OXIDE CATALYST AND METHOD FOR PRODUCING THE SAME, AND METHODS FOR PRODUCING UNSATURATED ALDEHYDE, DIOLEFIN, AND UNSATURATED NITRILE

• US 20150238939A1
• Filed: 09/27/2013
• Published: 08/27/2015
• Est. Priority Date: 09/28/2012
• Status: Active Grant

• Current Assignee: Asahi Kasei Chemicals Corporation (Asahi Kasei Corporation)
• Original Assignee: Asahi Kasei Chemicals Corporation (Asahi Kasei Corporation)
• Inventors: Yoshida, Jun, Yamaguchi, Tatsuo
• Granted Patent: US 9,364,817 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 23/88 Molybdenum
• CPC Class Codes: B01J 23/881 and iron
• CPC Class Codes: B01J 23/8871 Rare earth metals or actinides
• CPC Class Codes: B01J 23/8872 Alkali or alkaline earth metals
• CPC Class Codes: B01J 23/8876 Arsenic, antimony or bismuth
• CPC Class Codes: B01J 23/8898 containing also molybdenum
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/13 Potassium
• CPC Class Codes: B01J 2523/14 Rubidium
• CPC Class Codes: B01J 2523/15 Caesium
• CPC Class Codes: B01J 2523/22 Magnesium
• CPC Class Codes: B01J 2523/23 Calcium
• CPC Class Codes: B01J 2523/27 Zinc
• CPC Class Codes: B01J 2523/3706 Lanthanum
• CPC Class Codes: B01J 2523/3712 Cerium
• CPC Class Codes: B01J 2523/3718 Praseodymium
• CPC Class Codes: B01J 2523/41 Silicon
• CPC Class Codes: B01J 2523/44 Lead
• CPC Class Codes: B01J 2523/54 Bismuth
• CPC Class Codes: B01J 2523/68 : Molybdenum
• CPC Class Codes: B01J 2523/72 : Manganese
• CPC Class Codes: B01J 2523/842 : Iron
• CPC Class Codes: B01J 2523/845 : Cobalt
• CPC Class Codes: B01J 2523/847 : Nickel
• CPC Class Codes: B01J 35/30 : characterised by their physical properties
• CPC Class Codes: B01J 35/393 : Metal or metal oxide crystallite size
• CPC Class Codes: B01J 35/40 : characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/50 : characterised by their shape or configuration
• CPC Class Codes: B01J 35/612 : less than 10 m2/g
• CPC Class Codes: B01J 37/0009 : Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0045 : Drying a slurry, e.g. spray drying
• CPC Class Codes: B01J 37/04 : Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 : Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C07C 11/12 : Alkadienes
• CPC Class Codes: C07C 11/167 : 1, 3-Butadiene
• CPC Class Codes: C07C 2523/18 : Arsenic, antimony or bismuth
• CPC Class Codes: C07C 2523/28 : Molybdenum
• CPC Class Codes: C07C 2523/31 : combined with bismuth
• CPC Class Codes: C07C 2523/745 : Iron
• CPC Class Codes: C07C 2523/887 : containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
• CPC Class Codes: C07C 253/26 : containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
• CPC Class Codes: C07C 255/08 : Acrylonitrile; Methacrylonitrile
• CPC Class Codes: C07C 45/35 : in propene or isobutene
• CPC Class Codes: C07C 47/02 : Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
• CPC Class Codes: C07C 47/22 : Acryaldehyde; Methacryaldehyde
• CPC Class Codes: C07C 5/3332 : with metal oxides or metal sulfides
• CPC Class Codes: C07C 5/48 : with oxygen as an acceptor
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

An object of the present invention is to provide an oxide catalyst that prevents the reduction degradation of the catalyst even during industrial operation for a long time and less reduces unsaturated aldehyde yields, diolefin yields, or unsaturated nitrile yields, and a method for producing the same, and methods for producing unsaturated aldehyde, diolefin, and unsaturated nitrile using the oxide catalyst. The present invention provides an oxide catalyst for use in the production of unsaturated aldehyde, diolefin, or unsaturated nitrile from olefin and/or alcohol, the oxide catalyst satisfying the following (1) to (3): (1) the oxide catalyst comprises molybdenum, bismuth, iron, cobalt, and an element A having an ion radius larger than 0.96 Å (except for potassium, cesium, and rubidium); (2) an atomic ratio a of the bismuth to 12 atoms of the molybdenum is 1≦a≦5, an atomic ratio b of the iron to 12 atoms of the molybdenum is 1.5≦b≦6, an atomic ratio c of the element A to 12 atoms of the molybdenum is 1≦c≦5, and an atomic ratio d of the cobalt to 12 atoms of the molybdenum is 1≦d≦8; and (3) the oxide catalyst comprises a disordered phase consisting of a crystal system comprising the molybdenum, the bismuth, the iron, and the element A.

