Method and catalyst for selective oligomerization of ethylene

Patent metadata

Field	Value
Publication number	US-11298693-B2
Application number	US-201916446454-A
Country	US
Kind code	B2
Filing date	Jun 19, 2019
Priority date	Jun 22, 2018
Publication date	Apr 12, 2022
Grant date	Apr 12, 2022

Abstract

The present disclosure provides a method and a catalyst for selective oligomerization of ethylene. The raw material for the catalyst consists of a dehydropyridine annulene-type ligand, a transition metal compound, and an organometallic compound in a molar ratio of 1:0.5-100:0.1-5000. The present disclosure also provides a method for selective oligomerization of ethylene accomplished by using the above-mentioned catalyst. The catalyst for selective oligomerization of ethylene has high catalytic activity, high selectivity for the target products 1-hexene and 1-octene, and low selectivity for 1-butene and 1-C10+.

First claim

What is claimed is:

1. A catalyst for selective oligomerization of ethylene, wherein the raw material for the catalyst consists of: a dehydropyridine annulene ligand, a transition metal compound, and an organometallic compound in a molar ratio of 1:0.5-100:0.1-5000; wherein the dehydropyridine annulene ligand has a structural formula as shown in Formula I:

with R 1 , R 2 , R 3 each independently selected from an alkyl group or an aryl group, wherein the transition metal compound is a compound of a metal from Group IVB-VIIIB, and wherein the organometallic compound is a compound containing a Group IIIA metal.

2. The catalyst according to claim 1 , wherein R 1 , R 2 , R 3 are independently selected from methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl, 2,4-dibutylphenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-dibutylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, naphthyl, anthryl, and biphenyl.

3. The catalyst according to claim 1 , wherein the dehydropyridine annulene ligand consists of a plurality of the compounds of Formula I.

4. The catalyst according to claim 1 , wherein the transition metal compound is a compound of at least one or more of chromium, molybdenum, tungsten, titanium, cobalt, tantalum, vanadium, zirconium, iron, nickel, or palladium.

5. The catalyst according to claim 4 , wherein the compound of chromium has a general formula of CrR n m , wherein R n is an organic anion or a neutral molecule, R n contains 1-10 carbon atoms, and n is an integer of 1-6.

6. The catalyst according to claim 5 , wherein the compound of chromium includes one or more of chromium acetate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, chromium diisoprene, diphenyl chromium, CrCl 3 (THF) 3 , CrCl 2 (THF) 2 , (phenyl)tricarbonylchromium, or hexacarbonylchromium.

7. The catalyst according to claim 1 , wherein the organometallic compound includes one or more of an alkyl aluminum compound, an aluminoxane compound, an organoboron compound, and an organic salt.

8. The catalyst according to claim 7 , wherein the alkyl aluminum compound includes an alkyl aluminum compound and an aluminoxane compound;
wherein the aluminoxane compound is methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and modified aluminoxane; wherein the molar ratio of the aluminoxane compound to the alkyl aluminum compound is 100-0.01:1.

9. The catalyst according to claim 7 , wherein the alkyl aluminum compound is one or more of alkyl aluminum halide, alkyl aluminum hydride, or alkyl aluminum sesquichloride.

10. The catalyst according to claim 7 , wherein the organic salt is methyl lithium or methyl magnesium bromide; the inorganic acid is a tetrafluoroboric acid ether complex; the inorganic salt is tetrafluoroborate or hexafluoroantimonate; the organoboron compound includes one or more of boroxine, sodium borohydride, triethylborane, tris(pentafluorophenyl)boron, or tributylborate.

Assignees

• Petrochina Co Ltd

Inventors

• Yu Buwei
• Jiang Tao
• Wang Sihan
• Chu Hongling
• Jiang Yan
• Huo Hongliang
• Xu Xianming
• Wang Libo
• Shao Huaiqi
• Wang Yali
• Cao Yuanyuan
• Liu Tong
• Ma Kecun
• Huang Fuling
• Wang Xiuhui
• Sun Enhao
• Wang Yulong

Classifications

• C07C2/32 Primary

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title

• B01J31/146

  of boron · CPC title

• B01J31/121

  Metal hydrides · CPC title

• C07C2531/22

  Organic complexes · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title