CN103145897B

CN103145897B - The preparation and application of a kind of load metal oxide double activity center ethylene rolymerization catalyst

Info

Publication number: CN103145897B
Application number: CN201210118427.2A
Authority: CN
Inventors: 程瑞华; 薛新; 董璇; 何芸; 何雪莲; 刘振; 刘柏平
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2012-04-20
Filing date: 2012-04-20
Publication date: 2017-12-29
Anticipated expiration: 2032-04-20
Also published as: CN103145897A

Abstract

The preparation and application of a kind of supported chrome vanadium metal oxide double activity center ethylene rolymerization catalyst.It is characterized in that：The vanadium active component of load is introduced on Phillips chromium-based catalysts.The catalyst composition includes two kinds of active components of inorganic carrier and load, and two kinds of active components include chromated oxide and barium oxide.The preparation method of the catalyst is：By the method for substep or co-impregnation, chromic salts and vanadic salts are immersed on inorganic carrier according to certain ratio, obtained after drying by high-temperature roasting.Support type chrome alum double activity center catalyst described in the invention is a kind of catalyst for efficiently preparing polyethylene, available for the homopolymer or ethene and the copolymer of alhpa olefin for preparing ethene.Polymerization catalyst activity height, polyethylene product molecular weight distribution wide (portioned product is in bimodal distribution), hydrogen response and copolymerization performance are good, the existing device using Phillips catalyst preparation polyethylene need not be transformed, you can facilitate popularization and application.

Description

A kind of preparation of load metal oxide double activity center ethylene rolymerization catalyst and Using

Technical field

The present invention relates to a kind of preparation of supported chrome vanadium metal oxide double activity center ethylene rolymerization catalyst and answer With, it is characterised in that：The vanadium active component of load is introduced on traditional support type Phillips chromium-based catalysts, described urges Agent composition includes two kinds of active components of inorganic carrier and load, and two kinds of active components include chromated oxide and barium oxide. The present invention relates to the preparation method of novel supported chrome alum double activity center catalyst and its Alathon and ethene and α- Application in olefin copolymer production.The active high, wide (portion of molecular weight distribution of the support type chrome alum double activity center catalyst Point product be in bimodal distribution), hydrogen adjusts and responds and the characteristics such as copolymerization performance is superior.

Background technology

Polyethylene as a kind of general plastics, due to its excellent mechanical property, electrical insulating property, chemical resistance and Resistance to low temperature, it is widely used in the every field of industry, agricultural, automobile, communication and daily life, these have Optimality The polyethylene product of energy has close relationship with used catalyst.Phillips chromium-based catalysts produce in the world 40% or so high density polyethylene (HDPE), because its product carries a small amount of long-chain branch, thus with unique rheology and processability Can, especially suitable for the Gas Pipe and feed pipe, automotive oil tank etc. of processing Large Hollow Container, resistance to long term hydrostatic, and these are produced Can not also be by Ziegler-Natta catalyst, new metallocene catalyst and late transition metal polyolefin catalyst before items Product is substituted.At present, Phillips catalyst has very important status in polyolefin industry production, in recent years China also increases Phillips polyethylene process and the introduction dynamics of device technique.

Phillips catalyst is two researchers of J.P Hogan and R.L.Bank by Phillips oil companies earliest Reported in patent US2825721.The patent have studied at different conditions using chromium oxide as raw material, including polymerization temperature, The ratio between polymerization time, monomer concentration and catalyst amount, the load chromium content of catalyst, support modification, catalyst preparation conditions etc., it is right The influence of Phillips catalyst olefinic polymerization performances.Later, US4295997, US4528338, US5401820 developed Phillips catalyst, for example the chromic salt of hypotoxicity is used as raw material, to avoid the CrO using high toxic₃Raw material.

Traditional vanadium series catalyst is used in homogeneous Ziegler-Natta catalyst vinyl polymerization system, is mainly used in adjusting The molecular weight distribution of Ziegler-Natta catalyst product and the distribution situation of comonomer are saved, to enhance product performance, performance ：The polymer molecular weight narrow distribution of production, molecular weight are higher；Ethylene/alpha-olefin copolymer is produced, and comonomer inserts Measure more；Can also synthesis of syndiotactic polypropylene etc..

Zakharov etc. has been investigated VCl₄It is supported on MgCl₂The polymerization of catalyst is prepared on carrier, finds the catalysis Agent can produce the polyethylene of wide molecular weight distribution, and have very high response to hydrogen tune, reference can be made to document Chinese Journal Of Polymer Science, 2008,26,553-559.

Patent US4199475 has reported the catalyst for being supported on tetraethyl titanate and vanadium oxytrichloride and being prepared on silica gel, With very high ethylene polymerization activity.

At present, correlation there is no to use report of the load-type vanadium oxide as olefinic polyreaction activated centre, equally The relevant report of Phillips chromium-based catalysts is not introduced using load-type vanadium oxide as active component.

The content of the invention

It is an object of the present invention to produce a kind of to efficiently synthesize the new of Alathon and ethene and alpha olefin copolymer Chrome alum double activity center catalyst, the polyethylene that it is produced is set to improve comonomer on the premise of ensureing that molecular weight distribution is wide Content and its distribution, it is reduced in low molecule amount end insertion, and increase in HMW end insertion, so as to easily be formed More tie molecules, the more preferable polyethylene product of performance is developed, while also there is catalyst higher activity, hydrogen to adjust response Performance etc..

The present invention provides a kind of preparation method of support type chrome alum double activity center catalyst, it is therefore an objective to which preparing one kind will Chromium, barium oxide are supported on double activity center's ethylene rolymerization catalyst on inorganic carrier.Present invention also offers the support type Chrome alum double activity center catalyst is in ethylene homo and ethene and the application in alpha-olefin copolymer.

Inorganic carrier of the present invention is selected from silica, alundum (Al2O3), titanium dioxide, zirconium oxide, magnesia, oxidation Calcium, inorganic clay and combinations thereof, the inorganic clay can include such as montmorillonite.According to one of present invention implementation Scheme, the inorganic carrier are selected from silica gel, particularly unformed Bio-sil.These carriers are it is known in the art that can be with business Purchase is synthesized by known method.As an example of silica gel, it can be mentioned that Davison 955.

According to one embodiment of the invention, the specific surface area of inorganic carrier used is generally in 50~500m²/ g, preferably 100~300m²/ g, the pore volume of inorganic carrier is 0.1~5.0cm³/ g, preferably 0.5~3.0cm³/g.Used in the present invention Inorganic carrier can be typically used for any inorganic carrier in prepared by olefin polymerization catalysis.

The barium oxide and chromated oxide that the double activity center of catalyst of the present invention is loaded by catalyst surface provide.Vanadium Source has water solubility to contain vanadic salts：Such as hexafluoro ammonium vanadate, nitric acid vanadium, vanadyl oxalate, ammonium metavanadate, vanadic sulfate, sulfuric acid oxidation vanadium (IV) hydrate, vanadic sulfate (III), three chloro vanadium oxides, sodium orthovanadate, sodium metavanadate etc., and water-insoluble contain vanadic salts：Such as Bis-acetylacetonate vanadium oxide, Triisopropoxyvanadium(V) oxide, three propyl alcohol vanadium oxides, vanadium acetylacetonate, oxidation triethoxy vanadium, chlorination oxygen Vanadium, the vanadium of silication three, other suitable soluble vanadic salts and combinations thereof.Chromium source used is selected from chromium trioxide, chromic nitrate, vinegar Sour chromium, chromium chloride, chromium sulfate, ammonium chromate, ammonium dichromate, alkali formula chromic acetate, other suitable soluble chromic salts and they Combination.

For the present invention catalyst, on inorganic carrier the load capacity of chromium be generally total catalyst weight 0.01~ 10wt%, preferably 0.05~5wt%, based on the weight of chromium.

According to one embodiment of the invention, on inorganic carrier the load capacity of vanadium be generally chromium load capacity 10~ 500% (in terms of the weight of chromium and vanadium), preferably 20~400%, vanadium load capacity be generally total catalyst weight 0.01~ 10wt%, preferably 0.05~5wt%.

According to an aspect of the present invention, the method that offer of the present invention prepares support type chrome alum double activity center catalyst, One of which method comprises the following steps：

I) inorganic carrier is impregnated into the solution containing vanadium, then dried, then the calcination activation at 300~900 DEG C of high temperature；

Ii the product obtained by step i)) is impregnated into the solution containing chromium, then dried, then at 300~900 DEG C of high temperature Calcination activation, obtain the catalyst and save backup.

According to a preferable method for preparing support type chrome alum double activity center catalyst, comprise the following steps：

I) by the salt solution impregnation of vanadium on inorganic carrier, dip time is 1~12h, preferably 4~8h, and dipping temperature is 10~80 DEG C, preferably 20~70 DEG C, then dried at 90~250 DEG C, it is preferably 100~200 DEG C, 6~20h of drying time, excellent 8~15h is selected, vacuum drying can also be used in drying process；By above-mentioned sample in inert gas either oxygen or air High-temperature roasting activation is carried out, sintering temperature is at 300~900 DEG C, preferably 400~800 DEG C, and the time is 1~10h, preferably 4~6h, Then cooled down, wherein switching to inert gas such as nitrogen or argon gas etc., natural cooling when being cooled to 300~400 DEG C；

Ii) by the salt solution impregnation of chromium on the above-mentioned inorganic carrier for being loaded with vanadium, dip time is 1~12h, preferably 4 ~8h, dipping temperature are 10~80 DEG C, preferably 15~60 DEG C, are then dried between 90~250 DEG C, preferably 100~150 DEG C, 6~20h of drying time, preferably 8~15h, vacuum drying can also be used in drying process；By above-mentioned sample in inert gas or Calcination activation is carried out in person's oxygen or air, sintering temperature is at 300~900 DEG C, preferably 400~800 DEG C, the time be 1~ 10h, preferably 3~8h, are then cooled down, and inert gas such as nitrogen or argon gas etc. are switched to when being cooled to 300~400 DEG C, Natural cooling, obtain the catalyst and save backup.

