CN105199021A

CN105199021A - Titanium fluoride modified load type chrome alum double-active center catalyst and preparation method thereof

Info

Publication number: CN105199021A
Application number: CN201410249913.7A
Authority: CN
Inventors: 李留忠; 孙巧巧; 范大鹏; 程瑞华; 严婕; 刘柏平
Original assignee: China Petroleum and Chemical Corp
Current assignee: China Petroleum and Chemical Corp
Priority date: 2014-06-06
Filing date: 2014-06-06
Publication date: 2015-12-30

Abstract

The invention belongs to polyethylene catalysts, and particularly relates to a titanium fluoride modified load type chrome alum double-active center catalyst. The titanium fluoride modified load type chrome alum double-active center catalyst comprises an inorganic carrier and loaded active components and modified components. The active components comprise chromium oxides and vanadium oxides, and the modified components comprise fluorine and titanium. According to the catalyst, the content and distribution of comonomers are improved, the number of the comonomers inserted into a low molecular weight end is reduced, the number of the comonomers inserted into a high molecular weight end is increased, and therefore more chalaza molecules can be formed easily, and polyethylene products with better performance are prepared. Meanwhile, the catalyst has the advantages of being high in activity, sensitive in hydrogen regulation response performance and the like. The invention further provides a preparation method of the catalyst. The inorganic carrier is firstly loaded with one of the modified components, and then loaded with the rest of the components, the process is reasonable, and industrial production is easy.

Description

The loading type chrome alum double activity center Catalysts and its preparation method of titanium fluorine richness

Technical field

The invention belongs to a kind of polyethylene catalysts, be specifically related to a kind of loading type chrome alum double activity center Catalysts and its preparation method of titanium fluorine richness.

Background technology

Polyethylene catalysts known at present mainly contains the catalyzer of Ziegler-Natta catalyst, chromium-based catalysts and metallocene catalyst and some other Nonmetallocene class.Wherein chromium-based catalysts is subject to the favor in market with the irreplaceability of its outstanding contributions and products thereof on high density polyethylene(HDPE) is produced, and the whole world still has the high density polyethylene(HDPE) of about 50% to be produced by it even to this day.

J.PHogan and R.L.Bank two people reports the chromium oxide catalyst of silica gel load in patent US2825721, is namely first-generation Phillips catalyzer that people know afterwards.Some patents such as US4294724, US4295997, US4528338, US5401820, US6388017 etc. have carried out study on the modification to this type of supported chromium oxide catalyzer, have developed Phillips catalyzer.

Phillips catalyzer is responsive to carrier composition change in elevation, therefore by changing the composition of carrier or the type of carrier, produce liquid oligopolymer and low-molecular-weight wax or ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE), the molecular weight distribution of its product can in very large range regulate and control.Two common traits of s-generation Phillips catalyzer are: 1) by preparing the catalyzer and polyethylene product with new capability to the surface modification of carrier; 2) chromium is the sole active component in modification Phillips catalyzer.The support modification method of s-generation Phillips catalyzer comprises: titania modified, magnesium oxide modified, fluorine richness, alumina modified, alkali metals modified, boron modification etc.At present, s-generation modification Phillips catalyzer has been used for the polymkeric substance of the different grades producing various commercial use.Wherein, the carrier of catalyzer, after titania modified, can strengthen the activity of chromium significantly, shortens induction time, improves the polymerization activity of catalyzer and chain termination speed, reduces the molecular-weight average of polymkeric substance, and this is concerning normally favourable polymerization.The carrier of catalyzer, after fluorine richness, can strengthen the activity of catalyzer significantly, shortens induction time, provides a kind of method of polyethylene, ethene and the-olefin copolymer of producing narrow molecular weight distributions.

Wherein, the R.Dietz (US3887494) of Phillips company, the T.Pullukat (US378001) of B.Horvath (US3622521) and ChemplexCompany company has all carried out the research of this respect, and Liang Ge company carrier used is respectively the Davison series of Grace company of the U.S. and is now the polyolefine silica gel special carrier of Pq Corp.'s production.The mode introducing titanium dioxide mainly contains two kinds, and one is that titanium and silicon deposit rear reshaping in the mode of cogelled (co-gel), and the Ti content on carrier element phase and surface is suitable; One is that titanium dioxide is coated on in type silica-gel carrier, and now titanium dioxide is mainly distributed in the surface of carrier.Pertinent literature can see JournalofCatalysis, 1983,82,118-126.

Wherein fluorine richness adopts surperficial fluorine richness agent can roll into a ball react with the silicone hydroxyl on surface as ammonium hexafluorosilicate etc. and discharge water outlet, while at Silica Surface formation Si-F key.The modified silica-gel F atom that electronegativity is stronger on the surface can cause the transfer transport on neighboring atom, thus weakens silicone hydroxyl key, adds the acidity of Silica Surface by this, and pertinent literature can see JournalofCatalysis, and 2 (2), 145,1963.The people such as Rebenstrof have carried out FTIR spectrum sign to non-modified with through two kinds of Phillips catalyzer of F modification, find that the intensity of the surface silanol group stretching vibration peak (3746cm-1) of F modified catalyst obviously declines, show that F is conducive to removing the silicone hydroxyl group of Silica Surface.In addition author to think on the Si atom that the OH group removed not yet at 800 DEG C connects can not simultaneously with F atom Cheng Jian.Afterwards, low temperature CO infrared spectrum characterization is utilized to find, after the surface modification of ammonium hexafluorosilicate, cloud density around Cr atom reduces, and meanwhile, the distribution in active centre is improved, pertinent literature can see JournalofMolecularCatalysis, 66 (1), 59,1991.

Point out in an earlier patents of Hogan that the fluorine richness of Phillips catalyzer can adopt following two kinds of modes to realize: (1) is directly mixed into (NH4) 2SiF6 in dried Phillips catalyzer; (2) solution of (NH4) 2SiF6 and CrO3 is immersed in Silica Surface altogether.Polymerization result shows, no matter be ethylene homo reaction, or the copolyreaction of the alpha-olefin such as ethene and propylene, 1-butylene, 1-amylene, 1-octene, the catalytic activity of the fluorine richness catalyzer that co-impregnation obtains is than the height of powder mixing process.When adopting silica gel-fluorine as carrier, along with the add-on of ammonium hexafluorosilicate in system is higher to 3.5wt.% from 0.5wt.%, apparent polymerization activity shows the trend raised gradually, and the density of the introducing of fluorine to polymerisate has obvious regulating effect, show that fluorine can promote the insertion reaction of comonomer.Kallenbach (US:3445367,1969) employ direct dry mix and four kinds of different fluorine cpd (NH4) 2SiF6, CuSiF6, NH4BF6 and CuBF6 are carried out modification to Phillips catalyzer, contrast conventional P hillips catalyzer, the catalyzer of these F modifications can both produce the narrower HDPE of relative molecular weight distribution.

Original silica gel is immersed in (NH4) 2SiF6 solution by McDaniel, afterwards respectively at 420,650 and 870 DEG C of three roasting temperatures, again by the CH3CN solution impregnation of the silica gel CrO3 of this fluoridation, finally in air by catalyzer high-temperature activation.Researchist activates the catalyst sample of different F content under different maturing temperature, finds the catalyzer through fluorine richness, and the saturated charge capacity of its Cr (VI) decreases.Under same maturing temperature, the maximum charge capacity of Cr (VI) declines rapidly along with the increasing of F charge capacity, and the sample of 870 DEG C declines at most, and this shows that fluorochemical may accelerate the sintering of silica gel under high temperature.Pertinent literature can see JournalofCatalysis, and 76 (1), 37,1982.

A kind of novel supported chrome vanadium metal oxide compound double activity center ethylene rolymerization catalyst is reported in patent (application number 201210118427.2), as the third generation Phillips catalyzer representative with Cr-V double activity center, it is characterized in that the vanadium active ingredient introducing load on Phillips chromium-based catalysts becomes the Chromium-polyethylencatalyst catalyst with Cr-V two kinds of active centre, adopt unmodified silica gel as support of the catalyst, reach the object that relative molecular mass distribution is wide, but it is bad that comonomer inserts effect, report again about titania modified supported chrome vanadium metal oxide compound double activity center polyethylene catalysts in silica gel patent (application number 201210134632.8), catalyst preparation is carried out by titanium modified silica-gel, improve catalyst activity, add polymerisate relative molecular mass distribution width, but the object improving copolymerization performance cannot be reached.The supported chrome vanadium metal oxide compound double activity center polyethylene catalysts about fluorine richness is reported again in patent (application number 201210235852.X), by silica gel is carried out fluorine richness, Polymer Molecular Weight can be improve, improve the copolymerization performance of catalyzer simultaneously, but DeGrain is promoted to polymerization activity.

Have not yet to see the report of the supported chrome vanadium metal oxide compound double activity center ethylene rolymerization catalyst of the common modification of titanium fluorine, namely the present invention introduces modified component titanium and fluorine further on the basis of supported chrome vanadium metal oxide compound double activity center polyethylene catalysts, copolymerization performance is promoted while raising catalyst activity, increase polyethylene product relative molecular mass distribution width, improve polyvinyl resin performance.

Summary of the invention

For the deficiencies in the prior art, the object of this invention is to provide a kind of loading type chrome alum double activity center catalyzer of titanium fluorine richness, improve content and the distribution thereof of comonomer, it is made to reduce in lower molecular weight end insertion, increase in high molecular end insertion, thus easily form more tie molecule, prepare the better polyethylene product of performance, this catalyzer also has higher activity simultaneously, responsive hydrogen adjusts the advantages such as response performance; The present invention also provides its preparation method, rational technology, is easy to suitability for industrialized production.

