CN107778385A

CN107778385A - A kind of supported chrome tungsten bimetallic catalyst and its preparation method and application

Info

Publication number: CN107778385A
Application number: CN201610742122.7A
Authority: CN
Inventors: 李留忠; 程瑞华; 范大鹏; 马越; 严婕; 刘柏平; 徐晓; 齐立芳
Original assignee: China Petroleum and Chemical Corp
Current assignee: China Petroleum and Chemical Corp
Priority date: 2016-08-29
Filing date: 2016-08-29
Publication date: 2018-03-09

Abstract

The invention belongs to catalyst technical field, and in particular to a kind of supported chrome tungsten bimetallic catalyst and its preparation method and application.The catalyst includes inorganic carrier and the chromated oxide and tungsten oxide of load, and its preparation method is：Solution containing tungsten and chromium is impregnated into inorganic carrier jointly, then dried, calcination activation obtains catalyst, can also add organic metal co-catalyst as needed and carry out pre-reduction treatment to it.The catalyst can produce Alathon and ethylene-alpha-olefin copolymer with wide molecular weight distribution (MWD=20 40) in single-reactor, have the advantages that catalytic activity is high, preparation is simple, cost is low, hydrogen regulation sensitiveness is high and copolymerization performance is superior, polyethylene product molecular weight is high, molecular weight distribution is wide.

Description

A kind of supported chrome tungsten bimetallic catalyst and its preparation method and application

Technical field

The invention belongs to catalyst technical field, and in particular to a kind of supported chrome tungsten bimetallic catalyst and its preparation side Method and application.

Background technology

Polyethylene (PE) resin is a kind of thermoplastic formed by vinyl monomer polymerization, be in the world today yield and One of maximum general-purpose plastics product of consumption figure, mainly including low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), high density polyethylene (HDPE) (HDPE) and some there is the polyethylene of property.PE have excellent mechanical property, Electrical insulating property, chemical resistance, lower temperature resistance and excellent processing characteristics.PE products are widely used in industry, agricultural, vapour The every field such as car, communication and daily life.

The polyethylene catalysts being currently known mainly have Z-N (Z-N) type catalyst, chromium-based catalysts and cyclopentadienyl gold The catalyst of metal catalyst and some other Nonmetallocene class.Wherein chromium-based catalysts are with its protrusion tribute in HDPE productions The irreplaceability offered and products thereof and favored by market, and still have 40% HDPE even to this day by its production.

The people of J.P Hogan and R.L.Bank two reports the chromium oxide catalyst of silica gel load in patent US2825721, That is first generation Phillips catalyst well known later.Some patents are on the basis of US2825721 to such support type Chromium oxide catalyst is modified and studied, including US2951816, US2959577 and US4194073.Some United States Patent (USP)s Such as US4294724, US4295997, US4528338, US5401820, US6388017 etc. are directed to Phillips catalyst.

Phillips catalyst forms that change in elevation is sensitive to carrier, therefore can be by changing the composition or carrier of carrier Type, the oligomer of liquid and the wax or ultra-high molecular weight polyethylene (UHMWPE) of low molecule amount are produced, its product Molecular weight distribution can regulate and control in very large range.Two common traits of second generation Phillips catalyst are：1) by carrying The surface of body is modified to prepare the catalyst and polyethylene product with new capability；2) chromium is in modified Phillips catalyst Sole active component.The support modification method of second generation Phillips catalyst includes：Titania modified, magnesium oxide modified, Fluorine richness, alumina modified, alkali metals modified, boron modification etc..At present, the second generation is modified Phillips catalyst and has used next life Produce the different grades of polymer of various commercial uses.Wherein, the carrier of catalyst, can be significant after titania modified Strengthen the activity of chromium, shorten induction time, improve the polymerization activity and chain termination speed of catalyst, reduce the average mark of polymer Son amount, this is typically favourable for polymerization.The R.Dietz (US3887494) of Phillips companies, B.Horvath (US3622521) and the T.Pullukat (US378001) of Chemplex Company companies has carried out the research of this respect, Carrier used in Liang Ge companies is respectively the Davison series of Grace companies of the U.S. and is now that the polyolefin that Pq Corp. produces is special Use silica-gel carrier.The mode for introducing titanium dioxide mainly has two kinds, and one kind is that titanium and silicon are sunk in a manner of cogelled (co-gel) The Ti contents on reshaping after product, carrier element phase and surface are suitable；A kind of is that titanium dioxide is coated on molded silica-gel carrier On, now titanium dioxide is mainly distributed on the surface of carrier.Pertinent literature can be found in Journal of Catalysis, and 1983, 82,118-126。