Usually, the present invention is that by vanadium source dipping thereon first, then high temperature roasts by the use of inorganic compound as carrier Burn, the catalyst Precursors of load vanadium are made；Then in the solution containing above-mentioned catalyst Precursors, add inorganic chromium source and born Carry, so as to prepare support type chrome alum double activity center catalyst.

Above-mentioned steps i) is the method being carried on vanadium source on inorganic carrier (such as inorganic carrier described above).For The method that vanadium source is carried on inorganic carrier can be known any method that can be carried on vanadium on carrier.According to this One embodiment of invention, method vanadium source being carried on inorganic carrier include being carried with vanadium source solution impregnated porous inorganic Body.According to an embodiment, in dipping process, it is possible to implement stirring, preferably continuously stir.Usually, the stirring continues About 1~12h, preferably from about 4~8h, dipping temperature are 10~80 DEG C, preferably 20~70 DEG C.According to an embodiment, vanadium load Measure 0.01~10wt% for total catalyst weight, preferably from about 0.05~5wt%.Then the load for being loaded with vanadium component that will be obtained Body is dried.The drying is generally carried out in room temperature~250 DEG C, preferably in about 90~250 DEG C, further preferably about 100~200 ℃.According to an embodiment, the drying is in about 120 DEG C of progress.The drying can also be carried out under vacuum.To this dry into The capable time is not particularly limited, but the drying typically lasts for about 6~20h, preferably from about 7~18h, further preferably about 8~ 15h.After dry finish, the inorganic carrier for being loaded with vanadium component is calcined.The mode carried out to roasting is not special Limit, but the roasting is carried out preferably in fluid bed.According to an embodiment, the roasting is generally carried out with two stages, That is cold stage and hot stage.Cold stage is generally in about 100~300 DEG C of progress.The hot stage generally about 300~ 900 DEG C of progress.Without being bound by any theory, the mechanical water adsorbed in the cold stage carrier is substantially eliminated, and in institute The part of hydroxyl stated on hot stage inorganic carrier is removed.According to an embodiment, it is small that the cold stage continues 1~10 When, preferably 2~9 hours, more preferably 3~8 hours.According to another embodiment, the hot stage continues 1~10 hour, It is preferred that 2~9 hours, more preferably 3~8 hours.According to an embodiment, the cold stage is in inert gas or air gas Carry out under atmosphere, preferably carry out under inert gas atmosphere, the inert gas is, for example, the atmosphere such as nitrogen, helium, argon gas, preferably Carry out in a nitrogen atmosphere, such as high pure nitrogen.According to an embodiment, the hot stage roasting is in air or oxygen Under the conditions of carry out, carried out preferably under the conditions of dry air.After the roasting terminates, inorganic oxide is loaded with by what is obtained The inorganic carrier of form vanadium cools down from hot stage., can when being cooled to 300~400 DEG C of temperature according to an embodiment To convert atmosphere, such as from air it is changed into inert gas, such as nitrogen, argon gas etc..According to an embodiment, this is cooled to certainly Right cooling down.

Above-mentioned steps ii) be inorganic chromium source is carried on prepare in step i) be loaded with the inorganic carrier of vanadium (on such as Inorganic carrier described in text) on method.Method for inorganic chromium source to be carried on the inorganic carrier for being pre-loaded with vanadium can To be any method that can be carried on chromium on carrier well known by persons skilled in the art, such as can be mentioned that conventionally known The method for preparing Phillips catalyst.The inorganic chromium source can be inorganic chromium source described above.According to an embodiment party Case, in dipping process, it is possible to implement stirring, preferably continuously stir.Usually, the stirring lasts about 1~about 12 hour, preferably About 4~8 hours.According to an embodiment, the load capacity of inorganic chromium is about 0.01~about 10wt% of total catalyst weight, excellent Select about 0.05~5wt%, about further preferably 0.1~3wt%.Then obtained carrier is dried.The drying generally exists About room temperature to 200 DEG C of temperature is carried out；Such as carried out at about 15 DEG C to 250 DEG C, preferably enter one to 250 DEG C at about 90 DEG C Preferably from about 100 DEG C to 200 DEG C of step.According to an embodiment, the drying is in about 120 DEG C of progress.The time carried out to the drying It is not particularly limited, but the drying typically lasts for about 6~20 hours, preferably from about 7~18 hours, further preferably about 8~15 Hour.After dry finish, the inorganic carrier for loading upper metal is calcined.The mode carried out to roasting does not limit especially It is fixed, but the roasting is carried out preferably in fluid bed.According to an embodiment, the roasting is generally carried out with two stages, i.e., Cold stage and hot stage.The cold stage is generally in about 100~300 DEG C of progress.The hot stage generally about 300~ 900 DEG C of progress.It is without being bound by any theory, it is believed that the mechanical water adsorbed in the cold stage carrier is removed, and in institute The part of hydroxyl stated on hot stage inorganic carrier is removed.According to an embodiment, it is small that the cold stage continues 1~10 When, preferably 2~8 hours.According to another embodiment, the hot stage continues 1~10 hour, preferably 2~9 hours, more It is preferred that 3~8 hours.According to an embodiment, the cold stage is carried out under inert gas or air atmosphere, preferably Carry out, inert gas atmosphere such as nitrogen, helium, argon gas, preferably carry out in a nitrogen atmosphere, example under an inert gas Such as high pure nitrogen.According to an embodiment, the hot stage roasting is carried out under air or Oxygen Condition, preferably dry Carried out under dry air conditionses.After the roasting terminates, the inorganic carrier of metal in obtained load is cooled down from hot stage. According to an embodiment, when being cooled to 300~400 DEG C of temperature after high-temperature roasting, atmosphere can be converted, such as from sky Gas is changed into inert gas, such as nitrogen etc..According to an embodiment, this is cooled to Temperature fall cooling.The catalysis that will be obtained Agent saves backup under inert gas atmosphere.

As an example, preparing the concrete operations of catalyst of the present invention includes：

Porous amorphous silica gel is immersed in certain density ammonium metavanadate solution, vanadium load capacity is total relative to catalyst Weight meets this paper requirement (such as 0.1~10wt%, in terms of the weight of vanadium)；Continuously stirring certain time (such as 4~8 Hour) after, heat up drying；The silica-gel carrier for being loaded with ammonium metavanadate is subjected to high-temperature roasting in fluid bed, wherein in low temperature Stage (such as 100 DEG C~300 DEG C) is calcined the mechanical water in removing carrier in nitrogen atmosphere, in (such as 300 DEG C of hot stage ~900 DEG C) part of hydroxyl of roasting removing Silica Surface in dry air, kept for certain time (such as 3 in this hot stage ~8 hours)；Temperature fall cools down, and switches to nitrogen to protect when being cooled to 300~400 DEG C, and the catalyst mother for carrying vanadium is made Body.Then, inorganic chromium source is supported on as made from the above method on catalyst Precursors, chromium load capacity meets this paper requirement (being, for example, 0.1~1wt% of total catalyst weight, in terms of the weight of chromium) continuously stirs certain time (such as 4~8 hours) Afterwards, heat up drying；Then high-temperature roasting is carried out in fluid bed, wherein in cold stage (such as 100 DEG C~300 DEG C) in nitrogen The mechanical water adsorbed in atmosphere in roasting removing silica-gel carrier, in hot stage (such as 300 DEG C~900 DEG C) in dry air The part of hydroxyl of roasting removing Silica Surface, is kept for certain time (such as 3~8 hours) in this hot stage；Temperature fall Cooling, switches to nitrogen to protect, shifts under nitrogen protection, catalyst saves backup when being cooled to 300~400 DEG C.

A kind of preparation method that the present invention provides support type chrome alum double activity center catalyst comprises the following steps：

I) inorganic carrier is impregnated into the solution containing vanadium and chromium, then dried；

Ii) by the product obtained by i) at 300 DEG C~900 DEG C of high temperature calcination activation, obtain the catalyst and save backup.

Step is included according to a preferable method for preparing support type chrome alum double activity center catalyst：

I) mixing salt solution containing chrome alum is supported on inorganic carrier by the method for co-impregnation, dip time 1 ~12h, preferably 4~8h, dipping temperature are 10~80 DEG C, preferably 20~70 DEG C, are then dried between 90~250 DEG C, preferably 100~200 DEG C, preferably 6~20h of drying time, 8~15h, vacuum drying can also be used in drying process；

Ii above-mentioned sample) is subjected to high-temperature roasting activation in inert gas either oxygen or air, sintering temperature exists 300~900 DEG C, preferably 400~800 DEG C of times are 1~10h, preferably 3~8h, are then cooled down, are being cooled to 300~400 DEG C when switch to inert gas such as nitrogen or argon gas etc., natural cooling, obtain the catalyst and save backup.

