# US 10,500,559 B2 · System and method of dehydrogenative coupling

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- Number: US 10,500,559 B2
- Document ID: US10500559B2
- Status: Granted
- Kind: B2
- Application number: 13/886,464
- Filed: 2013-05-03
- Published: 2013-11-07
- Granted: 2019-12-10
- Earliest claimed: 2012-05-05
- Assignees: King Abdullah University of Science and Technology
- Applicants: King Abdullah University of Science and Technology
- Inventors: Kuo-Wei Huang; Zhiping Lai
- Web page: https://patentgrep.com/patent/US10500559B2

## CPC

- B01J 16/005: {in the presence of catalytically active bodies, e.g. porous plates}
- B01J 8/009: {Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane}
- B01J 8/0257: {in a cylindrical annular shaped bed}
- B01J 15/005: {in the presence of catalytically active bodies, e.g. porous plates}
- B01J 19/2475: {Membrane reactors}
- B01J 23/462: {Ruthenium}
- B01J 31/189: {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
- C07C 67/00: Preparation of carboxylic acid esters
- C07C 67/40: by oxidation of primary alcohols
- B01J 2219/00135: Electric resistance heaters
- B01J 2231/49: Esterification or transesterification
- B01J 2531/0244: Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
- B01J 2531/821: Ruthenium
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Dehydrogenative coupling can be achieved in nearly quantitative conversions and yields using a membrane reactor.

## Claims

### Claim 1

A system for producing a dehydrogenative coupling product comprising:
a reactor including a reactor shell and a selectively permeable tubular membrane placed inside the reactor shell so that a reaction zone is defined between an outer surface of the selectively permeable tubular membrane and an inner surface of the reactor shell, and a gas release zone is defined by an inner surface of the selectively permeable tubular membrane;
a sweep gas line connected to the gas release zone for removing hydrogen from the gas release zone, and
a catalyst selected from the group consisting of:
wherein the selectively permeable tubular membrane permits the hydrogen to pass through the membrane and substantially blocks a substrate and its dehydrogenative coupling product from passing through the membrane,
wherein the substrate comprises a C1-C16 primary alcohol,
wherein the selectively permeable tubular membrane includes a metal membrane formed on a solid support, the metal membrane including palladium and silver, and the solid support including aluminum oxide.

### Claim 2 (depends on 1)

The system of claim 1, wherein the gas release zone is configured to transport hydrogen out of the reactor.

### Claim 3 (depends on 1)

The system of claim 1, wherein the reaction zone surrounds the gas release zone.

### Claim 4 (depends on 1)

The system of claim 1, wherein the selectively permeable tubular membrane is cylindrical.

### Claim 5 (depends on 1)

The system of claim 1, wherein a thickness of the metal membrane is 5 μm.

### Claim 6 (depends on 1)

The system of claim 1, wherein the substrate and the catalyst are substantially free of solvent.

### Claim 7

A system for producing a dehydrogenative coupling product comprising:
a reactor including a reactor shell and a selectively permeable tubular membrane,
wherein a reaction zone is defined between an outer surface of the selectively permeable tubular membrane and an inner surface of the reactor shell,
wherein a gas release zone, which is separated by the selectively permeable tubular membrane from the reaction zone, is defined by an inner surface of the selectively permeable tubular membrane,
wherein the selectively permeable tubular membrane permits hydrogen to pass through the membrane and substantially blocks a substrate and its dehydrogenative coupling product from passing through the membrane,
wherein the selectively permeable membrane includes a metal membrane formed on a solid support, the metal membrane including palladium and silver, and the solid support including aluminum oxide;
a sweep gas line connected to the gas release zone, defined by the selectively permeable tubular membrane, for removing hydrogen from the gas release zone; and
a catalyst selected from the group consisting of:

### Claim 8 (depends on 7)

The system of claim 7, wherein the gas release zone is configured to transport hydrogen out of the reactor.

### Claim 9 (depends on 7)

The system of claim 7, wherein the reaction zone surrounds the gas release zone.

### Claim 10 (depends on 7)

The system of claim 7, wherein the selectively permeable tubular membrane is cylindrical.

### Claim 11 (depends on 7)

The system of claim 7, wherein a thickness of the metal membrane is 5 μm.

### Claim 12 (depends on 7)

The system of claim 7, wherein the substrate and the catalyst are substantially free of solvent.