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Composite oxide, metal-supported material, and ammonia synthesis catalyst

Foreign code F210010516
File No. AF40-05WO
Posted date 2021年7月30日
Country 中華人民共和国
Application number 201980028367
Gazette No. 112041271
Date of filing 令和元年5月7日(2019.5.7)
Gazette Date 令和2年12月4日(2020.12.4)
International application number JP2019018225
International publication number WO2019216304
Date of international filing 令和元年5月7日(2019.5.7)
Date of international publication 令和元年11月14日(2019.11.14)
Priority data
  • 特願2018-089516 (2018.5.7) JP
  • 2018JP34515 (2018.9.18) WO
  • 特願2019-059200 (2019.3.26) JP
  • 2019JP18225 (2019.5.7) WO
Title Composite oxide, metal-supported material, and ammonia synthesis catalyst
Abstract The present invention is a composite oxide including a metal element represented by the composition of general formula (6), wherein the composite oxide comprises an oxide of A and an oxide of X in a mixed state. General formula (6): AnXy (in general formula (6), A represents an element selected from the group consisting of Sc, Y, and lanthanoids (III); X represents an element selected from the group consisting of Ca, Sr, and Ba; n is 0 < n < 1; y is 0 < y < 1; and n + y = 1). The present invention is also a metal-supported material characterized in that cobalt particles are supported on the aforementioned composite oxide.
Outline of related art and contending technology BACKGROUND ART
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 6-079177
Patent document 2: japanese patent laid-open publication No. 2013-111562
Patent document 3: state patent and open No. 2016/133213
Patent document 4: japanese patent laid-open publication No. 2017-018907
Non-patent document
Non-patent document 1: niwa and K.Aika, Chemistry Letters, (1996) 3-4
Non-patent document 2: X.Luo et al, Catalysis Letters 133,382(2009)
Non-patent document 3: A.S.Ivanova et al, Kinetics and Catalysis, Vol.45, No.4,2004, pp.541-546. Translated from Kinetika i Kataliz, Vol.45, No.4,2004, pp.574-579.
Non-patent document 4: y. Ogura et al, "Efficient ammonia synthesis over a Ru/La0.5Ce0.5O1.75catalyst pre-reduced at high temperature ", Chemical Science, volume 9, pages 2230-2237
Non-patent document 5: m.kitano et al, angelw.chem.int.ed., 130(2018)2678
Non-patent document 6: gao et al, ACS catal, 7(2017)3654
Scope of claims [claim1]
1. A composite oxide containing a metal element represented by the composition of the general formula (6), wherein an oxide of A and an oxide of X are mixed:
AnXy (6)
in the general formula (6) described above,
a represents an element selected from the group consisting of Sc, Y and a lanthanide of valence III,
x represents an element selected from the group consisting of Ca, Sr and Ba,
n is more than 0 and less than 1,
y is more than 0 and less than 1,
and n + y is 1.

[claim2]
2. A composite oxide containing a metal element represented by the composition of the general formula (7), wherein an oxide of A and an oxide of X are mixed:
AnXyOx (7)
in the general formula (7) described above,
a represents an element selected from the group consisting of Sc, Y and a lanthanide of valence III,
x represents an element selected from the group consisting of Ca, Sr and Ba,
n is more than 0 and less than 1,
y is more than 0 and less than 1,
and n + y is 1, and n + y is,
x represents the number of oxygen atoms necessary for the complex oxide to maintain electrical neutrality.

[claim3]
3. The composite oxide according to claim 1 or 2, wherein A is selected from the group consisting of Sc, Y, La, Nd, Pm, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Lu.

[claim4]
4. The composite oxide according to claim 1 or 2, wherein a is La and X is Ba.

[claim5]
5. The composite oxide according to claim 1 or 2, wherein an amount of carbonate ions is 10 mol% or less compared with the X.

[claim6]
6. The composite oxide according to claim 5, wherein the oxide particles of X are deposited on the surfaces of the oxide particles of A.

[claim7]
7. The composite oxide according to claim 1, comprising a metal element represented by a composition of the general formula (6A):
AnXyMm (6A)
in the general formula (6A) described above,
a and X are as defined in claim 1,
m is any one of group 1 elements of the periodic table, group 2 elements selected from the group consisting of Ca, Sr, Ba and lanthanoids, and represents an element different from the A and the X,
n is more than 0 and less than 1,
y is more than 0 and less than 1,
m is more than or equal to 0 and less than 1,
and n + y + m is 1.

[claim8]
8. The composite oxide according to claim 7, wherein the composite oxide contains a solid solution of tetragonal or cubic crystals.

[claim9]
9. The composite oxide according to claim 7, wherein at least 1 of the elements A, X, M contained in the composite oxide is a partial negative charge (-O) A value of (b) is 0.50 or more.

[claim10]
10. The composite oxide according to claim 7, wherein the compositional ratio of each element contained in the composite oxide is represented by ni,when the degree of electronegativity of each element is represented by χ i, the value of partial negative charge of oxygen represented by the following formula (A) (-O) Is above 0.52:
((Π(χini) F (1/Sigma ni) — 5.21)/-4.75. formula (A)
Wherein i represents all elements in the composite oxide containing A, X, M, O.

[claim11]
11. The composite oxide according to claim 7, wherein X in the general formula (6A) is Ba, and an amount of carbonate ions contained in the composite oxide is 10 mol% or less relative to Ba.

[claim12]
12. A metal supporting object, wherein cobalt particles are supported on the composite oxide according to claim 1.

[claim13]
13. The metal support according to claim 12, wherein the cobalt particles have a layer formed of fine particles of the oxide of a and the oxide of X.

[claim14]
14. The metal support of claim 12, wherein H is passed through2Value D of Co dispersity obtained by pulse chemical adsorption methodadsValue D of Co dispersion degree expected from mean particle diameter of Co particles obtained from TEM imageTEMThe ratio of (A) to (B) satisfies 0 < Dads/DTEM<1。

[claim15]
15. The metal-loaded article according to claim 12, wherein the cobalt particles loaded on the composite oxide have an average particle diameter of 100nm or less.

[claim16]
16. A catalyst for ammonia synthesis, characterized by using the metal support of claim 12.

[claim17]
17. A method for manufacturing a metal supporting article according to claim 12, comprising:
a mixing step of mixing an A precursor containing the A and an X precursor containing the X to obtain a mixture;
a firing step of firing the mixture at a temperature of 600 ℃ or higher to obtain a support composed of a composite oxide;
a supporting step of supporting a cobalt-containing compound on the composite oxide to prepare a pre-reduction-treatment supporting object;
a reduction step of subjecting the support to reduction treatment at a temperature of 400 ℃ or higher.

[claim18]
18. A process for producing ammonia by bringing hydrogen and nitrogen into contact with a catalyst, characterized in that the catalyst is the catalyst for ammonia synthesis according to claim 16.
  • Applicant
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
  • Inventor
  • NAGAOKA KATSUTOSHI
  • OGURA YUTA
  • SATO KATSUTOSHI
IPC(International Patent Classification)
Reference ( R and D project ) CREST Creation of Innovative Core Technology for Manufacture and Use of Energy Carriers from Renewable Energy AREA
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