# US 10,766,019 B2 · Olefin metathesis reaction catalyst and preparation method therefor

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,766,019 B2
- Document ID: US10766019B2
- Status: Granted
- Kind: B2
- Application number: 16/329,469
- Filed: 2017-11-09
- Published: 2019-07-18
- Granted: 2020-09-08
- Earliest claimed: 2016-11-09
- Assignees: Korea Research Institute of Chemical Technology
- Applicants: Korea Research Institute of Chemical Technology
- Inventors: Jong Yeol Jeon; Man Jae Gil; Dong Won Hwang; Young Kyu Hwang; Yoo Han Han
- Web page: https://patentgrep.com/patent/US10766019B2

## CPC

- B01J 23/36: Rhenium
- B01J 21/04: Alumina
- B01J 21/08: Silica
- B01J 23/06: of zinc, cadmium or mercury
- B01J 23/08: of gallium, indium or thallium
- B01J 23/20: Vanadium, niobium or tantalum
- B01J 23/28: Molybdenum
- B01J 23/40: of the platinum group metals
- B01J 23/6567: {Rhenium}
- B01J 23/745: Iron
- B01J 23/75: Cobalt
- B01J 29/0333: {Iron group metals or copper}
- B01J 29/0341: {containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium}
- B01J 31/069: {Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups (nitrogen containing groups on mineral substrates B01J31/0254; organometallic polymers B01J31/123; coordination complexes immobilised on an inorganic support B01J31/1616; coordination polymers, e.g. metal-organic frameworks B01J31/1691)}
- B01J 31/12: containing organo-metallic compounds or metal hydrides
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/0209: {involving a reaction between the support and a fluid}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C07C 6/04: at a carbon-to-carbon double bond
- B01J 21/12: Silica and alumina
- B01J 31/122: {Metal aryl or alkyl compounds}
- B01J 2231/543: alkene metathesis
- C07C 2523/08: of gallium, indium or thallium
- C07C 2523/14: of germanium, tin or lead
- C07C 2523/20: Vanadium, niobium or tantalum
- C07C 2523/28: Molybdenum
- C07C 2523/36: Rhenium
- C07C 2523/46: Ruthenium, rhodium, osmium or iridium
- C07C 2523/745: Iron
- C07C 2523/75: Cobalt
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to an olefin metathesis reaction catalyst where rhenium (Re) oxide or molybdenum (Mo) oxide is supported, as a catalyst main component, on a surface-modified mesoporous silica or mesoporous alumina support, and a preparation method therefor. The olefin metathesis reaction catalyst of the present invention allows highly efficient metathesis of long-chain unsaturated hydrocarbons having at least eight carbons at a low temperature of 150° C. or lower. The catalyst can be separated readily from reaction solution, regenerated at a low temperature of 400° C. or lower by removing toxins accumulated on it during the metathesis reaction, and used repeatedly in metathesis reaction many times, thereby being made good use in commercial olefin metathesis processes.

## Claims

### Claim 1

A method of olefin metathesis comprising the step of contacting olefin with an olefin metathesis catalyst, in which rhenium (Re) oxide or molybdenum (Mo) oxide is supported on the surface-modified mesoporous silica support which is surface modified with an oxide of an element selected from the group consisting of Al, Nb, Fe, Co, Zn, Ga and Sn, and characteristically prepared by the processes of:
reacting the —OH group existing on the surface of the mesoporous silica support with a compound in which 1˜4 C1-C5 alkoxy groups are linked to the element selected from the group consisting of Al, Nb, Fe, Co, Zn, Ga and Sn in order to graft the compound on the surface of the support; and eliminating the unreacted compounds from the support, followed by calcining; and
impregnating the mesoporous silica support with a rhenium (Re) oxide or molybdenum (Mo) oxide precursor solution, followed by calcining, to convert the rhenium (Re) oxide or molybdenum (Mo) oxide precursor to rhenium (Re) oxide or molybdenum (Mo) oxide on the surface modified silica support;
the catalyst additionally containing one or more platinum group metals selected from the group consisting of Pt, Pd and Rh, at a concentration of 3 weight part or less, by total weight of the catalyst.

