Composite oxide catalyst and method for producing the same

Patent metadata

Field	Value
Publication number	US-9855546-B2
Application number	US-201113992031-A
Country	US
Kind code	B2
Filing date	Dec 27, 2011
Priority date	Dec 27, 2010
Publication date	Jan 2, 2018
Grant date	Jan 2, 2018

Abstract

A method for producing a complex oxide catalyst containing a complex oxide represented by the formula:

Mo 1 V a Sb b Nb c W d Z e O n

(wherein a component Z represents an element such as La, Ce, Pr, Yb, Y, Sc, Sr, and Ba; a, b, c, d, e, and n each represent an atomic ratio of an element to one Mo atom; 0.1≦a≦0.4, 0.1≦b≦0.4, 0.01≦c≦0.3, 0≦d≦0.2, and 0≦e≦0.1; an atomic ratio a/b is 0.85≦a/b<1.0, and an atomic ratio a/c is 1.4<a/c<2.3.), the method including: a step of preparing a specific raw material-formulated solution containing Mo, V, Sb, Nb, W, and Z; a step of drying the raw material-formulated solution to obtain a dry powder; a step of pre-stage calcining the dry powder to obtain a pre-stage calcined product; a step of main-calcining the pre-stage calcined product to obtain a calcined product having a protrusion on the surface of the particle; and a step of removing the protrusion by an air stream, wherein the reduction rate of the pre-stage calcined product is 8 to 12%, and the specific surface area of the calcined product is 7 to 20 m 2 /g.

First claim

What is claimed is:

1. A complex oxide catalyst used for a vapor-phase catalytic oxidation reaction or vapor-phase catalytic ammoxidation reaction of propane or isobutane, the catalyst comprising a complex oxide represented by the following formula (1):
Mo 1 V a Sb b Nb c W d Z e O n   (1)

wherein a component Z represents Ce and optionally one or more elements selected from La, Pr, Yb, Y, Sc, Sr, and Ba; a, b, c, d, e, and n each represent an atomic ratio of an element to one Mo atom; 0.1≦a≦0.24, 0.1≦b≦0.258, 0.01≦c≦0.3, 0≦d≦0.2, and 0≦e≦0.1; an atomic ratio a/b is 0.85≦a/b<1.0, and an atomic ratio a/c is 1.4<a/c<2.27, and
wherein an amount of protrusions is not more than 2% by mass based on a total mass of the complex oxide catalyst.

2. The complex oxide catalyst according to claim 1 , comprising 20 to 70% by mass of silica in terms of SiO 2 .

3. A method for producing a complex oxide catalyst comprising a complex oxide represented by the following formula (1):
Mo 1 V a Sb b Nb c W d Z e O n   (1)

(wherein a component Z represents one or more elements selected from La, Ce, Pr, Yb, Y, Sc, Sr, and Ba; a, b, c, d, e, and n each represent an atomic ratio of an element to one Mo atom; 0.1≦a≦0.4, 0.1≦b≦0.4, 0.01≦c≦0.3, 0≦d≦0.2, and 0≦e≦0.1; an atomic ratio a/b is 0.85≦a/b <1.0, and an atomic ratio a/c is 1.4<a/c<2.3), the method comprising the steps (I) to (V):
(I) preparing a raw material-formulated solution comprising Mo, V, Sb, Nb, W, and Z, wherein an atomic ratio a of V to one Mo atom is 0.1≦a≦0.5, an atomic ratio b of Sb to one Mo atom is 0.1≦b≦0.5, an atomic ratio c of Nb to one Mo atom is 0.01≦c≦0.5, an atomic ratio d of W to one Mo atom is 0≦d≦0.4, and an atomic ratio e of Z to one Mo atom is 0≦e≦0.2;
(II) drying the raw material-formulated solution to obtain a dry powder;
(III) pre-stage calcining the dry powder to obtain a pre-stage calcined product;
(IV) main-calcining the pre-stage calcined product to obtain a calcined product having a protrusion on a surface of a particle; and
(V) removing the protrusion existing on the surface of the particle of the calcined product by an air stream,
wherein a reduction rate of the pre-stage calcined product is 8 to 12%, and a specific surface area of the calcined product is 7 to 20 m 2 /g.

4. The method for producing a complex oxide catalyst according to claim 3 , wherein a content of particles having a particle size of not more than 25 μm in the dry powder is not more than 20% by mass, and an average particle size of the dry powder is 35 to 75 μm.

5. The method for producing a complex oxide catalyst according to claim 3 , wherein in the step (V), the protrusion is removed so that the amount of the protrusion that the calcined product has is not more than 2% by mass based on a total mass of the calcined product.