Recently, a kind of new supported chrome vanadium metal oxide is reported in patent (application number 201210118427.2) Double activity center's ethylene rolymerization catalyst, represented as the third generation Phillips catalyst with Cr-V double activity center, its It is characterized in that the vanadium active component that load is introduced on Phillips chromium-based catalysts is become with two kinds of activated centres of Cr-V Chromium-polyethylencatalyst catalyst.Although a variety of different polyolefin catalysts be present, still suffer to new capability The demand of catalyst.

The content of the invention

To solve the above-mentioned problems in the prior art, present invention offer is a kind of to prepare simple and low cost load Type chromium tungsten bimetallic catalyst and its preparation method and application.

The present invention provides a kind of supported chrome tungsten bimetallic catalyst, it include the chromated oxide of inorganic carrier and load with Tungsten oxide.

According to one embodiment of the invention, the raw material sources of the chromated oxide are in inorganic chromium source, the inorganic chromium Source can be selected from chromium trioxide, chromic nitrate, chromic acetate, chromium chloride, chromium sulfate, ammonium chromate, ammonium dichromate, alkali formula chromic acetate, its Its suitable chromium soluble-salt and combinations thereof；It is preferred that chromic acetate and alkali formula chromic acetate.

According to one embodiment of the invention, the raw material sources of the tungsten oxide are in inorganic tungsten source：As tungstic acid, Ammonium tungstate, sodium phosphotungstate, sodium tungstate, potassium tungstate, tungstosilicic acid, water-insoluble Tungstenic compound：As tungsten carbonyl, isopropyl acetone tungsten, Double (tertbutylimidos) double (dimethylamino) tungsten, and other suitable soluble water-insoluble Tungstenic compounds and it Combination；It is preferred that tungsten acid and tungstosilicic acid.

For the catalyst of the present invention, the Cr total load amounts on inorganic carrier are generally the 0.01- of total catalyst weight 5wt%, preferably 0.05-4wt%, more preferably 0.1-2wt%, based on Cr weight.

For the catalyst of the present invention, the W total load amounts on inorganic carrier are generally the 0.01- of total catalyst weight 5wt%, preferably 0.05-4wt%, more preferably 0.1-2wt%, based on W weight.

The inorganic carrier used in the present invention can be typically used for any porous in prepared by olefin polymerization catalysis Inorganic carrier.According to one embodiment of the invention, the inorganic carrier is selected from silica, alundum (Al2O3), titanium dioxide Titanium, zirconium oxide, magnesia, calcium oxide, inorganic clay and combinations thereof.The inorganic clay can include such as montmorillonite Deng.According to another embodiment of the invention, the inorganic carrier is selected from silica gel that is unmodified or being modified through Ti, Al or F, special It is not amorphous Bio-sil.These carriers are it is known in the art that can be commercially available or being synthesized by known method.As silicon One example of glue, it can be mentioned that Davison 955.

According to an embodiment, the pore volume of the inorganic carrier is 0.5-5cm³/ g, preferably 1.0-3.0cm³/ g, more It is preferred that 1.3-2.5cm³/ g, further preferred 1.5-1.8cm³/g.According to another embodiment, the surface of the inorganic carrier Product is 100-600m²/ g, preferably 150-500m²/ g, more preferably 220-400m²/ g, further preferred 250-350m²/g.It is described Pore volume and surface area are determined using BET method.BET methods are that well known to a person skilled in the art measure pore volume and surface area Common method

The average grain diameter of inorganic carrier is 1-100 microns, preferably 5-80 microns, more preferably 10-60 microns.The granularity Test is measured using method well known in the art, such as is measured using laser particle size method.For example, granulometry can enter as follows OK：The table of granularity and its distribution is carried out to sample using U.S.'s Beckman-Coulter Corporation's LS230 laser diffraction particle size analyzers Sign, measured for example with progress particle diameter after wet dispersion sample and particle diameter distribution.

The present invention provides the preparation method of the supported chrome tungsten bimetallic catalyst, and it is comprised the following steps：

I) solution containing tungsten and chromium is immersed on inorganic carrier jointly, then dry；

II) by step I) obtained by product calcination activation, obtain the catalyst and save backup.