Above-mentioned steps i) is by inorganic vanadium source and vanadium source while to be carried on inorganic carrier (such as described above without airborne Body) on method.The inorganic chromium source can be inorganic chromium source described above, and vanadium source can be any vanadium described above Source.According to an embodiment, in dipping process, it is possible to implement heating stirring, preferably laser heating stir.Usually, should Stirring lasts about 1~12 hour, preferably from about 4~8 hours, and dipping temperature is 10~80 DEG C, preferably 20~70 DEG C.According to a reality Apply scheme, the load capacity of inorganic chromium is 0.01~10wt%, the preferably 0.05~5wt% of total catalyst weight, further preferably 0.1~2wt%.Vanadium load capacity is the 0.01~10wt%, preferably from about 0.05~5wt% of total catalyst weight.Then will obtain Carrier be dried.The drying is generally carried out in about room temperature to 250 DEG C of temperature；It is preferred that 90 DEG C to 250 DEG C, it is further excellent Select 100 DEG C to 200 DEG C.The time carried out to the drying is not particularly limited, but the drying typically lasts for about 6~20 hours, Preferably from about 7~18 hours, further preferably about 8~15 hours.

Above-mentioned steps ii) it is after dry finish, the inorganic carrier for being impregnated with chromium and vfanadium compound is calcined, and Most chrome alum is oxide carried in inorganic carrier surface at last.The mode carried out to roasting is not particularly limited, but the roasting is excellent It is selected in fluid bed and carries out.According to an embodiment, the roasting is generally carried out with two stages, i.e. cold stage and high temperature rank Section.The cold stage is generally in about 100~300 DEG C of progress.The hot stage is generally in about 300~900 DEG C of progress.Not by any Theory limitation, it is believed that the mechanical water adsorbed in the cold stage carrier is removed, and in the hot stage inorganic carrier On part of hydroxyl be removed.According to an embodiment, the cold stage continues 1~10 hour, preferably 2~9 hours. According to another embodiment, the hot stage continues 1~10 hour, preferably 2~9 hours, more preferably 3~8 small When.According to an embodiment, the cold stage is carried out under inert gas or air atmosphere, preferably under an inert gas Carry out, inert gas atmosphere such as nitrogen, helium, argon gas, preferably carry out in a nitrogen atmosphere, such as high pure nitrogen. According to an embodiment, the hot stage roasting is carried out under air or Oxygen Condition, preferably in dry air condition Lower progress.After the roasting terminates, the inorganic carrier of metal oxide in obtained load is cooled down from hot stage.According to One embodiment, when being cooled to 300~400 DEG C of temperature after high-temperature roasting, atmosphere can be converted, such as become from air For inert gas, such as nitrogen.According to an embodiment, this is cooled to Temperature fall cooling.By obtained catalyst lazy Saved backup under property gas atmosphere.

Porous amorphous silica gel is immersed in the aqueous solution of certain density ammonium metavanadate and alkali formula chromic acetate, vanadium and chromium Load capacity meet this paper requirement (such as 0.1~10wt% of vanadium, 0.1~2wt% of chromium) relative to total catalyst weight；Even After continuous stirring certain time (such as 4~8 hours), heat up drying；Then high-temperature roasting is carried out in fluid bed, wherein in low temperature Stage (such as 100 DEG C~300 DEG C) is calcined the mechanical water that adsorbs in removing carrier in nitrogen atmosphere, hot stage (such as 300 DEG C~900 DEG C) part of hydroxyl of roasting removing Silica Surface in dry air, kept for certain time in this hot stage (such as 3~8 hours)；Temperature fall cools down, and switches to nitrogen to protect when being cooled to 300~400 DEG C, under nitrogen protection Transfer, catalyst save backup.

Another preparation method that the present invention provides support type chrome alum double activity center catalyst comprises the following steps：

I) inorganic carrier is impregnated into the solution containing chromium, then dried, be then calcined and live at 300 DEG C~900 DEG C of high temperature Change；

Ii the product obtained by step i)) is impregnated into the solution containing vanadium, then dried, then in 300 DEG C~900 DEG C of high temperature Lower calcination activation, obtains catalyst and saves backup.

Comprised the following steps according to a preferable method for preparing support type chrome alum double activity center catalyst：

I) by the salt solution impregnation of chromium on inorganic carrier, dip time is 1~12h, preferably 4-8h, dipping temperature 10 ~80 DEG C, preferably 20~70 DEG C, then dried between 90~250 DEG C, it is preferably 100~150 DEG C, 6~20h of drying time, excellent 8~15h is selected, vacuum can also be used in drying process；Above-mentioned sample is carried out in inert gas either oxygen or air High-temperature roasting activates, and sintering temperature is at 300~900 DEG C, preferably 400~800 DEG C, and the time is 1~10h, preferably 3~8h, then Cooled down, inert gas such as nitrogen or argon gas etc. are switched to when being cooled to 300~400 DEG C, natural cooling, is loaded with The catalyst Precursors of chromium；

Ii) by the salt solution impregnation of vanadium to the above-mentioned inorganic carrier for being loaded with chromium, dip time is 1~12h, preferably 3- 8h, dipping temperature are 10~80 DEG C, preferably 20~70 DEG C, then dry, preferably 100~150 DEG C, do between 90~250 DEG C Dry 6~20h of time, preferably 8~15h, vacuum can also be used in drying process；By above-mentioned sample in inert gas or oxygen Or high-temperature roasting activation is carried out in air, sintering temperature is at 300~900 DEG C, preferably 400~800 DEG C, and the time is 1~10h, It is preferred that 3~8h, is then cooled down, inert gas such as nitrogen or argon gas etc. are switched to when being cooled to 300~400 DEG C, it is natural Cooling, obtains the catalyst and saves backup.

Above-mentioned steps i) is the method being carried on inorganic chromium source on inorganic carrier (such as inorganic carrier described above). Method for inorganic chromium source to be carried on inorganic carrier can be well known by persons skilled in the art any can bear chromium The method being loaded on carrier, such as can be mentioned that the conventionally known method for preparing Phillips catalyst.The inorganic chromium source It can be inorganic chromium source described above.According to an embodiment, in dipping process, it is possible to implement stirring, preferably continuously Stirring.Usually, the stirring lasts about 1~12 hour, preferably from about 4~8 hours.According to an embodiment, the load capacity of chromium For about 0.01~10wt% of total catalyst weight, preferably from about 0.05~5wt%, about further preferably 0.1~2wt%.Then Obtained carrier is dried.The drying is generally carried out in about room temperature to 200 DEG C of temperature；Such as at 15 DEG C to 200 DEG C Carry out, preferably 20 DEG C to 200 DEG C, further preferred 100 DEG C to 200 DEG C.According to an embodiment, the drying is at about 120 DEG C Carry out.The time carried out to the drying is not particularly limited, but the drying typically lasts for about 6~20 hours, and preferably from about 7~18 Hour, further preferably about 8~15 hours.After dry finish, the inorganic carrier for loading upper metal is calcined.To roasting Burn into capable mode to be not particularly limited, but the roasting is carried out preferably in fluid bed.According to an embodiment, the roasting Generally carried out with two stages, i.e. cold stage and hot stage.The cold stage is generally in about 100~300 DEG C of progress.The height Thermophase is generally in about 300 DEG C~900 DEG C progress.It is without being bound by any theory, it is believed that to be adsorbed in the cold stage carrier Mechanical water be removed, and the part of hydroxyl on the hot stage inorganic carrier is removed.According to an embodiment, institute State cold stage and continue 1~10 hour, preferably 2~9 hours.According to another embodiment, the hot stage continues 1~10 Hour, preferably 2~9 hours, more preferably 3~8 hours.According to an embodiment, the cold stage in inert gas or Carry out under air atmosphere, preferably inert gas gas, more preferably carry out in a nitrogen atmosphere, such as high pure nitrogen.According to one Embodiment, the high-temperature roasting stage are being carried out in inert gas or air, preferably dry high pure air.In the roasting After sintering beam, the inorganic carrier of metal in obtained load is cooled down from hot stage.According to an embodiment, roasted in high temperature When being cooled to 300~400 DEG C of temperature after burning, atmosphere can be switched, such as be changed into inert gas, such as nitrogen from air. According to an embodiment, this is cooled to Temperature fall cooling.Obtained catalyst is preserved under inert gas atmosphere stand-by.

Above-mentioned steps ii) be vanadium source is further carried on prepare in step i) be loaded with chromium inorganic carrier (such as Inorganic carrier described above) on method.Method for vanadium source to be carried on inorganic carrier can be known any The method that vanadium can be carried on carrier.According to one embodiment of the invention, vanadium source is carried on and is pre-loaded with chromium Method on inorganic carrier includes impregnating the porous inorganic carrier for being pre-loaded with chromium with vanadium source solution.According to an embodiment party Case, in dipping process, it is possible to implement stirring, preferably continuously stir.Usually, the stirring lasts about 1~12 hour, preferably from about 4~8 hours, dipping temperature was 10~80 DEG C, preferably 20~70 DEG C.According to an embodiment, vanadium load capacity is that catalyst is total 0.01~10wt% of weight, preferably from about 0.05~5wt%.Then the obtained carrier for being impregnated with vanadium component is dried. The drying is generally carried out in the temperature of about room temperature~200 DEG C；Such as carried out at about 15~200 DEG C, preferably 20~200 DEG C, Further preferably about 100~200 DEG C.According to an embodiment, the drying is in about 120 DEG C of progress.The drying also can be in vacuum Under the conditions of carry out.The time carried out to the drying is not particularly limited, but the drying typically lasts for about 6~20 hours, preferably About 7~18 hours, further preferably about 8~15 hours.After dry finish, the sample for being impregnated with vanadium component is roasted Burn.The mode carried out to roasting is not particularly limited, but the roasting is carried out preferably in fluid bed.According to an embodiment party Case, the roasting are generally carried out with two stages, i.e. cold stage and hot stage.Cold stage generally enters at about 100~300 DEG C OK.The hot stage is generally in about 300~900 DEG C of progress.It is without being bound by any theory, it will be inhaled in the cold stage in carrier Attached mechanical water removes substantially, and removes the part of hydroxyl on inorganic carrier in the hot stage.According to an embodiment party Case, the cold stage continue 1~10 hour, preferably 2~9 hours.According to another embodiment, the hot stage is held It is continuous 1~10 hour, preferably 2~9 hours, more preferably 3~8 hours.According to an embodiment, the cold stage is in indifferent gas Carry out under body or air atmosphere, preferably carry out under inert gas atmosphere, the inert gas is, for example, above-described lazy Property gas.According to an embodiment, the hot stage roasting is carried out under air or Oxygen Condition, is preferably drying sky Carried out under the conditions of gas.After the roasting terminates, by the obtained inorganic carrier for being loaded with inorganic oxide form vanadium and chromium from Hot stage cools down.According to an embodiment, when being cooled to 300~400 DEG C of temperature, atmosphere can be converted, such as from Air is changed into inert gas, such as nitrogen, argon gas etc..According to an embodiment, this is cooled to Temperature fall cooling, urged Agent saves backup.

