product, wherein the method may include exposing a substrate to a catalyst in a reaction zone of a reactor; coupling the substrate to form the dehydrogenative coupling product and hydrogen; and separating the hydrogen from the dehydrogenative coupling product using a selectively permeable membrane and passing the hydrogen to a gas release zone of the reactor.

First claim

What is claimed is:

1. A method of producing a dehydrogenative coupling product, comprising:
exposing a substrate to a catalyst in a reaction zone of a reactor, wherein the catalyst includes at least one of the following chemical structures:

coupling the substrate to form the dehydrogenative coupling product and hydrogen; and
separating the hydrogen from the dehydrogenative coupling product using a selectively permeable membrane and passing the hydrogen to a gas release zone of the reactor.

2. The method of claim 1 , wherein the selectively permeable membrane includes a metal membrane on a solid support.

3. The method of claim 2 , wherein the metal membrane includes palladium.

4. The method of claim 2 , wherein the solid support includes a silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, magnesium oxide, cerium oxide, zinc oxide, molybdenum oxide, iron oxide, nickel oxide, cobalt oxide, graphite, or stainless steel.

5. The method of claim 1 , wherein the substrate is a C1-C16 primary alcohol, a C1-C8 primary alcohol, or a C1-C5 primary alcohol, or a mixture of two or more of said alcohols.

6. The method of claim 1 , wherein the dehydrogenative coupling product is an ester.

7. The method of claim 1 , wherein the dehydrogenative coupling product is an alkyl ester of an alcohol.

8. The method of claim 1 , wherein the dehydrogenative coupling product is methyl formate, ethyl acetate, propyl propanoate, butyl butanoate, or pentyl pentanoate.

9. The method of claim 1 , wherein the catalyst is a dearomatized PNN-Ru(II) catalyst.

10. The method of claim 1 , wherein the substrate and the catalyst are free of solvent.

11. The method of claim 1 , wherein the coupling proceeds in the absence of acid promoters, base promoters, hydrogen acceptors, or combinations thereof.

Assignees

• Univ King Abdullah Sci & Tech

Inventors

• Huang Kuo-Wei
• Lai Zhiping

Classifications

• B01J15/005 Primary

  in the presence of catalytically active bodies, e.g. porous plates · CPC title

• B01J2531/821

  Ruthenium · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• C07C67/00

  Preparation of carboxylic acid esters · CPC title

• B01J2531/0244

  Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds · CPC title