The loading type chrome alum double activity center catalyzer of titanium fluorine richness of the present invention, comprise inorganic carrier, the active ingredient of load and modified component, wherein: active ingredient is chromated oxide and barium oxide, modified component is fluorine and titanium.

Inorganic carrier is one or more in silicon-dioxide, aluminium sesquioxide, titanium dioxide, zirconium white, magnesium oxide, calcium oxide, inorganic clay.Described inorganic clay can comprise such as montmorillonite, and 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 be synthesized by known method.When inorganic carrier is silica gel, preferred Davison955.

The specific surface area of inorganic carrier is 50 ~ 800m ²/ g, preferably 100 ~ 300m ²/ g, pore volume is 0.1 ~ 5.0cm ³/ g, preferably 0.5 ~ 3.0cm ³/ g, mean pore size is 1 ~ 50nm.The inorganic carrier used in the present invention can be conventional for any inorganic carrier in olefin polymerization catalysis preparation.

The content of chromium element is 0.01 ~ 10wt% of total catalyst weight, preferably 0.05 ~ 5wt%; The content of v element is 0.01 ~ 10wt% of total catalyst weight, preferably 0.05 ~ 5wt%; The content of fluorine element is the 0.01-10wt% of total catalyst weight, preferably 0.05 ~ 20wt%; The content of titanium elements is 0.01 ~ 30wt% of total catalyst weight.Wherein the content of v element is preferably 10 ~ 500% of chromium constituent content, is more preferably 20 ~ 400%.

The precursor of chromium element for containing chromic salts, for water soluble or organic solvent containing chromic salts, be preferably one or more in chromium trioxide, chromium nitrate, chromium acetate, chromium chloride, chromium sulphate, ammonium chromate, ammonium dichromate or alkali formula chromium acetate;

The precursor of v element is for containing vanadic salts, for water soluble or organic solvent containing vanadic salts, be preferably one or more in hexafluoro ammonium vanadate, nitric acid vanadium, vanadyl oxalate, ammonium meta-vanadate, vanadylic sulfate, sulfuric acid oxidation vanadium hydrate, Vanadosulfuric acid, three chloro vanadium oxides, vanadic acid sodium, sodium metavanadate, bis-acetylacetonate vanadium oxide, Triisopropoxyvanadium(V) oxide, three propyl alcohol vanadium oxides, vanadium acetylacetonate, oxidation triethoxy vanadium, vanadyl chloride or silication three vanadium;

The precursor of fluorine element is for containing villiaumite, for water soluble or organic solvent containing villiaumite, be preferably one or more in Neutral ammonium fluoride, Ammonium bi-fluoride, ammonium borofluoride, cupric fluoborate, silver fluoborate, fluoroboric acid gold, cuprichexafluorosilicate, silver silicofluoride, silicofluoric acid gold, ammonium borofluoride, hexafluoro ammonium vanadate, ammonium hexafluorosilicate, zinc fluoroborate, magnesium silicofluoride, zine fluosilicate or Sodium tetrafluoroborate;

The precursor of titanium elements is for containing titanium salt, for water soluble or organic solvent containing titanium salt, be preferably one or more in methyl ethyl diketone oxygen titanium, titanous chloride, titanium tetrachloride, trimethyl carbinol titanium, tetra-n-butyl titanate, titanyl sulfate, titanium sulfate, isopropyl titanate or tetraethyl titanate.

The present invention also provides a kind of preparation method of loading type chrome alum double activity center catalyzer of described titanium fluorine richness: by the one in inorganic carrier first loaded modified component, and then load remaining ingredient.Be preferably the one in inorganic carrier first loaded modified component, and then the another kind in loaded modified component, final load vanadium and chromium.

Wherein load step is: dipping contains the solution of active ingredient or modified component, then calcination activation at 200 ~ 900 DEG C; Wherein: the solution containing active ingredient or modified component is be dissolved in water or organic solvent by the salt containing active ingredient or modified component.

Preferred as one of the present invention, inorganic carrier is loaded modified component titanium first, and then load remaining ingredient.Wherein the preparation method of the loaded modified component titanium of inorganic carrier is following methods one wherein:

(1) pickling process: titanium compound is dissolved in solvent and reacts with inorganic carrier stirring and evenly mixing, then dry, then calcination activation at high temperature 300 ~ 900 DEG C, obtains the inorganic carrier of described titanium modification;

(2) coprecipitation method: titanium compound and silicate compound mixing are reacted, then dry, then calcination activation at high temperature 300 ~ 900 DEG C, obtains the inorganic carrier of described titanium modification;

(3) sol-gel method: titanium compound and water and dehydrated alcohol are hydrolyzed and react, add mineral acid more after completion of the reaction and inorganic carrier reacts, then dry, then calcination activation at high temperature 300 ~ 900 DEG C, obtains the inorganic carrier of described titanium modification;

(4) sol-gel method: stir after titanium compound and organic solvent are mixed, add sour back flow reaction, then add inorganic carrier reaction, then dry, then calcination activation at high temperature 300 ~ 900 DEG C, obtains the inorganic carrier of described titanium modification.

Wherein method (1) pickling process, specifically comprises following steps:

I) titanium compound is dissolved in solvent, then be immersed on inorganic carrier, dipping time is 1 ~ 12h, preferably 4 ~ 8h, and dipping temperature is 10 ~ 80 DEG C, preferably 20 ~ 70 DEG C, then dry at 50 ~ 200 DEG C, preferably 70 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process;

II) above-mentioned sample is carried out high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 300 ~ 900 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 4 ~ 6h, then cooling, wherein switching to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling.The titania modified inorganic carrier obtained is transferred to wide-necked bottle, is placed in moisture eliminator and saves backup.

Above-mentioned steps i) be the compound of titanium be impregnated on inorganic carrier (inorganic carrier such as mentioned above).Described titanium compound is with above-mentioned.According to one embodiment of the invention, the method be carried on by titanium compound on inorganic carrier comprises the solution impregnation porous inorganic carrier with titanium compound.According to an embodiment, in steeping process, can implement to stir, preferred continuously stirring.Usually, this stirring continues about 1 ~ 12h, preferably about 4 ~ 8h, and dipping temperature is 10 ~ 80 DEG C, preferably 20 ~ 70 DEG C.According to an embodiment, titanium charge capacity is 0.01 ~ 30wt% of total catalyst weight, preferably 0.05 ~ 20wt%.Then the carrier being impregnated with titanium compound obtained is carried out drying.Wherein, the time that drying is carried out is not particularly limited, but this drying continues about 6 ~ 20h usually, preferably about 7 ~ 18h, further preferred about 8 ~ 15h.Drying temperature, in room temperature ~ 250 DEG C, preferably 50 ~ 200 DEG C, preferably 70 ~ 150 DEG C further, also can adopt vacuum-drying in drying process.

Above-mentioned steps II) be that the inorganic carrier being impregnated with titanium compound 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. cold stage and hot stage.Cold stage carries out at about 100 ~ 300 DEG C usually.This hot stage carries out at about 300 ~ 900 DEG C usually.Be not bound by any theory, the mechanical water adsorbed in described cold stage carrier is removed substantially, and the part of hydroxyl on described hot stage inorganic carrier is removed.According to an embodiment, described cold stage continues 1 ~ 10 hour, preferably 2 ~ 9 hours, more preferably 3 ~ 8 hours.According to another embodiment, described hot stage continues 1 ~ 10 hour, preferably 2 ~ 9 hours, more preferably 3 ~ 8 hours.According to an embodiment, described cold stage carries out under rare gas element or air atmosphere, preferably carries out under inert gas atmosphere, and described noble gasses is the atmosphere such as nitrogen, helium, argon gas in this way, preferably carries out in a nitrogen atmosphere, such as high pure nitrogen.According to an embodiment, described hot stage roasting is carried out under air or Oxygen Condition, preferably carries out under dry air condition.After described roasting terminates, the inorganic carrier of titanium dioxide there is is to cool from hot stage the load obtained.According to an embodiment, when being cooled to the temperature of 300 ~ 400 DEG C, can atmosphere being converted, such as, become rare gas element from air, such as nitrogen, argon gas etc.According to an embodiment, this is cooled to Temperature fall cooling.The titania modified inorganic carrier obtained is transferred to wide-necked bottle, is placed in moisture eliminator and saves backup.

