Supported vanadium-chromium double-center composite catalyst as well as preparation method and application thereof

Abstract

The invention belongs to the field of catalysts and discloses a supported vanadium-chromium double-center composite catalyst as well as a preparation method and application thereof. The double-centercomposite catalyst comprises a porous inorganic supporter, a catalyst modification component, a vanadium-containing active component and a chromium-containing active component. On the basis of a supported vanadium-chromium double-center vinyl polymerization catalyst, the catalyst modification component is introduced, the catalyst is applied to homopolymerization of ethylene and copolymerization catalysis of ethylene / alpha-olefin, and compared with a double-center ethylene polymerization catalyst without the catalyst modification component, the catalyst has high and stable activity and excellent comonomer intercalation performance and hydrogen regulation response, and tests show that in the presence of the catalyst modification component, two metal centers have remarkable synergetic effects. An organic metallic promoter is also introduced into the double-center composite catalyst to implement pretreatment activation on the double-center composite catalyst, and the activity of the catalyst after pretreatment activation is also remarkably better than that of a catalyst without pretreatment activation.

Description

technical field

[0001] The invention belongs to the field of catalysts, in particular to a supported vanadium and chromium double-center composite catalyst and its preparation method and application. Background technique

[0002] As a general-purpose plastic, polyethylene is widely used in various fields of industry, agriculture, automobiles, communications and daily life due to its excellent mechanical properties, electrical insulation, chemical corrosion resistance and low temperature resistance. A key factor in the performance of ethylene products is their corresponding catalyst technology. Phillips inorganic chromium catalyst produces more than 40% of high-density polyethylene in the world. Because of its wide molecular weight distribution and the ability to form a small amount of long and short branched chains in situ, it has unique rheological and processing properties, and is especially suitable for Production of large hollow containers, long-term static pressure res...

Examples

Embodiment 1

[0121] 10gSiO 2 / Al 2 o 3 (The pore volume is 1.5-1.7cm 3 / g, the surface area is 400-500m 2 / g) immersed in the aqueous solution of ammonium sulfate, vanadyl oxalate and chromium nitrate (according to the total weight of the catalyst, the loading of sulfur, vanadium and chromium is respectively 3wt%, 0.48wt% and 1wt%), 40 ℃ oil Stir and impregnate continuously under the bath for 5 hours, then heat up to 120°C and dry for 5 hours, then transfer to 120°C oven and dry for 6 hours; place the impregnated material in a quartz fluidized bed for roasting and activation, keep it in high-purity air at 500°C for 4 hours, and the roasted product is finally in The temperature was naturally lowered and cooled under nitrogen, and the obtained catalyst was preserved for later use.

Embodiment 2

[0123] 10gSiO 2 / TiO 2 (The pore volume is 1.1-1.4cm 3 / g, the surface area is 350-400m 2 / g) immersed in an aqueous solution of ammonium sulfate and vanadyl oxalate (according to the total weight of the catalyst, the loadings of sulfur and vanadium are respectively 3wt% and 0.48wt%), continuously stirred and impregnated in an oil bath at 40°C for 5h, and then Heat up to 120°C for 5 hours, then transfer to 120°C oven for 6 hours; place the impregnated material in a quartz fluidized bed for calcination and activation, keep it in high-purity air at 500°C for 4 hours, and finally cool the calcined product naturally under nitrogen, then in Transfer to a two-necked flask under nitrogen protection, and then configure a certain concentration of bistriphenylsilane chromate (synthetic method with reference to "Wang Jun, Li Yun, Li Cuiqin, etc. Research on the synthesis process of bistriphenylsilane chromate [J].Chemical Industry and Engineering, 2012,29(1):21-25 ") n-hexane solution...

