# US 11,306,261 B2 · Nanowire-based hydrodesulfurization catalysts for hydrocarbon fuels

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

- Number: US 11,306,261 B2
- Document ID: US11306261B2
- Status: Granted
- Kind: B2
- Application number: 16/841,401
- Filed: 2020-04-06
- Published: 2020-07-23
- Granted: 2022-04-19
- Earliest claimed: 2016-12-30
- Applicants: Advanced Energy Materials, LLC
- Inventors: Mahendra K. Sunkara; Sivakumar Vasireddy; Juan He; Vivekanand Kumar
- Web page: https://patentgrep.com/patent/US11306261B2

## CPC

- C10G 47/04: Oxides
- B01J 21/04: Alumina
- B01J 21/063: {Titanium; Oxides or hydroxides thereof}
- B01J 21/08: Silica
- B01J 23/14: of germanium, tin or lead
- B01J 27/0515: {with iron group metals or platinum group metals}
- B01J 35/393: {Metal or metal oxide crystallite size}
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/45: Nanoparticles
- B01J 35/58: Fabrics or filaments
- B01J 37/20: Sulfiding
- B01J 37/346: {of microwave energy}
- B01J 37/349: {making use of flames, plasmas or lasers}
- C10G 47/12: Inorganic carriers
- B01J 23/882: and cobalt
- B01J 23/883: and nickel
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C01P 2004/03: obtained by SEM
- C01P 2004/13: Nanotubes
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/207: Acid gases, e.g. H2S, COS, SO2, HCN
- C10G 2400/04: Diesel oil
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

The present development is a metal particle coated nanowire catalyst for use in the hydrodesulfurization of fuels and a process for the production of the catalyst. The catalyst comprises titanium(IV) oxide nanowires wherein the nanowires are produced by exposure of a TiO2—KOH paste to microwave radiation. Metal particles selected from the group consisting of molybdenum, nickel, cobalt, tungsten, or a combination thereof, are impregnated on the metal oxide nanowire surface. The metal impregnated nanowires are sulfided to produce catalytically-active metal particles on the surface of the nanowires The catalysts of the present invention are intended for use in the removal of thiophenic sulfur from liquid fuels through a hydrodesulfurization (HDS) process in a fixed bed reactor. The presence of nanowires improves the HDS activity and reduces the sintering effect, therefore, the sulfur removal efficiency increases.

## Claims

### Claim 1

A catalyst comprising metal oxide nanowires decorated with particles adhered to the surface of the nanowires, wherein the metal oxide nanowires comprise titanium(IV) oxide powder, and wherein the particles decorating the metal oxide nanowires are selected from the group consisting of molybdenum oxide, nickel oxide, cobalt oxide, tungsten oxide, an alloy of molybdenum oxide and nickel oxide, an alloy of molybdenum oxide and cobalt oxide, an alloy of molybdenum oxide and tungsten oxide, an alloy of nickel oxide and cobalt oxide, an alloy of nickel oxide and tungsten oxide, an alloy of cobalt oxide and tungsten oxide, and combinations thereof.

### Claim 2 (depends on 1)

The catalyst of claim 1 wherein the decorated metal oxide nanowire catalyst has a metal loading from 3 wt% to 20 wt %.

### Claim 3 (depends on 1)

The catalyst of claim 1 wherein the titanium(IV) oxide powder comprises a binder at a concentration of up to 25 wt % of the nanowire, and wherein the binder is selected from the group consisting of alumina, bentonite clay, and combinations thereof.

### Claim 4 (depends on 1)

The catalyst of claim 1 wherein the metal oxide nanowires have diameters from 5 nm to 200 nm and lengths from 0.5 microns to 50 microns.

### Claim 5 (depends on 1)

The catalyst of claim 1 wherein the metal oxide nanowires have surface areas ranging from 2 m2/g to 75 m2/g.

### Claim 6 (depends on 1)

The catalyst of claim 1 wherein the diameter of the decorating particles is from about 2 nm to about 20 nm.

### Claim 7 (depends on 1)

The catalyst of claim 1 wherein the decorated metal oxide nanowires are dried and shaped into extrudates and are calcined.

### Claim 8 (depends on 7)

The catalyst of claim 7 wherein the extrudates are calcined at from about 400° C. to about 500° C. for from about 2 hours to about 4 hours.