Wherein method (2) precipitator method, specifically comprise following steps:

I) the solution mixing of titanium compound and silicate compound is carried out coprecipitation reaction, temperature of reaction 10 ~ 100 DEG C, preferably 20 ~ 60 DEG C, reaction times 2 ~ 10h, preferably 3 ~ 8h.Then dry at 50 ~ 200 DEG C, preferably 70 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process;

Wherein method (3) sol-gel method, specifically comprises following steps:

Wherein preferably prepare the method for the inorganic carrier of titanium modification as method (3), comprise following steps:

I) titanium compound is dissolved in dehydrated alcohol wiring solution-forming A, (mineral acid adjust ph is wherein added in solution B 1 ~ 5 in the mixing solutions B of instillation distilled water and dehydrated alcohol, preferably between 2 ~ 4), titanium compound hydrolysis can obtain TiO2 colloidal sol.Inorganic carrier is added in above-mentioned TiO2 colloidal sol, fully stir, whipping temp 10 ~ 100 DEG C, preferably 20 ~ 60 DEG C, churning time 2 ~ 10h, preferably 3 ~ 8h.Then dry at 60 ~ 200 DEG C, preferably 70 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process;

Wherein method (4) sol-gel method, specifically comprises following steps:

I) titanium compound is dissolved in organic solvent, then add sour back flow reaction, back flow reaction temperature is 10-80 DEG C, preferred 20-60 DEG C, and the time is 3-7 hour, preferred 4-6 hour; Product after backflow is transferred to configuration bottle, adds inorganic carrier and stirs, whipping temp 10 ~ 100 DEG C, preferably 20 ~ 60 DEG C, reaction times 2 ~ 10h, preferably 3 ~ 8h.Then dry at 60 ~ 200 DEG C, preferably 70 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process;

Preferred as one of the present invention, inorganic carrier is loaded modified component fluorine first, and then load remaining ingredient.Wherein the preparation method of inorganic carrier loaded modified component fluorine is identical with the preparation method of inorganic carrier loaded modified component titanium.

The one of the preparation method of the loaded modified component fluorine of inorganic carrier is preferably as follows:

I) fluorine cpd are dissolved in solvent and react with inorganic carrier stirring and evenly mixing, after reaction, product is carried out drying;

II) by the roasting at high temperature 200 ~ 900 DEG C of dried product, obtain the inorganic carrier of described fluorine richness.

Preferably prepare the method for the inorganic carrier of fluorine richness according to one, comprise following steps:

I) fluorine cpd are dissolved in solvent, then be immersed on inorganic carrier, dipping time is 1 ~ 12h, preferably 4 ~ 8h, and dipping temperature is 10 ~ 80 DEG C, preferably 20 ~ 70 DEG C, then dry at 50 ~ 200 DEG C, preferably 70 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process;

II) above-mentioned sample is carried out high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 200 ~ 900 DEG C, preferably 400 ~ 800 DEG C, roasting time is 1 ~ 10h, preferably 4 ~ 6h, then cooling, wherein switching to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling.The inorganic carrier of the fluorine richness obtained is transferred to wide-necked bottle, is placed in moisture eliminator and saves backup.

The preparation method of preferred a kind of titanium fluorine loading type chrome alum double activity center of the present invention catalyzer is as follows:

I) prepare the inorganic carrier of titanium modification;

II) by step I) solution of inorganic carrier dipping containing fluorine of the titanium modification that obtains, then dry, then calcination activation at high temperature 200 ~ 900 DEG C;

III) by step II) solution of the product that obtains dipping containing vanadium, then dry, then calcination activation at high temperature 300 ~ 900 DEG C;

Iv) by step III) solution of the product of gained dipping containing chromium, then dry, then calcination activation at high temperature 300 ~ 900 DEG C, obtains described catalyzer and saves backup.

The method of preferred preparation titanium fluorine of the present invention loading type chrome alum double activity center catalyzer, specifically comprises following steps:

I) inorganic carrier of titanium modification is prepared according to the above-mentioned inorganic carrier method preparing titanium modification;

II) by the salt solution impregnation of fluorine on the inorganic carrier of titanium modification, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 20 ~ 70 DEG C, then dry at 90 ~ 250 DEG C, preferably 100 ~ 200 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process; Above-mentioned sample is carried out high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 200 ~ 900 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 4 ~ 6h, then cooling, wherein switching to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling;

III) by the salt solution impregnation of vanadium in II) in product titanium fluorine richness inorganic carrier on, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 20 ~ 70 DEG C, then dry at 90 ~ 250 DEG C, preferably 100 ~ 200 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process; Above-mentioned sample is carried out high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 300 ~ 900 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 4 ~ 6h, then cooling, wherein switching to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling;

Iv) by the salt solution impregnation of chromium on above-mentioned catalyst Precursors, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 15 ~ 60 DEG C, then dry between 90 ~ 250 DEG C, preferably 100 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum 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 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 3 ~ 8h, then cools, and switches to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling, obtains described catalyzer and saves backup.

The preparation method of the loading type chrome alum double activity center catalyzer of titanium fluorine richness of the present invention, wherein a kind of preferred method comprises following steps:

I) inorganic carrier of titanium modification is prepared according to the above-mentioned method preparing the inorganic carrier of titanium modification;

III) by step II) solution of the product that obtains dipping containing chromium, then dry, then calcination activation at high temperature 300 ~ 900 DEG C;

Iv) by step III) solution of the product of gained dipping containing vanadium, then dry, then calcination activation at high temperature 300 ~ 900 DEG C, obtains described catalyzer and saves backup.

III) by the salt solution impregnation of chromium in II) in product titanium fluorine richness inorganic carrier on, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 20 ~ 70 DEG C, then dry at 90 ~ 250 DEG C, preferably 100 ~ 200 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process; Above-mentioned sample is carried out high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 300 ~ 900 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 4 ~ 6h, then cooling, wherein switching to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling;

Iv) by the salt solution impregnation of vanadium in above-mentioned III) on catalyst Precursors, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 15 ~ 60 DEG C, then dry between 90 ~ 250 DEG C, preferably 100 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum 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 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 3 ~ 8h, then cools, and switches to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling, obtains described catalyzer and saves backup.

II) by step I) solution of inorganic carrier dipping containing chromium of the titanium modification that obtains, then dry, then calcination activation at high temperature 300 ~ 900 DEG C;

III) by step II) solution of the product that obtains dipping containing fluorine, then dry, then calcination activation at high temperature 200 ~ 900 DEG C;

Preferably prepare the method for titanium fluorine loading type chrome alum double activity center catalyzer according to one, comprise following steps:

II) by the salt solution impregnation of chromium on the inorganic carrier of titanium modification, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 20 ~ 70 DEG C, then dry at 90 ~ 250 DEG C, preferably 100 ~ 200 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process; Above-mentioned sample is carried out high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 300 ~ 900 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 4 ~ 6h, then cooling, wherein switching to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling;

III) by II) in product dipping with the salts solution of fluorine, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 20 ~ 70 DEG C, then dry at 90 ~ 250 DEG C, preferably 100 ~ 200 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum-drying in drying process; Above-mentioned sample is carried out high-temperature roasting activation in rare gas element or oxygen or air, maturing temperature is at 200 ~ 900 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 4 ~ 6h, then cooling, wherein switching to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling;

Iv) by above-mentioned III) in product impregnated in the salts solution of vanadium, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 15 ~ 60 DEG C, then dry between 90 ~ 250 DEG C, preferably 100 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum 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 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 3 ~ 8h, then cools, and switches to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling, obtains described catalyzer and saves backup.

II) by step I) solution of inorganic carrier dipping containing vanadium of the titanium modification that obtains, then dry, then calcination activation at high temperature 300 ~ 900 DEG C;

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

Iv) by above-mentioned III) in product impregnated in the salts solution of chromium, dipping time is 1 ~ 12h, preferably 4 ~ 8h, dipping temperature is 10 ~ 80 DEG C, preferably 15 ~ 60 DEG C, then dry between 90 ~ 250 DEG C, preferably 100 ~ 150 DEG C, time of drying 6 ~ 20h, preferably 8 ~ 15h, also can adopt vacuum 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 DEG C, preferably 400 ~ 800 DEG C, time is 1 ~ 10h, preferably 3 ~ 8h, then cools, and switches to rare gas element as nitrogen or argon gas etc. when being cooled to 300 ~ 400 DEG C, naturally cooling, obtains described catalyzer and saves backup.

I) inorganic carrier of titanium modification is prepared according to above-mentioned any one method prepared in the inorganic carrier method of titanium modification;

II) by step I) solution of inorganic carrier dipping containing fluorine, vanadium of the titanium modification of gained, then dry, then calcination activation at high temperature 200 DEG C ~ 900 DEG C;

III) by step II) solution of the product of gained dipping containing chromium, then dry, then calcination activation at high temperature 300 DEG C ~ 900 DEG C, obtains catalyzer and saves backup.

II) by step I) solution of inorganic carrier dipping containing fluorine, chromium of the titanium modification of gained, then dry, then calcination activation at high temperature 200 DEG C ~ 900 DEG C;

III) by step II) solution of the product of gained dipping containing vanadium, then dry, then calcination activation at high temperature 300 DEG C ~ 900 DEG C, obtains catalyzer and saves backup.

II) by step I) solution of inorganic carrier dipping containing fluorine, chromium, vanadium of the titanium modification of gained, then dry, then calcination activation at high temperature 200 DEG C ~ 900 DEG C, obtains catalyzer and saves backup.

I) inorganic carrier of fluorine richness is prepared according to above-mentioned any one method prepared in the inorganic carrier method of fluorine richness;

II) by step I) solution of inorganic carrier dipping containing titanium, chromium, vanadium of the titanium modification of gained, then dry, then calcination activation at high temperature 200 DEG C ~ 900 DEG C, obtains catalyzer and saves backup.

The preparation method of the loading type chrome alum double activity center catalyzer of titanium fluorine richness of the present invention, wherein a kind of preferred method comprises following steps: the catalyzer any one preparation method above-mentioned prepared, add organo-metallic promotor and carry out prereduction activation treatment, after drying, obtain product; Wherein: organo-metallic promotor is one or several in organo-aluminium compound, organolithium compound, organoboron compound.