Comprised the following steps according to a preferable method for preparing supported chrome tungsten double activity center catalyst：

I) mixing salt solution containing chromium and tungsten is immersed on inorganic carrier jointly, dip time is 1~12h, preferably 4 ~8h, dipping temperature are 10~80 DEG C, preferably 20~70 DEG C, are then dried between 90~250 DEG C, preferably 100~200 DEG C, 6~20h of drying time, preferably 8~15h, vacuum can also be used in drying process；

II) by step I) obtained sample carries out high-temperature roasting activation, roasting in inert gas either oxygen or air Temperature is burnt at 300~900 DEG C, and preferably 400~800 DEG C, the time is 1~10h, preferably 3~8h, is then cooled down, and is being cooled down Inert gas such as nitrogen or argon gas etc. are switched to during to 300~400 DEG C, natural cooling, the catalyst is obtained and saves backup.

Above-mentioned steps I) it is by chromium source and tungsten source while is impregnated in the method on inorganic carrier.The chromium source can be above Described any chromium source, tungsten source can be any tungsten sources described above., can in dipping process according to an embodiment To implement heating stirring, preferably laser heating stirs.Usually, the stirring lasts about 1~12 hour, preferably from about 4~8 hours, Dipping temperature is 10~80 DEG C, preferably 20~70 DEG C.According to an embodiment, the load capacity of chromium is total catalyst weight 0.01~10wt%, preferably 0.05~5wt%；Tungsten load amount be total catalyst weight 0.01~10wt%, preferably from about 0.05 ~5wt%.Then obtained sample is dried.The drying is generally carried out in the temperature of about room temperature~250 DEG C, and preferably 90 DEG C~250 DEG C, further preferred 100 DEG C~200 DEG C.The time carried out to the drying is not particularly limited, but the drying is led to Often last about 6~20 hours, preferably from about 7~18 hours, further preferably about 8~15 hours, can also be used in drying process Vacuum.

Above-mentioned steps II) it is after dry finish, the carrier for being impregnated with chromium and tungsten compound is calcined, and finally Chromium tungsten oxide is carried on carrier surface.The mode carried out to roasting is not particularly limited, but the roasting is preferably fluidizing Carried out in bed.According to an embodiment, the roasting is generally carried out with two stages, i.e. cold stage and hot stage.This is low Thermophase is generally in about 100~300 DEG C of progress.The hot stage is generally in about 300~900 DEG C of progress.Not by any theoretical limit System, the mechanical water adsorbed in the cold stage carrier is removed, and the part of hydroxyl on the carrier of the hot stage It is removed.According to an embodiment, the cold stage continues 1~10 hour, preferably 2~9 hours.According to another reality Scheme is applied, the hot stage continues 1~10 hour, preferably 2~9 hours, more preferably 3~8 hours.According to a reality Scheme is applied, the cold stage is carried out under inert gas or air atmosphere, is preferably carried out under an inert gas, the inertia Gas atmosphere such as nitrogen, helium, argon gas, is preferably carried out in a nitrogen atmosphere, such as high pure nitrogen.According to an embodiment party Case, the hot stage roasting are carried out under air or Oxygen Condition, carried out preferably under the conditions of dry air.In the roasting After sintering beam, the obtained catalyst for being loaded with chromium tungsten is cooled down from hot stage.According to an embodiment, in high-temperature roasting When being cooled to 300~400 DEG C of temperature afterwards, atmosphere can be converted, such as be changed into inert gas, such as nitrogen from air.Root According to an embodiment, this is cooled to Temperature fall cooling.Obtained catalyst is saved backup under inert gas atmosphere.

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

Silica gel is immersed in the aqueous solution of certain density ammonium tungstate and alkali formula chromic acetate, the load capacity of tungsten and chromium is relative Meet this paper requirement (such as 0.1~10wt% of tungsten, 0.1~3wt% of chromium, respectively with tungsten and the weight of chromium in total catalyst weight Gauge)；After certain time (such as 4~8 hours) is continuously stirred, heat up drying；Then high-temperature roasting is carried out in fluid bed, The mechanical water adsorbed in removing carrier is wherein calcined in nitrogen atmosphere in cold stage (such as 100 DEG C~300 DEG C), in high temperature Stage (such as 300 DEG C~900 DEG C) is calcined the part of hydroxyl on removing inorganic carrier surface in dry air, in this hot stage Kept for certain time (such as 3~8 hours)；Temperature fall cools down, and switches to nitrogen to protect when being cooled to 300~400 DEG C, Shift under nitrogen protection, catalyst saves backup.

