Bismuth molybdate-based catalyst having zeolite coating layer, method of preparing the same, and method of preparing 1,3-butadiene using the same

Patent metadata

Field	Value
Publication number	US-9925525-B2
Application number	US-201414427207-A
Country	US
Kind code	B2
Filing date	Nov 18, 2014
Priority date	Nov 18, 2013
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

The present invention relates to a bismuth molybdate-based composite oxide catalyst having a microporous zeolite coating layer on the surface thereof and thus having high selectivity for 1,3-butadiene, a method of preparing the same, and a method of preparing 1,3-butadiene using the same. The catalyst has a microporous zeolite coating layer, and thus enables only gaseous products (light) to selectively pass through the zeolite coating layer, improving selectivity for 1,3-butadiene.

First claim

The invention claimed is:

1. A bismuth molybdate-based composite oxide catalyst for preparing 1,3-butadiene, comprising:
a bismuth molybdate-based composite oxide having a molar ratio of metal components of Formula 1:
Mo a Bi b Fe c Co d E e O y   [Formula 1]

wherein:
E is at least one selected from the group consisting of nickel, sodium, potassium, rubidium, and cesium;
the a, b, c, d and e each is a number from 0.001 to 1; and
the y is a value determined to adjust a valence by other element; and
a zeolite coating layer having micropores and formed on the surface of the bismuth molybdate-based composite oxide,
wherein the micropores have a diameter of 0.2 to 1.5 nm and the zeolite coating layer has a thickness of 50 to 1,000 nm.

2. The bismuth molybdate-based composite oxide catalyst according to claim 1 , wherein the E is at least one selected from the group consisting of cesium and potassium.

3. The bismuth molybdate-based composite oxide catalyst according to claim 1 , wherein the zeolite is silicon-based zeolite.

4. The bismuth molybdate-based composite oxide catalyst according to claim 1 , wherein the bismuth molybdate-based composite oxide catalyst is in the form of a pellet.

5. A method of preparing a bismuth molybdate-based composite oxide catalyst for preparing 1,3-butadiene, the bismuth molybdate-based composite oxide catalyst including a zeolite coating layer having micropores on the surface thereof, the method comprising:
1) preparing a bismuth molybdate-based composite oxide expressed by Formula 1:
Mo a Bi b Fe c Co d E e O y   [Formula 1]

wherein:
E is at least one selected from the group consisting of nickel, sodium, potassium, rubidium, and cesium;
the a, b, c, d and e each is 0.001 to 1; and
the y is a value determined to adjust a valence by other element;
2) pouring a zeolite seed solution over the prepared bismuth molybdate-based composite oxide and leaving the bismuth molybdate-based composite oxide as it is, then drying and firing the bismuth molybdate-based composite oxide to form zeolite seeds on the surface of the bismuth molybdate-based composite oxide; and
3) impregnating, into a zeolite synthesizing solution, the bismuth molybdate-based composite oxide with the zeolite seeds formed, to allow the seeds to grow, and then drying the bismuth molybdate-based composite oxide,
wherein the micropores have a diameter of 0.2 to 1.5 nm and the zeolite coating layer is formed to have a thickness of 50 to 1,000 nm.

6. The method according to claim 5 , wherein the bismuth molybdate-based composite oxide in step 1) is prepared by:
preparing a first solution including a bismuth-containing precursor; an iron-containing precursor; a cobalt-containing precursor; and precursor(s) containing at least one metal selected from the group consisting of nickel, sodium, potassium, rubidium and cesium;
adding the first solution to a second solution in which a molybdenum-containing precursor is dissolved, and then mixing the first and second solutions to induce a reaction; and
drying, forming and firing the mixed solution after the reaction.

7. The method according to claim 5 , wherein the zeolite is silicon-based zeolite.

8. The method according to claim 5 , wherein the drying in step 2) is performed by heat treatment for 5 to 100 hours at 90 to 200° C.

9. The method according to claim 5 , wherein the firing in step 2) is performed by heat treatment for 2 to 40 hours at 400 to 600° C.

10. The method according to claim 5 , wherein the drying in step 3) is performed by heat treatment for 1 to 24 hours at 110 to 200° C.

11. The method according to claim 5 , wherein the bismuth molybdate-based composite oxide catalyst is in the form of a pellet.

12. A method of preparing 1,3-butadiene, the method comprising:
filling a reactor with the bismuth molybdate-based composite oxide catalyst for preparing 1,3-butadiene according to claim 1 as a fixed bed; and
performing oxidative dehydrogenation while continuously passing reactants containing C4 compounds including n-butene through a layer of the bismuth molybdate-based composite oxide catalyst of the reactor filled with the bismuth molybdate-based composite oxide catalyst.

13. The method according to claim 12 , wherein the oxidative dehydrogenation is performed at a reaction temperature of 250 to 450° C. and at a space velocity of 50 to 5,000 h −1 based on the n-butene.

Assignees

• Lg Chemical Ltd

Inventors

• Choi Dae Heung
• Ko Dong Hyun
• Kang Jun Han
• Cha Kyong Yong
• Kim Dae Chul
• Lee Joo Hyuck
• Nam Hyun Seok
• Suh Myung Ji
• Hwang Ye Seul
• Han Jun Kyu
• Han Sang Jin

Classifications

• B01J23/002

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• B01J37/0246

  Coatings comprising a zeolite · CPC title

• C07C2523/31

  combined with bismuth · CPC title

• C07C2523/75

  Cobalt · CPC title

• B01J23/8876 Primary

  Arsenic, antimony or bismuth · CPC title