Preferably prepare the method for the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to one, comprise following steps:

I) adopt in aforesaid method that any one prepares the loading type chrome alum double activity center catalyzer of titanium fluorine richness;

II) under an inert atmosphere the catalyzer obtained is added organo-metallic promotor, prereduction activation treatment is carried out to catalyzer, then dry 2-8 hour between 60-120 DEG C, also can adopt vacuum in drying process, then preserves stand-by under an inert gas.

Usually, aforesaid method carries out prereduction activation treatment to the loading type chrome alum double activity center catalyzer of the titanium fluorine richness obtained.Step I) be the loading type chrome alum double activity center catalyzer preparing titanium fluorine richness by any one method in aforesaid method, step II) be add organo-metallic promotor under an inert atmosphere to carry out prereduction activation treatment to this catalyzer, above-mentioned organo-metallic promotor includes machine aluminium compound, organolithium compound, organoboron compound etc. and well known to a person skilled in the art any one promotor for olefinic polyreaction or their combination.According to an embodiment, organo-aluminium compound as promotor can comprise trialkylaluminium AlR3, dialkyl group aluminum alkoxide AlR2OR, dialkylaluminum halides AlR2X, aikyiaiurnirsoxan beta, ethyl sesquialter aluminium muriate etc., wherein R is alkyl, such as there is the alkyl of 1-12 carbon atom, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, dodecyl etc., X is halogen, such as fluorine, chlorine, bromine and iodine, preferred chlorine.Described aikyiaiurnirsoxan beta can comprise the reactant of all aluminum alkylss such as methylaluminoxane (MAO) and water.The described organo-aluminium compound as promotor can be used alone or two or more combinationally uses.As object lesson, described aluminum compound can mention triethyl aluminum, triisobutyl aluminium, diethylaluminum ethoxide, aluminium diethyl monochloride and methylaluminoxane etc.According to an embodiment, when adopting the loading type chrome alum double activity center catalyzer of organoaluminum promotor to titanium fluorine richness to carry out prereduction activation treatment, aluminium/chromium mol ratio is between 0 ~ 1000, preferably 0 ~ 100, more preferably 0 ~ 50, reduction activation treatment temp is between room temperature ~ 100 DEG C, between preferred room temperature ~ 60 DEG C, 0.5 ~ 20 hour reduction activation treatment time, preferably 0.5 ~ 10 hour, reduction activation process adopts alr mode, preferred continuously stirring, after being disposed between 60 ~ 120 DEG C dry 2 ~ 8 hours again, drying is carried out under inert gas atmosphere, such as at nitrogen, helium, carry out under the atmosphere such as argon gas, preferably carry out in a nitrogen atmosphere, this drying process also can be carried out under vacuum.The loading type chrome alum double activity center catalyzer of the titanium fluorine richness through prereduction activation obtained is preserved stand-by under inert gas atmosphere.

As one preferably, the concrete operations preparing catalyzer of the present invention comprise:

By wiring solution-forming soluble in water for ammonium hexafluorosilicate, wherein fluorine charge capacity meets requirement (such as 0.01 ~ 10wt% herein relative to total catalyst weight, weighing scale with F), silica gel dipping is added in above-mentioned solution, at room temperature after continuously stirring certain hour (such as 4 ~ 8h), then heat up dry 8 ~ 15h; Dried product is carried out high-temperature roasting in fluidized-bed, wherein remove the mechanical water in carrier in cold stage (such as 100 ~ 300 DEG C) roasting in nitrogen atmosphere, remove the part of hydroxyl of carrier surface in hot stage (such as 300 DEG C ~ 900 DEG C) roasting in dry air, keep certain hour (such as 3 ~ 8 hours) at this hot stage; Temperature fall cools, and switching to nitrogen protection, obtaining the silica gel of described fluorine richness, be transferred to wide-necked bottle, being placed in moisture eliminator and saving backup when being cooled to 300 ~ 400 DEG C.Isopropyl titanate is dissolved in wiring solution-forming in normal hexane, wherein titanium charge capacity meets requirement (such as 0.05 ~ 20wt% herein relative to total catalyst weight, weighing scale with Ti), the silica gel dipping of above-mentioned fluorine richness is added in above-mentioned solution, at room temperature after continuously stirring certain hour (such as 4 ~ 8h), then at 70 ~ 150 DEG C of drying 8 ~ 15h; Dried product is carried out high-temperature roasting in fluidized-bed, wherein remove the mechanical water in carrier in cold stage (such as 100 ~ 300 DEG C) roasting in nitrogen atmosphere, remove the part of hydroxyl of carrier surface in hot stage (such as 300 DEG C ~ 900 DEG C) roasting in dry air, keep certain hour (such as 3 ~ 8 hours) at this hot stage; Temperature fall cools, and switching to nitrogen protection, obtaining the silica gel of described titanium fluorine richness, being transferred to wide-necked bottle, being placed in moisture eliminator and saving backup when being cooled to 300 ~ 400 DEG C.Be immersed in certain density ammonium metavanadate solution by the silica gel of the titanium fluorine richness obtained, vanadium charge capacity meets requirement (such as 0.1 ~ 10wt%, the weighing scale with vanadium) herein relative to total catalyst weight; After continuously stirring certain hour (such as 4 ~ 8 hours), heat up dry; The silica gel of the fluorine richness containing ammonium meta-vanadate is carried out high-temperature roasting in fluidized-bed, wherein remove in cold stage (such as 100 DEG C ~ 300 DEG C) roasting in nitrogen atmosphere the mechanical water adsorbed in carrier, remove the part of hydroxyl of carrier surface in hot stage (such as 300 DEG C ~ 900 DEG C) roasting in dry air, keep certain hour (such as 3 ~ 8 hours) at this hot stage; Temperature fall cools, and switches to nitrogen protection when being cooled to 300 ~ 400 DEG C, the obtained catalyst Precursors carrying vanadium.Then, by the load of inorganic chromium source on the catalyst Precursors obtained by aforesaid method, chromium charge capacity heats up dry after meeting requirement herein (being such as 0.1 ~ 3wt% of total catalyst weight, the weighing scale with chromium) continuously stirring certain hour (such as 3 ~ 8 hours); Then in fluidized-bed, high-temperature roasting is carried out, wherein remove in cold stage (such as 100 DEG C ~ 300 DEG C) roasting in nitrogen atmosphere the mechanical water adsorbed in carrier, remove the part of hydroxyl on inorganic carrier surface in hot stage (such as 300 DEG C ~ 900 DEG C) roasting in dry air, keep certain hour (such as 3 ~ 8 hours) at this hot stage; Temperature fall cools, and switching to nitrogen protection, shifting under nitrogen protection, preserving stand-by when being cooled to 300 ~ 400 DEG C.Then add triethyl aluminum and prereduction activation treatment is carried out to catalyzer, aluminium/chromium mol ratio is between 0 ~ 50, treatment temp is in room temperature ~ 60 DEG C, continuously stirring 0.5 ~ 10 hour, and then between 60 ~ 120 DEG C dry 2 ~ 8 hours, this drying is carried out under inert gas atmosphere, such as, carry out under the atmosphere such as nitrogen, helium, argon gas, preferably carry out in a nitrogen atmosphere, this drying process also can be carried out under vacuum.The loading type chrome alum double activity center catalyzer of the titanium fluorine richness through prereduction activation obtained is preserved stand-by under inert gas atmosphere.

The loading type chrome alum double activity center catalyzer of titanium fluorine richness of the present invention can be used for the homopolymerization of ethene or the copolymerization of ethene and alpha-olefin at (comprising the loading type chrome alum double activity center catalyzer of the above titanium fluorine richness through organo-metallic promotor prereduction activation).Organic metal promoters, hydrogen etc. can be added as required in polymerization process.

Therefore, according to another aspect of the present invention, provide and adopt the loading type chrome alum double activity center Catalyst Production Alathon of titanium fluorine richness of the present invention and the method for ethylene/alpha-olefin copolymer.

For aforesaid method, be polymerized the alkene used and generally comprise ethene as polymerization single polymerization monomer.In one embodiment, the alkene that described polymerization uses 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 be used alone or can two or more combinationally use.Described comonomer is preferably 1-butylene, 1-hexene, 1-octene and 1-decene.When comonomer exists, the amount of comonomer is generally 0 ~ 30vol%, preferably 0 ~ 10vol%, based on the volumetric concentration of comonomer during polymerization.

Organic metal promoters (organo-metallic promotor such as mentioned above) can be added as required again in polymerization system in polymerization process, according to an embodiment, described organo-metallic promotor can use organo-aluminium compound, and organo-aluminium compound can mention triethyl aluminum, triisobutyl aluminium, diethylaluminum ethoxide, aluminium diethyl monochloride and methylaluminoxane etc.The usage quantity of described organo-metallic aluminum compound normally presses aluminium/chromium molar ratio computing 0 ~ 1000, and preferably 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 in its polymerization process.The supported chrome barium oxide double activity center Catalyst Production Alathon of above-mentioned employing titanium fluorine richness of the present invention or the method for ethene and alpha-olefin copolymer can comprise gas phase polymerization process, slurry phase polymerisation process, suspension polymerization, bulk polymerization, solution polymerization process conventional implementation and polymerizing condition etc. implement.In one embodiment, use slurry phase polymerisation process, comprise and add ethene in reactor, then add solvent and optionally add promotor (organo-metallic promotor such as mentioned above), hydrogen and comonomer, the loading type chrome alum double activity center catalyzer finally adding titanium fluorine richness of the present invention starts 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 be used alone or can two or more combinationally use.The preferred Trimethylmethane of described solvent, iso-pentane, normal hexane, hexanaphthene, normal heptane etc.