According to being actually needed, the preparation method of the supported chrome tungsten bimetal polyethylene catalyst is also comprising following step Suddenly：In step II under inert atmosphere) organic metal co-catalyst is added in obtained catalyst carries out prereduction activation process, do It is dry, preserve stand-by.

Preferably, 2-8 hours are dried between 60-120 DEG C, vacuum can also be used in drying process, then in inertia Preserved under gas stand-by.

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

Silica gel is immersed in the aqueous solution of certain density sodium tungstate and alkali formula chromic acetate, the load capacity of tungsten and chromium is relative Meet this paper requirement (such as 0.1~10wt% of tungsten, 0.1~3wt% of chromium, respectively with tungsten and the weight of chromium in total catalyst weight Gauge)；After certain time (such as 4~8 hours) is continuously stirred, heat up drying；Then high-temperature roasting is carried out in fluid bed, The mechanical water adsorbed in removing carrier is wherein calcined in nitrogen atmosphere in cold stage (such as 100 DEG C~300 DEG C), in high temperature Stage (such as 300 DEG C~900 DEG C) is calcined the part of hydroxyl on removing inorganic carrier surface in dry air, in this hot stage Kept for certain time (such as 3~8 hours)；Temperature fall cools down, and switches to nitrogen to protect when being cooled to 300~400 DEG C, Shift under nitrogen protection, catalyst saves backup.Then add triethyl aluminum and prereduction activation process carried out to catalyst, For aluminium/chromium mol ratio between 0~50, treatment temperature continuously stirs 0.5~10 hour in room temperature~60 DEG C, then again 60~ To be dried 2~8 hours between 120 DEG C, the drying is carried out under inert gas atmosphere, such as under the atmosphere such as nitrogen, helium, argon gas Carry out, preferably carry out in a nitrogen atmosphere, the drying process can also be carried out under vacuum.What is obtained activates by prereduction Supported chrome tungsten double activity center catalyst preserve under inert gas atmosphere it is stand-by.

The catalyst of the present invention is the Cr active components of inorganic oxide form and the W of inorganic oxide form while existed Catalyst on same inorganic carrier.This catalyst is different from urging the Cr active components with inorganic oxide form The catalyst that agent (such as Phillips catalyst) and the W with inorganic oxide form catalyst physical are mixed to get； It is inactive under the W individualisms of inorganic oxide form in the latter.

Wherein, the Cr active sites of inorganic oxide form are well known by persons skilled in the art, such as be may refer to Journal of Molecular Catalysis A:Chemical 172(2001)227–240。

Supported chrome tungsten bimetallic catalyst of the present invention can be used for producing olefin polymer.

Therefore, according to another aspect of the present invention, there is provided use supported chrome tungsten bimetallic catalytic of the present invention The method of the method that agent produces olefin polymer, particularly olefin polymer of the production with wide molecular weight distribution, this method bag Include makes alkene be contacted with the catalyst compounded of catalytic amount under polymerization conditions, and it includes the supported chrome tungsten bimetallic of the present invention and urged Agent and at least one cocatalyst component.

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

Above-mentioned co-catalyst includes aluminium compound, zinc alkyl and tin alkyl.Aluminium compound as co-catalyst is ability Known to field technique personnel.The aluminium compound can include trialkylaluminium AlR₃, dialkyl group aluminum alkoxide AlR₂OR, dialkyl group Aluminum halide AlR₂X, aikyiaiurnirsoxan beta, sesquialter aluminium etc., wherein R is alkyl, such as with 1-12 carbon atom, e.g. methyl, second Base, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, dodecyl Deng X is halogen, such as fluorine, chlorine, bromine and iodine, preferably chlorine.The aikyiaiurnirsoxan beta can include MAO (MAO).The conduct The aluminium compound of co-catalyst can be used alone or two or more is applied in combination.The alkane of zinc alkyl and tin alkyl weight Base, has a 1-12 carbon atom, e.g. methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, just oneself Base, n-heptyl, n-octyl, n-nonyl, dodecyl etc..As specific example, the aluminium compound can be mentioned that triethyl group Aluminium, triisobutyl aluminium.