Porous amorphous silica gel is immersed in the aqueous solution in inorganic chromium source, chromium load capacity meet this paper requirement (such as For 0.1~2wt% of total catalyst weight, in terms of the weight of chromium) continuously stir certain time (such as 3~8 hours) after, heating Dry；Then high-temperature roasting is carried out in fluid bed, wherein in cold stage (such as 100 DEG C~300 DEG C) in nitrogen atmosphere The mechanical water adsorbed in roasting removing carrier, removing silicon is calcined in dry air in hot stage (such as 300 DEG C~900 DEG C) The part of hydroxyl on glue surface, kept for certain time (such as 3~8 hours) in this hot stage；Temperature fall cools down, and is cooling down Switch to nitrogen to protect during to 300~400 DEG C, shift under nitrogen protection, preserve stand-by, the catalyst Precursors that then will be obtained Be immersed in certain density ammonium metavanadate solution, vanadium load capacity meet relative to total catalyst weight this paper requirement (such as 0.1~10wt%, in terms of the weight of vanadium)；After certain time (such as 4~8 hours) is continuously stirred, heat up drying；Will dipping The catalyst Precursors for having ammonium metavanadate carry out high-temperature roasting in fluid bed, wherein at cold stage (such as 100 DEG C~300 DEG C) The mechanical water adsorbed in nitrogen atmosphere in roasting removing carrier, in hot stage (such as 300 DEG C~900 DEG C) dry air The part of hydroxyl of roasting removing Silica Surface, is kept for certain time (such as 3~8 hours) in this hot stage；Temperature fall Cooling, switches to nitrogen to protect, shifts under nitrogen protection when being cooled to 300~400 DEG C, and it is stand-by to obtain catalyst preservation.

I) the chrome alum double activity center catalyst prepared using any one method in above-mentioned three kinds of methods, including first carry Vanadium carry chromium, chrome alum while load again and first carry chromium carry again it is any one in the double center catalyst of three kinds of support type chrome alums of vanadium Kind；

Ii) organic metal is added in a kind of support type chrome alum double activity center catalyst of any of the above prepared to help and urge Agent carries out prereduction activation process, is then dried and saves backup.

I) support type chrome alum double activity center catalyst is prepared using any in above-mentioned three kinds of methods；

Ii obtained catalyst) is added into organic metal co-catalyst under an inert atmosphere, prereduction is carried out to catalyst Activation process, 2-8 hours are then dried between 60-120 DEG C, vacuum can also be used in drying process, then in indifferent gas Preserved under body stand-by.

Usually, the above method is that obtained support type chrome alum double activity center catalyst is carried out at prereduction activation Reason.Step i) is to prepare support type chrome alum double activity center catalyst, step with any of three of the above method method Ii it is) to add organic metal co-catalyst under an inert atmosphere to carry out prereduction to the support type chrome alum double activity center catalyst Activation process, above-mentioned organic metal co-catalyst include the abilities such as organo-aluminum compound, organo-lithium compound, organoboron compound The known any co-catalyst for olefinic polyreaction of field technique personnel either combinations thereof.According to a reality Scheme is applied, the organo-aluminum compound as co-catalyst can include trialkylaluminium AlR₃, dialkyl group aluminum alkoxide AlR₂OR, two Aikyl aluminum halide AlR₂X, aikyiaiurnirsoxan beta, ethyl sesquialter aluminium chloride etc., wherein R is alkyl, such as with 1-12 carbon atom Alkyl, e.g. methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, n-hexyl, n-heptyl, just pungent Base, n-nonyl, dodecyl etc., X are halogens, such as fluorine, chlorine, bromine and iodine, preferably chlorine.The aikyiaiurnirsoxan beta can include methyl The reactant of all alkyl aluminums and water such as aikyiaiurnirsoxan beta (MAO).The organo-aluminum compound as co-catalyst can individually make With or two or more be applied in combination.As specific example, the aluminium compound can be mentioned that triethyl aluminum, triisobutyl Aluminium, diethylaluminum ethoxide, aluminium diethyl monochloride and MAO etc..According to an embodiment, helped and urged using organo-aluminium When agent carries out prereduction activation process to chrome alum double activity center catalyst, aluminium/chromium mol ratio is between 0-1000, preferably 0- 100, more preferably 0-50, reduction activation treatment temperature is between -100 DEG C of room temperature, preferably between -60 DEG C of room temperature, at reduction activation Manage hour time 0.5-20, preferably 0.5-10 hours, reduction activation processing uses agitating mode, preferably continuously stirs, has handled Bi Houzai is dried 2~8 hours between 60~120 DEG C, and drying is carried out under inert gas atmosphere, such as in nitrogen, helium, argon Carry out under the atmosphere such as gas, preferably carry out in a nitrogen atmosphere, the drying process can also be carried out under vacuum.Obtained process The support type chrome alum composite catalyst of prereduction activation preserves stand-by under inert gas atmosphere.

Porous amorphous silica gel is immersed in certain density ammonium metavanadate solution, vanadium load capacity is total relative to catalyst Weight meets this paper requirement (such as 0.1~10wt%, in terms of the weight of vanadium)；Continuously stirring certain time (such as 4~8 Hour) after, heat up drying；The silica-gel carrier for being loaded with ammonium metavanadate is subjected to high-temperature roasting in fluid bed, wherein in low temperature Stage (such as 100 DEG C~300 DEG C) is calcined the mechanical water that adsorbs in removing carrier in nitrogen atmosphere, hot stage (such as 300 DEG C~900 DEG C) part of hydroxyl of roasting removing Silica Surface in dry air, kept for certain time in this hot stage (such as 3~8 hours)；Temperature fall cools down, and switches to nitrogen to protect when being cooled to 300~400 DEG C, is made and carries urging for vanadium Agent parent.Then, inorganic chromium source is supported on as made from the above method on catalyst Precursors, chromium load capacity meets this paper's It is required that (being, for example, 0.1~3wt% of total catalyst weight, in terms of the weight of chromium) continuously stirs certain time, (such as 3~8 is small When) after, heat up drying；Then high-temperature roasting is carried out in fluid bed, wherein existing in cold stage (such as 100 DEG C~300 DEG C) The mechanical water adsorbed in nitrogen atmosphere in roasting removing carrier, in hot stage (such as 300 DEG C~900 DEG C) in dry air The part of hydroxyl of roasting removing Silica Surface, is kept for certain time (such as 3~8 hours) in this hot stage；Temperature fall Cooling, switches to nitrogen to protect, shifts under nitrogen protection when being cooled to 300~400 DEG C, preserves stand-by.Then three are added Aluminium ethide carries out prereduction activation process to catalyst, and aluminium/chromium mol ratio in 0-50, continuously stir in -60 DEG C of room temperature by treatment temperature 0.5-10 hours are mixed, are then dried 2~8 hours between 60~120 DEG C again, the drying is carried out under inert gas atmosphere, example Such as carry out under nitrogen, helium, argon gas atmosphere, preferably carry out in a nitrogen atmosphere, the drying process also can be in vacuum condition Lower progress.The obtained chrome alum composite catalyst by prereduction activation preserves stand-by under inert gas atmosphere.

Support type chrome alum double activity center catalyst of the present invention (is lived more than including by the prereduction of organic metal co-catalyst The chrome alum double activity center catalyst of change) it can be used for the homopolymerization of ethene or the copolymerization of ethene and alpha-olefin.Basis in polymerization process Need that organic metal promoters, hydrogen etc. can be added.

Therefore, according to another aspect of the present invention, there is provided using the double center catalysis of support type chrome alum of the present invention The method that agent produces Alathon and ethylene/alpha-olefin copolymer, particularly alkene of the production with wide molecular weight distribution The method of polymer.

For the above method, alkene used in polymerization generally comprises ethene as polymerized monomer.In an embodiment In, the alkene used that polymerize also includes comonomer.The comonomer can be the α-alkene for having 3-20 carbon atom Hydrocarbon, such as propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 1- nonenes, 1- decene, 1- dodecylenes, 4- first Base -1- amylenes, 4- methyl isophthalic acids-hexene etc.；These can be used alone or can be applied in combination with two or more.The copolymerization Monomer is preferably 1- butylene, 1- hexenes, 1- octenes and 1- decene.In the presence of comonomer, the amount of comonomer is generally 0- 30vol%, preferably 0-10vol%, the volumetric concentration based on comonomer when polymerizeing.