6. The method for producing a complex oxide catalyst according to claim 3 , wherein a length of the air stream in a direction of the air stream flowing is not less than 55 mm, and an average flow rate of the air stream is not less than 80 m/s and not more than 500 m/s as a linear velocity at 15° C. and 1 atmospheric pressure.

7. The method for producing a complex oxide catalyst according to claim 3 , wherein the step (I) comprises the steps (a) to (d):
(a) preparing an aqueous mixed-solution comprising Mo, V, Sb, and the component Z;
(b) adding silica sol and a hydrogen peroxide solution to the aqueous mixed-solution obtained in the step (a);
(c) mixing an aqueous solution comprising Nb, dicarboxylic acid, and the hydrogen peroxide solution and a W compound with the solution obtained in the step (b); and
(d) adding a powder silica-containing suspension to the solution obtained in the step (c) and aging the solution.

8. The method for producing a complex oxide catalyst according to claim 3 , wherein the (III) pre-stage calcination step and/or the (IV) main calcination step comprises the steps (i) and (ii):
(i) giving impact to a calcining apparatus in which the pre-stage calcined product and/or the calcined product is calcined; and
(ii) annealing the pre-stage calcined product and/or the calcined product at a temperature lower than the calcining temperature in the main calcination.

9. A method for producing an unsaturated acid using the complex oxide catalyst according to claim 1 , wherein propane or isobutane is subjected to a vapor-phase catalytic oxidation reaction to produce a corresponding unsaturated acid.

10. A method for producing an unsaturated nitrile using the complex oxide catalyst according to claim 1 , wherein propane or isobutane is subjected to a vapor-phase catalytic ammoxidation reaction to produce a corresponding unsaturated nitrile.

11. The method for producing a complex oxide catalyst according to claim 4 , wherein in the step (V), the protrusion is removed so that the amount of the protrusion that the calcined product has is not more than 2% by mass based on a total mass of the calcined product.

12. The method for producing a complex oxide catalyst according to claim 4 , wherein a length of the air stream in a direction of the air stream flowing is not less than 55 mm, and an average flow rate of the air stream is not less than 80 m/s and not more than 500 m/s as a linear velocity at 15° C. and 1 atmospheric pressure.

13. The method for producing a complex oxide catalyst according to claim 5 , wherein a length of the air stream in a direction of the air stream flowing is not less than 55 mm, and an average flow rate of the air stream is not less than 80 m/s and not more than 500 m/s as a linear velocity at 15° C. and 1 atmospheric pressure.

14. The method for producing a complex oxide catalyst according to claim 4 , wherein the step (I) comprises the steps (a) to (d):
(a) preparing an aqueous mixed-solution comprising Mo, V, Sb, and the component Z;
(b) adding silica sol and a hydrogen peroxide solution to the aqueous mixed-solution obtained in the step (a);
(c) mixing an aqueous solution comprising Nb, dicarboxylic acid, and the hydrogen peroxide solution and a W compound with the solution obtained in the step (b); and
(d) adding a powder silica-containing suspension to the solution obtained in the step (c) and aging the solution.

15. The method for producing a complex oxide catalyst according to claim 5 , wherein the step (I) comprises the steps (a) to (d):
(a) preparing an aqueous mixed-solution comprising Mo, V, Sb, and the component Z;
(b) adding silica sol and a hydrogen peroxide solution to the aqueous mixed-solution obtained in the step (a);
(c) mixing an aqueous solution comprising Nb, dicarboxylic acid, and the hydrogen peroxide solution and a W compound with the solution obtained in the step (b); and
(d) adding a powder silica-containing suspension to the solution obtained in the step (c) and aging the solution.

16. The method for producing a complex oxide catalyst according to claim 6 , wherein the step (I) comprises the steps (a) to (d):
(a) preparing an aqueous mixed-solution comprising Mo, V, Sb, and the component Z;
(b) adding silica sol and a hydrogen peroxide solution to the aqueous mixed-solution obtained in the step (a);
(c) mixing an aqueous solution comprising Nb, dicarboxylic acid, and the hydrogen peroxide solution and a W compound with the solution obtained in the step (b); and
(d) adding a powder silica-containing suspension to the solution obtained in the step (c) and aging the solution.

17. The method for producing a complex oxide catalyst according to claim 4 , wherein the (III) pre-stage calcination step and/or the (IV

Assignees

• Ishii Yusuke
• Kato Takaaki
• Asahi Kasei Chemicals Corp

Inventors

• Ishii Yusuke
• Kato Takaaki

Classifications

• B01J35/1009

  Operations & Transport · mapped topic

• B01J2523/55

  Vanadium · CPC title

• B01J2523/69

  Tungsten · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• B01J2523/41

  Silicon · CPC title