# US 12,215,025 B1 · Fibrous silica zinc oxide-supported nickel catalyst for dry reforming of methane and methods of preparation thereof

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- Number: US 12,215,025 B1
- Document ID: US12215025B1
- Status: Granted
- Kind: B1
- Application number: 18/774,551
- Filed: 2024-07-16
- Granted: 2025-02-04
- Earliest claimed: 2024-07-16
- Assignees: King Fahd University of Petroleum and Minerals
- Applicants: King Fahd University of Petroleum and Minerals
- Inventors: Khalid Alhooshani; Mohammed Mosaad Awad; Ijaz Hussain
- Web page: https://patentgrep.com/patent/US12215025B1

## CPC

- C01B 3/26: using catalysts
- B01J 23/06: of zinc, cadmium or mercury
- B01J 23/755: Nickel
- B01J 23/80: with zinc, cadmium or mercury
- B01J 23/94: of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
- B01J 35/58: Fabrics or filaments
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/12: Oxidising
- C01B 3/40: characterised by the catalyst
- C01B 3/42: using moving solid particles, e.g. fluidised bed technique
- C01B 2203/0277: containing a catalytic decomposition step
- C01B 2203/1058: Nickel catalysts
- C01B 2203/1241: Natural gas or methane
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A method for dry reformation of methane (DRM) includes introducing a H2-containing feed gas stream into a reactor, including a nickel-containing fibrous silica zinc oxide (Ni/FSZ) catalyst, passing the H2-containing feed gas stream through the reactor to contact the H2-containing feed gas stream with particles of the Ni/FSZ catalyst at a temperature of from 500 to 900 degrees Celsius (° C.) to form a reduced catalyst; terminating the introduction of the H2-containing feed gas stream and introducing and passing a mixed feed gas stream including CH4 and CO2 through the reactor to contact the mixed feed gas stream with the reduced catalyst at a temperature of from 500 to 1000° C. thereby converting at least a portion of the CH4 and CO2 to H2 and CO; and regenerating the Ni/FSZ catalyst particles to form a regenerated catalyst and producing a residue gas stream leaving the reactor.

## Claims

### Claim 1

A method for dry reformation of methane (DRM), including:
introducing a H2-containing feed gas stream into a reactor including a nickel-containing fibrous silica zinc oxide (Ni/FSZ) catalyst;
passing the H2-containing feed gas stream through the reactor to contact the H2-containing feed gas stream with particles of the Ni/FSZ catalyst at a temperature of from 500 to 900 degrees Celsius (° C.) to form a reduced catalyst;
terminating the introducing the H2-containing feed gas stream; and
introducing and passing a mixed feed gas stream including CH4 and CO2 through the reactor to contact the mixed feed gas stream with the reduced catalyst at a temperature of from 500 to 1000° C. thereby converting at least a portion of the CH4 and CO2 to H2 and CO and regenerating the Ni/FSZ catalyst particles to form a regenerated catalyst, and producing a residue gas stream leaving the reactor.

### Claim 2 (depends on 1)

The method of claim 1, further includes preparing the Ni/FSZ catalyst by:
mixing a nickel (Ni) salt, a fibrous silica zinc oxide (FSZ) catalyst, and water to form a first mixture; and
drying and calcining the first mixture at a temperature of about 700° C.

### Claim 3 (depends on 2)

The method of claim 2, wherein the Ni salt includes nickel sulfate, nickel acetate, nickel citrate, nickel iodide, nickel chloride, nickel perchlorate, nickel nitrate, nickel phosphate, nickel triflate, nickel bis(trifluoromethanesulfonyl)imide, nickel tetrafluoroborate, nickel bromide, and/or its hydrate.

### Claim 4 (depends on 2)

The method of claim 2, wherein the Ni/FSZ catalyst includes about 15 to 35 wt. % of Zn, 2 to 15 wt. % of Ni, 28 to 48 wt. % of oxygen (O), and 20 to 40 wt. % of silica (Si) as determined by energy-dispersive X-ray spectroscopy (EDS), and each wt. % based on a total weight of the Ni/FSZ catalyst.

### Claim 5 (depends on 2)

The method of claim 2, wherein the FSZ catalyst includes about 5 to 30 wt. % of Zn as determined by EDS, and each wt. % based on a total weight of the FSZ catalyst.

