CN103145897A - Supported metal oxide double-active center ethylene-polymerization catalyst and its preparation method and use - Google Patents

Abstract

Preparation and application of a supported chromium vanadium metal oxide double active center ethylene polymerization catalyst. It is characterized in that: the loaded vanadium active component is introduced on the Phillips chromium series catalyst. The catalyst composition includes an inorganic carrier and supported two active components, and the two active components include chromium oxide and vanadium oxide. The preparation method of the catalyst is as follows: the chromium salt and the vanadium salt are impregnated on the inorganic support according to a certain ratio through the step-by-step or co-impregnation method, and the catalyst is obtained by roasting at high temperature after drying. The supported chromium-vanadium double-active center catalyst described in the invention is a catalyst for efficiently preparing polyethylene, and can be used for preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins. The catalyst has high polymerization activity, wide molecular weight distribution of polyethylene products (some products show bimodal distribution), hydrogen adjustment sensitivity and good copolymerization performance, and it is not necessary to modify the existing equipment for preparing polyethylene using Phillips catalyst, so it can be easily popularized and applied .

Description

Preparation and the application of a kind of load metal oxide double activity center ethylene rolymerization catalyst

Technical field

The present invention relates to preparation and the application of a kind of supported chrome vanadium metal oxide compound double activity center ethylene rolymerization catalyst, it is characterized in that: the vanadium active ingredient of introducing load on traditional loading type Phillips chromium-based catalysts, described catalyzer forms two kinds of active ingredients that comprise inorganic carrier and load, and two kinds of active ingredients comprise chromated oxide and barium oxide.The present invention relates to preparation method and the application in Alathon and ethene and alpha-olefin copolymer are produced thereof of novel supported chrome alum double activity center catalyzer.This loading type chrome alum double activity center catalyzer has active high, the characteristic such as molecular weight distribution is wide (portioned product is bimodal distribution), hydrogen is transferred response and copolymerization performance is superior.

Background technology

Polyethylene is as a kind of general plastics, due to its good mechanical property, electrical insulating property, chemical resistance and resistance to low temperature, the every field that is widely used in industry, agricultural, automobile, communication and daily life, these polyethylene products with premium properties have close relationship with the catalyzer that uses.The Phillips chromium-based catalysts is being produced the high density polyethylene(HDPE) of 40% left and right in the world, due to its product with a small amount of long-chain branch, thereby have unique rheology and a processing characteristics, be specially adapted to gas line and water service pipe, the automotive oil tank etc. of machining large hollow container, anti-long-term static pressure, and these products can't be substituted by the product of Ziegler-Natta catalyst, novel metallocene catalyst and rear transition metal polyolefin catalyst also at present.At present, the Phillips catalyzer has very important status in polyolefin industry is produced, and China has also strengthened the introduction dynamics of Phillips polyethylene process and device technique in recent years.

The Phillips catalyzer is that J.P Hogan and two researchers of R.L.Bank by the Phillips oil company report in patent US2825721 the earliest.This patent is take chromic oxide as raw material, studied under different condition, comprise polymerization temperature, polymerization time, monomer concentration and catalyst levels ratio, catalyzer carry chromium amount, support modification, catalyzer preparation condition etc., on the impact of Phillips catalyst olefinic polymerization performance.Afterwards, US4295997, US4528338, US5401820 had developed the Phillips catalyzer, were raw material such as adopting hypotoxic chromic salt, to avoid using the CrO of high toxic ₃Raw material.

Traditional vanadium series catalyst is used in homogeneous phase Ziegler-Natta catalyst vinyl polymerization system, be mainly used in regulating the molecular weight distribution of Ziegler-Natta catalyst product and the distribution situation of comonomer, enhance product performance, show: the molecular weight distribution of production is narrower, molecular weight is higher; Produce ethylene/alpha-olefin copolymer, and comonomer insertion amount is more; But synthesis of syndiotactic polypropylene etc. also.

Zakharov etc. have investigated VCl ₄Load on MgCl ₂The polymerization of Kaolinite Preparation of Catalyst on carrier, but the polyethylene of this catalyzer production wide molecular weight distribution found, and hydrogen is transferred very high response value is arranged, can be referring to document Chinese Journal of Polymer Science, 2008,26,553-559.

Patent US4199475 has reported tetraethyl titanate and vanadium oxytrichloride has been loaded on the catalyzer for preparing on silica gel, has very high ethylene polymerization activity.

At present, there is no the relevant load-type vanadium oxide compound that adopts as the report in olefinic polyreaction active centre, equally also the load-type vanadium oxide compound is not introduced the relevant report of Phillips chromium-based catalysts as active ingredient.

Summary of the invention

Target of the present invention is to produce the novel chrome alum double activity center catalyzer of a kind of efficient synthesizing ethylene homopolymer and ethene and alpha-olefin copolymer, the polyethylene of its production is being guaranteed under the wide prerequisite of molecular weight distribution, improve content and the distribution thereof of comonomer, it is reduced in lower molecular weight end insertion amount, and increase in high molecular end insertion amount, thereby easily form more tie molecule, develop the better polyethylene product of performance, catalyzer also has higher activity simultaneously, hydrogen is transferred response performance etc.

The invention provides the preparation method of a kind of loading type chrome alum double activity center catalyzer, to be that preparation is a kind of load on double activity center's ethylene rolymerization catalyst on inorganic carrier with chromium, barium oxide to purpose.The present invention also provides this application of loading type chrome alum double activity center's catalyzer in ethylene homo and ethene and alpha-olefin copolymer.

Inorganic carrier of the present invention is selected from silicon-dioxide, aluminium sesquioxide, titanium dioxide, zirconium white, magnesium oxide, calcium oxide, inorganic clay and their combination, and described inorganic clay can comprise such as montmorillonite etc.According to one embodiment of the invention, described inorganic carrier is selected from silica gel, particularly unformed porous silica gel.These carriers are well known in the art, can be purchased or synthesize by known method.As an example of silica gel, can mention Davison 955.

According to one embodiment of the invention, the specific surface area of inorganic carrier used is usually at 50～500m ²/ g, preferred 100～300m ²/ g, the pore volume of inorganic carrier are 0.1～5.0cm ³/ g, preferred 0.5～3.0cm ³/ g.The inorganic carrier that uses in the present invention can be any inorganic carrier that is generally used in the olefin polymerization catalysis preparation.

The double activity center of catalyzer of the present invention is provided by barium oxide and the chromated oxide of catalyst surface load.There is the water-soluble vanadic salts that contains in the source of vanadium: as hexafluoro ammonium vanadate, nitric acid vanadium, oxalic acid vanadyl, ammonium meta-vanadate, vanadylic sulfate, sulfuric acid oxidation vanadium (IV) hydrate, Vanadosulfuric acid (III), three chloro vanadium oxides, sodium orthovanadate, sodium metavanadate etc., and the water-insoluble vanadic salts that contains: as bis-acetylacetonate vanadium oxide, Triisopropoxyvanadium(V) oxide, three propyl alcohol vanadium oxides, vanadium acetylacetonate, oxidation triethoxy vanadium, vanadyl chloride, silication three vanadium, other suitable solubility vanadic salts and their combination.Chromium used source is selected from chromium trioxide, chromium nitrate, chromium acetate, chromium chloride, chromium sulphate, ammonium chromate, ammonium dichromate, alkali formula chromium acetate, other suitable solubility chromic salts and their combination.

For catalyzer of the present invention, the charge capacity of chromium is generally 0.01～10wt% of total catalyst weight on inorganic carrier, and preferred 0.05～5wt% presses the weighing scale of chromium.

According to one embodiment of the invention, the charge capacity of vanadium is generally 10～500% weighing scale of chromium and vanadium (all with) of chromium charge capacity on inorganic carrier, be preferably 20～400%, the vanadium charge capacity is generally 0.01～10wt% of total catalyst weight, preferred 0.05～5wt%.

According to an aspect of the present invention, the invention provides the method for preparing loading type chrome alum double activity center catalyzer, wherein a kind of method comprises following steps:

I) the inorganic carrier dipping is contained the solution of vanadium, then dry, then at 300～900 ℃ of lower calcination activations of high temperature;

Ii) with step I) product of gained dipping contains the solution of chromium, and is then dry, and then at 300～900 ℃ of lower calcination activations of high temperature, obtain described catalyzer and save backup.