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

The supported chrome barium oxide double activity center catalyzer of titanium fluorine richness of the present invention can be produced in single reaction vessel or combined reactor has the wider Alathon of molecular weight distribution controlled range and ethylene/alpha-olefin copolymer, has higher ethylene homo and ethene and alpha-olefin copolymer reactive behavior.Use the loading type chrome alum double activity center catalyzer of titanium fluorine richness of the present invention, by changing the factors such as promotor consumption, polymerization temperature, molecular weight regulator, can facilitate and easily adjust the molecular weight and molecualr weight distribution of Alathon and ethylene/alpha-olefin copolymer and co-monomer content and distribution, thus the polymeric articles with desired properties can be prepared.

In sum, the present invention has the following advantages:

(1) present invention improves content and the distribution thereof of comonomer, make it reduce in lower molecular weight end insertion, increase in high molecular end insertion, thus easily form more tie molecule, prepare the better polyethylene product of performance.Carry out titanium fluorine richness to carrier, can improve the activity of catalyzer simultaneously, make relative molecular mass distribution wider, also improve copolymerization performance, this catalyzer also has the advantages such as higher hydrogen response simultaneously;

(2) the present invention also provides the preparation method of titanium fluorine richness silica gel and the preparation method of catalyzer, rational technology, be easy to carry out suitability for industrialized production under the condition not transforming existing industrial equipments, not only can increase polyethylene product added value, the polyethylene product of production better properties, also saves facility investment simultaneously.

Accompanying drawing explanation

Accompanying drawing 1 is carrier calcination program schematic diagram 1 in embodiment.

Accompanying drawing 2 is carrier calcination program schematic diagram 2 in embodiment.

Accompanying drawing 3 is carrier calcination program schematic diagram 3 in embodiment.

Accompanying drawing 4 is carrier calcination program schematic diagram 4 in embodiment.

Embodiment

The preparation method mentioned in embodiment is ordinary method if no special instructions.Described material is commercial if no special instructions.The silica gel adopted in embodiment is commercially available Davison955.

Various polymer properties in embodiment are measured according to following methods:

High temperature gel chromatogram (HT-GPC)

The weight-average molecular weight of polyethylene product and molecular weight distribution high temperature gel chromatographic determination: this experiment adopts PL-220 type high-temperature gel permeation chromatography instrument (PolymerLaboratories company) to measure molecular weight of polyethylene and molecular weight distribution thereof.In experiment with 1,2,4-trichlorobenzene for solvent, at 160 DEG C measure.Adopt Narrow distribution polystyrene as the universal calibration method processing data of standard specimen.

Dsc (DSC)

The fusing point determine with dsc method of polyethylene product: this experiment adopts TAQ200 type differential scanning calorimeter to test under nitrogen protection.Sample first with the speed of 10 DEG C/min from room temperature to 150 DEG C, and constant temperature 5min, then drops to room temperature naturally.Then with the speed heating scan (room temperature to 150 DEG C) of 10 DEG C/min, record DSC curve.

Embodiment 1

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the hexane solution of tetra-n-butyl titanate (titanium charge capacity is 3wt%), after continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that pickling process is obtained.The titanium modified silica-gel obtained is immersed in (fluorine charge capacity is 1.5wt%) in the aqueous solution of ammonium hexafluorosilicate.After continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 550 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 2, obtains the titanium fluorine richness silica gel that pickling process is obtained.Then, the silica gel of the titanium fluorine richness obtained by aforesaid method is immersed in (vanadium charge capacity is 0.48wt%) in the aqueous solution of ammonium meta-vanadate, and at 45 DEG C, continuously stirring 4 hours is until react completely.Then, under 120 DEG C of oil baths after dry 6h, 120 DEG C of oven drying 8h are transferred to; Be placed in quartzy fluidized-bed by the sample of drying and carry out calcination activation, be incubated 4h, under nitrogen protection naturally cooling in air at 450 DEG C, calcination procedure as shown in Figure 3.Then, be again immersed in by gained sample (chromium charge capacity is 1wt%) in the aqueous solution of alkali formula chromium acetate, under room temperature, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 600 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 2

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the hexane solution of tetra-n-butyl titanate (titanium charge capacity is 3wt%), after continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that pickling process is obtained.The titanium modified silica-gel obtained is immersed in (fluorine charge capacity is 1.5wt%) in the aqueous solution of ammonium hexafluorosilicate.After continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 550 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 2, obtains the titanium fluorine richness silica gel that pickling process is obtained.Then, the silica gel of the titanium fluorine richness obtained by aforesaid method is immersed in (vanadium charge capacity is 0.48wt%) in the aqueous solution of ammonium meta-vanadate, and at 45 DEG C, continuously stirring 4 hours is until react completely.Then, under 120 DEG C of oil baths after dry 6h, 120 DEG C of oven drying 8h are transferred to; Be placed in quartzy fluidized-bed by the sample of drying and carry out calcination activation, be incubated 4h, under nitrogen protection naturally cooling in air at 450 DEG C, calcination procedure as shown in Figure 3.Then, be again immersed in by gained sample (chromium charge capacity is 1wt%) in the aqueous solution of alkali formula chromium acetate, under room temperature, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 500 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 3

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the hexane solution of tetra-n-butyl titanate (titanium charge capacity is 6wt%), after continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that pickling process is obtained.The titanium modified silica-gel obtained is immersed in (fluorine charge capacity is 1.5wt%) in the aqueous solution of ammonium hexafluorosilicate.After continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 550 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 2, obtains the titanium fluorine richness silica gel that pickling process is obtained.Then, the silica gel of the titanium fluorine richness obtained by aforesaid method is immersed in (vanadium charge capacity is 0.48wt%) in the aqueous solution of ammonium meta-vanadate, and at 45 DEG C, continuously stirring 4 hours is until react completely.Then, under 120 DEG C of oil baths after dry 6h, 120 DEG C of oven drying 8h are transferred to; Be placed in quartzy fluidized-bed by the sample of drying and carry out calcination activation, be incubated 4h, under nitrogen protection naturally cooling in air at 450 DEG C, calcination procedure as shown in Figure 3.Then, be again immersed in by gained sample (chromium charge capacity is 1wt%) in the aqueous solution of alkali formula chromium acetate, under room temperature, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 500 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 4

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the hexane solution of tetra-n-butyl titanate, (titanium charge capacity is 6wt%).After continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that pickling process is obtained.The titanium modified silica-gel obtained is immersed in the aqueous solution of ammonium hexafluorosilicate (fluorine charge capacity is 1.5wt%) and ammonium meta-vanadate (vanadium charge capacity is 0.48wt%), at 45 DEG C after continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 3, obtains the catalyst Precursors that pickling process is obtained.Then, be immersed in basic carbonate chromium solution (chromium charge capacity is 1wt%) by catalyst Precursors obtained for aforesaid method, under room temperature, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 500 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 5

Take the tetra-n-butyl titanate (titanium charge capacity is 5wt%) of respective quality, with dehydrated alcohol 1:2 wiring solution-forming A by volume, again by distilled water and dehydrated alcohol 95:1 wiring solution-forming B by volume, the pH adding concentrated nitric acid acid-conditioning solution B is 2 ~ 3, by solution A and solution B mixing, obtained TiO 2 sol.By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) add in above-mentioned colloidal sol, continuously stirring is after 4 hours, oil bath 80 DEG C of dryings 4 hours, then adopt vacuum-drying 2h to remove solvent in silica-gel carrier duct further, then in air dry oven 80 DEG C of dry 8h, then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, the last cooling of Temperature fall under a nitrogen of silica gel, above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that sol-gel method is obtained.Then, the titania modified silica gel obtained by aforesaid method is immersed in the aqueous solution of ammonium hexafluorosilicate (fluorine charge capacity is 3wt%), ammonium meta-vanadate (vanadium charge capacity is 0.48wt%), alkali formula chromium acetate (chromium charge capacity is 1wt%), at 45 DEG C after continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 6

Take the tetra-n-butyl titanate (titanium charge capacity is 5wt%) of respective quality, with dehydrated alcohol 1:2 wiring solution-forming A by volume, again by distilled water and dehydrated alcohol 95:1 wiring solution-forming B by volume, the pH adding concentrated nitric acid acid-conditioning solution B is 2 ~ 3, by solution A and solution B mixing, obtained TiO 2 sol.By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) add in above-mentioned colloidal sol, continuously stirring is after 4 hours, oil bath 80 DEG C of dryings 4 hours, then adopt vacuum-drying 2h to remove solvent in silica-gel carrier duct further, then in air dry oven 80 DEG C of dry 8h, then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, the last cooling of Temperature fall under a nitrogen of silica gel, above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that sol-gel method is obtained.The titanium modified silica-gel obtained is immersed in the aqueous solution of ammonium hexafluorosilicate (fluorine charge capacity is 1.5wt%) and basic carbonate chromium solution (chromium charge capacity is 1wt%), under normal temperature after continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 4, obtains the catalyst Precursors that pickling process is obtained.Then, be immersed in ammonium meta-vanadate (vanadium charge capacity is 0.48wt%) by catalyst Precursors obtained for aforesaid method, under room temperature, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 500 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 3.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 7