The usage amount of the aluminium compound is typically 1-1000 moles/moles, preferably 2-70 moles/moles based on aluminium, and More preferably 3-50 moles/moles, relative to every 1 mole of Cr.

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

The above-mentioned polymer manufacture method of the present invention is without any particular limitation in terms of its polymerization.It is above-mentioned to use this The method of invention composite catalyst production olefin polymer can include gas phase polymerization process, slurry phase polymerisation process, suspension polymerisation Method, bulk polymerization, solution polymerization process etc..As the skilled person will appreciate, to using the present invention The method of the production olefin polymer of composite catalyst is not particularly limited, and can use gas-phase polymerization side known in the art Method, slurry phase polymerisation process, suspension polymerization, bulk polymerization, the conventional implementation of solution polymerization process and polymerization bar Part etc. is implemented.

In one embodiment, using slurry phase polymerisation process, including ethene is added into reactor, then adds solvent With co-catalyst (aluminium compound) and be optionally added into hydrogen and comonomer, the composite catalyst for being eventually adding the present invention starts Polymerization.

More specifically, in one embodiment, polymerization is implemented using traditional slurry polymerization process, concrete operations are as follows： Polymerization reaction kettle is first subjected to heating in vacuum (100 DEG C), high pure nitrogen is then replaced into, operates three times repeatedly, then with a small amount of second Alkene monomer is replaced once, and finally ethene will be full of in reactor to pressure-fired (0.12MPa)；It is de- that dehydration is added into reactor Refining solvent after oxygen processing, a certain amount of alkyl aluminum also need to be separately added into as co-catalyst in hydrogen reconciles copolymerization experiments A certain amount of hydrogen and comonomer, the catalyst for being eventually adding the present invention start polymerisation；Online acquisition in course of reaction The instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) of monomer ethylene and by computer record, certain At a temperature of after (such as 35 DEG C -90 DEG C) reaction carries out certain time (such as 1 hour), add hydrochloric acid/alcohol mixed solution and terminate Reaction；Polymer is scrubbed, weighs and analyzes after vacuum drying.

The present invention is by the way that by two kinds of different source metals, i.e., inorganic tungsten source and chromium source mutual load are in same catalyst carrier On be prepared for a kind of new chromium tungsten bimetallic catalyst, it can be produced in single-reactor has wide molecular weight distribution (MWD =20-40) Alathon and ethene-alpha-olefin copolymer.Using the composite catalyst of the present invention, by changing co-catalysis The factors such as agent dosage, polymerization temperature, molecular weight regulator, it can conveniently and easily adjust Alathon and ethene-α-alkene The molecular weight and molecualr weight distribution of hydrocarbon copolymer, so as to conveniently and easily obtain the polymer with required performance.

Catalyst of the present invention has catalytic activity height, preparation is simple, cost is low, hydrogen regulation sensitiveness is high and common The advantages that poly- superior performance, polyethylene product molecular weight are high, molecular weight distribution is wide.

Brief description of the drawings

Fig. 1 is carrier or catalyst Precursors calcination procedure schematic diagram.

Embodiment

With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute It is conventional method unless otherwise instructed to state method.The material can obtain from open commercial sources unless otherwise instructed.It is real It is commercially available Davison 955 to apply the silica gel used in example.

Various polymer properties in embodiment measure according to following methods：

High temperature gel chromatogram (HT-GPC)

Weight average molecular weight and molecular weight distribution the high temperature gel chromatographic determination of polyethylene product：This experiment uses PL-220 Type high-temperature gel permeation chromatography instrument (Polymer Laboratories companies) divides to determine molecular weight of polyethylene and its molecular weight Cloth.Determined in experiment with 1,2,4- trichloro-benzenes for solvent at 160 DEG C.Using Narrow distribution polystyrene as the pervasive of standard specimen Correction method processing data.

Differential scanning calorimetric analysis instrument (DSC)

The fusing point of polyethylene product is determined with differential scanning calorimetry：This experiment uses TA Q200 type means of differential scanning calorimetry Analyzer is tested under nitrogen protection.Sample is first with 10 DEG C/min speed from room temperature to 150 DEG C, and constant temperature 5min, then naturally ring to room temperature.Then with 10 DEG C/min speed heating scan (room temperature is to 150 DEG C), DSC curve is recorded.