According to a method that preferably prepares loading type chrome alum double activity center catalyzer, comprise following steps:

I) with the salt solution impregnation of vanadium on inorganic carrier, dipping time is 1～12h, preferred 4～8h, dipping temperature is 10～80 ℃, and is preferred 20～70 ℃, then dry under 90～250 ℃, preferred 100～200 ℃, time of drying 6～20h, preferred 8～15h also can adopt vacuum-drying in drying process; Above-mentioned sample is carried out the high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 300～900 ℃, preferred 400～800 ℃, time is 1～10h, preferred 4～6h, then carry out coolingly, wherein switch to rare gas element such as nitrogen or argon gas etc., naturally cooling when being cooled to 300～400 ℃;

Ii) salt solution impregnation with chromium has on the inorganic carrier of vanadium in above-mentioned load, dipping time is 1～12h, preferred 4～8h, dipping temperature is 10～80 ℃, and is preferred 15～60 ℃, then dry between 90～250 ℃, preferred 100～150 ℃, time of drying 6～20h, preferred 8～15h also can adopt vacuum-drying in drying process; Above-mentioned sample is carried out calcination activation in rare gas element or oxygen or air, maturing temperature is at 300～900 ℃, preferred 400～800 ℃, time is 1～10h, then preferred 3～8h carries out coolingly, switches to rare gas element such as nitrogen or argon gas etc. when being cooled to 300～400 ℃, naturally cooling obtains described catalyzer and saves backup.

Usually, the present invention utilizes mineral compound as carrier, and first with vanadium source dipping thereon, then high-temperature roasting makes the catalyst Precursors of load vanadium; Then in containing the solution of above-mentioned catalyst Precursors, add the inorganic chromium source to carry out load, thus preparation loading type chrome alum double activity center catalyzer.

Above-mentioned steps i) be that the vanadium source is carried on method on inorganic carrier (for example inorganic carrier mentioned above).The method that is used for the vanadium source is carried on inorganic carrier can be known any method that vanadium can be carried on carrier.According to one embodiment of the invention, the vanadium source is carried on method on inorganic carrier comprises with vanadium source solution impregnation porous inorganic carrier.According to an embodiment, in steeping process, can implement to stir preferred continuously stirring.Usually, this stirs and continues approximately 1～12h, preferred approximately 4～8h, and dipping temperature is 10～80 ℃, preferred 20～70 ℃.According to an embodiment, the vanadium charge capacity is 0.01～10wt% of total catalyst weight, preferred approximately 0.05～5wt%.Then the load that obtains there is the carrier of vanadium component to carry out drying.This drying ℃ is carried out in room temperature～250 usually, preferably at approximately 90～250 ℃, and further preferred approximately 100～200 ℃.According to an embodiment, this drying approximately 120 ℃ carry out.This drying also can be carried out under vacuum condition.The time that this drying is carried out is not particularly limited, but should drying usually continue approximately 6～20h, preferred approximately 7～18h, further preferred approximately 8～15h.After drying is complete, there is the inorganic carrier of vanadium component to carry out roasting load.The mode that roasting is carried out is not particularly limited, but this roasting is preferably carried out in fluidized-bed.According to an embodiment, this roasting is carried out with two stages usually, i.e. low thermophase and hot stage.Low thermophase usually approximately 100～300 ℃ carry out.This hot stage usually approximately 300～900 ℃ carry out.Be not bound by any theory, the mechanical water that adsorbs in described low thermophase carrier is removed substantially, and the part of hydroxyl on described hot stage inorganic carrier is removed.According to an embodiment, described low thermophase continues 1～10 hour, and preferred 2～9 hours, more preferably 3～8 hours.According to another embodiment, described hot stage continues 1～10 hour, and preferred 2～9 hours, more preferably 3～8 hours.According to an embodiment, described low thermophase carries out under rare gas element or air atmosphere, preferably carries out under inert gas atmosphere, and described rare gas element preferably carries out under nitrogen atmosphere, for example high pure nitrogen such as being the atmosphere such as nitrogen, helium, argon gas.According to an embodiment, described hot stage roasting is carried out under air or Oxygen Condition, preferably carries out under the dry air condition.After described roasting finishes, there is the inorganic carrier of inorganic oxide form vanadium cooling from hot stage the load that obtains.According to an embodiment, when the temperature that is cooled to 300～400 ℃, can conversion atmosphere, for example become rare gas element from air, such as nitrogen, argon gas etc.According to an embodiment, this is cooled to the nature cooling down.

Above-mentioned steps ii) be that the inorganic chromium source is carried on step I) in the load of preparation method on the inorganic carrier (for example inorganic carrier mentioned above) of vanadium is arranged.The method that is used for the inorganic chromium source is carried on the inorganic carrier that is loaded with in advance vanadium can be any method that chromium can be carried on carrier well known by persons skilled in the art, for example can mention the conventional known method for preparing the Phillips catalyzer.Described inorganic chromium source can be inorganic chromium source mentioned above.According to an embodiment, in steeping process, can implement to stir preferred continuously stirring.Usually, this stirs and continues approximately 1～approximately 12 hour, preferred approximately 4～8 hours.According to an embodiment, the charge capacity of inorganic chromium is approximately 0.01～approximately 10wt% of total catalyst weight, preferred approximately 0.05～5wt%, further preferred approximately 0.1～3wt%.Then the carrier that obtains is carried out drying.This drying is carried out in the temperature of about room temperature to 200 ℃ usually; For example carry out at about 15 ℃ to 250 ℃, preferably at approximately 90 ℃ to 250 ℃, further preferred approximately 100 ℃ to 200 ℃.According to an embodiment, this drying approximately 120 ℃ carry out.The time that this drying is carried out is not particularly limited, but should drying usually continue approximately 6～20 hours, and preferred approximately 7～18 hours, further preferred approximately 8～15 hours.After drying is complete, the inorganic carrier of metal in load is carried out roasting.The mode that roasting is carried out is not particularly limited, but this roasting is preferably carried out in fluidized-bed.According to an embodiment, this roasting is carried out with two stages usually, i.e. low thermophase and hot stage.Should low thermophase usually approximately 100～300 ℃ carry out.This hot stage usually approximately 300～900 ℃ carry out.Be not bound by any theory, believe that the mechanical water that adsorbs is removed in described low thermophase carrier, and the part of hydroxyl on described hot stage inorganic carrier be removed.According to an embodiment, described low thermophase continues 1～10 hour, preferred 2～8 hours.According to another embodiment, described hot stage continues 1～10 hour, and preferred 2～9 hours, more preferably 3～8 hours.According to an embodiment, described low thermophase carries out under rare gas element or air atmosphere, preferably carries out under rare gas element, and the atmosphere such as described rare gas element such as nitrogen, helium, argon gas are preferably carried out under nitrogen atmosphere, for example high pure nitrogen.According to an embodiment, described hot stage roasting is carried out under air or Oxygen Condition, preferably carries out under the dry air condition.After described roasting finishes, that the inorganic carrier of metal in the load that obtains is cooling from hot stage.According to an embodiment, when being cooled to the temperature of 300～400 ℃ after high-temperature roasting, can conversion atmosphere, for example become rare gas element from air, such as nitrogen etc.According to an embodiment, this is cooled to the nature cooling down.The catalyzer that obtains is saved backup under inert gas atmosphere.

As an example, the concrete operations of preparation catalyzer of the present invention comprise:

The porous amorphous silica gel is immersed in certain density ammonium metavanadate solution, and the vanadium charge capacity meets the requirement (for example 0.1～10wt%, with the weighing scale of vanadium) of this paper with respect to total catalyst weight; After continuously stirring certain hour (for example 4～8 hours), heat up dry; There is the silica-gel carrier of ammonium meta-vanadate to carry out high-temperature roasting in fluidized-bed load, the mechanical water during roasting removes carrier in nitrogen atmosphere at low thermophase (for example 100 ℃～300 ℃) wherein, remove the part of hydroxyl of Silica Surface in hot stage (for example 300 ℃～900 ℃) roasting in dry air, keep certain hour (for example 3～8 hours) at this hot stage; The nature cooling down switches to nitrogen protection when being cooled to 300～400 ℃, make the catalyst Precursors that carries vanadium.Then, the inorganic chromium source is loaded on the catalyst Precursors that is made by aforesaid method, after the chromium charge capacity meets requirement (for example being 0.1～1wt% of total catalyst weight, with the weighing scale of chromium) the continuously stirring certain hour (for example 4～8 hours) of this paper, heat up dry; Then carry out high-temperature roasting in fluidized-bed, the mechanical water that wherein adsorbs during roasting removes silica-gel carrier in nitrogen atmosphere at low thermophase (for example 100 ℃～300 ℃), remove the part of hydroxyl of Silica Surface in hot stage (for example 300 ℃～900 ℃) roasting in dry air, keep certain hour (for example 3～8 hours) at this hot stage; The nature cooling down switches to nitrogen protection when being cooled to 300～400 ℃, shift under nitrogen protection, and catalyzer saves backup.

