Ammoxidation catalyst for propylene, manufacturing method of the same catalyst, ammoxidation method using the same catalyst

Patent metadata

Field	Value
Publication number	US-12569835-B2
Application number	US-202117778744-A
Country	US
Kind code	B2
Filing date	Jul 13, 2021
Priority date	Jul 14, 2020
Publication date	Mar 10, 2026
Grant date	Mar 10, 2026

Abstract

The present disclosure relates to an ammoxidation catalyst for propylene, a manufacturing method of the same, and an ammoxidation method of propylene using the same. Specifically, in one embodiment of the present disclosure, there is provided a catalyst having a structure in which a metal oxide is supported on a silica support having a narrow particle size distribution, and excellent wear resistance.

First claim

The invention claimed is:

1 . An ammoxidation catalyst for propylene comprising:
a silica support containing a pore having a diameter of 2 to 15 nm and an apparent density of 0.25 to 1.0 g/cc; and a metal oxide represented by the following Chemical Formula 1 supported on the silica support,
Mo 12 Bi a Fe b A c B d C e O x ;  Chemical Formula 1:

wherein in Chemical Formula 1, A is at least one element of Ni, Mn, Co, Zn, Mg, Ca and Ba, B is at least one element of Li, Na, K, Rb and Cs, C is at least one element of Cr, W, B, Al, Ca and V, a to e and x are each a fraction of an atom or atomic group, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 2, e is 0 to 10, and x is 24 to 48.

2 . The ammoxidation catalyst of claim 1 ,
wherein the silica support contains a pore having a diameter of 2 to 13 nm.

3 . The ammoxidation catalyst of claim 1 ,
wherein the silica support has an apparent density of 0.3 to 1.0 g/cc.

4 . The ammoxidation catalyst of claim 1 ,
wherein the silica support has a D50 particle diameter of 50 to 150 μm.

5 . The ammoxidation catalyst of claim 1 ,
wherein the silica support has an ammonia (NH 3 ) desorption amount of 1.3 mmol/g or less, and greater than 0.0, measured by an ammonia temperature programmed desorption method.

6 . The ammoxidation catalyst of claim 1 ,
wherein the Chemical Formula 1 is the following Chemical Formula 1-1:
Mo 12 Bi a Fe b Co c K d O x   Chemical Formula 1-1

in the Chemical Formula 1-1, each definition of a to d and x is the same as in claim 1 .

7 . The ammoxidation catalyst of claim 1 ,
wherein a weight ratio of the metal oxide to the silica support is 15:85 to 35:65.

8 . The ammoxidation catalyst of claim 1 , wherein the catalyst comprises:
a silica support containing a second pore; an inner coating layer continuously coating a wall surface of the second pore and comprising the metal oxide represented by the Chemical Formula 1; and a first pore positioned inside the second pore and occupying an empty space excluding the inner coating layer.

9 . The ammoxidation catalyst of claim 1 ,
wherein the catalyst has a D10 particle size, a D50 particle size and a D90 particle size satisfying a relationship of Equation 1 below:
( D 90− D 10)/ D 50≤2.0  Equation 1.

10 . The ammoxidation catalyst of claim 1 ,
wherein the catalyst has an attrition loss of 10% or less according to an ASTM9797-00 method.

11 . A manufacturing method of an ammoxidation catalyst for propylene comprising the steps of:
preparing a first precursor aqueous solution containing a Mo precursor; preparing a second precursor aqueous solution containing a Bi precursor, a Fe precursor, an A precursor, and a B precursor, wherein the A precursor comprises at least one of Ni, Mn, Co, Zn, Mg, Ca, and Ba, and the B precursor comprises at least one of Li, Na, K, Rb and Cs; supporting a mixture of the first and second precursor aqueous solutions on a silica support containing a pore having a diameter of 2 to 15 nm and an apparent density of 0.25 to 1.0 g/cc; drying the silica support on which the mixture of the first and second precursor aqueous solutions is supported; and calcining the dried material.

12 . The manufacturing method of claim 11 ,
wherein in the preparing of the second precursor aqueous solution, the second precursor aqueous solution contains a Bi precursor, a Fe precursor, a Co precursor, and a K precursor.

13 . The manufacturing method of claim 11 ,
wherein in the preparing of the second precursor aqueous solution, the second precursor aqueous solution further contains a C precursor, wherein the C precursor comprises at least one of Cr, W, B, Al, Ca and V.

14 . The manufacturing method of claim 11 ,
wherein the mixture of the first and second precursor aqueous solutions has a molar ratio of the metals satisfying a stoichiometric molar ratio of the following Chemical Formula 1:
Mo 12 Bi a Fe b A c B d C e O x   Chemical Formula 1

in the Chemical Formula 1, A is at least one element of Ni, Mn, Co, Zn, Mg, Ca and Ba, B is at least one element of Li, Na, K, Rb and Cs, C is at least one element of Cr, W, B, Al, Ca and V, a to e and x are each a fraction of an atom or atomic group, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 2, e is 0 to 10, and x is 24 to 48.

15 . The manufacturing method of claim 11 ,
wherein the drying of the silica support on which the mixture of the first and second precursor aqueous solutions is supported comprises the steps of:
primarily vacuum-drying the silica support on which the mixture of the first and second precursor aqueous solutions is supported at 120 to 160 mbar; and
secondarily vacuum-drying the primarily vacuum-dried material at 30 to 50 mbar.

16 . The manufacturing method of claim 15 ,
further comprising a step of tertiarily drying the secondarily vacuum-dried material at atmospheric pressure.

17 . The manufacturing method of claim 11 ,
wherein the calcining of the dried material is carried out at 500 to 700° C.

18 . An ammoxidation method of propylene, comprising the step of reacting propylene and ammonia in the presence of the catalyst of claim 1 in a reactor.

Assignees

• Lg Chemical Ltd

Inventors

• Kang Kyungyeon
• Kim Ji Yeon
• Choi Jun Seon

Classifications

• B01J35/397

  Egg shell like · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• B01J35/38

  Abrasion or attrition resistance · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J35/647

  2-50 nm · CPC title