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the aqueous solution of titanium sulfate (titanium charge capacity is 6wt%), ammonium hexafluorosilicate (fluorine charge capacity is 3wt%), ammonium meta-vanadate (vanadium charge capacity is 0.48wt%), after 45 DEG C of continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 3, obtains catalyst Precursors.By the catalyst Precursors obtained in ammonium chromate (chromium charge capacity the is 0.5wt%) aqueous solution, under normal temperature after continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 8

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the hexane solution of tetra-n-butyl titanate (titanium charge capacity is 3wt%), after continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that pickling process is obtained.Then, the titania modified silica gel obtained by aforesaid method is immersed in the aqueous solution of ammonium hexafluorosilicate (fluorine charge capacity is 1.5wt%), ammonium meta-vanadate (vanadium charge capacity is 0.48wt%), alkali formula chromium acetate (chromium charge capacity is 1wt%), at 80 DEG C after continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 9

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the hexane solution of tetra-n-butyl titanate (titanium charge capacity is 3wt%), after continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that pickling process is obtained.Then, the titania modified silica gel obtained by aforesaid method is immersed in the aqueous solution of ammonium hexafluorosilicate (fluorine charge capacity is 1.5wt%), ammonium meta-vanadate (vanadium charge capacity is 0.48wt%), alkali formula chromium acetate (chromium charge capacity is 1wt%), at 80 DEG C after continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 500 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 10

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the hexane solution of tetra-n-butyl titanate (titanium charge capacity is 6wt%), after continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that pickling process is obtained.Then, the titania modified silica gel obtained by aforesaid method is immersed in the aqueous solution of ammonium hexafluorosilicate (fluorine charge capacity is 1.5wt%), ammonium meta-vanadate (vanadium charge capacity is 0.48wt%), alkali formula chromium acetate (chromium charge capacity is 1wt%), at 80 DEG C after continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 500 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Embodiment 11

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the hexane solution of tetra-n-butyl titanate (titanium charge capacity is 6wt%), after continuously stirring 4h, oil bath 80 DEG C of dry 4h, then employing vacuum-drying 2h removes the solvent in silica-gel carrier duct further, is transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the titania modified silica gel that pickling process is obtained.The titanium modified silica-gel obtained is immersed in (fluorine charge capacity is 1.5wt%) in the aqueous solution of ammonium hexafluorosilicate.After continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 550 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 2, obtains the titanium fluorine richness silica gel that pickling process is obtained.Then, the silica gel of the titanium fluorine richness obtained by aforesaid method is immersed in (vanadium charge capacity is 0.48wt%) in the aqueous solution of ammonium meta-vanadate, and at 45 DEG C, continuously stirring 4 hours is until react completely.Then, under 120 DEG C of oil baths after dry 6h, 120 DEG C of oven drying 8h are transferred to; Be placed in quartzy fluidized-bed by the sample of drying and carry out calcination activation, be incubated 4h, under nitrogen protection naturally cooling in air at 450 DEG C, calcination procedure as shown in Figure 3.Then, be again immersed in by gained sample (chromium charge capacity is 1wt%) in the aqueous solution of alkali formula chromium acetate, under room temperature, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 500 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 4.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.Then add Al/Cr mol ratio=20, organo-metallic promotor---methylaluminoxane that concentration is 1mol/L, and then 100 DEG C of dryings 4 hours to remove solvent, this drying is carried out in a nitrogen atmosphere.The catalyzer obtained through prereduction activation is preserved stand-by in a nitrogen atmosphere.

Embodiment 12

Take catalyzer 160mg in embodiment 1 and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 40mL is refining successively, add the trimethyl aluminium (TEA) that consumption is Al/Cr=2.5 respectively and make promotor, then add 30mL dehydration and deoxidation refine after normal heptane solvent.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 13

Take catalyzer 160mg in embodiment 2 and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 12 and step, unique not being both adds the triisobutyl aluminium (TiBA) that consumption is Al/Cr=2.5 respectively and makes promotor.

Embodiment 14

Take catalyzer 160mg in embodiment 3 and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 13 and step, unique not being both adds the refining normal heptane solvent of 70mL in reactor.

Embodiment 15

Take catalyzer 160mg in embodiment 4 and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 13 and step.

Embodiment 16

Take catalyzer 160mg in embodiment 5 and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 13 and step.

Embodiment 17

Take catalyzer 160mg in embodiment 6 and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 13 and step.

Embodiment 18

Take catalyzer 160mg in embodiment 6 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TiBA) promotor that consumption is Al/Cr=2.5, add the 1-hexene of the 0.7mL through processed, namely 1-hexene is respectively 1 with the volume ratio of being polymerized solvent for use, add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.Constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 19

Take catalyzer 160mg in embodiment 7 and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 40mL is refining successively, add the triisobutyl aluminium (TiBA) that consumption is Al/Cr=2.5 and make promotor, then add 30mL dehydration and deoxidation refine after normal heptane solvent.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 20

Take catalyzer 160mg in embodiment 7 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 70mL successively and refine normal heptane solvent, add triisobutyl aluminium (TiBA) promotor that consumption is Al/Cr=2.5, add the 1-hexene of the 0.7mL through processed, namely 1-hexene is respectively 1 with the volume ratio of being polymerized solvent for use, regulates ethylene pressure to 0.15MPa.Constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 21

Take catalyzer 160mg in embodiment 8 respectively and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 19 and step, unique not being both add respectively consumption be Al/Cr=2.5,5,10, the triisobutyl aluminium (TiBA) of 15 makes promotor (distinguishing corresponding embodiment 21-1,21-2,21-3,21-4).

Embodiment 22

Take catalyzer 160mg in embodiment 8 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TIBA) that consumption is Al/Cr=2.5 as promotor, add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.When polymerization temperature is stabilized in 45 DEG C and 65 DEG C (respectively corresponding embodiment 22-1 and 22-2) respectively, adds catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 23

Take catalyzer 160mg in embodiment 8 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TiBA) promotor that consumption is Al/Cr=2.5, add the 1-hexene of 0.7mL, 2.1mL, the 3.5mL through processed, namely 1-hexene and the volume ratio of polymerization solvent for use are respectively 1,3,5 (respectively corresponding embodiment 23-1,23-2,23-3), add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.Constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 24

Take catalyzer 160mg in embodiment 8 respectively and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 19 and step, unique not being both add 30mL dehydration and deoxidation refine after normal heptane solvent, then add 10mLH respectively in still ₂.

Embodiment 25

Take catalyzer 160mg in embodiment 9 respectively and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 19 and step, unique not being both add respectively consumption be Al/Cr=2.5,5,10, the triisobutyl aluminium (TiBA) of 15 makes promotor (distinguishing corresponding embodiment 25-1,25-2,25-3,25-4).

Embodiment 26

Take catalyzer 160mg in embodiment 9 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TIBA) that consumption is Al/Cr=2.5 as promotor, add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.When polymerization temperature is stabilized in 45 DEG C and 65 DEG C (respectively corresponding embodiment 26-1 and 26-2) respectively, adds catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 27

Take catalyzer 160mg in embodiment 9 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TiBA) promotor that consumption is Al/Cr=2.5, add the 1-hexene of 0.7mL, 2.1mL, the 3.5mL through processed, namely 1-hexene and the volume ratio of polymerization solvent for use are respectively 1,3,5 (respectively corresponding embodiment 27-1,27-2,27-3), add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.Constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 28

Take catalyzer 160mg in embodiment 9 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 40mL is refining successively, add the triisobutyl aluminium (TiBA) that consumption is Al/Cr=2.5 and make promotor, then add 30mL dehydration and deoxidation refine after normal heptane solvent, then add 10mLH respectively in still ₂.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Embodiment 29

Take catalyzer 160mg in embodiment 10 respectively and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 19 and step, unique not being both add respectively consumption be Al/Cr=2.5,5,10, the triisobutyl aluminium (TiBA) of 15 makes promotor (distinguishing corresponding embodiment 29-1,29-2,29-3,29-4).

Embodiment 30

Take catalyzer 160mg in embodiment 10 respectively and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 26 and step, unique polymerization temperature that is not both when being stabilized in 45 DEG C and 65 DEG C (distinguishing corresponding embodiment 30-1 and 30-2) respectively, adding catalyzer and starts to react.

Embodiment 31

Take catalyzer 160mg in embodiment 10 respectively and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 14 and step.

Embodiment 32

Take catalyzer 160mg in embodiment 10 respectively and carry out polymerization under atmospheric pressure experiment.Adopt the test method identical with embodiment 26 and step.

Embodiment 33

Take catalyzer 160mg in embodiment 11 and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 70mL is refining.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 1

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in (vanadium charge capacity is 0.48wt%) in the aqueous solution of ammonium meta-vanadate, continuously stirring 4h at 45 DEG C is until react completely.Then, under 120 DEG C of oil baths after dry 6h, 120 DEG C of oven drying 8h are transferred to; Be placed in quartzy fluidized-bed by the sample of drying and carry out calcination activation, be incubated 4h, under nitrogen protection naturally cooling in air at 450 DEG C, calcination procedure as shown in Figure 2.Then, be again immersed in by gained sample (chromium charge capacity is 1wt%) in the aqueous solution of alkali formula chromium acetate, continuously stirring 4h under room temperature is until react completely.Then dry 6h under 120 DEG C of oil baths, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 500 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 3.Last being transferred in glove box by the unmodified loading type chrome alum double activity center catalyzer obtained under nitrogen protection saves backup.