Embodiment 1

Catalyst preparation process of the present invention is as follows, by 10g silica gel in certain density alkali formula chromic acetate and ammonium tungstate water Solution is impregnated, and wherein chromium load capacity (by mass) is 0.5%Cr, and tungsten load amount (in molar ratio) is W：Cr=1:1, i.e., Tungsten load amount (by mass) is 0.53%W.After continuously stirring 5 hours dippings, heat drying 8h.By the silica-gel carrier after load High-temperature roasting is carried out in fluid bed, in the mechanical water of low-temperature zone removing carrier, is stopped near the decomposition temperature in chromium source and tungsten source Stay one hour, the hydroxyl of Silica Surface is removed at 600 DEG C of high temperature section, kept for 4 hours in this high temperature section, finally protected in nitrogen Under shield, Temperature fall cooling, be made composite catalyst, preserve under nitrogen protection it is stand-by, above-mentioned calcination procedure as shown in figure 1, The catalyst is named as CrW/Si.Carry out diameter characterization to this silica gel supported composite catalyst, it is known that its pore volume is 1.2cm³/ g, surface area 233m²/g^-1。

Embodiment 2

10g silica gel is impregnated in certain density alkali formula chromic acetate and ammonium tungstate aqueous solution, wherein chromium load capacity (by mass) it is 0.5%Cr, tungsten load amount (in molar ratio) is W：Cr=1:2, i.e. W load capacity (by mass) is 0.87% W.After continuously stirring 5 hours dippings, heat drying 8h.Silica-gel carrier after load is subjected to high-temperature roasting in fluid bed, Low-temperature zone removes the mechanical water of carrier, is stopped one hour near the decomposition temperature in chromium source and tungsten source, de- at 600 DEG C of high temperature section Except the hydroxyl of Silica Surface, kept for 4 hours in this high temperature section, under nitrogen protection, Temperature fall cooling, be made compound finally Catalyst, preserves stand-by under nitrogen protection, and the catalyst is named as Cr0.5W/Si.To this silica gel supported composite catalyst Carry out diameter characterization, it is known that its pore volume is 1.3cm³/ g, surface area 257m²/g^-1。

Embodiment 3

10g silica gel is impregnated in certain density alkali formula chromic acetate and ammonium tungstate aqueous solution, wherein chromium load capacity (by mass) it is 0.5%Cr, tungsten load amount (in molar ratio) is W：Cr=2:1, i.e. tungsten load amount is (by mass) 3.54%W.After continuously stirring 5 hours dippings, heat drying 8h.Silica-gel carrier after load is subjected to high temperature roasting in fluid bed Burn, in the mechanical water of low-temperature zone removing carrier, stopped one hour near the decomposition temperature in chromium source and tungsten source, in high temperature section 600 The hydroxyl of Silica Surface is removed at DEG C, is kept for 4 hours in this high temperature section, under nitrogen protection finally, Temperature fall cooling, system Composite catalyst, preserve under nitrogen protection stand-by, the catalyst is named as Cr2W/Si.It is compound to this silica gel supported to urge The carry out diameter characterization of agent, it is known that its pore volume is 1.3cm³/ g, surface area 246m²/g^-1。

Embodiment 4

Weigh composite catalyst 150mg in embodiment 1 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, filled in most backward reactor Micro refined ethene is to 0.12MPa.The refined heptane conduct after the processing of 40mL or so dehydration and deoxidations is sequentially added into reactor Solvent, using triisobutyl aluminium (TiBA) as co-catalyst, wherein the concentration of co-catalyst is 0.986mmol/mL, and dosage is by it Cr mole proportionate relationship is quantified in Al mole and catalyst, respectively 0.072mL, 0.142mL, 0.216mL, 0.284mL, i.e. Al/Cr=5,10,15,20 (corresponding to embodiment 4-1,4-2,4-3,4-4 respectively), add 30mL dehydration and deoxidations Normal heptane solvent after refined, regulation ethylene pressure to 0.15MPa is constant after 80 DEG C after temperature in the kettle, is eventually adding compound Catalyst starts polymerisation, the instantaneous consumption of online acquisition monomer ethylene and by computer record in course of reaction, at 80 DEG C After reaction is carried out 1 hour, hydrochloric acid/alcohol mixed solution terminating reaction is added, weighs and analyzes after polymer vacuum drying.