Organic metal promoters can be added in polymerization process again as needed, and (such as organic metal described above is helped and urged Agent) into polymerization system, according to an embodiment, the organic metal co-catalyst can use organo-aluminum compound, Organo-aluminum compound can be mentioned that triethyl aluminum, triisobutyl aluminium, diethylaluminum ethoxide, aluminium diethyl monochloride and methyl alumina Alkane etc..The usage amount of the organic metal aluminium compound is typically to press aluminium/chromium molar ratio computing 0-1000, preferably 0-70, more preferably 0-50。

Above-mentioned polymerisation can include molecular weight regulator, as an example it can be mentioned that hydrogen.

The above-mentioned polymer manufacture method of the present invention is without any particular limitation in terms of its polymerization.It is above-mentioned to use this Invention chrome alum double activity center Catalyst Production Alathon or the method for ethene and alpha olefin copolymer can include gas phase Polymerization, slurry phase polymerisation process, suspension polymerization, bulk polymerization, solution polymerization process etc..Such as art technology As personnel understand, the method for the production olefin polymer using catalyst of the present invention is not particularly limited, can be adopted With gas phase polymerization process known in the art, slurry phase polymerisation process, suspension polymerization, bulk polymerization, polymerisation in solution side Conventional implementation and polymerizing condition of method etc. are implemented.

In one embodiment, using slurry phase polymerisation process, including ethene is added into reactor, then adds solvent With co-catalyst (organo-aluminum compound) and be optionally added into hydrogen and comonomer, be eventually adding the chrome alum double activated of the present invention Center catalyst starts to polymerize.

Solvent used in above-mentioned slurry polymerization is generally any solvent known in the field for olefinic polymerization.Institute It can be the alkane for having 3-20 carbon atom to state solvent, such as propane, normal butane, iso-butane, pentane, isopentane, new penta Alkane, n-hexane, hexamethylene, normal heptane, normal octane etc.；These solvents can be used alone or can be made with two or more combinations With.The preferred iso-butane of the solvent, isopentane, n-hexane, hexamethylene, normal heptane etc..

In one embodiment, polymerization is implemented using traditional slurry polymerization process, concrete operations are as follows：It will first polymerize anti- Answer kettle to carry out heating in vacuum removal of impurities, be then replaced into high pure nitrogen, operate three times repeatedly, then one is replaced with a small amount of vinyl monomer It is secondary, and finally ethene will be full of in reactor to pressure-fired (0.12MPa)；The essence added into reactor after dehydration and deoxidation processing Solvent processed such as normal heptane, a certain amount of alkyl aluminum also need to be separately added into necessarily as co-catalyst in hydrogen reconciles copolymerization experiments The hydrogen and comonomer of amount, treat that ethylene pressure is adjusted to 0.15MPa, and the catalyst for being eventually adding the present invention starts polymerisation； The instantaneous consumption of online acquisition monomer ethylene in course of reaction (by the high-accuracy Ethylene mass flowmeter for connecting computer) And by computer record, after (such as 35 DEG C -100 DEG C) reaction carries out certain time (such as 1 hour) at a certain temperature, add salt Acid/alcohol mixed solution terminating reaction；Polymer is scrubbed, weighs and analyzes after vacuum drying.

The present invention introduces the vanadium active component of load on traditional support type Phillips chromium-based catalysts, is invented Catalyst contains two kinds of active components, that is, the chromated oxide and barium oxide loaded.The catalyst of the present invention can be in single reaction In device production with wide molecular weight distribution Alathon and ethylene/alpha-olefin copolymer, have higher ethylene homo and Ethene and alpha-olefin copolymer reactivity.Using the chrome alum double activity center catalyst of the present invention, used by changing co-catalyst The factors such as amount, polymerization temperature, molecular weight regulator, it can conveniently and easily adjust Alathon and ethylene/alpha-olefin is total to The molecular weight and molecualr weight distribution and co-monomer content of polymers and distribution, so as to conveniently and easily obtain with institute Need the polymeric articles of performance.

Brief description of the drawings

Accompanying drawing 1 is carrier or catalyst Precursors calcination procedure schematic diagram 1.

Accompanying drawing 2 is carrier or catalyst Precursors calcination procedure schematic diagram 2.

Accompanying drawing 3 is pressurization ethylene homo polymer high temperature GPC spectrograms (comparative example 10,11 and the reality of three embodiments Apply example 20).

Accompanying drawing 4 is three embodiments pressurization ethene, 1- hervene copolymer polymer high temperature GPC spectrogram (comparative examples 12,13 With embodiment 21).

Specific implementation method

The present invention is explained in greater detail with reference to the following example, and these embodiments do not limit the scope of the invention.It is real It is commercially available Davison 955 to apply the silica gel used in example.

Various polymer properties in embodiment measure according to following methods：

High temperature gel chromatogram (HT-GPC)

Weight average molecular weight and molecular weight distribution high temperature gel chromatographic determination：This experiment is oozed using PL-220 type high temperature gels Saturating chromatograph (Polymer Laboratories companies) determines molecular weight of polyethylene and its molecular weight distribution.With 1 in experiment, 2,4- trichloro-benzenes are solvent, are determined at 160 DEG C.Number is handled using universal calibration method of the Narrow distribution polystyrene as standard specimen According to.

Differential scanning calorimetry (DSC)

The fusing point of test polymer：This experiment is surveyed under nitrogen protection using TA Q200 type differential scanning calorimeters Examination.Sample is first with 10 DEG C/min speed from room temperature to 150 DEG C, and constant temperature 5min, then naturally rings to room temperature.Then with 10 DEG C/min speed heating scan (room temperature is to 150 DEG C), record DSC curve.

Embodiment 1：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) to be immersed in vanadyl oxalate water-soluble In liquid (V load capacity is 0.48wt%), dipping 5h is continuously stirred under 40 DEG C of oil baths, then heats to 120 DEG C of dry 5h, Ran Houzhuan Move to 120 DEG C of oven drying 6h；The silica-gel carrier for being impregnated with vanadyl oxalate is placed in quartzy fluid bed and carries out calcination activation, it is high 450 DEG C of insulation 4h in pure air, finally Temperature fall cooling transfer, above-mentioned roasting process are as shown in Figure 1 under a nitrogen for silica gel.Will Obtained sample impregnates the alkali formula chromic acetate aqueous solution (Cr load capacity is 0.5wt%) again, after continuously stirring dipping 4h at room temperature, 120 DEG C of dry 4h, are then transferred to 120 DEG C of oven drying 6h；Dry sample is placed in quartzy fluid bed and carries out roasting work Change, 4h is calcined at 600 DEG C in air, then Temperature fall cooling transfer under nitrogen protection, above-mentioned calcination procedure such as Fig. 2 institutes Show, it is stand-by to obtain catalyst preservation.

Embodiment 2：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) be immersed in alkali formula chromic acetate with In the aqueous solution of ammonium metavanadate (Cr load capacity is 0.5wt%, and V load capacity is 0.48wt%), stirring dipping 4h under 60 DEG C of oil baths, 4h is dried at 120 DEG C, is then transferred to 120 DEG C of oven drying 6h；Dry sample is placed in quartzy fluid bed and is calcined Activate, 5h is incubated at 500 DEG C in air, then Temperature fall cooling transfer under nitrogen protection, it is stand-by to obtain catalyst preservation.

Embodiment 3：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) to be immersed in vanadic sulfate water-soluble In liquid (V load capacity 0.16wt%), continuously stir impregnate 4h at room temperature, 120 DEG C of oven dryings are transferred to after drying 4h at 120 DEG C 6h；Dry catalyst is placed in quartzy fluid bed and carries out calcination activation, 4h is incubated at 500 DEG C in air, is protected in nitrogen Lower natural cooling.Obtained sample is impregnated into alkali formula acetic acid chromium solution (Cr load capacity 0.5wt%) again, dipping 4h is stirred at room temperature Afterwards, 120 DEG C of dry 4h, are then transferred to oven drying 6h；Dry sample is placed in quartzy fluid bed and carries out calcination activation, In air at 600 DEG C, 4h is incubated, under nitrogen protection natural cooling, calcination procedure such as Fig. 2, it is stand-by to obtain catalyst preservation.

Embodiment 4：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) to be immersed in ammonium metavanadate water-soluble In liquid (V load capacity is 0.24wt%), dipping 4h is continuously stirred at 60 DEG C, 120 DEG C of dry 4h is then heated to, is transferred to 120 DEG C oven drying 6h；Dry sample is placed in quartzy fluid bed and carries out calcination activation, at high 450 DEG C of air atmosphere, insulation 4h, calcination procedure such as Fig. 1, the vanadium oxide catalyst loaded.Obtained sample is impregnated into the alkali formula chromic acetate aqueous solution again (Cr load capacity is 0.5wt%), after continuously stirring dipping 4h at room temperature, 120 DEG C of dry 4h is warming up to, baking oven is then transferred to and does Dry 6h；Dry sample is placed in quartzy fluid bed and carries out calcination activation, 4h is incubated at 600 DEG C, it is natural under nitrogen protection Cooling, it is stand-by to obtain catalyst preservation.

