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Multi-center supported catalyst as well as preparation method and application thereof

A supported catalyst, multi-center technology, applied in chemical instruments and methods, organic chemistry, titanium organic compounds, etc.

Active Publication Date: 2021-03-26
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Over the years, there have been many reports on the modification of Phillips chromium-based catalysts in the literature, but fewer reports on the modification of S-2 and S-9 catalysts, especially fewer reports on the modification of S-9 catalysts

Method used

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  • Multi-center supported catalyst as well as preparation method and application thereof
  • Multi-center supported catalyst as well as preparation method and application thereof
  • Multi-center supported catalyst as well as preparation method and application thereof

Examples

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preparation example Construction

[0149] The present invention also provides a preparation method for the above-mentioned supported multi-center composite catalyst, comprising the steps of:

[0150] Step 1, impregnating the carrier with a solution containing a vanadium source, drying and calcining;

[0151] Step 2, subjecting the carrier obtained in step 1 to dehydration and deoxidation activation treatment; and

[0152] Step 3, impregnating the activated support obtained in step 2 with a solution including an organic chromium source and a pyrrolene heterocyclic compound to obtain a multi-center supported catalyst;

[0153] Described organic chromium source comprises following structure:

[0154] R'-Cr-R

[0155] wherein R and R' are independently substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl;

[0156] The pyrrolene heterocyclic compound has the following formula I structure:

[0157]

[0158] Among them, R 1 , R 2 and R 3 independently selected from H, CH 3 -, saturated or dou...

Embodiment 1

[0191] Inorganic carrier-supported multi-center composite catalyst, wherein the inorganic carrier is silica (the pore volume is 0.8cm 3 / g; the surface area of ​​the inorganic carrier is 380m 2 / g); The inorganic vanadium source is vanadium nitrate, the organic chromium source is two (cyclopentadiene) chromium (II), and the pyrrolene heterocyclic compound is [(η 5 -C 9 h 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Zr(NMe 2 ) 2 .

[0192] The preparation method of pyrrololene heterocyclic compound is: the 3-CH 3 -4-CH 3 -5-CH 3 -2-Pyrrole formaldehyde and indene are cooled to -10°C, tetrahydropyrrole is added dropwise, the ratio of the three substances is 1:2:1, and then raised to room temperature and stirred for 10 hours to obtain nitrogen-containing fulvene; then cool down To -4°C, add lithium aluminum hydride dropwise, the molar ratio of nitrogen-containing fulvene to lithium aluminum hydride is 1:2, heat up to 70°C, stir and react for 10 hours to obtain a ligan...

Embodiment 2

[0195] Inorganic carrier-supported multi-center composite catalyst, wherein the inorganic carrier is silica (the pore volume is 1.3cm 3 / g; the surface area of ​​the inorganic carrier is 590m 2 / g); The inorganic vanadium source is vanadium sulfate, the organic chromium source is two (ethylcyclopentadiene) chromium (II), and the pyrrolene heterocyclic compound is [(η 5 -C 9 h 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 .

[0196] The preparation method of the pyrrololene heterocyclic compound is: the 3-CH 3 -4-CH 3 -2-Pyrrole formaldehyde and indene are cooled to -5°C, tetrahydropyrrole is added dropwise, the ratio of the three substances is 1:2:2, and then raised to room temperature and stirred for 5 hours to obtain nitrogen-containing fulvene; then cool down To -6°C, add lithium aluminum hydride dropwise, the molar ratio of nitrogen-containing fulvene to lithium aluminum hydride is 1:0.5, raise the temperature to 60°C, stir and react for 15 hours to obtain a...

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Abstract

The invention discloses a multi-center supported catalyst and a preparation method and application thereof. The multi-center supported catalyst comprises a carrier and active components, wherein the active components are vanadium oxide, a chromium-containing organic compound and a pyrrole metallocene heterocyclic compound, and the vanadium oxide, the chromium-containing organic compound and the pyrrole metallocene heterocyclic compound are loaded on the carrier; the chromium-containing organic compound comprises the following structure: Cr-R, and R is substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; the pyrrole metallocene heterocyclic compound has a structure shown as a formula I in the description, R1, R2 and R3 are respectively and independently selected from one ofH, CH3- and saturated or double-bond-containing straight-chain or branched-chain C2-C10 alkyl; R4 is a straight-chain or branched-chain C1-C5 alkyl group; and M is Ti or Zr. The catalyst provided by the invention has excellent copolymerization performance and can be used for producing ethylene homopolymers and ethylene / alpha-olefin copolymers.

Description

technical field [0001] The invention relates to an inorganic carrier-supported organometallic multi-center composite polyethylene catalyst, a preparation method and application thereof. Background technique [0002] Polyethylene is the variety with the largest output among general-purpose synthetic resins. It has the characteristics of chemical resistance, good mechanical strength, and electrical insulation; polypropylene is a thermoplastic synthetic resin with excellent performance, which is non-toxic, stable in chemical properties, It has the advantages of easy processing and other advantages, and is the product with the best heat resistance among general-purpose resins. Both polyethylene and polypropylene are widely used in human daily life, medical care, industry and agriculture, etc. These polyolefin products with excellent performance are closely related to the catalysts used. [0003] At present, the widely used industrial polyethylene catalysts mainly include Ziegle...

Claims

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Application Information

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IPC IPC(8): C08F10/00C08F110/02C08F210/16C08F210/14C08F4/02C08F4/69C08F4/685C08F4/6592C07F17/00C07F7/28C07F7/00
CPCC08F10/00C08F110/02C08F210/16C07F17/00C07F7/28C07F7/00C08F4/025C08F4/685C08F4/69C08F210/14C08F2500/04C08F4/6592
Inventor 王立娟张瑞任鹤王文燕孙彬彬杨琦和树立王华牛娜李冬霞宋磊杨国兴邹恩广张丽洋
Owner PETROCHINA CO LTD
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