### Claim 2 (depends on 1)

The method of olefin metathesis according to claim 1, wherein the catalyst provides at least about 90.7% conversion during olefin metathesis.

### Claim 3

A method of olefin metathesis comprising the step of contacting olefin with an olefin metathesis catalyst, in which rhenium (Re) oxide or molybdenum (Mo) oxide is supported on the surface-modified mesoporous alumina support which is surface modified with an oxide of an element selected from the group consisting of Si, Nb, Fe, Co, Zn, Ga and Sn, and characteristically prepared by the processes of:
reacting the —OH group existing on the surface of the mesoporous alumina support with a compound in which 1˜4 C1-C5 alkoxy groups are linked to the element selected from the group consisting of Si, Nb, Fe, Co, Zn, Ga and Sn in order to graft the compound on the surface of the support; and eliminating the unreacted compounds from the support, followed by calcining; and
impregnating the mesoporous silica support with a rhenium (Re) oxide or molybdenum (Mo) oxide precursor solution, followed by calcining, to convert the rhenium (Re) oxide or molybdenum (Mo) oxide precursor to rhenium (Re) oxide or molybdenum (Mo) oxide on the surface modified alumina support;
the catalyst additionally containing one or more platinum group metals selected from the group consisting of Pt, Pd and Rh, at a concentration of 3 weight part or less, by total weight of the catalyst.

### Claim 4 (depends on 3)

The method of olefin metathesis according to claim 3, wherein the catalyst provides at least about 90.9% conversion during olefin metathesis.

### Claim 5

A method of olefin metathesis of unsaturated hydrocarbons having at least 8 carbons, at relatively low temperature, the method comprising:
providing an olefin metathesis catalyst comprising:
a surface-modified mesoporous support that comprises silica or alumina;
wherein when the support is a silica support, the support is surface-modified with an oxide of one or more metal elements selected from the group consisting of Al, Nb, Fe, Co, Zn, Ga, and Sn;
wherein when the support is an alumina support, the support is surface-modified with an oxide of one or more metal elements selected from the group consisting of Si, Nb, Fe, Co, Zn, Ga, and Sn;
the surface-modified mesoporous support being prepared by:
reacting an —OH group on a surface of the mesoporous support with a compound in which 1˜4 C1-C5 alkoxy groups are linked to the metal element in order to graft a metal alkoxy compound onto the surface of the mesoporous support;
eliminating unreacted compound from the support, followed by calcining to convert the metal alkoxy compound to a metal oxide;
impregnating the surface-modified support with at least one of a rhenium (Re) oxide or molybdenum (Mo) oxide precursor solution, followed by calcining to convert the rhenium (Re) oxide or molybdenum (Mo) oxide precursor to rhenium (Re) oxide or molybdenum (Mo) oxide;
impregnating the surface-modified support with one or more platinum group metals selected from the group consisting of Pt, Pd, and Rh;
wherein the olefin metathesis catalyst includes at least one of rhenium (Re) oxide or molybdenum (Mo) oxide in an amount of 3% to 20% by weight;
wherein the olefin metathesis catalyst includes the one or more platinum group metals in an amount of 0.5% to 3% by weight; and
wherein the olefin metathesis catalyst has an average pore size of 30 Å to about 80 Å;
contacting an olefin with the catalyst at a temperature of 150° C. or less to produce an olefin having at least 8 carbons;
wherein the catalyst provides at least about 90.7% conversion during olefin metathesis, within a reaction time of no more than about 100 minutes.

### Claim 6 (depends on 5)

The method of claim 5, the method further comprising removing toxins accumulated on the catalyst during the metathesis reaction, by regenerating the catalyst by exposure to a temperature of 400° C. or less for a period of 2 hours.