Embodiment 5：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) it is immersed in bis-acetylacetonate oxygen Change in the ethanol solution of vanadium (V load capacity is 0.96wt%), 100 DEG C of dryings are warming up to after continuously stirring dipping 4h at room temperature 8h, it is then transferred to 120 DEG C of oven drying 6h；Dry catalyst is placed in quartzy fluid bed and carries out calcination activation, it is high-purity 4h is incubated in air at 600 DEG C, under nitrogen protection natural cooling.Obtained sample is impregnated into the alkali formula chromic acetate aqueous solution again (Cr load capacity is 0.5wt%).120 DEG C of dry 4h are warming up to after stirring dipping 4h at room temperature, 120 DEG C of baking ovens is then transferred to and does Dry 6h；Dry sample is placed in quartzy fluid bed and carries out calcination activation, at 600 DEG C of high pure air, is incubated 4h, calcination procedure Such as Fig. 2, natural cooling, it is stand-by to obtain catalyst preservation under nitrogen protection.

Embodiment 6：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) it is immersed in alkali formula chromic acetate water In solution (Cr load capacity is 0.5wt%), dipping 4h is continuously stirred, 120 DEG C of dry 4h is warming up to, is then transferred to 120 DEG C of bakings Case dries 6h；Dry sample is placed in quartzy fluid bed and carries out calcination activation, 600 DEG C of insulation 4h, roasting in high pure air Program such as Fig. 2 is burnt, under nitrogen protection natural cooling.Obtained sample is immersed in the aqueous solution of sodium metavanadate to (V is born again Carrying capacity is 0.24wt%).Stirring dipping 4h, is warming up to 120 DEG C of dry 4h, is then transferred to 120 DEG C of oven drying 6h at 40 DEG C； Dry sample is placed in quartzy fluid bed and carries out calcination activation, 600 DEG C of insulation 4h, are then protected in nitrogen in high pure air The lower natural cooling cooling of shield, it is stand-by to obtain catalyst preservation.

Embodiment 7：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) to be immersed in ammonium metavanadate water-soluble In liquid (V load capacity is 0.24wt%), dipping 4h is continuously stirred at 60 DEG C, 120 DEG C of dry 4h is then heated to, is transferred to baking oven Dry 6h；Dry sample is placed in quartzy fluid bed and carries out calcination activation, at high 600 DEG C of air atmosphere, 4h is incubated, obtains The vanadium catalyst of load.Obtained sample is impregnated into the alkali formula chromic acetate aqueous solution (Cr load capacity is 0.5wt%) again, at room temperature After continuously stirring dipping 4h, 120 DEG C of dry 4h are warming up to, are then transferred to oven drying 6h；Dry sample is placed in quartz Carry out calcination activation in fluid bed, at 600 DEG C, be incubated 4h, calcination procedure such as Fig. 2, under nitrogen protection natural cooling.Then plus Enter organic metal co-catalyst -- the MAO (Al/Cr mol ratio=30) that concentration is 1mol/L, it is then dry at 100 DEG C again To remove solvent, the drying is carried out in a nitrogen atmosphere within dry 4 hours.The catalyst activated by prereduction is protected in a nitrogen atmosphere Deposit stand-by.

Embodiment 8：

Weigh catalyst 160mg in embodiment 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then add successively into reactor Enter the refined normal heptane solvents of 40mL, add the triisobutyl aluminium (TIBA) that dosage is Al/Cr=10 and make co-catalyst, add Normal heptane solvent after 30mL dehydration and deoxidations are refined.Ethylene pressure is adjusted to 0.15MPa, it is constant after 90 DEG C after temperature in the kettle, Catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by connecting the high-precision of computer in course of reaction Close Ethylene mass flowmeter) and by computer record.Hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.By institute after filtering Obtain and weigh and analyze after polymer dries 4h in vacuum drying chamber at 60 DEG C.

Embodiment 9：

Weigh catalyst 160mg in embodiment 2 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then add successively into reactor Enter the refined normal heptane solvents of 40mL, add the triisobutyl aluminium (TIBA) that dosage is Al/Cr=10 and make co-catalyst, then add Enter the normal heptane solvent after 30mL dehydration and deoxidations refine, regulation ethylene pressure to 0.15MPa.Treat that temperature in the kettle is constant at 90 DEG C Afterwards, catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by the height for connecting computer in course of reaction Accurate Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.Filtering Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber afterwards.

Embodiment 10：

Weigh catalyst 160mg in embodiment 3 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then add successively into reactor Enter 40mL and refine normal heptane solvent, add the aluminium diethyl monochloride (DEAC) that dosage is Al/Cr=5 and be used as co-catalyst, then add Enter the normal heptane solvent after 30mL dehydration and deoxidations refine, regulation ethylene pressure to 0.15MPa.Treat that temperature in the kettle is constant at 90 DEG C Afterwards, catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by the height for connecting computer in course of reaction Accurate Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.Filtering Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber afterwards.

Embodiment 11：

Weigh catalyst 160mg in embodiment 5 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then add successively into reactor Enter 40mL and refine normal heptane solvent, add the MAO (MAO) that dosage is Al/Cr=20 and be used as co-catalyst, add Normal heptane solvent after 30mL dehydration and deoxidations are refined, regulation ethylene pressure to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, Catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by connecting the high-precision of computer in course of reaction Close Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.After filtering Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber.

Embodiment 12：

Weigh catalyst 160mg in embodiment 6 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then add successively into reactor Enter 40mL and refine normal heptane solvent, add the triisobutyl aluminium (TIBA) that dosage is Al/Cr=5 and be used as co-catalyst, add Normal heptane solvent after 30mL dehydration and deoxidations are refined, regulation ethylene pressure to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, Catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by connecting the high-precision of computer in course of reaction Close Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.After filtering Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber.

Embodiment 13：

Weigh catalyst 160mg in embodiment 7 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then added into reactor 70mL refines normal heptane solvent, regulation ethylene pressure to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, add catalyst and open Begin to react.The instantaneous consumption of online acquisition monomer ethylene is (by the high-accuracy Ethylene mass for connecting computer in course of reaction Flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.By resulting polymers after filtering Weigh and analyze after drying 4h at 60 DEG C in vacuum drying chamber.

Embodiment 14：

Weigh catalyst 160mg in embodiment 4 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then added into reactor 70mL refines normal heptane solvent, regulation ethylene pressure to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, add catalyst and open Begin to react.The instantaneous consumption of online acquisition monomer ethylene is (by the high-accuracy Ethylene mass for connecting computer in course of reaction Flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.By resulting polymers after filtering Weigh and analyze after drying 4h at 60 DEG C in vacuum drying chamber.

Embodiment 15：

Catalyst 160mg in embodiment 4 is weighed respectively carries out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent, is separately added into the triisobutyl aluminium (TIBA) that dosage is Al/Cr=5,10,15,20 Co-catalyst (corresponds to embodiment 15-1,15-2,15-3,15-4) respectively, adds the normal heptane after 30mL dehydration and deoxidations refine Solvent.Ethylene pressure is adjusted to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, add catalyst and start to react.Course of reaction The instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) of middle online acquisition monomer ethylene and by computer Record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.After filtering by resulting polymers 60 in vacuum drying chamber Weigh and analyze after drying 4h at DEG C.

Embodiment 16：

Catalyst 160mg in embodiment 4 is weighed respectively carries out polymerization under atmospheric pressure experiment at different temperatures respectively.It will polymerize anti- Answer kettle heating in vacuum to clean, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times. Then add 40mL into reactor successively and refine normal heptane solvent, add the triisobutyl aluminium (TIBA) that dosage is Al/Cr=5 As co-catalyst, the normal heptane solvent after 30mL dehydration and deoxidations refine, regulation ethylene pressure to 0.15MPa are added.Polymerization Temperature is stablized at 50 DEG C and 70 DEG C (corresponding to embodiment 16-1 and 16-2 respectively) respectively, adds catalyst and starts to react.Reaction During online acquisition monomer ethylene instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) and by Computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.By resulting polymers in vacuum drying chamber after filtering In dry 4h at 60 DEG C after weigh and analyze.

Embodiment 17：

Weigh catalyst 160mg in embodiment 4 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then add successively into reactor Enter the refined normal heptane solvents of 40mL, add the triethyl aluminum (TEA) that dosage is Al/Cr=5 and be used as co-catalyst, add Normal heptane solvent after 30mL dehydration and deoxidations are refined, regulation ethylene pressure to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, Catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by connecting the high-precision of computer in course of reaction Close Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.After filtering Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber.

Embodiment 18：

Catalyst 160mg in embodiment 4 is weighed respectively carries out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent, adds triisobutyl aluminium (TIBA) co-catalyst that dosage is Al/Cr=5, respectively Add through dewater treatment 0.7,2.1,3.5mL 1- hexenes, i.e., 1- hexenes and the volume ratio for polymerizeing solvent for use be respectively 1,3, 5vol%, (corresponding to embodiment 18-1,18-2,18-3 respectively), the normal heptane solvent after 30mL dehydration and deoxidations refine is added, is adjusted Ethylene pressure is saved to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, add catalyst and start to react.It is online in course of reaction Gather the instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) of monomer ethylene and by computer record.1h 50mL hydrochloric acid/alcohol mixed solution terminating reaction is added afterwards.Resulting polymers are done in vacuum drying chamber at 60 DEG C after filtering Weigh and analyze after dry 4h.

Embodiment 19：

Weigh catalyst 160mg in embodiment 4 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then added into reactor 40mL refines normal heptane solvent, adds triisobutyl aluminium (TIBA) co-catalyst that dosage is Al/Cr=5, adds 30mL and take off Normal heptane solvent after water deoxygenation is refined, then 10mLH is added into kettle₂, regulation ethylene pressure to 0.15MPa.Treat temperature in the kettle It is constant after 90 DEG C, add catalyst start to react.The instantaneous consumption of online acquisition monomer ethylene (passes through company in course of reaction Connect the high-accuracy Ethylene mass flowmeter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution is added after 1h to terminate Reaction.Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber after filtering.

