Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation

Patent metadata

Field	Value
Publication number	US-9732010-B2
Application number	US-201715443241-A
Country	US
Kind code	B2
Filing date	Feb 27, 2017
Priority date	Aug 3, 2007
Publication date	Aug 15, 2017
Grant date	Aug 15, 2017

Abstract

Disclosed is a catalyst for methanation reaction producing methane with high conversion by reaction of hydrogen with carbon dioxide, or a gas mixture of carbon dioxide and carbon monoxide, or a gas mixture containing these compounds as the main components. The catalyst is prepared by the steps of mixing (A) aqueous zirconia sol with salts of (B) stabilizing element(s), which is selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Ca and Mg, and (C) iron group element(s), drying and calcining the mixture to obtain a catalyst precursor, and subsequent reduction of the precursor. The catalyst comprises, by atomic %, A: 18-70%, B: 1-20% and C: 25-80% based on the elemental states of the metals. The catalyst is characterized by multiple oxide of tetragonal zirconia structure, in which not only the stabilizing element(s) but also a part of the iron group element(s) is incorporated, and on which the iron group element(s) in the metallic state is supported.

First claim

We claim:

1. A process for methanation of carbon oxides, which comprises contacting a mixed gas of carbon dioxide, mixture of carbon dioxide and carbon dioxide, or a mixture containing at least one of them as main components and hydrogen with a catalyst consisting of, based on the metals in the elemental state:
A) Zr for providing tetragonal zirconia supporter: 18-70 atomic %,
B) one or more of tetragonal zirconia-stabilizing element selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Ca and Mg (in case of two or more are used, in total): 1-20 atomic %, and
C) at least one of the iron group elements being supported on the tetragonal zirconia supporter and acting as the active site: 25-80 atomic %;
wherein the stabilizing element or elements and a portion of the iron group element or elements are incorporated in the tetragonal zirconia supporter; and
wherein the iron group element or elements not incorporated in the supporter are supported on the supporter in the metallic state.

2. The process of claim 1 , wherein:
the iron group element acting as the active site is Ni.

3. The process of claim 1 , wherein:
the iron group elements acting as the active site are Ni and one or both of Co and Fe, provided that Ni shares 0.6 or more based on the atomic ratio.

Assignees

• Hitachi Shipbuilding Eng Co
• Hashimoto Koji

Inventors

• Hashimoto Koji
• Takano Hiroyuki
• Izumiya Kouichi
• Kumagai Naokazu
• Kato Zenta
• Shinomiya Hiroyuki

Classifications

• C07C1/12 Primary

  from carbon dioxide with hydrogen · CPC title

• B01J23/83

  with rare earths or actinides · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C07C2523/83

  with rare earths or actinides · CPC title

• C07C1/044

  containing iron · CPC title