### Claim 9

A sulfided decorated metal oxide nanowire catalyst comprising:
(a) metal oxide nanowires, wherein the metal oxide nanowires are formed from metal oxide powder and the metal oxide powder is selected from the group consisting of titanium(IV) oxide, silicon oxide, tin oxide, alumina, and combinations thereof;
(b) particles adhered to the surface of the nanowires to form a metal particle decorated nanowire, wherein the particles decorating the metal oxide nanowires are selected from the group consisting of molybdenum, nickel, cobalt, tungsten, molybdenum oxide, nickel oxide, cobalt oxide, tungsten oxide, an alloy of molybdenum and nickel, an alloy of molybdenum and cobalt, an alloy of molybdenum and tungsten, an alloy of molybdenum and nickel oxide, an alloy of molybdenum and cobalt oxide, an alloy of molybdenum and tungsten oxide, an alloy of nickel and cobalt, an alloy of nickel and tungsten, an alloy of nickel and molybdenum oxide, an alloy of nickel and cobalt oxide, an alloy of nickel and tungsten oxide, an alloy of cobalt and tungsten, an alloy of cobalt and molybdenum oxide, an alloy of cobalt and nickel oxide, an alloy of cobalt and tungsten oxide, an alloy of tungsten and molybdenum oxide, an alloy of tungsten and nickel oxide, an alloy of tungsten and cobalt oxide, an alloy of molybdenum oxide and nickel oxide, an alloy of molybdenum oxide and cobalt oxide, an alloy of molybdenum oxide and tungsten oxide, an alloy of nickel oxide and cobalt oxide, an alloy of nickel oxide and tungsten oxide, an alloy of cobalt oxide and tungsten oxide, and combinations thereof; and,
(c) sulfiding agent, wherein the metal particle decorated nanowire is exposed to the sulfiding agent to produce the sulfided decorated metal oxide nanowire catalyst.

### Claim 10 (depends on 9)

The catalyst of claim 9 wherein the sulfiding agent is hydrogen sulfide or dimethyl disulfide.

### Claim 11 (depends on 10)

The catalyst of claim 10 wherein the diameter of the decorating particles is from about 2 nm to about 20 nm.

### Claim 12 (depends on 10)

The catalyst of claim 10 wherein the decorated metal oxide nanowire catalyst has a metal loading from about 3 wt % to about 20 wt %.

### Claim 13 (depends on 9)

The catalyst of claim 9 wherein the metal oxide powder is selected from titanium(IV) oxide powder and wherein the particles decorating the metal oxide nanowires are selected from the group consisting of molybdenum oxide, nickel oxide, cobalt oxide, tungsten oxide, an alloy of molybdenum oxide and nickel oxide, an alloy of molybdenum oxide and cobalt oxide, an alloy of molybdenum oxide and tungsten oxide, an alloy of nicke oxide and cobalt oxide, an alloy of nickel oxide and tungsten oxide, an alloy of cobalt oxide and tungsten oxide, and combinations thereof.

### Claim 14 (depends on 9)

The catalyst of claim 9 wherein the metal oxide powder comprises a binder at a concentration of up to 25 wt % of the nanowire, and wherein the binder is selected from the group consisting of alumina, bentonite clay, and combinations thereof.

### Claim 15 (depends on 9)

The catalyst of claim 9 wherein the metal oxide nanowires have diameters from 5 nm to 200 nm and lengths from 0.5 microns to 50 microns.

### Claim 16 (depends on 9)

The catalyst of claim 9 wherein the metal oxide nanowires have surface areas ranging from 2 m2/g to 75 m2/g.

### Claim 17

A catalyst comprising metal oxide nanowires with particles adhered to the surface of the nanowires to form a metal decorated nanowire catalyst wherein the metal oxide nanowires are formed from metal oxide powder and the metal oxide powder is selected from the group consisting of titanium(IV) oxide, silicon oxide, tin oxide, alumina, and combinations thereof, and wherein the particles decorating the metal oxide nanowires are selected from the group consisting of molybdenum, nickel, cobalt, tungsten, molybdenum oxide, nickel oxide, cobalt oxide, tungsten oxide, an alloy of molybdenum and nickel, an alloy of molybdenum and cobalt, an alloy of molybdenum and tungsten, an alloy of molybdenum and nickel oxide, an alloy of molybdenum and cobalt oxide, an alloy of molybdenum and tungsten oxide, an alloy of nickel and cobalt, an alloy of nickel and tungsten, an alloy of nickel and molybdenum oxide, an alloy of nickel and cobalt oxide, an alloy of nickel and tungsten oxide, an alloy of cobalt and tungsten, an alloy of cobalt and molybdenum oxide, an alloy of cobalt and nickel oxide, an alloy of cobalt and tungsten oxide, an alloy of tungsten and molybdenum oxide, an alloy of tungsten and nickel oxide, an alloy of tungsten and cobalt oxide, an alloy of molybdenum oxide and nickel oxide, an alloy of molybdenum oxide and cobalt oxide, an alloy of molybdenum oxide and tungsten oxide, an alloy of nickel oxide and cobalt oxide, an alloy of nickel oxide and tungsten oxide, an alloy of cobalt oxide and tungsten oxide, and combinations thereof.

### Claim 18 (depends on 17)

The catalyst of claim 17 wherein the metal oxide powder comprises a binder at a concentration of up to 25 wt % of the nanowire, and wherein the binder is selected from the group consisting of alumina, bentonite clay, and combinations thereof.

### Claim 19 (depends on 17)

The catalyst of claim 17 wherein the diameter of the decorating particles is from about 2 nm to about 20 nm.

### Claim 20 (depends on 17)

The catalyst of claim 17 wherein the decorated metal oxide nanowire catalyst has a metal loading from about 3 wt % to about 20 wt %.