Comparative example 2

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in the aqueous solution of ammonium hexafluorosilicate, ammonium meta-vanadate and alkali formula chromium acetate, (fluorine charge capacity is 1.5wt%, and vanadium charge capacity is 0.48wt%, and chromium charge capacity is 1wt%) continuously stirring 4h, after 120 DEG C of dry 6h of oil bath, be transferred to 120 DEG C of oven drying 8h; The sample of drying is placed in quartzy fluidized-bed and carries out calcination activation, be incubated 4h at 500 DEG C in air, under nitrogen protection naturally cooling.Naturally cooling under nitrogen protection, is finally transferred to catalyzer in glove box under nitrogen protection and saves backup.

Comparative example 3

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250-300m ²/ g) be immersed in (fluorine charge capacity is 1.5wt%) in the aqueous solution of ammonium hexafluorosilicate.Continuously stirring is after 4 hours, oil bath 120 DEG C of dryings 6 hours, 80 DEG C of dry 8h in air dry oven again, then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, the last cooling of Temperature fall under a nitrogen of silica gel, above-mentioned calcination procedure as shown in Figure 1, obtains the fluorine richness silica gel that pickling process is obtained.Then, the silica gel of the fluorine richness obtained by aforesaid method is immersed in (chromium charge capacity is 1wt%, and vanadium charge capacity is 0.48wt%) in the aqueous solution of alkali formula chromium acetate and ammonium meta-vanadate, and at 45 DEG C, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, 120 DEG C of dry 8h in air dry oven, then carry out high-temperature roasting by the sample obtained in fluidized-bed again, 500 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 3.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Comparative example 4

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250 ~ 300m ²/ g) be immersed in (fluorine charge capacity is 1.5wt%) in the aqueous solution of ammonium hexafluorosilicate.After continuously stirring 4h, oil bath 120 DEG C of dry 6h, are transferred to 80 DEG C of dry 8h in air dry oven; Then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains the fluorine richness silica gel that pickling process is obtained.Then, the silica gel of the fluorine richness obtained by aforesaid method is immersed in (vanadium charge capacity is 0.48wt%) in the aqueous solution of ammonium meta-vanadate, and at 45 DEG C, continuously stirring 4 hours is until react completely.Then, under 120 DEG C of oil baths after dry 6h, 120 DEG C of oven drying 8h are transferred to; Be placed in quartzy fluidized-bed by the sample of drying and carry out calcination activation, be incubated 4h, under nitrogen protection naturally cooling in air at 450 DEG C, calcination procedure as shown in Figure 2.Then, be again immersed in by gained sample (chromium charge capacity is 1wt%) in the aqueous solution of alkali formula chromium acetate, under room temperature, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 500 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 3.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Comparative example 5

By the silica gel of 10g, (pore volume is 1.5 ~ 1.7cm ³/ g, surface-area is 250-300m ²/ g) be immersed in (fluorine charge capacity is 1.5wt%) in the aqueous solution of ammonium hexafluorosilicate.Continuously stirring is after 4 hours, oil bath 120 DEG C of dryings 6 hours, 80 DEG C of dry 8h in air dry oven again, then dried sample is carried out calcination activation in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, the last cooling of Temperature fall under a nitrogen of silica gel, above-mentioned calcination procedure as shown in Figure 1, obtains the fluorine richness silica gel that pickling process is obtained.Then, the silica gel of the fluorine richness obtained by aforesaid method is immersed in (vanadium charge capacity is 0.48wt%) in the aqueous solution of vanadyl oxalate, and continuously stirring 4h under room temperature is until react completely.Then, under 120 DEG C of oil baths after dry 6h, 120 DEG C of oven drying 8h are transferred to; Be placed in quartzy fluidized-bed by the sample of drying and carry out calcination activation, be incubated 4h, under nitrogen protection naturally cooling in air at 450 DEG C, calcination procedure as shown in Figure 2.Then, be again immersed in by gained sample (chromium charge capacity is 1wt%) in the aqueous solution of chromium trioxide, under room temperature, continuously stirring 4 hours is until react completely.Then under 120 DEG C of oil baths dry 6 hours, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 600 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 3.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Comparative example 6

Isopropyl titanate is dissolved in normal hexane solvent, then adding concentrated nitric acid adjust ph is between 2 ~ 3, and reflux 5h at 50 DEG C.Product after backflow is transferred to configuration bottle, and (pore volume is 1.5 ~ 1.7cm to add the silica gel of 10g ³/ g, surface-area is 250 ~ 300m ²/ g) stirred at ambient temperature 4h is until react completely.Then oil bath is warming up to 95 DEG C, until precipitation occurs, then gained throw out is put into 80 DEG C of dry 8h of air dry oven.Then dried product is carried out high-temperature roasting in fluidized-bed, the lower 600 DEG C of insulation 4h of high pure air, silica gel is Temperature fall cooling under a nitrogen finally, and above-mentioned calcination procedure as shown in Figure 1, obtains titania modified silica gel.Then, the titania modified silica gel obtained by aforesaid method is immersed in (vanadium charge capacity is 0.24wt%) in the ethanol solution of vanadium acetylacetonate, and under room temperature, continuously stirring 4 hours is until react completely.Then, after 100 DEG C of dry 6h of oil bath, dry 8h in 100 DEG C of air dry ovens is transferred to; Be placed in quartzy fluidized-bed by the sample of drying and carry out calcination activation, be incubated 4h, under nitrogen protection naturally cooling in air at 450 DEG C, calcination procedure as shown in Figure 2.Then, be again immersed in by gained sample (chromium charge capacity is 0.5wt%) in the aqueous solution of ammonium chromate, continuously stirring 4h under room temperature is until react completely.Then dry 6h under 120 DEG C of oil baths, be transferred to 120 DEG C of dry 8h in air dry oven, then the sample obtained carried out high-temperature roasting in fluidized-bed, 600 DEG C of insulation 4h in high pure air, then Temperature fall cooling under a nitrogen, above-mentioned roasting process as shown in Figure 3.Last being transferred in glove box by catalyzer under nitrogen protection saves backup.

Comparative example 7

Take catalyzer 160mg in comparative example 1 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 40mL is refining successively, add respectively consumption be Al/Cr=2.5,5,10, the triisobutyl aluminium (TiBA) of 15 makes promotor (respectively corresponding comparative example 7-1,7-2,7-3,7-4), then add 30mL dehydration and deoxidation refine after normal heptane solvent.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 8

Take catalyzer 160mg in comparative example 1 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TIBA) that consumption is Al/Cr=2.5 as promotor, add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.When polymerization temperature is stabilized in 45 DEG C and 65 DEG C (respectively corresponding comparative example 8-1 and 8-2) respectively, adds catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 9

Take catalyzer 160mg in comparative example 1 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TiBA) promotor that consumption is Al/Cr=2.5, add the 1-hexene of 0.7mL, 2.1mL, the 3.5mL through processed respectively, namely 1-hexene and the volume ratio of polymerization solvent for use are respectively 1,3,5 (respectively corresponding comparative example 9-1,9-2,9-3), add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.Constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 10

Take catalyzer 160mg in comparative example 1 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 40mL is refining successively, add the triisobutyl aluminium (TiBA) that consumption is Al/Cr=2.5 and make promotor, then add 30mL dehydration and deoxidation refine after normal heptane solvent, then add 10mLH in still ₂.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 11

Take catalyzer 160mg in comparative example 2 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 40mL is refining successively, add respectively consumption be Al/Cr=2.5,5,10, the triisobutyl aluminium (TiBA) of 15 makes promotor (respectively corresponding comparative example 11-1,11-2,11-3,11-4), then add 30mL dehydration and deoxidation refine after normal heptane solvent.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 12

Take catalyzer 160mg in comparative example 2 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TIBA) that consumption is Al/Cr=2.5 as promotor, add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.When polymerization temperature is stabilized in 45 DEG C and 65 DEG C (respectively corresponding comparative example 12-1 and 12-2) respectively, adds catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 13

Take catalyzer 160mg in comparative example 2 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add 40mL successively and refine normal heptane solvent, add triisobutyl aluminium (TiBA) promotor that consumption is Al/Cr=2.5, add the 1-hexene of 0.7mL, 2.1mL, the 3.5mL through processed respectively, namely 1-hexene and the volume ratio of polymerization solvent for use are respectively 1,3,5 (respectively corresponding comparative example 13-1,13-2,13-3), add again 30mL dehydration and deoxidation refine after normal heptane solvent, regulate ethylene pressure to 0.15MPa.Constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.50mL hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 14

Take catalyzer 160mg in comparative example 2 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 40mL is refining successively, add the triisobutyl aluminium (TiBA) that consumption is Al/Cr=2.5 and make promotor, then add 30mL dehydration and deoxidation refine after normal heptane solvent, then add 10mLH in still ₂.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Comparative example 15

Take catalyzer 160mg in comparative example 3 respectively and carry out polymerization under atmospheric pressure experiment.By the removal of impurities of polymerization reaction kettle heating under vacuum, and with high pure nitrogen pump drainage three times, fill micro-purify ethylene in the most backward reactor to 0.12MPa.Then in reactor, add the normal heptane solvent that 40mL is refining successively, add respectively consumption be Al/Cr=2.5,5,10, the triisobutyl aluminium (TiBA) of 15 makes promotor (respectively corresponding comparative example 15-1,15-2,151-3,15-4), then add 30mL dehydration and deoxidation refine after normal heptane solvent.Regulate ethylene pressure to 0.15MPa, constant after 85 DEG C until temperature in the kettle, add catalyzer and start reaction.In reaction process online acquisition monomer ethylene instantaneous consumption (by connecting the high-accuracy Ethylene mass under meter of computer) and by computer record.Hydrochloric acid/alcohol mixed solution termination reaction is added after 1h.After filtration, resulting polymers weighed after dry 4h at 60 DEG C in vacuum drying oven and analyze.