A kind of preparation method who the invention provides loading type chrome alum double activity center catalyzer comprises following steps:

I) the inorganic carrier dipping is contained the solution of vanadium and chromium, then dry;

Ii) with i) product of gained is at 300 ℃～900 ℃ lower calcination activations of high temperature, and obtain described catalyzer and save backup.

Comprise step according to a method that preferably prepares loading type chrome alum double activity center catalyzer:

I) will contain the method that the mixing salt solution of chrome alum steeps by total immersion loads on inorganic carrier, dipping time is 1～12h, preferred 4～8h, dipping temperature is 10～80 ℃, and is preferred 20～70 ℃, then dry between 90～250 ℃, preferred 100～200 ℃, time of drying 6～20h, preferred 8～15h also can adopt vacuum-drying in drying process;

Ii) above-mentioned sample is carried out the high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 300～900 ℃, preferred 400～800 ℃ of times are 1～10h, preferred 3～8h, then carry out cooling, switch to rare gas element such as nitrogen or argon gas etc. when being cooled to 300～400 ℃, naturally cooling obtains described catalyzer and saves backup.

Above-mentioned steps i) be that inorganic vanadium source and vanadium source are carried on method on inorganic carrier (for example inorganic carrier mentioned above) simultaneously.Described inorganic chromium source can be inorganic chromium source mentioned above, and the vanadium source can be any vanadium source mentioned above.According to an embodiment, in steeping process, can implement heated and stirred, preferred laser heating stirs.Usually, this stirs and continues approximately 1～12 hour, and preferred approximately 4～8 hours, dipping temperature was 10～80 ℃, preferred 20～70 ℃.According to an embodiment, the charge capacity of inorganic chromium is 0.01～10wt% of total catalyst weight, preferred 0.05～5wt%, further preferred 0.1～2wt%.The vanadium charge capacity is 0.01～10wt% of total catalyst weight, preferred approximately 0.05～5wt%.Then the carrier that obtains is carried out drying.This drying is carried out in the temperature of about room temperature to 250 ℃ usually; Preferred 90 ℃ to 250 ℃, further preferred 100 ℃ to 200 ℃.The time that this drying is carried out is not particularly limited, but should drying usually continue approximately 6～20 hours, and preferred approximately 7～18 hours, further preferred approximately 8～15 hours.

Above-mentioned steps ii) be after drying is complete, the inorganic carrier that is impregnated with chromium and vanadium compound is carried out roasting, and chrome alum is oxide carried in the inorganic carrier surface the most at last.The mode that roasting is carried out is not particularly limited, but this roasting is preferably carried out in fluidized-bed.According to an embodiment, this roasting is carried out with two stages usually, i.e. low thermophase and hot stage.Should low thermophase usually approximately 100～300 ℃ carry out.This hot stage usually approximately 300～900 ℃ carry out.Be not bound by any theory, believe that the mechanical water that adsorbs is removed in described low thermophase carrier, and the part of hydroxyl on described hot stage inorganic carrier be removed.According to an embodiment, described low thermophase continues 1～10 hour, preferred 2～9 hours.According to another embodiment, described hot stage continues 1～10 hour, and preferred 2～9 hours, more preferably 3～8 hours.According to an embodiment, described low thermophase carries out under rare gas element or air atmosphere, preferably carries out under rare gas element, and the atmosphere such as described rare gas element such as nitrogen, helium, argon gas are preferably carried out under nitrogen atmosphere, for example high pure nitrogen.According to an embodiment, described hot stage roasting is carried out under air or Oxygen Condition, preferably carries out under the dry air condition.After described roasting finishes, that the inorganic carrier of metal oxide in the load that obtains is cooling from hot stage.According to an embodiment, when being cooled to the temperature of 300～400 ℃ after high-temperature roasting, can conversion atmosphere, for example become rare gas element from air, for example nitrogen.According to an embodiment, this is cooled to the nature cooling down.The catalyzer that obtains is saved backup under inert gas atmosphere.

As an example, the concrete operations of preparation catalyzer of the present invention comprise:

The porous amorphous silica gel is immersed in the aqueous solution of certain density ammonium meta-vanadate and alkali formula chromium acetate, the charge capacity of vanadium and chromium meets requirement (vanadium 0.1～10wt% for example, the chromium 0.1～2wt%) of this paper with respect to total catalyst weight; After continuously stirring certain hour (for example 4～8 hours), heat up dry; Then carry out high-temperature roasting in fluidized-bed, the mechanical water that wherein adsorbs during roasting removes carrier in nitrogen atmosphere at low thermophase (for example 100 ℃～300 ℃), remove the part of hydroxyl of Silica Surface in hot stage (for example 300 ℃～900 ℃) roasting in dry air, keep certain hour (for example 3～8 hours) at this hot stage; The nature cooling down switches to nitrogen protection when being cooled to 300～400 ℃, shift under nitrogen protection, and catalyzer saves backup.

The another kind of preparation method who the invention provides loading type chrome alum double activity center catalyzer comprises following steps:

I) the inorganic carrier dipping is contained the solution of chromium, then dry, then at 300 ℃～900 ℃ lower calcination activations of high temperature;

Ii) with step I) product of gained dipping contains the solution of vanadium, and is then dry, and then at 300 ℃～900 ℃ lower calcination activations of high temperature, obtain catalyzer and save backup.

Comprise following steps according to a method that preferably prepares loading type chrome alum double activity center catalyzer:

I) with the salt solution impregnation of chromium on inorganic carrier, dipping time is 1～12h, preferred 4-8h, dipping temperature is 10～80 ℃, and is preferred 20～70 ℃, then dry between 90～250 ℃, preferred 100～150 ℃, time of drying 6～20h, preferred 8～15h also can adopt vacuum in drying process; Above-mentioned sample is carried out the high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 300～900 ℃, preferred 400～800 ℃, time is 1～10h, then preferred 3～8h carries out coolingly, switches to rare gas element such as nitrogen or argon gas etc. when being cooled to 300～400 ℃, naturally cooling obtains the catalyst Precursors that load has chromium;

Ii) salt solution impregnation with vanadium has on the inorganic carrier of chromium to above-mentioned load, dipping time is 1～12h, preferred 3-8h, dipping temperature is 10～80 ℃, and is preferred 20～70 ℃, then dry between 90～250 ℃, preferred 100～150 ℃, time of drying 6～20h, preferred 8～15h also can adopt vacuum in drying process; Above-mentioned sample is carried out the high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 300～900 ℃, preferred 400～800 ℃, time is 1～10h, then preferred 3～8h carries out coolingly, switches to rare gas element such as nitrogen or argon gas etc. when being cooled to 300～400 ℃, naturally cooling obtains described catalyzer and saves backup.

Above-mentioned steps i) be that the inorganic chromium source is carried on method on inorganic carrier (for example inorganic carrier mentioned above).The method that is used for the inorganic chromium source is carried on inorganic carrier can be any method that chromium can be carried on carrier well known by persons skilled in the art, for example can mention the conventional known method for preparing the Phillips catalyzer.Described inorganic chromium source can be inorganic chromium source mentioned above.According to an embodiment, in steeping process, can implement to stir preferred continuously stirring.Usually, this stirs and continues approximately 1～12 hour, preferred approximately 4～8 hours.According to an embodiment, the charge capacity of chromium is the approximately 0.01～10wt% of total catalyst weight, preferred approximately 0.05～5wt%, further preferred approximately 0.1～2wt%.Then the carrier that obtains is carried out drying.This drying is carried out in the temperature of about room temperature to 200 ℃ usually; For example carry out at 15 ℃ to 200 ℃, preferred 20 ℃ to 200 ℃, further preferred 100 ℃ to 200 ℃.According to an embodiment, this drying approximately 120 ℃ carry out.The time that this drying is carried out is not particularly limited, but should drying usually continue approximately 6～20 hours, and preferred approximately 7～18 hours, further preferred approximately 8～15 hours.After drying is complete, the inorganic carrier of metal in load is carried out roasting.The mode that roasting is carried out is not particularly limited, but this roasting is preferably carried out in fluidized-bed.According to an embodiment, this roasting is carried out with two stages usually, i.e. low thermophase and hot stage.Should low thermophase usually approximately 100～300 ℃ carry out.This hot stage carries out at approximately 300 ℃～900 ℃ usually.Be not bound by any theory, believe that the mechanical water that adsorbs is removed in described low thermophase carrier, and the part of hydroxyl on described hot stage inorganic carrier be removed.According to an embodiment, described low thermophase continues 1～10 hour, preferred 2～9 hours.According to another embodiment, described hot stage continues 1～10 hour, and preferred 2～9 hours, more preferably 3～8 hours.According to an embodiment, described low thermophase carries out under rare gas element or air atmosphere, and preferred rare gas element gas more preferably carries out under nitrogen atmosphere, for example high pure nitrogen.According to an embodiment, the described high-temperature roasting stage is carrying out in rare gas element or air, preferred dry high pure air.After described roasting finishes, that the inorganic carrier of metal in the load that obtains is cooling from hot stage.According to an embodiment, when being cooled to the temperature of 300～400 ℃ after high-temperature roasting, can switch atmosphere, for example become rare gas element from air, for example nitrogen.According to an embodiment, this is cooled to the nature cooling down.Preserve the catalyzer that obtains stand-by under inert gas atmosphere.

