Nickel-based oligomerization catalysts and method for oligomerizing light olefins using the same

Patent metadata

Field	Value
Publication number	US-12042787-B2
Application number	US-201917297522-A
Country	US
Kind code	B2
Filing date	Nov 29, 2019
Priority date	Nov 30, 2018
Publication date	Jul 23, 2024
Grant date	Jul 23, 2024

Abstract

In the present disclosure, a heterogeneous nickel-based oligomerization catalyst in which nickel in the form of single atom is loaded on an Al-mesoporous silicate support by ion exchange and a method for producing the same, and a method for oligomerizing light olefins, specifically C4 olefins using the catalyst are described.

First claim

The invention claimed is:

1. A method for producing a heterogeneous oligomerization catalyst, the method comprising:
a) providing a Na-type Al-mesoporous silicate having a Si/Al atomic ratio in a range of 5 to 20 as a support, wherein aluminum (Al) forms acid sites on the mesoporous silicate and Na + ions are bound to the acid sites;
b) ion exchanging the Na + ions bound to the acid sites of the Na-type Al-mesoporous silicate with nickel ions using a nickel compound having an oxidation number of 2+, wherein the nickel ions are exchanged with the bound Na + ions, thereby being bound to the Al-mesoporous silicate; and
c) performing heat treatment of the Al-mesoporous silicate containing the exchanged nickel ion,
wherein nickel is supported on the support in a form of single atom of Ni and an amount of nickel supported is in a range of 0.1% to 10% by weight,
wherein an acid amount of the catalyst is less than 50 μmol/g, and
wherein a molar ratio of nickel (Ni)/aluminum (Al) is in a range of 0.3 to 1.

2. The method according to claim 1 , wherein at least 95% of Na + ions bound to acid sites of the Na-type Al-mesoporous silicate is exchanged with a nickel ion in the step b).

3. The method according to claim 1 , wherein the Al-mesoporous silicate is at least one selected from an AlMCM-based silicate or an AlSBA-based silicate.

4. The method according to claim 3 , wherein the Al-mesoporous silicate is at least one selected from AlMCM-48 or AlMCM-41.

5. The method according to claim 1 , wherein the Al-mesoporous silicate has a specific surface area (BET) of 200 to 1200 m 2 /g, a pore volume of 0.3 to 0.6 cc/g, and an average pore diameter of 18 to 40 Å.

6. The method according to claim 1 , wherein the nickel compound having an oxidation number of 2+is at least one selected from the group consisting of nickel nitrate, nickel sulfate, nickel phosphate, nickel halide, nickel carboxylate, nickel hydroxide, and nickel carbonate.

7. The method according to claim 1 , wherein a nickel concentration in an aqueous solution of the nickel compound having an oxidation number of 2+used during the ion exchange in the step b) is in a range of 0.01 to 10 M.

8. The method according to claim 7 , wherein ion exchange in the step b) is performed at 50° C. to 100° C.

9. The method according to claim 1 , wherein the step c) is carried out at 250° C. to 1000° C. in an oxygen-containing atmosphere.

10. The method according to claim 1 , wherein the step b) is carried out by directly ion exchanging the Na + ions of the Na-type Al-mesoporous silicate with nickel ions without passing through an exchange with ammonium ions.

11. The method according to claim 1 , wherein the oligomerization catalyst has a specific surface area (BET) of 150 to 1000 m 2 /g, a pore volume of 0.2 to 0.5 cc/g, and an average pore diameter of 10 to 35 Å.

12. The method according to claim 1 , wherein a particle size (diameter) of the oligomerization catalyst is in a range of 1 to 500 μm.

13. The method according to claim 1 , wherein the oligomerization catalyst substantially free of nickel oxide (NiO).

Assignees

• Sk Innovation Co Ltd
• Sk Geo Centric Co Ltd

Inventors

• Choi Jae Suk
• Kim Ka Young
• Kim Hee Soo
• Im Ju Hwan
• Choo Dae Hyun
• Lee Ho Won
• Lim Je Mi

Classifications

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J29/0356

  Iron group metals or copper · CPC title

• B01J35/647

  2-50 nm · CPC title

• B01J35/633

  less than 0.5 ml/g · CPC title

• B01J35/618

  more than 1000 m2/g · CPC title