Embodiment 5

Weigh composite catalyst 150mg in embodiment 1 and carry out polymerization experiment.Heating in vacuum is carried out to polymerization reaction kettle in advance (85 DEG C), are then replaced into high pure nitrogen, operate repeatedly three times, then are replaced once in most backward reactor with a small amount of monomer ethylene Micro refined ethene is filled to 0.12MPa.The refined heptane after the processing of 40mL or so dehydration and deoxidations is sequentially added into reactor to make For solvent, using triethyl aluminum (TEA) as co-catalyst, co-catalyst is that concentration is 1.82mmol/mL, dosage 0.072mL, That is Al/Cr=5, adds the normal heptane solvent after 30mL dehydration and deoxidations refine, and regulation ethylene pressure is treated in kettle to 0.15MPa Temperature is constant after 80 DEG C, is eventually adding composite catalyst and starts polymerisation, online acquisition monomer ethylene in course of reaction Instantaneous consumption and by computer record, after 80 DEG C of reactions are carried out 1 hour, adds hydrochloric acid/alcohol mixed solution terminating reaction, gathers Weigh and analyze after compound vacuum drying.

Embodiment 6

Weigh composite catalyst 150mg in embodiment 1 and carry out polymerization experiment.Heating in vacuum is carried out to polymerization reaction kettle in advance (80 DEG C), are then replaced into high pure nitrogen, operate three times repeatedly, then with the displacement of a small amount of monomer ethylene once, finally by reactor The interior ethene that is full of is to pressure-fired (0.12MPa).Polymerization temperature is controlled at 80 DEG C.70mL or so dehydrations are sequentially added into reactor Refined heptane after deoxidation treatment adds MAO (MAO) and is used as co-catalyst, co-catalyst is that concentration is as solvent 1.5mmol/mL (n-heptane solution), dosage 0.92mL, i.e. Al/Cr (mol ratio)=90, finally by ethene pressure in reactor Power heightens 0.15MPa, constant after 80 DEG C after temperature in the kettle, is eventually adding composite catalyst and starts polymerisation.Reacted The instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) of online acquisition monomer ethylene and by electricity in journey Brain records.After 80 DEG C of reactions are carried out 1 hour, hydrochloric acid/alcohol mixed solution terminating reaction is added, is claimed after polymer vacuum drying Weigh and analyze.

Embodiment 7

Weigh catalyst 150mg in embodiment 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is cleaned, and With high pure nitrogen pump drainage three times, micro refined ethene is filled in most backward reactor to 0.12MPa.Then added into reactor Normal heptane solvent refined 70mL.Ethylene pressure is adjusted to 0.15MPa, addition catalyst constant after 80 DEG C after temperature in the kettle Start to react.The instantaneous consumption of online acquisition monomer ethylene is (by the high-accuracy ethene matter for connecting computer in course of reaction Measure flowmeter) and by computer record.Hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.Resulting polymers are existed after filtering Weigh and analyze after drying 4h at 60 DEG C in vacuum drying chamber.

Embodiment 8

Weigh composite catalyst 150mg in embodiment 2 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature is controlled at 80 DEG C.After the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor Refined heptane is as solvent, and using triisobutyl aluminium (TiBA) as co-catalyst, the concentration of wherein co-catalyst is 0.986mmol/mL, dosage are quantified by the mole proportionate relationship of Cr in its Al mole and catalyst, are respectively 0.072mL, 0.142mL, 0.216mL, 0.284mL, i.e. Al/Cr=5,10,15,20 (correspond to embodiment 8-1,8-2,8- respectively 3rd, 8-4), it is eventually adding composite catalyst and starts polymerisation, the instantaneous consumption of online acquisition monomer ethylene in course of reaction And by computer record, after 80 DEG C of reactions are carried out 1 hour, hydrochloric acid/alcohol mixed solution terminating reaction is added, polymer vacuum is done Weigh and analyze after dry.

Embodiment 9

Weigh composite catalyst 150mg in embodiment 3 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature is controlled at 80 DEG C.After the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor Refined heptane is as solvent, and using triisobutyl aluminium (TiBA) as co-catalyst, the concentration of wherein co-catalyst is 0.986mmol/mL, dosage are quantified by the mole proportionate relationship of Cr in its Al mole and catalyst, are respectively 0.072mL, 0.142mL, 0.216mL, 0.284mL, i.e. Al/Cr=5,10,15,20 (correspond to embodiment 9-1,9-2,9- respectively 3rd, 9-4), it is eventually adding composite catalyst and starts polymerisation, the instantaneous consumption of online acquisition monomer ethylene in course of reaction And by computer record, after 80 DEG C of reactions are carried out 1 hour, hydrochloric acid/alcohol mixed solution terminating reaction is added, polymer vacuum is done Weigh and analyze after dry.