Above-mentioned steps ii) be that the vanadium source further is carried on step I) in the load of preparation method on the inorganic carrier (for example inorganic carrier mentioned above) of chromium is arranged.The method that is used for the vanadium source is carried on inorganic carrier can be known any method that vanadium can be carried on carrier.According to one embodiment of the invention, the vanadium source is carried on method on the inorganic carrier that is loaded with in advance chromium comprises that this is loaded with the porous inorganic carrier of chromium in advance with vanadium source solution impregnation.According to an embodiment, in steeping process, can implement to stir preferred continuously stirring.Usually, this stirs and continues approximately 1～12 hour, and preferred approximately 4～8 hours, dipping temperature was 10～80 ℃, preferred 20～70 ℃.According to an embodiment, the vanadium charge capacity is 0.01～10wt% of total catalyst weight, preferred approximately 0.05～5wt%.The carrier that is impregnated with the vanadium component that then will obtain carries out drying.This drying is carried out in the temperature of about room temperature～200 ℃ usually; For example carry out at about 15～200 ℃, preferred 20～200 ℃, further preferred approximately 100～200 ℃.According to an embodiment, this drying approximately 120 ℃ carry out.This drying also can be carried out under vacuum condition.The time that this drying is carried out is not particularly limited, but should drying usually continue approximately 6～20 hours, and preferred approximately 7～18 hours, further preferred approximately 8～15 hours.After drying is complete, the sample that is impregnated with the vanadium component is carried out roasting.The mode that roasting is carried out is not particularly limited, but this roasting is preferably carried out in fluidized-bed.According to an embodiment, this roasting is carried out with two stages usually, i.e. low thermophase and hot stage.Low thermophase usually approximately 100～300 ℃ carry out.This hot stage usually approximately 300～900 ℃ carry out.Be not bound by any theory, the mechanical water that adsorbs in carrier at described low thermophase is removed substantially, and at described hot stage, the part of hydroxyl on inorganic carrier is removed.According to an embodiment, described low thermophase continues 1～10 hour, preferred 2～9 hours.According to another embodiment, described hot stage continues 1～10 hour, and preferred 2～9 hours, more preferably 3～8 hours.According to an embodiment, described low thermophase carries out under rare gas element or air atmosphere, preferably carries out under inert gas atmosphere, and described rare gas element is for example above-described rare gas element.According to an embodiment, described hot stage roasting is carried out under air or Oxygen Condition, preferably carries out under the dry air condition.After described roasting finishes, there is the inorganic carrier of inorganic oxide form vanadium and chromium cooling from hot stage the load that obtains.According to an embodiment, when the temperature that is cooled to 300～400 ℃, can conversion atmosphere, for example become rare gas element from air, such as nitrogen, argon gas etc.According to an embodiment, this is cooled to the nature cooling down, obtains catalyzer and saves backup.

As an example, the concrete operations of preparation catalyzer of the present invention comprise:

The porous amorphous silica gel is immersed in the aqueous solution in inorganic chromium source, the requirement that the chromium charge capacity meets this paper (for example is 0.1～2wt% of total catalyst weight, weighing scale with chromium) after continuously stirring certain hour (for example 3～8 hours), heat up dry; Then carry out high-temperature roasting in fluidized-bed, the mechanical water that wherein adsorbs during roasting removes carrier in nitrogen atmosphere at low thermophase (for example 100 ℃～300 ℃), remove the part of hydroxyl of Silica Surface in hot stage (for example 300 ℃～900 ℃) roasting in dry air, keep certain hour (for example 3～8 hours) at this hot stage; The nature cooling down, switch to nitrogen protection when being cooled to 300～400 ℃, shift under nitrogen protection, preserve stand-by, then the catalyst Precursors that obtains is immersed in certain density ammonium metavanadate solution, the vanadium charge capacity meets the requirement (for example 0.1～10wt%, with the weighing scale of vanadium) of this paper with respect to total catalyst weight; After continuously stirring certain hour (for example 4～8 hours), heat up dry; The catalyst Precursors that is impregnated with ammonium meta-vanadate is carried out high-temperature roasting in fluidized-bed, the mechanical water that wherein adsorbs during roasting removes carrier in nitrogen atmosphere at low thermophase (for example 100 ℃～300 ℃), roasting removes the part of hydroxyl of Silica Surface in hot stage (for example 300 ℃～900 ℃) dry air, keeps certain hour (for example 3～8 hours) at this hot stage; The nature cooling down switches to nitrogen protection when being cooled to 300～400 ℃, shift under nitrogen protection, obtains catalyzer and preserves stand-by.

A kind of preparation method who the invention provides loading type chrome alum double activity center catalyzer comprises following steps:

I) the chrome alum double activity center catalyzer that adopts that in above-mentioned three kinds of methods, any one method is prepared comprises that first carrying vanadium carries chromium, chrome alum load simultaneously again and first carry chromium and carry any one in the two centers catalyse agent of three kinds of loading type chrome alums of vanadium again;

Ii) add the organo-metallic promotor to carry out the prereduction activation treatment in above any one loading type chrome alum double activity center catalyzer for preparing, then carry out kept dry standby.

According to a method that preferably prepares loading type chrome alum double activity center catalyzer, comprise following steps:

I) adopt in above-mentioned three kinds of methods any to prepare loading type chrome alum double activity center catalyzer;

Ii) under inert atmosphere, the catalyzer that obtains is added the organo-metallic promotor, catalyzer is carried out the prereduction activation treatment, then between 60-120 ℃ dry 2-8 hour, also can adopt vacuum in drying process, then preserve stand-by under rare gas element.

Usually, aforesaid method is that the loading type chrome alum double activity center catalyzer that obtains is carried out the prereduction activation treatment.Step I) be to prepare loading type chrome alum double activity center catalyzer with any method in above three kinds of methods, step I i) be to add the organo-metallic promotor to carry out the prereduction activation treatment to this loading type chrome alum double activity center catalyzer under inert atmosphere, above-mentioned organo-metallic promotor includes machine aluminium compound, organolithium compound, organoboron compound etc. and well known to a person skilled in the art for any promotor of olefinic polyreaction or their combination.According to an embodiment, the organo-aluminium compound that is used as promotor can comprise trialkylaluminium AlR ₃, dialkyl group aluminum alkoxide AlR ₂OR, dialkylaluminum halides AlR ₂X, aikyiaiurnirsoxan beta, ethyl sesquialter aluminium muriate etc., wherein R is alkyl, the alkyl that for example has 1-12 carbon atom, such as being methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, dodecyl etc., X is halogen, for example fluorine, chlorine, bromine and iodine, preferred chlorine.Described aikyiaiurnirsoxan beta can comprise the reactant of all aluminum alkylss such as methylaluminoxane (MAO) and water.Described organo-aluminium compound as promotor can use separately or two or more is used in combination.As object lesson, described aluminum compound can be mentioned triethyl aluminum, triisobutyl aluminium, diethylaluminum ethoxide, aluminium diethyl monochloride and methylaluminoxane etc.according to an embodiment, when adopting the organoaluminum promotor to carry out the prereduction activation treatment to chrome alum double activity center catalyzer, aluminium/chromium mol ratio is between 0-1000, preferred 0-100, more preferably 0-50, the reduction activation treatment temp is between room temperature-100 ℃, between preferred room temperature-60 ℃, 0.5-20 hour reduction activation treatment time, preferred 0.5-10 hour, reduction activation is processed and is adopted alr mode, preferred continuously stirring, after being disposed between 60～120 ℃ dry 2～8 hours again, drying is carried out under inert gas atmosphere, for example at nitrogen, helium, carry out under the atmosphere such as argon gas, preferably carry out under nitrogen atmosphere, this drying process also can be carried out under vacuum condition.The loading type chrome alum composite catalyst through the prereduction activation that obtains is preserved stand-by under inert gas atmosphere.

