# US 10,245,583 B1 · Use of charge-containing molecules linked with covalent bonds to enhance acetylene hydrogenation catalysts

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- Number: US 10,245,583 B1
- Document ID: US10245583B1
- Status: Granted
- Kind: B1
- Application number: 15/702,413
- Filed: 2017-09-12
- Published: 2019-03-14
- Granted: 2019-04-02
- Earliest claimed: 2017-09-12
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Ryan W. Snell; Zongxuan Hong
- Web page: https://patentgrep.com/patent/US10245583B1

## CPC

- B01J 31/0267: {Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen}
- B01J 21/04: Alumina
- B01J 23/44: Palladium
- B01J 23/66: Silver or gold
- B01J 27/13: Platinum group metals
- B01J 27/1856: {with platinum group metals}
- B01J 31/00: Catalysts comprising hydrides, coordination complexes or organic compounds (catalyst compositions used only in polymerisation reactions C08 {; catalytic antibodies C12N9/0002})
- B01J 31/28: of the platinum group metals, iron group metals or copper
- B01J 35/397: {Egg shell like}
- B01J 35/612: {less than 10 m2/g}
- B01J 35/613: {10-100 m2/g}
- B01J 37/0201: {Impregnation}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0205: {in several steps}
- B01J 37/024: {Multiple impregnation or coating}
- B01J 37/16: Reducing
- B01J 37/18: with gases containing free hydrogen
- C07C 7/167: for removal of compounds containing a triple carbon-to-carbon bond
- B01J 2231/645: of C=C or C-C triple bonds
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A composition containing a supported hydrogenation catalyst comprising palladium and a support, wherein the supported hydrogenation catalyst is capable of selectively hydrogenating highly unsaturated hydrocarbons to unsaturated hydrocarbons, and a dopant, wherein the dopant comprises at least one component selected from zwitterions, ylides, betaines, or combinations thereof. A method of making a selective hydrogenation catalyst by contacting a support with a palladium-containing compound to form a supported-palladium composition, contacting the supported-palladium composition with a dopant to form a selective hydrogenation catalyst precursor, wherein the dopant comprises at least one component selected from zwitterions, ylides, betaines, or combinations thereof, and reducing the selective hydrogenation catalyst precursor to form the selective hydrogenation catalyst. A selective hydrogenation catalyst produced via the method of making a selective hydrogenation catalyst, and a method of selectively hydrogenating highly unsaturated hydrocarbons to an unsaturated hydrocarbon enriched composition are also provided.

## Claims

### Claim 1

A composition comprising:
a supported hydrogenation catalyst comprising palladium and an inorganic support selected from the group consisting of aluminas, silicas, titanias, zirconias, aluminosilicates, spinels, and combinations thereof, wherein the supported hydrogenation catalyst is capable of selectively hydrogenating highly unsaturated hydrocarbons to unsaturated hydrocarbons; and
a dopant, wherein the dopant comprises at least one component selected from the group consisting of zwitterions, ylides, betaines, and combinations thereof.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the dopant is selected from ylides.

### Claim 3 (depends on 2)

The composition of claim 2, wherein the dopant is selected from phosphorus ylides.

### Claim 4 (depends on 3)

The composition of claim 3, wherein the dopant is selected from phosphorus ylides further comprising a carbonyl group.

### Claim 5 (depends on 2)

The composition of claim 2, wherein the ylide is classified as stabilized and of the form R13—P═CHR2, wherein R2 comprises a COX group or a CN group.

### Claim 6 (depends on 5)

The composition of claim 5, wherein the ylide is a phosphoranylidine selected from the group consisting of 1-(triphenylphosphoranylidene)-2-propanone (TPP-2P), 2-(Triphenylphosphoranlyidene) propionaldehyde, (triphenylphosphoranylidene)acetonitrile, (triphenylphosphoranlyidene) acetaldehyde, (triphenylphosphoranlyidene)ketene, (phenacylidene)triphenylphosphorane, ethyl(triphenylphosphoranylidene)pyruvate, and combinations thereof.

### Claim 7 (depends on 1)

The composition of claim 1, wherein the dopant has a boiling point of greater than or equal to about 200° C.

### Claim 8 (depends on 1)

The composition of claim 1 further comprising at least one selectivity enhancer selected from the group consisting of Group 1B metals, Group 1B metal compounds, silver compounds, fluorine, fluoride compounds, sulfur, sulfur compounds, alkali metal, alkali metal compounds, alkaline metals, alkaline metal compounds, iodine, iodide compounds, and combinations thereof disposed on the inorganic support.

### Claim 9 (depends on 1)

The composition of claim 1, wherein the palladium is present in an amount of from about 0.005 wt. % to about 5 wt. % based on the total weight of the catalyst.

### Claim 10 (depends on 1)

The composition of claim 1, wherein the dopant is present in an amount of from about 0.005 wt. % to about 5 wt. % based on the total weight of the catalyst.

### Claim 11 (depends on 1)

The composition of claim 1, wherein the inorganic support has a surface area of from about 2 m2/g to about 100 m2/g, and wherein greater than about 90 wt. % of the palladium is concentrated near a periphery of the inorganic support.

