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Supported metal oxide double-active center ethylene-polymerization catalyst and its preparation method and use

A catalyst, supported technology, applied in the production of bulk chemicals, etc.

Active Publication Date: 2013-06-12
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] At present, there is no report on the use of supported vanadium oxide as the active center of olefin polymerization, and there is also no report on the introduction of supported vanadium oxide as an active component into Phillips chromium-based catalysts.

Method used

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  • Supported metal oxide double-active center ethylene-polymerization catalyst and its preparation method and use
  • Supported metal oxide double-active center ethylene-polymerization catalyst and its preparation method and use
  • Supported metal oxide double-active center ethylene-polymerization catalyst and its preparation method and use

Examples

Experimental program
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Effect test

Embodiment 1

[0077] 10g silica gel (pore volume is 1.5-1.7cm 3 / g, the surface area is 250-300m 2 / g) impregnated in an aqueous solution of vanadyl oxalate (V load is 0.48wt%), continuously stirred and impregnated in an oil bath at 40°C for 5h, then heated to 120°C for 5h, and then transferred to 120°C for oven drying for 6h; the impregnated The silica gel carrier of vanadyl oxalate is placed in a quartz fluidized bed for roasting and activation. The high-purity air is kept at 450°C for 4 hours, and the silica gel is finally cooled and transferred under nitrogen. The above roasting process is as follows: figure 1 shown. The obtained sample was impregnated with basic chromium acetate aqueous solution (0.5wt% Cr loading) again, after impregnating with continuous stirring at room temperature for 4 hours, dried at 120°C for 4 hours, and then transferred to a 120°C oven for 6 hours; the dried sample was placed in a quartz Carry out roasting activation in the fluidized bed, roast at 600°C in t...

Embodiment 2

[0079] 10g silica gel (pore volume is 1.5-1.7cm 3 / g, the surface area is 250-300m 2 / g) immersed in an aqueous solution of basic chromium acetate and ammonium metavanadate (Cr load is 0.5wt%, V load is 0.48wt%), stirred and impregnated in an oil bath at 60°C for 4h, dried at 120°C for 4h, Then transferred to 120°C oven for drying for 6 hours; the dried sample was placed in a quartz fluidized bed for calcination and activation, kept in air at 500°C for 5 hours, and then cooled and transferred naturally under the protection of nitrogen to obtain the catalyst for storage until use.

Embodiment 3

[0081] 10g silica gel (pore volume is 1.5-1.7cm 3 / g, the surface area is 250-300m 2 / g) impregnated in an aqueous solution of vanadyl sulfate (V load 0.16wt%), continuously stirred and impregnated at room temperature for 4h, dried at 120°C for 4h, and then transferred to a 120°C oven for 6h; the dried catalyst was placed in a quartz fluidized bed Roasting and activation were carried out in the oven, kept at 500°C for 4 hours in the air, and cooled naturally under the protection of nitrogen. The obtained sample was impregnated with basic chromium acetate solution (Cr load 0.5wt%) again, stirred and impregnated at room temperature for 4h, dried at 120°C for 4h, and then transferred to an oven for 6h; the dried sample was placed in a quartz fluidized bed for Roasting activation, in the air at 600°C, keep warm for 4h, and cool naturally under the protection of nitrogen, the roasting procedure is as follows figure 2 , the catalyst is obtained and stored for later use.

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Abstract

The invention discloses a supported metal oxide double-active center ethylene-polymerization catalyst and its preparation method and use. The supported metal oxide double-active center ethylene-polymerization catalyst is characterized in that a supported vanadium active ingredient is introduced to a Phillips chromium-based catalyst; and the supported metal oxide double-active center ethylene-polymerization catalyst comprises the two active ingredients and an inorganic carrier, wherein the two active ingredients comprise a chromium oxide and a vanadium oxide. The preparation method of the supported metal oxide double-active center ethylene-polymerization catalyst comprises the following steps of coating a chromium salt and a vanadium salt on the inorganic carrier according to a certain ratio by a stepwise dipping or co-dipping method, carrying out drying, and carrying out high-temperature calcination. The supported metal oxide double-active center ethylene-polymerization catalyst is a catalyst for high-efficiency preparation of polyethylene, and can be used for preparation of an ethylene homopolymer or an ethylene-alpha olefin copolymer. The supported metal oxide double-active center ethylene-polymerization catalyst has high polymerization activity. Through the supported metal oxide double-active center ethylene-polymerization catalyst, polyethylene product molecular weight distribution is wide, wherein molecular weights of a part of polyethylene products are distributed in a double-peak way; hydrogen regulation sensibility and copolymerization performances are good; and the existing equipment utilizing a Phillips catalyst to realize preparation of polyethylene can be popularized and used without reforming.

Description

technical field [0001] The invention relates to the preparation and application of a supported chromium vanadium metal oxide double active center ethylene polymerization catalyst, which is characterized in that: a loaded vanadium active component is introduced into a traditional supported Phillips chromium catalyst, and the catalyst consists of It includes an inorganic carrier and supported two active components, and the two active components include chromium oxide and vanadium oxide. The invention relates to a preparation method of a novel supported chromium-vanadium double-active center catalyst and its application in the production of ethylene homopolymer and ethylene-α-olefin copolymer. The supported chromium-vanadium double-active center catalyst has the characteristics of high activity, wide molecular weight distribution (some products show bimodal distribution), hydrogen tuning response and excellent copolymerization performance. Background technique [0002] As a ge...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F110/02C08F210/16C08F210/02C08F4/69C08F4/68C08F4/02
CPCY02P20/52
Inventor 程瑞华薛新董璇何芸何雪莲刘振刘柏平
Owner EAST CHINA UNIV OF SCI & TECH
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