Supported three-center catalyst and preparation method and application

Patent metadata

Field	Value
Publication number	US-12252575-B2
Application number	US-202017434892-A
Country	US
Kind code	B2
Filing date	May 9, 2020
Priority date	May 9, 2019
Publication date	Mar 18, 2025
Grant date	Mar 18, 2025

Abstract

A supported three-center catalyst, a preparation method and the use are provided. The catalyst comprises a porous inorganic carrier, an organic chromium active component, an inorganic chromium active component and an inorganic vanadium active component, and may further comprise a catalyst modifying component. A method involves, by means of one or more steps of dipping and drying or dipping, drying and high-temperature roasting procedures, respectively converting an organic chromium source, a chromium source, a vanadium source and a Q component into an organic chromium active component precursor, an inorganic chromium active component precursor, an inorganic vanadium active component precursor and a catalyst modifying component that are supported on the surface of the porous inorganic carrier, and then activating same with an organometallic cocatalyst or a polymerization monomer, so as to obtain the supported three-center catalyst.

First claim

The invention claimed is:

1. A supported three-center catalyst, wherein:
the three-centered catalyst comprises a porous inorganic carrier, an organic chromium active component, an inorganic chromium active component, an inorganic vanadium active component, and optionally, a catalyst modification component;
the organic chromium active component is obtained after a precursor of the organic chromium active component is activated by an organometallic co-catalyst or a polymerization monomer, and the precursor of the organic chromium active component is obtained by loading an organic chromium source comprising at least one of a cyclopentadienyl ligand, an indenyl ligand, a fluorenyl ligand, a cyclopentadienyl derivative ligand, an indenyl derivative ligand, or a fluorenyl derivative ligand onto the surface of the porous inorganic carrier;
the inorganic chromium active component is obtained by activating a precursor of the inorganic chromium active component by an organometallic co-catalyst or a polymerization monomer, and the precursor of the inorganic chromium active component is a high-temperature calcined product of a chromium source on the surface of the porous inorganic carrier;
the inorganic vanadium active component is obtained after a precursor of the inorganic vanadium active component is activated by an organometallic co-catalyst or a polymerization monomer, and the precursor of the inorganic vanadium active component is a high-temperature calcined product of a vanadium source on the surface of the porous inorganic carrier;
the catalyst modification component is a high-temperature calcined product of a compound comprising sulfur, phosphorus or halogen element on the surface of the porous inorganic carrier, wherein the compound comprising sulfur, phosphorus or halogen element is referred to as a component Q;
the organometallic co-catalyst comprises at least one of an organoaluminum compound, an organolithium compound, or an organoboron compound, wherein the organoaluminum compound is at least one of trialkyl aluminum AlR 3 , dialkyl aluminum alkoxide AlR 2 OR, dialkyl aluminum halide AlR 2 X, aluminoxane, or ethyl sesquialuminum chloride, wherein R is an alkyl group, and wherein X is halogen; and
the polymerization monomer is ethylene or α-olefins.

2. The supported three-center catalyst according to claim 1 , wherein:
the organic chromium source has a structure according to the following formula CrCp* 1 Cp* 2 , wherein Cp* 1 and Cp* 2 are both cyclopentadienyl or derivatives thereof, indenyl or derivatives thereof, or fluorenyl or derivatives thereof, and whether Cp* 1 and Cp* 2 have the same structure is not limited; wherein the structure of Cp* 1 and Cp* 2 is one of the following structures:

wherein:
each R is independently an aliphatic, alicyclic, or aromatic hydrocarbyl group with 1 to 20 carbon atoms, and n is an integer from 0 to 5;
each Ra and each Ra′ is independently an aliphatic, alicyclic, or aromatic hydrocarbyl group with 1 to 10 carbon atoms, m is an integer from 0 to 4; and x is an integer from 0 to 3;
each Rb and each Rb′ is independently an aliphatic, alicyclic, or aromatic hydrocarbyl group with 1 to 10 carbon atoms, m′ and m″ are each an integer from 0 to 4, Y is H, Rb, or Rb′, and z is 0 or 1;