Embodiment 3

[0125] 10gSiO 2 / ZnO 2 (The pore volume is 1.1-1.3cm 3 / g, the surface area is 300-400m 2 / g) immersed in an aqueous solution of ammonium sulfate and vanadyl oxalate (according to the total weight of the catalyst, the loadings of sulfur and vanadium are respectively 3wt% and 0.48wt%), continuously stirred and impregnated in an oil bath at 40°C for 5h, and then Heat up to 120°C for 5 hours, then transfer to 120°C oven for 6 hours; place the impregnated material in a quartz fluidized bed for calcination and activation, keep it in high-purity air at 500°C for 4 hours, and finally cool the calcined product naturally under nitrogen, then in Transfer to a two-necked flask under the protection of nitrogen, and then configure a certain concentration of bisindenyl chromium (refer to "FREDERICK J.KAROL, WILLIAML.MUNN, GEORGE L.GOEKE, et al.Supported Bis(indenyl)-and Bis( fluorenyl)-Chromium Catalysts for EthylenePolymerization.JOURNAL OF POLYMER SCIENCE.Vol.16,771-778(1978)") n-hexane...

technical field

[0001] The invention belongs to the field of catalysts, in particular to a supported vanadium and chromium double-center composite catalyst and its preparation method and application. Background technique

[0002] As a general-purpose plastic, polyethylene is widely used in various fields of industry, agriculture, automobiles, communications and daily life due to its excellent mechanical properties, electrical insulation, chemical corrosion resistance and low temperature resistance. A key factor in the performance of ethylene products is their corresponding catalyst technology. Phillips inorganic chromium catalyst produces more than 40% of high-density polyethylene in the world. Because of its wide molecular weight distribution and the ability to form a small amount of long and short branched chains in situ, it has unique rheological and processing properties, and is especially suitable for Production of large hollow containers, long-term static pressure res...

Examples

Embodiment 1

[0121] 10gSiO 2 / Al 2 o 3 (The pore volume is 1.5-1.7cm 3 / g, the surface area is 400-500m 2 / g) immersed in the aqueous solution of ammonium sulfate, vanadyl oxalate and chromium nitrate (according to the total weight of the catalyst, the loading of sulfur, vanadium and chromium is respectively 3wt%, 0.48wt% and 1wt%), 40 ℃ oil Stir and impregnate continuously under the bath for 5 hours, then heat up to 120°C and dry for 5 hours, then transfer to 120°C oven and dry for 6 hours; place the impregnated material in a quartz fluidized bed for roasting and activation, keep it in high-purity air at 500°C for 4 hours, and the roasted product is finally in The temperature was naturally lowered and cooled under nitrogen, and the obtained catalyst was preserved for later use.

Embodiment 2

[0123] 10gSiO 2 / TiO 2 (The pore volume is 1.1-1.4cm 3 / g, the surface area is 350-400m 2 / g) immersed in an aqueous solution of ammonium sulfate and vanadyl oxalate (according to the total weight of the catalyst, the loadings of sulfur and vanadium are respectively 3wt% and 0.48wt%), continuously stirred and impregnated in an oil bath at 40°C for 5h, and then Heat up to 120°C for 5 hours, then transfer to 120°C oven for 6 hours; place the impregnated material in a quartz fluidized bed for calcination and activation, keep it in high-purity air at 500°C for 4 hours, and finally cool the calcined product naturally under nitrogen, then in Transfer to a two-necked flask under nitrogen protection, and then configure a certain concentration of bistriphenylsilane chromate (synthetic method with reference to "Wang Jun, Li Yun, Li Cuiqin, etc. Research on the synthesis process of bistriphenylsilane chromate [J].Chemical Industry and Engineering, 2012,29(1):21-25 ") n-hexane solution...

Embodiment 3

[0125] 10gSiO 2 / ZnO 2 (The pore volume is 1.1-1.3cm 3 / g, the surface area is 300-400m 2 / g) immersed in an aqueous solution of ammonium sulfate and vanadyl oxalate (according to the total weight of the catalyst, the loadings of sulfur and vanadium are respectively 3wt% and 0.48wt%), continuously stirred and impregnated in an oil bath at 40°C for 5h, and then Heat up to 120°C for 5 hours, then transfer to 120°C oven for 6 hours; place the impregnated material in a quartz fluidized bed for calcination and activation, keep it in high-purity air at 500°C for 4 hours, and finally cool the calcined product naturally under nitrogen, then in Transfer to a two-necked flask under the protection of nitrogen, and then configure a certain concentration of bisindenyl chromium (refer to "FREDERICK J.KAROL, WILLIAML.MUNN, GEORGE L.GOEKE, et al.Supported Bis(indenyl)-and Bis( fluorenyl)-Chromium Catalysts for EthylenePolymerization.JOURNAL OF POLYMER SCIENCE.Vol.16,771-778(1978)") n-hexane...

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