### Claim 7

A preparation method for an olefin metathesis catalyst in which rhenium (Re) oxide or molybdenum (Mo) oxide is supported on the surface-modified mesoporous silica support which is surface modified with an oxide of an element selected from the group consisting of Al, Nb, Fe, Co, Zn, Ga and Sn, and characteristically prepared by the processes of: reacting the —OH group existing on the surface of the mesoporous silica support with a compound in which 1˜4 C1-C5 alkoxy groups are linked to the element selected from the group consisting of Al, Nb, Fe, Co, Zn, Ga and Sn in order to graft the compound on the surface of the support; and eliminating the unreacted compounds from the support, followed by calcining; and impregnating the mesoporous silica support with a rhenium (Re) oxide or molybdenum (Mo) oxide precursor solution, followed by calcining, to convert the rhenium (Re) oxide or molybdenum (Mo) oxide precursor to rhenium (Re) oxide or molybdenum (Mo) oxide on the surface modified silica support; the catalyst additionally containing one or more platinum group metals selected from the group consisting of Pt, Pd and Rh, at a concentration of 3 weight part or less, by total weight of the catalyst, the preparation method comprising the following steps:
modifying the surface of the mesoporous silica comprising reacting an —OH group present on the surface with a compound in which one or more C1-C5 alkoxy groups are linked to one or more elements selected from the group consisting of Al, Nb, Fe, Co, Zn, Ga and Sn, removing the unreacted compound from the support and then calcining to bond the one or more elements to the surface of the mesoporous silica support (step 1);
impregnating the surface-modified support of step 1 with rhenium (Re) oxide or molybdenum (Mo)oxide precursor solution, followed by drying and calcining (step 2); and
impregnating the support with a precursor solution comprising one or more metals selected from the group consisting of Pt, Pd, and Rh (step 3).

### Claim 8 (depends on 7)

The method according to claim 7, wherein the C1-C5 alkoxy groups linked to one or more elements selected from the group consisting of Al, Nb, Fe, Co, Zn, Ga and Sn are represented by formula 1 below:
In formula 1 above,
M is at least one element selected from the group consisting of Al, Nb, Fe, Co, Zn, Ga and Sn;
n is an integer of 2 to 4;
R is C1-C5 alkyl, and when n is 3 or 4, they may be respectively different or the same.

### Claim 9

A preparation method for an olefin metathesis catalyst in which rhenium (Re) oxide or molybdenum (Mo) oxide is supported on the surface-modified mesoporous alumina support which is surface modified with an oxide of an element selected from the group consisting of Si, Nb, Fe, Co, Zn, Ga and Sn, and characteristically prepared by the processes of: reacting the —OH group existing on the surface of the mesoporous alumina support with a compound in which 1˜4 C1-C5 alkoxy groups are linked to the element selected from the group consisting of Si, Nb, Fe, Co, Zn, Ga and Sn in order to graft the compound on the surface of the support; and eliminating the unreacted compounds from the support, followed by calcining; and impregnating the mesoporous silica support with a rhenium (Re) oxide or molybdenum (Mo) oxide precursor solution, followed by calcining, to convert the rhenium (Re) oxide or molybdenum (Mo) oxide precursor to rhenium (Re) oxide or molybdenum (Mo) oxide on the surface modified alumina support; the catalyst additionally containing one or more platinum group metals selected from the group consisting of Pt, Pd and Rh, at a concentration of 3 weight part or less, by total weight of the catalyst, the preparation method comprising the following steps:
modifying the surface of the mesoporous alumina comprising reacting an —OH group present on the surface with a compound in which one or more C1-C5 alkoxy groups are linked to one or more elements selected from the group consisting of Si, Nb, Fe, Co, Zn, Ga and Sn, removing the unreacted compound from the support and then calcining to bond the one or more elements to the surface of the mesoporous alumina support (step 1);
impregnating the surface-modified support of step 1 with rhenium (Re) oxide or molybdenum (Mo) oxide precursor solution, followed by drying and calcining (step 2); and
impregnating the support with a precursor solution comprising one or more metals selected from the group consisting of Pt, Pd, and Rh (step 3).

### Claim 10 (depends on 9)

The method according to claim 9, wherein the C1-C5 alkoxy groups linked to one or more elements selected from the group consisting of Si, Nb, Fe, Co, Zn, Ga and Sn are represented by formula 1 below:
In formula 1 above,
M is at least one element selected from the group consisting of Si, Nb, Fe, Co, Zn, Ga and Sn;
n is an integer of 2 to 4;
R is C1-C5 alkyl, and when n is 3 or 4, they may be respectively different or the same.