Claims

1. An oxide catalyst for use in the production of unsaturated aldehyde, diolefin, or unsaturated nitrile from olefin and/or alcohol, the oxide catalyst satisfying the following (1) to (3):

(1) the oxide catalyst comprises molybdenum, bismuth, iron, cobalt, and an element A having an ion radius larger than 0.96 Å

(except for potassium, cesium, and rubidium);

(2) an atomic ratio a of the bismuth to 12 atoms of the molybdenum is 1≦

a≦

5, an atomic ratio b of the iron to 12 atoms of the molybdenum is 1.5≦

b≦

6, an atomic ratio c of the element A to 12 atoms of the molybdenum is 1≦

c≦

5, and an atomic ratio d of the cobalt to 12 atoms of the molybdenum is 1≦

d≦

8; and

(3) the oxide catalyst comprises a disordered phase consisting of a crystal system comprising the molybdenum, the bismuth, the iron, and the element A.

2. The oxide catalyst according to claim 1, wherein the oxide catalyst has a single peak in each range of diffraction angles (2θ

) of 18.30°

±

0.2°

, 28.20°

±

0.2°

, 33.65°

±

0.2°

, and 46.15°

±

0.2°

in X-ray diffraction, and

an intensity ratio (Ia/Ib) of intensity (Ia) of peak a at 2θ

=33.65°

±

0.2°

to intensity (Ib) of peak b at 2θ

=34.10°

±

0.2°

is 2.0 or larger.

3. The oxide catalyst according to claim 1, wherein the oxide catalyst has a composition represented by the following composition formula (1):

Mo₁₂Bi_aFe_bA_cCo_dB_eC_fO_g 

 

(1)

wherein Mo represents molybdenum;

Bi represents bismuth;

Fe represents iron;

the element A represents an element having an ion radius larger than 0.96 Å

(except for potassium, cesium, and rubidium);

Co represents cobalt;

an element B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin;

an element C represents at least one element selected from the group consisting of potassium, cesium, and rubidium;

a to g each represent the atomic ratio of each element to 12 Mo atoms wherein the atomic ratio a of Bi is 1≦

a≦

5, the atomic ratio b of Fe is 1.5≦

b≦

6, the atomic ratio c of the element A is 1≦

c≦

5, and the atomic ratio d of Co is 1≦

d≦

8, an atomic ratio e of the element B is 0≦

e<

3, an atomic ratio f of the element C is 0≦

f≦

2, and an ratio of Fe/Co is 0.8≦

b/d; and

g represents an atomicity of oxygen determined by an valences of constituent elements other than oxygen.

4. The oxide catalyst according to claim 1, further comprising at least one selected from the group consisting of silica, alumina, titania, and zirconia as a carrier.

8. A method for producing unsaturated aldehyde, comprising an unsaturated aldehyde production step of oxidizing olefin and/or alcohol using the oxide catalyst according to claim 1 to obtain the unsaturated aldehyde.

9. The method for producing unsaturated aldehyde according to claim 8, wherein the olefin and/or the alcohol is at least one selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol.

10. The method for producing unsaturated aldehyde according to claim 8, wherein the unsaturated aldehyde production step comprises a discharging step of discharging a product gas comprising the unsaturated aldehyde from a fluidized-bed reactor through the gas-phase catalytic oxidation reaction of the olefin and/or the alcohol with an oxygen source in the fluidized-bed reactor.

11. The method for producing unsaturated aldehyde according to claim 8, wherein

the gas-phase catalytic oxidation reaction is performed at a reaction temperature of 400 to 500°

C., and

the product gas discharged from the fluidized-bed reactor has an oxygen concentration of 0.03 to 0.5% by volume.

12. A method for producing diolefin, comprising a diolefin production step of oxidizing monoolefin having 4 or more carbon atoms using the oxide catalyst according to claim 1 to obtain the diolefin.

13. A method for producing unsaturated nitrile, comprising an unsaturated nitrile production step of reacting at least one selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol, with molecular oxygen and ammonia in a fluidized-bed reactor using the oxide catalyst according to claim 1 to obtain the unsaturated nitrile.

5. A method for producing an oxide catalyst, comprising:

a mixing step of mixing a starting material constituting the catalyst, comprising molybdenum, bismuth, iron, cobalt, and an element A having an ion radius larger than 0.96 Å

(except for potassium, cesium, and rubidium), to obtain a slurry;

a drying step of drying the slurry thus obtained to obtain a dried product; and

a calcination step of calcining the dried product thus obtained, wherein

the calcination step comprises a heating step of gradually heating the dried product from 100°

C. to 200°

C. over 1 hour or longer.

6. The method for producing the oxide catalyst according to claim 5, wherein the slurry has a pH of 8 or lower.

7. The method for producing the oxide catalyst according to claim 5, wherein the calcination step comprises:

a preliminary calcination step of preliminarily calcining the dried product at a temperature of 200 to 300°

C. to obtain a preliminarily calcined product; and

a final calcination step of finally calcining the preliminarily calcined product thus obtained at a temperature of 300°

C. or higher to obtain the catalyst.