As an example, the concrete operations of preparation catalyzer of the present invention comprise:

The porous amorphous silica gel is immersed in certain density ammonium metavanadate solution, and the vanadium charge capacity meets the requirement (for example 0.1～10wt%, with the weighing scale of vanadium) of this paper with respect to total catalyst weight; After continuously stirring certain hour (for example 4～8 hours), heat up dry; There is the silica-gel carrier of ammonium meta-vanadate to carry out high-temperature roasting in fluidized-bed load, the mechanical water that wherein adsorbs during roasting removes carrier in nitrogen atmosphere at low thermophase (for example 100 ℃～300 ℃), remove the part of hydroxyl of Silica Surface in hot stage (for example 300 ℃～900 ℃) roasting in dry air, keep certain hour (for example 3～8 hours) at this hot stage; The nature cooling down switches to nitrogen protection when being cooled to 300～400 ℃, make the catalyst Precursors that carries vanadium.Then, the inorganic chromium source is loaded on the catalyst Precursors that is made by aforesaid method, after the chromium charge capacity meets requirement (for example being 0.1～3wt% of total catalyst weight, with the weighing scale of chromium) the continuously stirring certain hour (for example 3～8 hours) of this paper, heat up dry; Then carry out high-temperature roasting in fluidized-bed, the mechanical water that wherein adsorbs during roasting removes carrier in nitrogen atmosphere at low thermophase (for example 100 ℃～300 ℃), remove the part of hydroxyl of Silica Surface in hot stage (for example 300 ℃～900 ℃) roasting in dry air, keep certain hour (for example 3～8 hours) at this hot stage; The nature cooling down switches to nitrogen protection when being cooled to 300～400 ℃, shift under nitrogen protection, preserves stand-by.Then add triethyl aluminum to carry out the prereduction activation treatment to catalyzer, aluminium/chromium mol ratio is at 0-50, treatment temp is in room temperature-60 ℃, continuously stirring 0.5-10 hour, and then between 60～120 ℃ dry 2～8 hours, this drying is carried out under inert gas atmosphere, such as carrying out under the atmosphere such as nitrogen, helium, argon gas, preferably carry out under nitrogen atmosphere, this drying process also can be carried out under vacuum condition.The chrome alum composite catalyst through the prereduction activation that obtains is preserved stand-by under inert gas atmosphere.

Loading type chrome alum of the present invention double activity center catalyzer (comprising above chrome alum double activity center catalyzer through organo-metallic promotor prereduction activation) can be used for the homopolymerization of ethene or the copolymerization of ethene and alpha-olefin.Can add organic metal promoters, hydrogen etc. as required in polymerization process.

Therefore, according to another aspect of the present invention, provide the method that adopts the two centers catalyse agent of loading type chrome alum of the present invention to produce Alathon and ethylene/alpha-olefin copolymer, the method for particularly producing the olefin polymer with wide molecular weight distribution.

For aforesaid method, the alkene that polymerization is used generally comprises ethene as polymerization single polymerization monomer.In one embodiment, the alkene of described polymerization use also comprises comonomer.Described comonomer can be the alpha-olefin with 3-20 carbon atom, such as propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene etc.; These can use separately or can two or more be used in combination.Described comonomer is 1-butylene, 1-hexene, 1-octene and 1-decene preferably.When comonomer existed, the amount of comonomer was generally 0-30vol%, preferred 0-10vol%, the volumetric concentration of comonomer during based on polymerization.

Can add again as required organic metal promoters (for example organo-metallic promotor mentioned above) in polymerization process in polymerization system, according to an embodiment, described organo-metallic promotor can use organo-aluminium compound, and organo-aluminium compound can be mentioned triethyl aluminum, triisobutyl aluminium, diethylaluminum ethoxide, aluminium diethyl monochloride and methylaluminoxane etc.The usage quantity of described organo-metallic aluminum compound is normally pressed aluminium/chromium molar ratio computing 0-1000, preferred 0-70, more preferably 0-50.

Above-mentioned polyreaction can comprise molecular weight regulator, can mention hydrogen as an example.

Above-mentioned polymers manufacturing method of the present invention is without any particular limitation aspect its polymerization process.The method of above-mentioned employing chrome alum of the present invention double activity center's Catalyst Production Alathon or ethene and alpha-olefin copolymer can comprise gas phase polymerization process, slurry phase polymerisation process, suspension polymerization, bulk polymerization, solution polymerization process etc.As skilled in the art to understand, method to the production olefin polymer that adopts catalyzer of the present invention is not particularly limited, and can adopt the conventional embodiment of gas phase polymerization process known in the art, slurry phase polymerisation process, suspension polymerization, bulk polymerization, solution polymerization process and polymerizing condition etc. to implement.

In one embodiment, use slurry phase polymerisation process, comprise in reactor adding ethene, then add solvent and promotor (organo-aluminium compound) and randomly add hydrogen and comonomer, add at last chrome alum of the present invention double activity center catalyzer to begin polymerization.

The solvent that above-mentioned slurry polymerization uses is generally any solvent for olefinic polymerization known in the field.Described solvent can be the alkane with 3-20 carbon atom, such as propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, normal hexane, hexanaphthene, normal heptane, octane etc.; These solvents can use separately or can two or more be used in combination.The preferred Trimethylmethane of described solvent, iso-pentane, normal hexane, hexanaphthene, normal heptane etc.

In one embodiment, adopt traditional slurry polymerization process to implement polymerization, concrete operations are as follows: first polymerization reaction kettle is carried out the heating under vacuum removal of impurities, then be replaced into high pure nitrogen, repeatable operation three times, replace once with a small amount of vinyl monomer again, and will be full of ethene in reactor to pressure-fired (0.12MPa) at last; Add refining solvent such as normal heptane after dehydration and deoxidation is processed in the reactor, a certain amount of aluminum alkyls is as promotor, in being in harmonious proportion copolymerization experiments, hydrogen also need add respectively a certain amount of hydrogen and comonomer, treat that ethylene pressure transfers to 0.15MPa, add at last catalyzer of the present invention to begin polyreaction; The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record, after certain hour (for example 1 hour) is carried out in (for example 35 ℃-100 ℃) reaction at a certain temperature, add hydrochloric acid/alcohol mixed solution termination reaction; Polymkeric substance is weighed after vacuum-drying and analyzes through washing.

The present invention introduces the vanadium active ingredient of load on traditional loading type Phillips chromium-based catalysts, the catalyzer of inventing contains two kinds of active ingredients, the i.e. chromated oxide of load and barium oxide.Catalyzer of the present invention can be produced Alathon and the ethylene/alpha-olefin copolymer with wide molecular weight distribution in single reaction vessel, have higher ethylene homo and ethene and alpha-olefin copolymer reactive behavior.Use chrome alum of the present invention double activity center catalyzer, by changing the factors such as promotor consumption, polymerization temperature, molecular weight regulator, can facilitate and easily adjust molecular weight and molecualr weight distribution and co-monomer content and the distribution of Alathon and ethylene/alpha-olefin copolymer, thereby can facilitate and easily obtain having the polymeric articles of desired properties.

Description of 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 the pressurization ethylene homo polymkeric substance high temperature GPC spectrogram (comparative example 10,11 and embodiment 20) of three embodiment.

Accompanying drawing 4 is pressurize ethene, 1-hervene copolymer polymkeric substance high temperature GPC spectrogram (comparative example 12,13 and embodiment 21) of three embodiment.

Specific implementation method

The present invention explains in more detail with reference to the following example, and these embodiment do not limit the scope of the invention.The silica gel that adopts in embodiment is commercially available Davison 955.

Various polymer properties in embodiment are measured 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 adopts PL-220 type high-temperature gel permeation chromatography instrument (Polymer Laboratories company) to measure molecular weight of polyethylene and molecular weight distribution thereof.Be solvent with 1,2,4-trichlorobenzene in experiment, measure under 160 ℃.Adopt Narrow distribution polystyrene as the universal calibration method processing data of standard specimen.