Embodiment 20：

Weigh catalyst 100mg in embodiment 4 and carry out pressure polymerization experiment.Stainless steel kettle solvent wiping is clean, will Catalyst loads, and uses high-purity N in case of heating₂Pump drainage 30min.With ethylene gas displacement once, and adjust kettle pressure to 0.12MPa, the interior injection 200mL of kettle refine normal heptane solvent, and the triisobutyl aluminium (TIBA) that addition dosage is Al/Cr=20, which helps, urges Agent.It is constant after 90 DEG C after temperature in the kettle, regulation ethylene pressure to 0.4MPa, it will crush and start anti-in catalyst bottle kettle Should.The instantaneous consumption of online acquisition monomer ethylene is (by the high-accuracy Ethylene mass flow for connecting computer in course of reaction Meter) and by computer record.Polymer and solvent are poured into 100mL hydrochloric acid/alcohol mixed solution terminating reaction after 1h.Will after filtering Resulting polymers are weighed and analyzed after drying 4h at 60 DEG C in vacuum drying chamber.

Embodiment 21：

Weigh catalyst 100mg in embodiment 4 and carry out pressure polymerization experiment.Stainless steel kettle solvent wiping is clean, will Catalyst loads, and uses high-purity N in case of heating₂Pump drainage 30min.With ethylene gas displacement once, and adjust kettle pressure to 0.12MPa, the interior injection 200mL of kettle refine normal heptane solvent, and the triisobutyl aluminium (TIBA) that addition dosage is Al/Cr=20, which helps, urges Agent, add refined 6mL1- hexenes.Constant after 90 DEG C after temperature in the kettle, regulation ethylene pressure will urge to 0.4MPa Crushed in agent bottle kettle and start to react.The instantaneous consumption of online acquisition monomer ethylene is (by connecting computer in course of reaction High-accuracy Ethylene mass flowmeter) and by computer record.Polymer and solvent are poured into 100mL hydrochloric acid/ethanol after 1h to mix Close solution terminating reaction.Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber after filtering.

Comparative example 1：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) it is immersed in alkali formula chromic acetate water In solution (chromium load capacity is 0.5wt%), dipping 4h is continuously stirred at room temperature, is warming up at 120 DEG C and dries 4h, be then transferred to Oven drying 6h；Dry sample is placed in quartzy fluid bed, 600 DEG C of roastings 4h, calcination procedure such as Fig. 2 under high pure air Shown, then natural cooling shifts under nitrogen protection, obtains Phillips chromium-based catalysts and saves backup.

Comparative example 2：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) to be immersed in ammonium metavanadate water-soluble In liquid (vanadium load capacity is 0.24wt%), after dipping 4h is continuously stirred at 60 DEG C, it is warming up at 120 DEG C and dries 4h, then shift To oven drying 6h；Dry sample is placed in quartzy fluid bed, 600 DEG C of roasting 4h in high pure air, then in nitrogen The lower Temperature fall transfer of protection, the vanadium catalyst loaded save backup.

Comparative example 3：

By 10g silica gel (pore volume 1.5-1.7cm³/ g, surface area 250-300m²/ g) to be immersed in chromium trioxide water-soluble In liquid (chromium load capacity is 1wt%), after dipping 4h is stirred at room temperature, 120 DEG C of dry 6h are warming up to, are then transferred to oven drying 6h；Dry sample is placed in quartzy fluid bed, 600 DEG C of calcination activation 4h in high pure air, obtains Phillips catalyst. 10g silica-gel carriers are immersed in ammonium metavanadate aqueous solution (vanadium load capacity is 0.48wt%), at 50 DEG C after stirring dipping 4h, done It is dry to be then transferred to oven drying 6h；Dry sample is placed in quartzy fluid bed 600 DEG C of roastings are carried out in high pure air 4h is activated, under nitrogen protection natural cooling, the vanadium catalyst loaded.By Phillips catalyst obtained above and bear The vanadium catalyst of load under nitrogen protection, mixes according to the machinery of Cr/V mol ratios 2: 1, obtains mixed catalyst and save backup.

Comparative example 4：

Weigh catalyst 160mg in comparative example 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent, the triisobutyl aluminium (TIBA) that dosage is Al/Cr=5 is added and is used as co-catalyst, N-heptane solution is refined with 30mL rinse kettle wall, regulation ethylene pressure to 0.15MPa again.It is constant after 90 DEG C after temperature in the kettle, Catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by connecting the high-precision of computer in course of reaction Close Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.After filtering Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber.

Comparative example 5：

Weigh catalyst 160mg in comparative example 2 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent, the triisobutyl aluminium (TIBA) that dosage is Al/V=5 is added and is used as co-catalyst；Again N-heptane solution, which is refined, with 30mL rinses kettle wall, regulation ethylene pressure to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, add Enter catalyst to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by connecting the high-accuracy of computer in course of reaction Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.Will after filtering Resulting polymers are weighed and analyzed after drying 4h at 60 DEG C in vacuum drying chamber.

Comparative example 6：

Weigh catalyst 160mg in comparative example 3 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent；Add the triisobutyl aluminium (TIBA) that dosage is Al/Cr=5 and be used as co-catalyst； N-heptane solution is refined with 30mL rinse kettle wall, regulation ethylene pressure to 0.15MPa again.It is constant after 90 DEG C after temperature in the kettle, Catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by connecting the high-precision of computer in course of reaction Close Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.After filtering Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber..

Comparative example 7：

Weigh catalyst 160mg in comparative example 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent, adds triisobutyl aluminium (TIBA) co-catalyst that dosage is Al/Cr=5, respectively Add through dewater treatment 0.7,2.1,3.5mL 1- hexenes, i.e., 1- hexenes and the volume ratio for polymerizeing solvent for use be respectively 1,3, 5vol%, (corresponding to comparative example 7-1,7-2,7-3 respectively), and refine n-heptane solution with 30mL and rinse kettle wall, adjust second Alkene pressure is to 0.15MPa.It is constant after 90 DEG C after temperature in the kettle, add catalyst and start to react.Online acquisition in course of reaction The instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) of monomer ethylene and by computer record.Add after 1h Enter 50mL hydrochloric acid/alcohol mixed solution terminating reaction.After filtering resulting polymers are dried into 4h in vacuum drying chamber at 60 DEG C After weigh and analyze.

Comparative example 8：

Weigh catalyst 160mg in comparative example 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent, the triisobutyl aluminum cocatalyst that dosage is Al/Cr=5 is added, adds 30mL Normal heptane solvent after dehydration and deoxidation is refined, then 10mLH is added into kettle₂, regulation ethylene pressure to 0.15MPa.Treat warm in kettle Spend it is constant after 90 DEG C, add catalyst start to react.The instantaneous consumption of online acquisition monomer ethylene (passes through in course of reaction Connect the high-accuracy Ethylene mass flowmeter of computer) and by computer record.It is whole that 50mL hydrochloric acid/alcohol mixed solution is added after 1h Only react.Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber after filtering.

Comparative example 9：

Weigh catalyst 160mg in comparative example 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent, the triethyl aluminum (TEA) for adding Al/Cr=5 is co-catalyst, adds 30mL and takes off Normal heptane solvent after water deoxygenation is refined, regulation ethylene pressure to 0.15MPa.Constant after 90 DEG C after temperature in the kettle, addition is urged Agent starts to react.The instantaneous consumption of online acquisition monomer ethylene is (by the high-accuracy second for connecting computer in course of reaction Alkene mass flowmenter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.By gained after filtering Polymer is weighed and analyzed after drying 4h at 60 DEG C in vacuum drying chamber.

Comparative example 10：

Weigh catalyst 100mg in comparative example 1 and carry out pressure polymerization experiment respectively.By stainless steel kettle solvent wiping Totally, catalyst is loaded, uses high-purity N in case of heating₂Pump drainage 30min.With ethylene gas displacement once, and kettle is adjusted For pressure to 0.12MPa, injection 200mL refines normal heptane solvent in kettle, adds Al/Cr=20 triisobutyl aluminium.Treat warm in kettle Constant after 90 DEG C, regulation ethylene pressure to 0.4MPa is spent, will be crushed in catalyst bottle kettle and start to react.In course of reaction Line gathers the instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) of monomer ethylene and by computer record. Polymer and solvent are poured into 100mL hydrochloric acid/alcohol mixed solution terminating reaction after 1h.By resulting polymers in vacuum after filtering Weigh and analyze after drying 4h at 60 DEG C in drying box.

Comparative example 11：

Weigh catalyst 100mg in comparative example 2 and carry out pressure polymerization experiment respectively.By stainless steel kettle solvent wiping Totally, catalyst is loaded, uses high-purity N in case of heating₂Pump drainage 30min.With ethylene gas displacement once, and kettle is adjusted For pressure to 0.12MPa, injection 200mL refines normal heptane solvent in kettle, adds Al/V=40 triisobutyl aluminium.Treat temperature in the kettle It is constant after 90 DEG C, regulation ethylene pressure will be crushed in catalyst bottle kettle and start to react to 0.4MPa.It is online in course of reaction Gather the instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) of monomer ethylene and by computer record.1h Polymer and solvent are poured into 100mL hydrochloric acid/alcohol mixed solution terminating reaction afterwards.Resulting polymers are done in vacuum after filtering Weigh and analyze after drying 4h at 60 DEG C in dry case.