### Claim 12

A method of making a selective hydrogenation catalyst, the method comprising:
contacting an inorganic support selected from the group consisting of aluminas, silicas, titanias, zirconias, aluminosilicates, spinels, and combinations thereof with a palladium-containing compound to form a supported-palladium composition;
contacting the supported-palladium composition with a dopant to form a selective hydrogenation catalyst precursor, wherein the dopant comprises at least one component selected from the group consisting of zwitterions, ylides, betaines, and combinations thereof; and
reducing the selective hydrogenation catalyst precursor to form the selective hydrogenation catalyst.

### Claim 13 (depends on 12)

The method of claim 12, wherein the dopant is selected from ylides.

### Claim 14 (depends on 13)

The method of claim 13, wherein the dopant is selected from phosphorus ylides.

### Claim 15 (depends on 14)

The method of claim 14, wherein the dopant is selected from phosphorus ylides further comprising a carbonyl group.

### Claim 16 (depends on 13)

The method of claim 13, wherein the ylide is classified as stabilized and of the form R13—P═CHR2, wherein R2 comprises a COX group or a CN group.

### Claim 17 (depends on 16)

The method of claim 16, wherein ylide is a phosphoranylidine selected from the group consisting of 1-(triphenylphosphoranylidine)-2-propanone (TPP-2P), (triphenylphosphoranylidene) acetonitrile, (triphenylphosphoranlyidene)ketene, (phenacylidene)triphenylphosphorane, (triphenyl phosphoranlyidene)acetaldehyde, ethyl(triphenylphosphoranylidene)pyruvate, 2-(triphenyl phosphoranlyidene) propionaldehyde, and combinations thereof.

### Claim 18 (depends on 12)

The method of claim 12, wherein the dopant has a boiling point of greater than or equal to about 200° C.

### Claim 19 (depends on 12)

The method of claim 12, further comprising contacting the inorganic support, the supported-palladium composition, the selective hydrogenation catalyst precursor, or the selective hydrogenation catalyst with at least one selectivity enhancer selected from the group consisting of Group 1B metals, Group 1B metal compounds, silver compounds, fluorine, fluoride compounds, sulfur, sulfur compounds, alkali metal, alkali metal compounds, alkaline metals, alkaline metal compounds, iodine, iodide compounds, and combinations thereof.

### Claim 20 (depends on 19)

The method of claim 19, wherein the selectivity enhancer comprises elemental silver, silver nitrate, silver acetate, silver bromide, silver chloride, silver iodide, silver fluoride, or a combination thereof.

### Claim 21 (depends on 19)

The method of claim 19, wherein the selectivity enhancer comprises elemental alkali metal, alkali metal fluoride, alkali metal chloride, alkali metal bromide, alkali metal iodide, alkali metal oxide, alkali metal carbonate, alkali metal sulfate, alkali metal phosphate, alkali metal borate, potassium fluoride, or a combination thereof.

### Claim 22 (depends on 19)

The method of claim 19, wherein the selectivity enhancer comprises silver and potassium fluoride.

### Claim 23 (depends on 19)

The method of claim 19, wherein the selectivity enhancer is present in an amount of from about 0.005 wt. % to about 5 wt. % based on the total weight of the selective hydrogenation catalyst.

### Claim 24 (depends on 19)

The method of claim 19, wherein contacting the inorganic support, the supported-palladium composition, the selective hydrogenation catalyst precursor, or the selective hydrogenation catalyst with the at least one selectivity enhancer comprises incipient wetness impregnation.

### Claim 25 (depends on 12)

The method of claim 12, wherein the palladium is present in an amount of from about 0.005 wt. % to about 5 wt. % Pd based on the total weight of the selective hydrogenation catalyst.

### Claim 26 (depends on 12)

The method of claim 12, wherein the dopant is present in an amount of from about 0.005 wt. % to about 5 wt. % based on the total weight of the selective hydrogenation catalyst.

### Claim 27 (depends on 12)

A selective hydrogenation catalyst prepared according the method of claim 12.

### Claim 28 (depends on 12)

The method of claim 12, wherein contacting the inorganic support with the palladium-containing compound to form the supported-palladium composition and contacting the supported-palladium composition with the dopant comprise incipient wetness impregnation.

### Claim 29

A method of selectively hydrogenating highly unsaturated hydrocarbons to an unsaturated hydrocarbon enriched composition, the method comprising:
contacting a supported catalyst comprising palladium and a dopant with a feed comprising highly unsaturated hydrocarbon under conditions suitable for hydrogenating at least a portion of the highly unsaturated hydrocarbon feed to form the unsaturated hydrocarbon enriched composition, wherein the dopant comprises at least one component selected from the group consisting of zwitterions, ylides, betaines, and combinations thereof.

### Claim 30 (depends on 29)

The method of claim 29, wherein the highly unsaturated hydrocarbons comprise at least one component selected from the group consisting of acetylene, methylacetylene, propadiene, butadiene, and combinations thereof.

### Claim 31 (depends on 29)

The method of claim 29, wherein the conditions suitable for hydrogenation include conducting the step of contacting at a temperature less than about the boiling point of the dopant.

### Claim 32 (depends on 31)

The method of claim 31 further comprising increasing the temperature to a temperature greater than or equal to about the boiling point of the dopant.