Synthesis of oxygen-mobility enhanced ceo2 and use thereof

Patent metadata

Field	Value
Publication number	US-2017001176-A1
Application number	US-201615191844-A
Country	US
Kind code	A1
Filing date	Jun 24, 2016
Priority date	Jul 1, 2015
Publication date	Jan 5, 2017
Grant date	—

Abstract

Disclosed are catalysts capable of catalyzing the dry reforming of methane. The catalysts have a core-shell structure with the shell surrounding the core. The shell has a redox-metal oxide phase that includes a metal dopant incorporated into the lattice framework of the redox-metal oxide phase. An active metal(s) is deposited on the surface of the shell.

First claim

1 . A catalyst capable of catalyzing a dry reformation of methane reaction, the catalyst comprising a core-shell structure having:
a metal oxide core, a clay core, or a zeolite core; a shell surrounding the core, wherein the shell has a redox-metal oxide phase that includes a metal dopant incorporated into the lattice framework of the redox-metal oxide phase; and an active metal deposited on the surface of the shell.

2 . The catalyst of claim 1 , wherein the redox-metal oxide phase is cerium oxide (CeO 2 ) and the metal dopant is niobium (Nb), indium (In), or lanthanum (La), or any combination thereof.

3 . The catalyst of claim 2 , wherein the metal oxide core is an alkaline earth metal aluminate core selected from aluminate, magnesium aluminate, calcium aluminate, strontium aluminate, barium aluminate, or any combination thereof.

4 . The catalyst of claim 3 , wherein the alkaline earth metal aluminate core is magnesium aluminate.

5 . The catalyst of claim 4 , comprising:
65 wt. % to 85 wt. % magnesium aluminate; 10 wt. % to 20 wt. % cerium oxide; and 5 wt. % to 10 wt. % nickel.

6 . The catalyst of claim 5 , comprising 0.5 wt. % to 2 wt. % of niobium incorporated into the lattice framework of the cerium oxide phase.

7 . The catalyst of claim 5 , comprising 0.5 wt. % to 2 wt. % of indium incorporated into the lattice framework of the cerium oxide phase.

8 . The catalyst of claim 5 , comprising 0.5 wt. % to 2 wt. % of lanthanum incorporated into the lattice framework of the cerium oxide phase.

9 . The catalyst of claim 2 , wherein the metal oxide core is Al 2 O 3 .

10 . The catalyst of claim 1 , wherein the core is Al 2 O 3 , the redox-metal oxide phase is cerium dioxide, the metal dopant is indium or niobium or both, and the metal deposited on the surface of the shell is nickel, rhodium, ruthenium, or platinum or any combination thereof.

11 . The catalyst of claim 1 , wherein the metal deposited on the surface of the shell is nickel, rhodium, ruthenium, iridium, platinum, palladium, gold, silver, palladium, cobalt, manganese, copper, or any combination thereof.

12 . The catalyst of claim 1 , wherein the shell has a thickness of one atomic monolayer to 100 atomic multilayers.

13 . The catalyst of claim 1 , wherein the catalyst includes 5 to 50 wt. % of the redox metal oxide phase, 0.1 to 5 wt. % of the metal dopant, and/or 1 to 40 wt. % of the metal deposited on the surface of the shell.

14 . The catalyst of claim 1 , wherein the catalyst is in particulate form having a mean particle size of 100 to 1000 μm.

15 . A system for producing hydrogen (H 2 ) and carbon monoxide (CO) from methane (CH 4 ) and carbon dioxide (CO 2 ), the system comprising:
an inlet for a reactant feed comprising CH 4 and CO 2; a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone comprises the catalyst of claim 1 ; and an outlet configured to be in fluid communication with the reaction zone and configured to remove a first product stream comprising H 2 and CO from the reaction zone.

16 . A method of producing hydrogen (H 2 ) and carbon monoxide (CO) from methane (CH 4 ) and carbon dioxide (CO 2 ), the method comprising contacting a reactant gas stream that includes CH 4 and CO 2 with the catalyst of claim 1 under substantially dry reaction conditions sufficient to produce a product gas stream comprising H2 and CO.

17 . The method of claim 16 , wherein the reaction conditions include a temperature of 700° C. to 950° C., a pressure of about 1 bara, and a gas hourly space velocity of 500 h −1 to 100,000 h −1 .

18 . The method of claim 16 , wherein coke formation on the catalyst is substantially or completely inhibited.

19 . A method of making the catalyst of claim 1 , the method comprising:
(a) obtaining a solution comprising a first metal salt and a second metal salt solubilized in the solution, wherein the weight ratio of the first metal salt to the second metal salt present in the solution is at least 5:1, preferably 5:1 to 30:1, more preferably 7:1 to 20:1, and most preferably 10:1 to 15:1; (b) impregnating a metal oxide core, a clay core, or a zeolite core, with the solution to obtain an impregnated material; (c) drying and calcining the impregnated material to obtain a core-shell structure having:
(i) a metal oxide core, a clay core, or a zeolite core; and
(ii) a shell surrounding the core, wherein the shell has a redox-metal oxide phase formed from the first metal salt and a metal dopant formed from the second metal salt that is incorporated into the lattice framework of the redox-metal oxide phase; and
(d) depositing one or more active metals on the surface of the shell.

20 . The method of claim 19 , wherein the impregnated material is dried at a temperature of 50 to 150° C. for 2 to 10 hours and calcined at a temperature of 500 to 800° C. for 2 to 4 hours.

Assignees

• Sabic Global Technologies Bv

Inventors

• D'Souza Lawrence
• Viswanath Vinu
• Scaranto Jessica
• Ravon Ugo

Classifications

• B01J37/0201

  Impregnation · CPC title

• C01B3/40

  characterised by the catalyst · CPC title

• C01B2203/1082

  Composition of support materials · CPC title

• C01B2203/107

  Platinum catalysts · CPC title

• C01B2203/1064

  Platinum group metal catalysts · CPC title