Comparative example 12：

Weigh catalyst 100mg in comparative example 1 and carry out pressure polymerization experiment.Stainless steel kettle is done with solvent wiping Only, catalyst is loaded, uses high-purity N in case of heating₂Pump drainage 30min.With ethylene gas displacement once, and kettle pressure is adjusted Power the refined normal heptane solvents of the interior injection 200mL of kettle, adds Al/Cr=20 triisobutyl aluminium, then adds 6ml to 0.12MPa Refined 1- hexenes.It is constant after 90 DEG C after temperature in the kettle, regulation ethylene pressure to 0.4MPa, it will be crushed in catalyst bottle kettle And start to react.The instantaneous consumption of online acquisition monomer ethylene is (by the high-accuracy ethene for connecting computer in course of reaction Mass flowmenter) and by computer record.Polymer and solvent are poured into 100mL hydrochloric acid/alcohol mixed solution terminating reaction after 1h. Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber after filtering.

Comparative example 13：

Weigh catalyst 100mg in comparative example 2 and carry out pressure polymerization experiment.Stainless steel kettle is done with solvent wiping Only, catalyst is loaded, uses high-purity N in case of heating₂Pump drainage 30min.With ethylene gas displacement once, and kettle pressure is adjusted Power the refined normal heptane solvents of the interior injection 200mL of kettle, adds Al/V=40 triisobutyl aluminium, then adds 6ml to 0.12MPa Refined 1- hexenes.It is constant after 90 DEG C after temperature in the kettle, regulation ethylene pressure to 0.4MPa, it will be crushed in catalyst bottle kettle And start to react.The instantaneous consumption of online acquisition monomer ethylene is (by the high-accuracy ethene for connecting computer in course of reaction Mass flowmenter) and by computer record.Polymer and solvent are poured into 100mL hydrochloric acid/alcohol mixed solution terminating reaction after 1h. Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber after filtering.

The ethylene polymerization activity of 1 each embodiment of table

Note：Every its polymerization activity of the catalyst containing chromium of the present invention is calculated with unit mole chromium, and the pure catalyst containing vanadium Its polymerization activity is then calculated with unit mole vanadium, hereafter together.

(1) influence of co-catalyst

The co-catalyst dosage of table 1 is catalyzed the influence of ethylene homo to chrome alum composite catalyst

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature=90 DEG C；Normal heptane=70mL； Cr=0.5% (wt), V=0.24% (wt)；Co-catalyst=TiBA, embodiment 14,15.

It is representative with embodiment 14 and 15, has investigated the second of chrome alum double activity center catalyst under different co-catalyst dosages Polyamino alkenyl activity, such as table 1.

As known from Table 1, under conditions of using TiBA as co-catalyst, with the aluminium chromium ratio of co-catalyst from 5 to 20 it is continuous Increase, the process of a decline is presented in the activity of chrome alum double activity center catalyst ethylene homopolymerization, and it is high living that explanation will reach polymerization Property, the dosage of co-catalyst is that have suitable a value or scope, and catalyst is when Al/Cr is 5, active highest.

2. different co-catalysts of table are to chrome alum double activity center catalyst and Phillips catalyst ethylene homos Influence

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature=90 DEG C；Normal heptane=70mL： Cr=0.5% (wt), comparative example 4,9 and embodiment 15-1,17.

Table 2 is represented using different co-catalysts to chrome alum double activity center catalyst and Phillips catalyst ethene The influence of homopolymerization activity.Co-catalyst activity is done using TEA be less than and with TiBA do co-catalyst.Further by the said goods The analysis of polyethylene understands that the product polyethylene under the effect of different co-catalysts has a similar fusing point, but its molecular weight Differ widely with molecular weight distribution, illustrate co-catalyst to after the reducing degree of catalyst active center and reduction be distributed with compared with Big influence.

(2) influence of the polymerization temperature to polymerization

Influence of the polymerization temperature of table 3 to chrome alum double activity center catalyst ethylene homo

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Normal heptane=70mL；Cr=0.5% (wt), V =0.24% (wt)；Co-catalyst=TiBA, embodiment 16,15-1.

Table 3 is that the ethene of the chrome alum double activity center catalyst under different polymerization temperatures (the embodiment 15-1 of embodiment 16) gathers Close result.Catalyst has most highly active at 50 DEG C, is decreased with the rise polymerization catalyst activity of temperature, at 90 DEG C When there is lowest activity.The polyethylene product obtained under different polymerization temperatures has similar fusing point, and its molecular weight is with polymerization The rise of temperature, there is the trend reduced, illustrate that polymerization temperature rise is more favourable to polymerisation chain tra nsfer.

(3) comparison of the catalyst difference preparation method to ethylene homo performance

The polymerization of catalyst obtained by 4 different preparation methods of table

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature：90 DEG C, normal heptane=70mL； Cr=0.5% (wt), V=0.48% (wt)；Co-catalyst=TiBA；Embodiment 8 and embodiment 9.

Embodiment 8 and embodiment 9 are that chrome alum prepared by two kinds of different loads modes of step impregnation and co-impregnation is respectively adopted The polymerization activity of catalyst under the same conditions, it is seen that the activity of composite catalyst prepared by step impregnation is higher.

(4) influence of the dosage of 1- hexenes to ethene/1- hervene copolymer performances

The ethene of table 5,1- hervene copolymers are to chrome alum double activity center catalyst and the shadow of Phillips catalyst copolymerized characteristics Ring

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature：90 DEG C, normal heptane=70mL； Cr=0.5% (wt)；Co-catalyst=TiBA, embodiment 15-1,18 and comparative example 4,7.

Table 5 gives the result of chrome alum double activity center catalyst and Phillips catalyst ethylenes/1- hexene oligomerizations.Chromium The ethene of vanadium double activity center catalyst/1- hervene copolymer activity shows the trend of reduction, with reference to the knot of ethylene homo before Fruit, show that ethene/1- hervene copolymer activity is below the activity of ethylene homo.The ethene of Phillips catalyst/1- hexenes are total to Poly- activity shows the trend reduced after first slightly increasing.1- hexenes are added, the polymerization of other chrome alum double activity center catalyst is lived Property equally declines.

Fig. 3 and Fig. 4 is respectively chrome alum double activity center catalyst, Phillips catalyst and load barium oxide catalysis The Alathon and ethene of agent are compared with the GPC spectrograms of 1- hexene copolymer products.

(5) influence of the hydrogen to polymerization

Influence of the hydrogen of table 6. to ethylene homo

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature：90 DEG C, normal heptane=70mL； Cr=0.5% (wt)；Co-catalyst=TiBA；Comparative example 4,8 and embodiment 15-1,19.

Table 6 is visible, and the ethylene homo activity of different catalysts is than all decreasing and gathering under the conditions of existing for no hydrogen The molecular weight and fusing point of ethene all decrease, and illustrate that hydrogen plays a part of chain-transferring agent and caused under its molecular weight and fusing point Drop.

Claims

A kind of 1. support type chrome alum double activity center catalyst for being used to prepare polyethylene, it is characterised in that：Catalyst composition bag Two kinds of active components of inorganic carrier and load are included, two kinds of active components include chromated oxide and barium oxide,

The preparation method of the catalyst is selected from：

Method 1：I) inorganic carrier is impregnated into the solution containing vanadium, then dried, be then calcined and live at 300~900 DEG C of high temperature Change；

Ii the product obtained by step i)) is impregnated into the solution containing chromium, then dried, is then calcined at 300~900 DEG C of high temperature Activation, obtains the catalyst and saves backup；

Or

Method 2：I) inorganic carrier is impregnated into the solution containing chromium, then dried, be then calcined and live at 300~900 DEG C of high temperature Change；

Ii the product obtained by step i)) is impregnated into the solution containing vanadium, then dried, is then calcined at 300~900 DEG C of high temperature Activation, obtains the catalyst and saves backup.
2. catalyst according to claim 1, it is characterised in that：The inorganic carrier is selected from silica, three oxidations two Aluminium, titanium dioxide, zirconium oxide, magnesia, calcium oxide, inorganic clay and combinations thereof.
3. catalyst according to claim 1, it is characterised in that：Carrier material is porous inorganic carrier, specific surface area For 50~500m²/g。
4. catalyst according to claim 1, it is characterised in that：The pore volume of inorganic carrier used is 0.1~5.0cm³/ G, average pore size is in 1~50nm.
5. catalyst according to claim 1, it is characterised in that：Cr load capacity on inorganic carrier is total catalyst weight 0.01~10wt%, based on Cr weight.
6. catalyst according to claim 1, it is characterised in that：V loads based on the weight by vanadium on inorganic carrier Amount, it is 10~500% of the Cr load capacity in terms of the weight of chromium, vanadium load capacity is 0.01~10wt% of total catalyst weight.
7. catalyst according to claim 1, it is characterised in that：The raw material of chromium active component is to be water-soluble containing chromic salts, three Chromium oxide and combinations thereof.
8. catalyst according to claim 1, it is characterised in that：The raw material of vanadium active component for it is water-soluble containing vanadic salts, it is non- Water solubility contains vanadic salts and combinations thereof.
9. catalyst according to claim 1, a kind of preparation method is as follows：

Support type chrome alum double activity center catalyst prepared by any one method in claim 1, is further added organic Metal promoters carry out prereduction activation process, and the catalyst that prereduction activation is obtained after drying saves backup.
10. the support type chrome alum double activity center catalyst according to any one of claim 1~9 is used to produce ethylene homo The purposes of thing and ethylene/alpha-olefin copolymer, organic metal promoters, hydrogen can be added again as needed in polymerization process.
11. purposes according to claim 10, organic metal co-catalyst includes organo-aluminum compound, organolithium chemical combination Any one in thing, organoboron compound or combinations thereof.