the chromium source is selected from at least one of chromium trioxide, chromium nitrate, chromium acetate, chromium chloride, chromium sulfate, ammonium chromate, ammonium dichromate, or chromium acetate hydroxide;
the vanadium source is selected from at least one of ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium (IV) oxide sulfate hydrate, vanadium (III) sulfate, vanadium oxytrichloride, sodium orthovanadate, sodium metavanadate, a non-water-soluble vanadium-containing salt, vanadium triisopropoxy oxide, vanadium (V) oxytripropoxide, vanadium acetylacetonate, vanadium oxytriethoxide, vanadyl chloride, or vanadium silicide;
the component Q is selected from: sulfuric acid, persulfuric acid, pyrosulfuric acid, sulfurous acid, taurine, ammonium sulfate, ammonium sulfite, ammonium persulfate, titanium sulfate, zirconium sulfate, vanadium sulfate, iron sulfate, ferrous sulfate, ammonium ferrous sulfate, nickel sulfate, zinc sulfate, aluminum sulfate, tin sulfate, antimony sulfate, phosphoric acid, pyrophosphoric acid, superphosphoric acid, phosphorous acid, metaphosphoric acid, ammonium phosphate, ammonium pyrophosphate, ammonium superphosphate, ammonium phosphite, ammonium hypophosphite, ammonium metaphosphate, titanium phosphate, zirconium phosphate, iron phosphate, nickel phosphate, zinc phosphate, aluminum phosphate, tin phosphate, antimony phosphate, hydrofluoric acid, ammonium fluoride, fluorosilicic acid, fluoroboric acid, ammonium fluoroborate, ammonium bifluoride, ammonium hexafluorosilicate, boron trifluoride, aluminum fluoride, antimony fluoride, ammonium hexafluorophosphate, ammonium hexafluorotitanate, hydrochloric acid, chlorosulfonic acid, ammonium chloride, ferrous chloride, ferric chloride, aluminum chloride, titanium tetrachloride, hydrobromic acid, ammonium bromide, iron bromide, ferrous bromide or aluminum bromide, or any combination thereof; and
the porous inorganic carrier is at least one of silicon oxide, aluminum oxide, aluminosilicate, inorganic clay, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, iron oxide, tin oxide, zinc oxide, boron oxide, tungsten oxide, or niobium oxide; and
the porous inorganic carrier has a specific surface area of 50-800 m 2 /g, a pore volume of 0.1-5.0 cm 3 /g, and an average pore size of 1-50 nm.

3. The supported three-center catalyst according to claim 1 , wherein:
in the supported three-center catalyst, a content of Cr in the precursor of the organic chromium active component is 0.1-12 wt % based on a total weight of the supported three-center catalyst; a content of Cr in the precursor of the inorganic chromium active component is 0.05-12 wt % based on the total weight of the supported three-center catalyst; a content of V in the precursor of the inorganic vanadium active component is 0.05-10 wt % based on the total weight of the supported three-center catalyst; and a content of sulfur, phosphorus and halogen elements in the catalyst modification component is 0.1-20 wt % based on the total weight of the supported three-center catalyst.

4. The supported three-center catalyst according to claim 1 , wherein an active center precursor structure of the supported three-center catalyst is as follows:

wherein structure a is the precursor of the inorganic chromium active component, structure b is the precursor of the inorganic vanadium active component, structure c is the precursor of the organic chromium active component, and L in structure c is one of cyclopentadienyl or a derivative thereof, indenyl or a derivative thereof, or fluorenyl or a derivative thereof.

5. A method for preparing the supported three-center catalyst according to claim 1 , wherein:
the preparation steps of the supported three-center catalyst comprise preparation of a precursor of the supported three-center catalyst and activation of the precursor of the supported three-center catalyst;
when the supported three-center catalyst comprises the porous inorganic carrier, the organic chromium active component, the inorganic chromium active component, the inorganic vanadium active component, and the catalyst modification component, the preparation of the precursor of the supported three-center catalyst comprises the following steps:
(1.1)

Assignees

• Univ South China Agricult

Inventors

• Jin Yulong
• Liu Boping

Classifications

• B01J31/36

  of vanadium, niobium or tantalum · CPC title

• B01J31/34

  of chromium, molybdenum or tungsten · CPC title

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F210/16

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

• C08F110/02 Primary

  Ethene · CPC title