Ethylene polymerization activity table in each embodiment of table 1

Note: every its polymerization activity of catalyzer containing chromium of the present invention calculates with unit mole chromium, Hereinafter the same.

(1) cocatalyst concentration is on the impact of polymerization activity and product property.

The impact of table 2 promotor consumption and product property active on catalyst ethylene homo

Polymerizing condition: ethylene pressure=0.15MPa; Polymerization time=1h; Polymerization temperature=85 DEG C; Normal heptane=70mL; Promotor=TiBA; Cr=1wt%.

As known from Table 2, titanium fluorine richness supported chrome vanadium metal oxide compound double activity center's catalyzer and other different catalysts (embodiment 21-1 under the condition being promotor with triisobutyl aluminium (TiBA), 21-2, 21-3, 21-4, 25-1, 25-2, 25-3, 25-4, 29-1, 29-2, 29-3, 29-4 and comparative example 7-1, 7-2, 7-3, 7-4, 11-1, 11-2, 11-3, 11-4, 15-1, 15-2, 15-3, activity data 15-4) and homopolymerization products performance data, along with continuing to increase (aluminium chromium is than constantly increasing) of promotor consumption, the activity of titanium fluorine richness supported chrome vanadium metal oxide compound double activity center's catalyzer and other catalyst ethylene homos all presents downward trend, therefore titanium fluorine richness supported chrome vanadium metal oxide compound double activity center catalyzer is existed to reasonable value or the scope of a promotor use.Simultaneously we find that the molecular weight of the ethylene homo polymkeric substance of titanium fluorine richness supported chrome vanadium metal oxide compound double activity center catalyzer increases with promotor the trend presenting and first raise and reduce afterwards, and other comparative catalyst's products do not show this characteristic.

(2) polymerization temperature is on the impact of polymerization activity and product property

The impact of table 3 temperature and product property active on catalyst ethylene homo

Polymerizing condition: ethylene pressure=0.15MPa; Polymerization time=1h; Normal heptane=70mL; Promotor=TiBA; Al/Cr=2.5; Cr=1wt%.

Table 3 is titanium fluorine richness supported chrome vanadium metal oxide compound double activity center's catalyzer under different polymerization temperature and unmodified modified load-type chrome alum metal oxide double activity center catalyzer, ethylene homo activity (the embodiment 22-1 of fluorine richness modified load-type chrome alum metal oxide double activity center catalyzer, 22-2, 21-1, 26-1, 26-2, 25-1, 30-1, 30-2, 29-1 and comparative example 8-1, 8-2, 7-1, 12-1, 12-2, 11-1, 16-1, 16-2, 15-1) and the performance of homopolymerization products.Activity when catalyzer activity is at low temperatures greater than high temperature as can be seen from Table 3, the molecular weight of the ethylene homo product of different catalysts all raises with polymerization temperature and reduces, and illustrates that polymerization temperature rising is more favourable to polyreaction chain tra nsfer.The polyethylene product obtained under different polymerization temperature has similar fusing point.

(3) 1-hexene consumption is on the impact of ethene/1-hervene copolymer performance

The impact of table 41-hexene consumption and product property active on catalyst ethene/1-hervene copolymer

Polymerizing condition: ethylene pressure=0.15MPa; Polymerization time=1h; Polymerization temperature=85 DEG C; Normal heptane=70mL; Promotor=TiBA; Al/Cr=2.5; Cr=1wt%.

Table 4 gives the activity (embodiment 21-1,23-1,23-2,23-3,25-1,27-1,27-2,27-3 and comparative example 7-1,9-1,9-2,9-3,11-1,13-1,13-2,13-3,15-1) of titanium fluorine richness supported chrome vanadium metal oxide compound double activity center's catalyzer and unmodified modified load-type chrome alum metal oxide double activity center catalyzer, fluorine richness modified load-type chrome alum metal oxide double activity center catalyst ethene/1-hexene oligomerization.Along with the increase of 1-hexene consumption, the ethene/1-hervene copolymer activity of titanium fluorine richness supported chrome vanadium metal oxide compound double activity center catalyzer presents the trend of reduction, and ethene/1-hervene copolymer polymericular weight constantly declines.

(4) hydrogen is on the impact of polymerization

The impact of table 5 hydrogen and product property active on catalyst ethylene homo

Polymerizing condition: ethylene pressure=0.15MPa; Polymerization time=1h; Polymerization temperature=85 DEG C; Normal heptane=70mL; Promotor=TiBA,

Al/Cr＝2.5。

The impact that when titanium fluorine richness supported chrome vanadium metal oxide compound double activity center's catalyzer and unmodified modified load-type chrome alum metal oxide double activity center catalyzer, fluorine richness modified load-type chrome alum metal oxide double activity center catalyzer carry out ethylene homo polyreaction, hydrogen is adjusted as shown in table 5 (embodiment 21-1,24,25-1,28 and comparative example 7-1,10,11-1,14,15-1,18).Visible, decrease under the ethylene homo specific activity of titanium fluorine richness supported chrome vanadium metal oxide compound double activity center catalyzer does not have hydrogen existence condition, and poly molecular weight significantly reduces, the effect playing an obvious chain-transfer agent at this hydrogen result in poly molecular weight and molecular weight.Visible titanium fluorine richness supported chrome vanadium metal oxide compound double activity center catalyzer adjusts response responsive to hydrogen.

Claims

1. a loading type chrome alum double activity center catalyzer for titanium fluorine richness, is characterized in that: comprise inorganic carrier, the active ingredient of load and modified component, wherein: active ingredient is chromated oxide and barium oxide, modified component is fluorine and titanium.

2. the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to claim 1, is characterized in that: inorganic carrier is one or more in silicon-dioxide, aluminium sesquioxide, titanium dioxide, zirconium white, magnesium oxide, calcium oxide, inorganic clay.

3. the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to claim 1, is characterized in that: the specific surface area of inorganic carrier is 50 ~ 800m ²/ g, pore volume is 0.1 ~ 5.0cm ³/ g, mean pore size is 1 ~ 50nm.

4. the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to claim 1, is characterized in that: the content of chromium element is 0.01 ~ 10wt% of total catalyst weight; The content of v element is 0.01 ~ 10wt% of total catalyst weight; The content of fluorine element is the 0.01-10wt% of total catalyst weight; The content of titanium elements is 0.01 ~ 30wt% of total catalyst weight.

5. the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to claim 1, is characterized in that: the precursor of chromium element is for containing chromic salts; The precursor of v element is for containing vanadic salts; The precursor of fluorine element is for containing villiaumite; The precursor of titanium elements is for containing titanium salt.

6. the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to claim 5, is characterized in that: the precursor of chromium element is one or more in chromium trioxide, chromium nitrate, chromium acetate, chromium chloride, chromium sulphate, ammonium chromate, ammonium dichromate or alkali formula chromium acetate;

The precursor of v element is one or more in hexafluoro ammonium vanadate, nitric acid vanadium, vanadyl oxalate, ammonium meta-vanadate, vanadylic sulfate, sulfuric acid oxidation vanadium hydrate, Vanadosulfuric acid, three chloro vanadium oxides, vanadic acid sodium, sodium metavanadate, bis-acetylacetonate vanadium oxide, Triisopropoxyvanadium(V) oxide, three propyl alcohol vanadium oxides, vanadium acetylacetonate, oxidation triethoxy vanadium, vanadyl chloride or silication three vanadium;

The precursor of fluorine element is one or more in Neutral ammonium fluoride, Ammonium bi-fluoride, ammonium borofluoride, cupric fluoborate, silver fluoborate, fluoroboric acid gold, cuprichexafluorosilicate, silver silicofluoride, silicofluoric acid gold, ammonium borofluoride, hexafluoro ammonium vanadate, ammonium hexafluorosilicate, zinc fluoroborate, magnesium silicofluoride, zine fluosilicate or Sodium tetrafluoroborate;

The precursor of titanium elements is one or more in methyl ethyl diketone oxygen titanium, titanous chloride, titanium tetrachloride, trimethyl carbinol titanium, tetra-n-butyl titanate, titanyl sulfate, titanium sulfate, isopropyl titanate or tetraethyl titanate.

7. a preparation method for the loading type chrome alum double activity center catalyzer of the arbitrary described titanium fluorine richness of claim 1-6, is characterized in that: by the one in inorganic carrier first loaded modified component, and then load remaining ingredient.

8. the preparation method of the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to claim 7, is characterized in that: by the one in inorganic carrier first loaded modified component, and then the another kind in loaded modified component, final load vanadium and chromium.

9. the preparation method of the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to claim 7, is characterized in that: load step is: dipping contains the solution of active ingredient or modified component, then calcination activation at 200 ~ 900 DEG C; Wherein: the solution containing active ingredient or modified component is be dissolved in water or organic solvent by the salt containing active ingredient or modified component.

10. the preparation method of the loading type chrome alum double activity center catalyzer of titanium fluorine richness according to claim 7, is characterized in that: by the catalyzer prepared, adds organo-metallic promotor and carry out prereduction activation treatment, obtain product after drying; Wherein: organo-metallic promotor is one or several in organo-aluminium compound, organolithium compound, organoboron compound.