Dsc (DSC)

The fusing point of test polymer: this experiment adopts TA Q200 type differential scanning calorimeter to test under nitrogen protection.Sample first is warmed up to 150 ℃ with the speed of 10 ℃/min from room temperature, and constant temperature 5min, then naturally drops to room temperature.Then with the scanning (room temperature to 150 ℃) that heats up of the speed of 10 ℃/min, record the DSC curve.

Embodiment 1:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) being immersed in (the V charge capacity is 0.48wt%) in the oxalic acid vanadyl aqueous solution, under 40 ℃ of oil baths, continuously stirring dipping 5h, then be warming up to 120 ℃ of dry 5h, then is transferred to 120 ℃ of oven drying 6h; The silica-gel carrier that is impregnated with the oxalic acid vanadyl is placed in carries out calcination activation in quartzy fluidized-bed, 450 ℃ of insulation 4h in high pure air, silica gel natural cooling down transfer under nitrogen at last, above-mentioned roasting process is as shown in Figure 1.The sample that obtains is flooded the alkali formula chromium acetate aqueous solution (the Cr charge capacity is 0.5wt%) again, and under room temperature, after continuously stirring dipping 4h, then 120 ℃ of dry 4h are transferred to 120 ℃ of oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, 600 ℃ of lower roasting 4h in air, then natural cooling down shifts under nitrogen protection, and above-mentioned calcination procedure obtains catalyzer and preserves stand-by as shown in Figure 2.

Embodiment 2:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) be immersed in the aqueous solution of alkali formula chromium acetate and ammonium meta-vanadate (the Cr charge capacity is 0.5wt%, and the V charge capacity is 0.48wt%), stir dipping 4h under 60 ℃ of oil baths, then dry 4h under 120 ℃ is transferred to 120 ℃ of oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, be incubated 5h under 500 ℃ in air, then natural cooling down shifts under nitrogen protection, obtains catalyzer and preserves stand-by.

Embodiment 3:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) being immersed in (V charge capacity 0.16wt%) in the vanadylic sulfate aqueous solution, continuously stirring dipping 4h under room temperature is transferred to 120 ℃ of oven drying 6h after dry 4h under 120 ℃; The catalyzer of drying is placed in carries out calcination activation in quartzy fluidized-bed, be incubated 4h under 500 ℃ in air, naturally cooling under nitrogen protection.The sample that obtains is flooded alkali formula chromium acetate solution (Cr charge capacity 0.5wt%) again, and after stirring at room dipping 4h, then 120 ℃ of dry 4h are transferred to oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, in air under 600 ℃, insulation 4h, naturally cooling under nitrogen protection, calcination procedure such as Fig. 2 obtain catalyzer and preserve stand-by.

Embodiment 4:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) being immersed in (the V charge capacity is 0.24wt%) in ammonium metavanadate aqueous solution, then 60 ℃ of lower continuously stirring dipping 4h are warming up to 120 ℃ of dry 4h, are transferred to 120 ℃ of oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, under 450 ℃ of high air atmosphere, insulation 4h, calcination procedure such as Fig. 1 obtain the vanadium oxide catalyst of load.The sample that obtains is flooded the alkali formula chromium acetate aqueous solution (the Cr charge capacity is 0.5wt%) again, after continuously stirring dipping 4h, be warming up to 120 ℃ of dry 4h under room temperature, then be transferred to oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, be incubated 4h under 600 ℃, naturally cooling under nitrogen protection obtains catalyzer and preserves stand-by.

Embodiment 5:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) be immersed in the ethanol solution of bis-acetylacetonate vanadium oxide (the V charge capacity is 0.96wt%), be warming up to 100 ℃ of dry 8h after continuously stirring dipping 4h under room temperature, then be transferred to 120 ℃ of oven drying 6h; The catalyzer of drying is placed in carries out calcination activation in quartzy fluidized-bed, be incubated 4h under 600 ℃ in high pure air, naturally cooling under nitrogen protection.The sample that obtains is flooded the alkali formula chromium acetate aqueous solution (the Cr charge capacity is 0.5wt%) again.Be warming up to 120 ℃ of dry 4h after stirring dipping 4h under room temperature, then be transferred to 120 ℃ of oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, under 600 ℃ of high pure air, insulation 4h, calcination procedure such as Fig. 2, naturally cooling under nitrogen protection obtains catalyzer and preserves stand-by.

Embodiment 6:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) being immersed in (the Cr charge capacity is 0.5wt%) in the alkali formula chromium acetate aqueous solution, continuously stirring dipping 4h is warming up to 120 ℃ of dry 4h, then is transferred to 120 ℃ of oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, 600 ℃ of insulation 4h in high pure air, calcination procedure such as Fig. 2, naturally cooling under nitrogen protection.The sample that obtains is immersed in again in the aqueous solution of sodium metavanadate (the V charge capacity is 0.24wt%).Stir dipping 4h under 40 ℃, be warming up to 120 ℃ of dry 4h, then be transferred to 120 ℃ of oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, 600 ℃ of insulation 4h in high pure air, then naturally cooling cooling under nitrogen protection obtains catalyzer and preserves stand-by.

Embodiment 7:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) being immersed in (the V charge capacity is 0.24wt%) in ammonium metavanadate aqueous solution, then 60 ℃ of lower continuously stirring dipping 4h are warming up to 120 ℃ of dry 4h, are transferred to oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, under 600 ℃ of high air atmosphere, insulation 4h obtains the vanadium catalyst of load.The sample that obtains is flooded the alkali formula chromium acetate aqueous solution (the Cr charge capacity is 0.5wt%) again, after continuously stirring dipping 4h, be warming up to 120 ℃ of dry 4h under room temperature, then be transferred to oven drying 6h; The sample of drying is placed in carries out calcination activation in quartzy fluidized-bed, under 600 ℃, insulation 4h, calcination procedure such as Fig. 2, naturally cooling under nitrogen protection.Then adding concentration is the organo-metallic promotor of 1mol/L--methylaluminoxane (Al/Cr mol ratio=30), and then 100 ℃ of dryings 4 hours to remove solvent, this drying is carried out under nitrogen atmosphere.Catalyzer through the prereduction activation is preserved stand-by under nitrogen atmosphere.

Embodiment 8:

Take in embodiment 1 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add the refining normal heptane solvent of 40mL successively in reactor, adding consumption is that the triisobutyl aluminium (TIBA) of Al/Cr=10 is made promotor, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining.Regulate ethylene pressure to 0.15MPa, constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 9:

Take in embodiment 2 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add the refined normal heptane solvent of 40mL successively in reactor, adding consumption is that the triisobutyl aluminium (TIBA) of Al/Cr=10 is made promotor, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining, regulates ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 10:

Take in embodiment 3 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, add consumption be the aluminium diethyl monochloride (DEAC) of Al/Cr=5 as promotor, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining is regulated ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 11:

Take in embodiment 5 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, add consumption be the methylaluminoxane (MAO) of Al/Cr=20 as promotor, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining is regulated ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 12:

Take in embodiment 6 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, add consumption be the triisobutyl aluminium (TIBA) of Al/Cr=5 as promotor, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining is regulated ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 13:

Take in embodiment 7 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 70mL to make with extra care normal heptane solvent in reactor, regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 14:

Take in embodiment 4 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 70mL to make with extra care normal heptane solvent in reactor, regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 15:

Take respectively in embodiment 4 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, adding respectively consumption is Al/Cr=5,10,15,20 triisobutyl aluminium (TIBA) promotor (corresponding embodiment 15-1,15-2,15-3,15-4 respectively), then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining.Regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 16:

Take respectively in embodiment 4 catalyzer 160mg and carry out respectively the polymerization under atmospheric pressure experiment under differing temps.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, add consumption be the triisobutyl aluminium (TIBA) of Al/Cr=5 as promotor, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining is regulated ethylene pressure to 0.15MPa.When polymerization temperature is stabilized in respectively 50 ℃ and 70 ℃ (corresponding embodiment 16-1 and 16-2 respectively), add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 17:

Take in embodiment 4 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add the refining normal heptane solvent of 40mL successively in reactor, add consumption be the triethyl aluminum (TEA) of Al/Cr=5 as promotor, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining is regulated ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 18:

Take respectively in embodiment 4 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, adding consumption is triisobutyl aluminium (TIBA) promotor of Al/Cr=5, add respectively through processed 0.7,2.1,3.5mL 1-hexene, be that the volume ratio of 1-hexene and polymerization solvent for use is respectively 1,3,5vol%, (corresponding embodiment 18-1,18-2,18-3 respectively), normal heptane solvent after adding again the 30mL dehydration and deoxidation refining is regulated ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 19:

Take in embodiment 4 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor, adding consumption is triisobutyl aluminium (TIBA) promotor of Al/Cr=5, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining, then adds 10mLH in still ₂, regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 20:

Take in embodiment 4 catalyzer 100mg and carry out the pressure polymerization experiment.The stainless steel still is clean with solvent wiping, catalyzer is packed into, in the situation that the heating high-purity N ₂Pump drainage 30min.With the ethylene gas displacement once, and regulate still pressure to 0.12MPa, inject the refining normal heptane solvent of 200mL in still, adding consumption is triisobutyl aluminium (TIBA) promotor of Al/Cr=20.Constant after 90 ℃ until temperature in the kettle, regulate ethylene pressure to 0.4MPa, with broken in catalyzer bottle still and begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Pour polymkeric substance and solvent into 100mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

Embodiment 21:

Take in embodiment 4 catalyzer 100mg and carry out the pressure polymerization experiment.The stainless steel still is clean with solvent wiping, catalyzer is packed into, in the situation that the heating high-purity N ₂Pump drainage 30min.With the ethylene gas displacement once, and regulate still pressure to 0.12MPa, inject the refining normal heptane solvent of 200mL in still, adding consumption is triisobutyl aluminium (TIBA) promotor of Al/Cr=20, then adds refined 6mL1-hexene.Constant after 90 ℃ until temperature in the kettle, regulate ethylene pressure to 0.4MPa, with broken in catalyzer bottle still and begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Pour polymkeric substance and solvent into 100mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 1:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) being immersed in (the chromium charge capacity is 0.5wt%) in the alkali formula chromium acetate aqueous solution, under room temperature, continuously stirring dipping 4h, be warming up to dry 4h under 120 ℃, then is transferred to oven drying 6h; The sample of drying is placed in quartzy fluidized-bed, 600 ℃ of roasting 4h under high pure air, calcination procedure as shown in Figure 2, then naturally cooling shifts under nitrogen protection, obtains the Phillips chromium-based catalysts and saves backup.

The comparative example 2:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) be immersed in (the vanadium charge capacity is 0.24wt%) in ammonium metavanadate aqueous solution, after 60 ℃ of lower continuously stirring dipping 4h, be warming up to dry 4h under 120 ℃, then be transferred to oven drying 6h; The sample of drying is placed in quartzy fluidized-bed, 600 ℃ of roasting 4h in high pure air, then cooling transfer naturally under nitrogen protection, the vanadium catalyst that obtains load saves backup.

The comparative example 3:

(pore volume is 1.5-1.7cm with 10g silica gel ³/ g, surface-area are 250-300m ²/ g) be immersed in (the chromium charge capacity is 1wt%) in the chromium trioxide aqueous solution, after stirring at room dipping 4h, be warming up to 120 ℃ of dry 6h, then be transferred to oven drying 6h; The sample of drying is placed in quartzy fluidized-bed, and in high pure air, 600 ℃ of calcination activation 4h, obtain the Phillips catalyzer.The 10g silica-gel carrier is immersed in (the vanadium charge capacity is 0.48wt%) in ammonium metavanadate aqueous solution, and after stirring dipping 4h under 50 ℃, then drying is transferred to oven drying 6h; The sample of drying is placed in the inherent high pure air of quartzy fluidized-bed carries out 600 ℃ of calcination activation 4h, naturally cooling under nitrogen protection obtains the vanadium catalyst of load.The vanadium catalyst of Phillips catalyzer obtained above and load under nitrogen protection, according to 2: 1 mechanical mixings of Cr/V mol ratio, is obtained mixed catalyst and saves backup.

The comparative example 4:

Take in comparative example 1 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, add consumption be the triisobutyl aluminium (TIBA) of Al/Cr=5 as promotor, then rinse the still wall with the refining n-heptane solution of 30mL, regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 5:

Take in comparative example 2 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, adding consumption is that the triisobutyl aluminium (TIBA) of Al/V=5 is as promotor; Rinse the still wall with the refining n-heptane solution of 30mL again, regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 6:

Take in comparative example 3 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively; Adding consumption is that the triisobutyl aluminium (TIBA) of Al/Cr=5 is as promotor; Rinse the still wall with the refining n-heptane solution of 30mL again, regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.。

The comparative example 7:

Take in comparative example 1 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, adding consumption is triisobutyl aluminium (TIBA) promotor of Al/Cr=5, add respectively through processed 0.7,2.1,3.5mL 1-hexene, be that the volume ratio of 1-hexene and polymerization solvent for use is respectively 1,3,5vol%, (corresponding comparative example 7-1,7-2,7-3 respectively), and rinse the still wall with the refining n-heptane solution of 30mL, regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 8:

Take in comparative example 1 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, adding consumption is the triisobutyl aluminum cocatalyst of Al/Cr=5, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining, then adds 10mLH in still ₂, regulate ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 9:

Take in comparative example 1 catalyzer 160mg and carry out the polymerization under atmospheric pressure experiment.With the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill the refining ethene of trace in the most backward reactor to 0.12MPa.Then add 40mL to make with extra care normal heptane solvent in reactor successively, adding the triethyl aluminum (TEA) of Al/Cr=5 is promotor, then the normal heptane solvent after adding the 30mL dehydration and deoxidation refining, regulates ethylene pressure to 0.15MPa.Constant after 90 ℃ until temperature in the kettle, add catalyzer to begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Add 50mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 10:

Take in comparative example 1 catalyzer 100mg and carry out respectively the pressure polymerization experiment.The stainless steel still is clean with solvent wiping, catalyzer is packed into, in the situation that the heating high-purity N ₂Pump drainage 30min.With the ethylene gas displacement once, and regulate still pressure to 0.12MPa, inject the refining normal heptane solvent of 200mL in still, add the triisobutyl aluminium of Al/Cr=20.Constant after 90 ℃ until temperature in the kettle, regulate ethylene pressure to 0.4MPa, with broken in catalyzer bottle still and begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Pour polymkeric substance and solvent into 100mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 11:

Take in comparative example 2 catalyzer 100mg and carry out respectively the pressure polymerization experiment.The stainless steel still is clean with solvent wiping, catalyzer is packed into, in the situation that the heating high-purity N ₂Pump drainage 30min.With the ethylene gas displacement once, and regulate still pressure to 0.12MPa, inject the refining normal heptane solvent of 200mL in still, add the triisobutyl aluminium of Al/V=40.Constant after 90 ℃ until temperature in the kettle, regulate ethylene pressure to 0.4MPa, with broken in catalyzer bottle still and begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Pour polymkeric substance and solvent into 100mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 12:

Take in comparative example 1 catalyzer 100mg and carry out the pressure polymerization experiment.The stainless steel still is clean with solvent wiping, catalyzer is packed into, in the situation that the heating high-purity N ₂Pump drainage 30min.With the ethylene gas displacement once, and regulate still pressure to 0.12MPa, inject the refining normal heptane solvent of 200mL in still, add the triisobutyl aluminium of Al/Cr=20, then add the refined 1-hexene of 6ml.Constant after 90 ℃ until temperature in the kettle, regulate ethylene pressure to 0.4MPa, with broken in catalyzer bottle still and begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Pour polymkeric substance and solvent into 100mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The comparative example 13:

Take in comparative example 2 catalyzer 100mg and carry out the pressure polymerization experiment.The stainless steel still is clean with solvent wiping, catalyzer is packed into, in the situation that the heating high-purity N ₂Pump drainage 30min.With the ethylene gas displacement once, and regulate still pressure to 0.12MPa, inject the refining normal heptane solvent of 200mL in still, add the triisobutyl aluminium of Al/V=40, then add the refined 1-hexene of 6ml.Constant after 90 ℃ until temperature in the kettle, regulate ethylene pressure to 0.4MPa, with broken in catalyzer bottle still and begin reaction.The instantaneous consumption of online acquisition monomer ethylene in reaction process (by connecting the high-accuracy ethene mass flowmeter of computer) and by computer record.Pour polymkeric substance and solvent into 100mL hydrochloric acid/alcohol mixed solution termination reaction after 1h.After filtration, resulting polymers is weighed after dry 4h under 60 ℃ in vacuum drying oven and analyzed.

The ethylene polymerization activity of each embodiment of table 1

Annotate: every its polymerization activity of catalyzer that contains chromium of the present invention calculates with unit mole chromium, and pure its polymerization activity of catalyzer that contains vanadium calculates with unit mole vanadium, Hereinafter the same.