### Claim 6 (depends on 2)

The method of claim 2, wherein the FSZ catalyst has a porous structure including a plurality of spherical-like lamellar particles having an average particle size of 300 to 500 micrometers (μm).

### Claim 7 (depends on 6)

The method of claim 6, wherein each of the plurality of spherical-like lamellar particles includes a fibrous network of interconnected rounded-shaped nanospheres and cockscomb-like nanostructures.

### Claim 8 (depends on 2)

The method of claim 2, further includes preparing the FSZ catalyst by:
mixing urea, a quaternary ammonium surfactant, toluene, an alcohol solvent, and water to form a second mixture;
mixing zinc oxide (ZnO), a tetraalkyl orthosilicate, and the second mixture at a temperature of from 100 to 150° C. to form a third mixture; and
calcining the third mixture at a temperature of about 500 to 600° C.

### Claim 9 (depends on 8)

The method of claim 8, wherein the quaternary ammonium surfactant is at least one selected from the group consisting of cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTACl), tetradecyltrimethylammonium bromide (TTAB), tetradecyltrimethylammonium chloride (TTACl), dodecyltrimethylammonium bromide (DTAB), dodecyltrimethylammonium chloride (DTACl), dodecylethyldimethylammonium bromide (DEDTAB), decyltrimethylammonium bromide (D10TAB), and dodecyltriphenylphosphonium bromide (DTPB).

### Claim 10 (depends on 8)

The method of claim 8, wherein the tetraalkyl orthosilicate is at least one selected from the group consisting of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate.

### Claim 11 (depends on 1)

The method of claim 1, wherein H2 is present in the H2-containing feed gas stream at a concentration of 1 to 20 volume percentage (vol. %) based on a total volume of the H2-containing feed gas stream.

### Claim 12 (depends on 1)

The method of claim 1, wherein the H2-containing feed gas stream further includes an inert gas selected from the group consisting of nitrogen, argon, and helium.

### Claim 13 (depends on 1)

The method of claim 1, wherein the mixed feed gas stream further includes an inert gas selected from the group consisting of nitrogen, argon, and helium.

### Claim 14 (depends on 1)

The method of claim 1, wherein the reactor is at least one selected from the group consisting of a fixed-bed reactor, a trickle-bed reactor, a moving bed reactor, a rotating bed reactor, a fluidized bed reactor, and a slurry reactor.

### Claim 15 (depends on 1)

The method of claim 1, wherein the reactor is a fixed bed reactor in the form of a cylindrical reactor including:
a top portion;
a cylindrical body portion;
a bottom portion;
a housing having an open top and open bottom supportably maintained with the cylindrical body portion;
wherein the Ni/FSZ catalyst is supportably retained within the housing permitting fluid flow therethrough;
at least one propeller agitator disposed in the bottom portion of the reactor;
wherein the bottom portion is cone shaped or pyramidal; and
wherein a plurality of recirculation tubes fluidly connects the bottom portion of the cylindrical reactor with the cylindrical body portion of the cylindrical reactor.

### Claim 16 (depends on 1)

The method of claim 1, wherein the passing the H2-containing feed gas stream through the reactor is carried out at a flow rate of about 10 to 30 milliliters per minute (mL/min) at a temperature of about 700° C.

### Claim 17 (depends on 1)

The method of claim 1, wherein the passing the mixed feed gas stream through the reactor is carried out at a flow rate of about 10 to 30 mL/min.

### Claim 18 (depends on 1)

The method of claim 1, wherein a weight ratio of H2 to CO present in the residue gas stream is in a range of 0.001 to 2.0.

### Claim 19 (depends on 1)

The method of claim 1, having a H2 yield of 10 to 90% based on CH4 conversion at a temperature of from 700 to 1000° C., and wherein the CH4 conversion is based on an initial concentration of the CH4 in the mixed feed gas stream.

### Claim 20 (depends on 1)

The method of claim 1, having a CO yield of 5 to 49% based on a conversion of CH4 and CO2 at a temperature of from 700 to 1000° C., and wherein the conversion of CH4 and CO2 is based on an initially combined concentration of the CH4 and CO2 present in the mixed feed gas stream.