Supported double center hybrid polyethylene catalyst, process for preparing the same and use thereof

Patent metadata

Field	Value
Publication number	US-9611339-B2
Application number	US-201314394269-A
Country	US
Kind code	B2
Filing date	Apr 15, 2013
Priority date	Apr 16, 2012
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

The present invention relates to a carriered hybrid vanadium-chromium-based catalyst, characterized in the catalyst is carriered on a porous inorganic carrier and a V active site and an organic Cr active site are present on the porous inorganic carrier at the same time. The present invention further relates to a process for producing a carriered hybrid vanadium-chromium-based catalyst. The catalyst of the present invention can be used for producing ethylene homopolymers and ethylene/α-olefin copolymers. The hybrid vanadium-chromium-based catalyst can have high activity and produce polyethylene polymers having the properties of broad molecular weight distribution (Part of the products are bimodal distribution) and excellent α-olefin copolymerization characteristic.

First claim

What is claimed is:

1. A supported hybrid vanadium-chromium-based catalyst, characterized in that the catalyst is supported on a porous inorganic carrier and wherein an organic Cr active site and V active site are present on the porous inorganic carrier at the same time; wherein the organic Cr active site is in a form of

wherein each R is identical or different from each other and is a hydrocarbyl radical containing from 1 to 14 carbon atoms; and
wherein a calcined vanadium precursor forms the V active site.

2. The catalyst according to claim 1 , wherein the inorganic carrier is selected from the group consisting of silica, alumina, titania, zirconia, magnesia, calcium oxide and inorganic clays, and combinations thereof.

3. The catalyst according to claim 2 , wherein the silica is selected from the group consisting of unmodified or Ti-, Al- or F-modified amorphous porous silica gel.

4. The catalyst according to claim 2 , wherein the inorganic carrier has a pore volume of from 0.5 to 5.0 cm 3 /g.

5. The catalyst according to claim 2 , wherein the inorganic carrier has a surface area of from 50 to 600 m 2 /g.

6. The catalyst according to claim 1 , wherein the vanadium precursor of the V active site is selected from the group consisting of vanadic nitrate, vanadic phosphate, vanadic sulfate, vanadic acetate, ammonium hexafluorovanadate, vanadic acetate, vanadic nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium sulfate oxide hydrate, vanadic sulfate, vanadyl trichloride, sodium orthovanadate, sodium metavanadate, vanadyl bis(acetylacetone), vanadic triisopropoxide oxide, vanadic oxytripropoxide, vanadic acetylacetone, vanadic oxytriethoxide, vanadyl chloride, vanadic silicide, and combinations thereof.

7. The catalyst according to claim 1 , wherein an organic chromium precursor of the organic Cr active site is a compound of the following formula

wherein R, which is identical or different from each other, is a hydrocarbyl radical containing from 1 to 14 carbon atoms.

8. The catalyst according to claim 7 , wherein R is an alkyl radical or an aryl radical containing 1 to 14 carbon atoms.

9. The catalyst according to claim 7 , wherein the organic chromium precursor is selected from the group consisting of bis-trimethylsilylchromate, bis-triethylsilylchromate, bis-tributylsilylchromate, bis-triisopentylsilylchromate, bis-tri-2ethylhexylsilylchromate, bis-tridecylsilylchromate, bis-tri(tetradecyl) silylchromate, bis-tribenzylsilylchromate, bis-triphenethylsilylchromate, bis- triphenylsilylchromate, bis-tritolylsilylchromate, bis-trixylylsilylchromate, bis-trinaphthylsilylchromate, bis-triethylphenylsilylchromate, bis-trimethyl-naphthylsilylchromate, polydiphenylsilylchromate, polydiethylsilylchromate, and combinations thereof.

10. The catalyst according to claim 1 , wherein the chromium loading on the inorganic carrier is, based on the weight of chromium, from 0.01 to 10.00 wt. % of the total weight of the catalyst.

11. The catalyst according to claim 1 , wherein the chromium loading on the inorganic carrier is, based on the weight of the chromium, from 0.01 to 10.00 wt. %, based on the weight of chromium and vanadium.

Assignees

• Univ East China Science & Tech

Inventors

• Zhao Ning
• Cheng Ruihua
• He Xuelian
• Liu Zhen
• Liu Boping

Classifications

• C08F2410/04

  Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene · CPC title

• C08F4/69

  Chromium, molybdenum, tungsten or compounds thereof · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F10/02 Primary

  Ethene · CPC title