(1) impact of promotor

The impact of table 1 promotor consumption on the homopolymerization of chrome alum composite catalyst catalyzed ethylene

Polymerizing condition: ethylene pressure=0.15MPa; Polymerization time=1hr; Polymerization temperature=90 ℃; Normal heptane=70mL; Cr=0.5% (wt), V=0.24% (wt); Promotor=TiBA, embodiment 14,15.

Take embodiment 14 and 15 as representative, the ethylene homo of having investigated chrome alum under different promotor consumptions double activity center catalyzer is active, as table 1.

As known from Table 1, under the condition take TiBA as promotor, along with the aluminium chromium of promotor continues to increase than from 5 to 20, the activity of chrome alum double activity center catalyzer ethylene homo presents the process of a decline, explanation will reach the polymerization high reactivity, the consumption of promotor is that a suitable value or scope are arranged, and catalyzer is 5 o'clock at Al/Cr, and activity is the highest.

The impact of the different promotors of table 2. on chrome alum double activity center's catalyzer and Phillips catalyst ethylene homo

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

Table 2 expression adopts different promotors on the impact of chrome alum double activity center's catalyzer and Phillips catalyst ethylene homo activity.Adopt TEA to do the promotor activity lower than doing promotor with TiBA.Further pass through to the poly analysis of the said products as can be known, product polyethylene under different promotor effects has similar fusing point, but its molecular weight and molecualr weight distribution differs widely, and the larger impact that is distributed with after promotor is on the reducing degree of catalyst active center and reduction is described.

(2) impact of polymerization temperature on polymerization

The impact of table 3 polymerization temperature on 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); Promotor=TiBA, embodiment 16,15-1.

Table 3 is the vinyl polymerization result of the chrome alum double activity center catalyzer under different polymerization temperatures (embodiment 16 embodiment 15-1).Catalyzer has high reactivity in the time of 50 ℃, along with the rising polymerization catalyst activity of temperature decreases, have lowest activity in the time of 90 ℃.The polyethylene product that obtains under different polymerization temperatures has similar fusing point, and its molecular weight the trend of reduction occurs along with the rising of polymerization temperature, illustrates that polymerization temperature raises more favourable to the transfer of polyreaction chain.

(3) comparison of the different preparation methods of catalyzer to the ethylene homo performance

The polymerization of the different preparation method gained of table 4 catalyzer

Polymerizing condition: ethylene pressure=0.15MPa; Polymerization time=1hr; Polymerization temperature: 90 ℃, normal heptane=70mL; Cr=0.5% (wt), V=0.48% (wt); Promotor=TiBA; Embodiment 8 and embodiment 9.

Embodiment 8 and embodiment 9 adopt respectively step impregnation and two kinds of chrome alum catalyzer polymerization activities under the same conditions that the different loads mode prepares of total immersion stain, and the activity of the composite catalyst of visible step impregnation preparation is higher.

(4) impact of the consumption of 1-hexene on ethene/1-hervene copolymer performance

The impact on chrome alum double activity center's catalyzer and Phillips catalyzer copolymerized characteristic of table 5 ethene, 1-hervene copolymer

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

Table 5 has provided the result of chrome alum double activity center's catalyzer and Phillips catalyzer ethene/1-hexene oligomerization.The ethene of chrome alum double activity center catalyzer/1-hervene copolymer activity presents the trend of reduction, in conjunction with before the result of ethylene homo, show that ethene/1-hervene copolymer is active all lower than the activity of ethylene homo.The trend that the ethene of Phillips catalyzer/1-hervene copolymer activity reduces after presenting and first slightly increasing.Add the 1-hexene, the polymerization activity of other chrome alums double activity center catalyzer descends equally.

The GPC spectrogram that Fig. 3 and Fig. 4 are respectively the Alathon of chrome alum double activity center catalyzer, Phillips catalyzer and load vanadium oxide catalysts and ethene and 1-hexene copolymer product relatively.

(5) impact of hydrogen on polymerization

The impact of table 6. hydrogen on ethylene homo

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

As seen from Table 6, the ethylene homo specific activity of different catalysts does not have all to decrease under the condition of hydrogen and poly molecular weight and fusing point all decrease, and illustrates that effect that hydrogen plays chain-transfer agent causes the decline of its molecular weight and fusing point.

Claims (14)

1. one kind is used for the poly loading type chrome alum of efficient preparation double activity center catalyzer, and it is characterized in that: described catalyzer forms two kinds of active ingredients that comprise inorganic carrier and load, and two kinds of active ingredients comprise chromated oxide and barium oxide.

2. catalyzer according to claim 1, is characterized in that described inorganic carrier is selected from silicon-dioxide, aluminium sesquioxide, titanium dioxide, zirconium white, magnesium oxide, calcium oxide, inorganic clay and their combination.

3. catalyzer according to claim 1, solid support material is the inorganic carrier of porous, specific surface area is 50～500m ²/ g.

4. catalyzer according to claim 1, the pore volume of its inorganic carrier used is 0.1～5.0cm ³/ g, mean pore size is at 1～50nm.

5. catalyzer according to claim 1, the Cr charge capacity on inorganic carrier is 0.01～10wt% of total catalyst weight, presses the weighing scale of Cr.

6. catalyzer according to claim 1, it is characterized in that the V charge capacity (pressing the weighing scale of vanadium) on inorganic carrier is 10～500% of Cr charge capacity (with the weighing scale of chromium), generally speaking, the vanadium charge capacity is the 0.01～10wt% (pressing the weighing scale of vanadium) of total catalyst weight.

7. catalyzer according to claim 1, the raw material of chromium active ingredient is the water-soluble chromic salts that contains: as chromium trioxide, chromium nitrate, chromium acetate, chromium chloride, chromium sulphate, ammonium chromate, ammonium dichromate, alkali formula chromium acetate, other suitable solubility chromic salts and their combination.

8. catalyzer according to claim 1, the raw material of vanadium active ingredient is the water-soluble vanadic salts that contains: as hexafluoro ammonium vanadate, nitric acid vanadium, oxalic acid vanadyl, ammonium meta-vanadate, vanadylic sulfate, sulfuric acid oxidation vanadium (IV) hydrate, Vanadosulfuric acid (III), three chloro vanadium oxides, sodium orthovanadate, sodium metavanadate etc., and the water-insoluble vanadic salts that contains: as bis-acetylacetonate vanadium oxide, Triisopropoxyvanadium(V) oxide, three propyl alcohol vanadium oxides, vanadium acetylacetonate, oxidation triethoxy vanadium, vanadyl chloride, silication three vanadium, other suitable solubility vanadic salts and their combination.

9. catalyzer according to claim 1, a kind of preparation method is as follows:

I) the inorganic carrier dipping is contained the solution of vanadium, then dry, then at 300～900 ℃ of lower calcination activations of high temperature;

Ii) with step I) product of gained dipping contains the solution of chromium, and is then dry, and then at 300～900 ℃ of lower calcination activations of high temperature, obtain described catalyzer and save backup.

10. catalyzer according to claim 1, a kind of preparation method is as follows:

I) the inorganic carrier dipping is contained the solution of vanadium and chromium, then dry;

Ii) with i) product of gained is at 300～900 ℃ of lower calcination activations of high temperature, and obtain described catalyzer and save backup.

11. catalyzer according to claim 1, a kind of preparation method is as follows:

I) the inorganic carrier dipping is contained the solution of chromium, then dry, then at 300～900 ℃ of lower calcination activations of high temperature;

Ii) with step I) product of gained dipping contains the solution of vanadium, and is then dry, and then at 300～900 ℃ of lower calcination activations of high temperature, obtain described catalyzer and save backup.

12. catalyzer according to claim 1, a kind of preparation method is as follows:

Loading type chrome alum double activity center catalyzer with any one method preparation in the claims 9,10,11 further adds the organo-metallic promotor to carry out the prereduction activation treatment, and the catalyzer that obtains described prereduction activation after drying saves backup.

13. according to claim 1～12 described chrome alum double activity center catalyzer (comprising the chrome alum double activity center catalyzer through organo-metallic promotor prereduction activation) can be used for producing Alathon and ethylene/alpha-olefin copolymer.Can add again organic metal promoters, hydrogen etc. as required in polymerization process.

14. catalyzer according to claim 13, organo-metallic promotor include machine aluminium compound, organolithium compound, organoboron compound etc. and are commonly used for any in the olefinic polyreaction promotor or their combination.

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