Embodiment 10

Weigh composite catalyst 150mg in embodiment 1 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature controls respectively (corresponds to embodiment 10-1,10-2,10- respectively in 60 DEG C, 70 DEG C, 90 DEG C 3).The refined heptane after the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor as solvent, with triisobutyl aluminium (TiBA) it is used as co-catalyst, the wherein concentration of co-catalyst is 0.986mmol/mL, mole and catalysis of the dosage by its Al Cr mole proportionate relationship is quantified in agent, is 0.072mL, i.e. Al/Cr=5, is eventually adding composite catalyst and is started to gather Reaction is closed, the instantaneous consumption of online acquisition monomer ethylene and by computer record in course of reaction, is carried out 1 hour in 80 DEG C of reactions Afterwards, hydrochloric acid/alcohol mixed solution terminating reaction is added, weighs and analyzes after polymer vacuum drying.

Embodiment 11

Weigh composite catalyst 150mg in embodiment 1 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature is controlled at 80 DEG C.After the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor Refined heptane is as solvent, and using triisobutyl aluminium (TiBA) as co-catalyst, wherein the dosage of co-catalyst is 0.072mL, That is Al/Cr=5,10mL hydrogen is passed through, is passed through 10mL hydrogen.It is eventually adding composite catalyst and starts polymerisation, reacts During online acquisition monomer ethylene instantaneous consumption and by computer record, after 80 DEG C of reactions are carried out 1 hour, add salt Acid/alcohol mixed solution terminating reaction, weigh and analyze after polymer vacuum drying.

Embodiment 12

Weigh composite catalyst 150mg in embodiment 2 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature is controlled at 80 DEG C.After the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor Refined heptane is as solvent, and using triisobutyl aluminium (TiBA) as co-catalyst, the concentration of wherein co-catalyst is 0.986mmol/mL, dosage 0.072mL, i.e. Al/Cr=5.10mL hydrogen is passed through, composite catalyst is eventually adding and starts to gather Reaction is closed, the instantaneous consumption of online acquisition monomer ethylene and by computer record in course of reaction, is carried out 1 hour in 80 DEG C of reactions Afterwards, hydrochloric acid/alcohol mixed solution terminating reaction is added, weighs and analyzes after polymer vacuum drying.

Embodiment 13

Weigh composite catalyst 150mg in embodiment 3 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature is controlled at 80 DEG C.After the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor Refined heptane is as solvent, and using triisobutyl aluminium (TiBA) as co-catalyst, the concentration of wherein co-catalyst is 0.986mmol/mL, dosage 0.072mL, i.e. Al/Cr=5.10mL hydrogen is passed through, composite catalyst is eventually adding and starts to gather Reaction is closed, the instantaneous consumption of online acquisition monomer ethylene and by computer record in course of reaction, is carried out 1 hour in 80 DEG C of reactions Afterwards, hydrochloric acid/alcohol mixed solution terminating reaction is added, weighs and analyzes after polymer vacuum drying.

Embodiment 14

Weigh composite catalyst 150mg in embodiment 1 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature is controlled at 80 DEG C.After the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor Refined heptane is as solvent, the refined 1- hexenes after dehydration and deoxidation processing, using triisobutyl aluminium (TiBA) as co-catalyst, its The concentration of middle co-catalyst is 0.986mmol/mL, dosage 0.072mL, i.e. Al/Cr=5, is eventually adding composite catalyst and opens Beginning polymerisation.Wherein the dosage of 1- hexenes is 1.4mL, 2.8mL, 4.2mL, i.e. body of the 1- hexenes with polymerizeing solvent for use respectively Product ratio is 2vol%, 4vol%, 6vol% (corresponding to embodiment 14-1,14-2,14-3,14-4 respectively).It is online in course of reaction Gather the instantaneous consumption of monomer ethylene and by computer record, after 80 DEG C of reactions are carried out 1 hour, add hydrochloric acid/ethanol mixing Solution terminating reaction, weigh and analyze after polymer vacuum drying.

Embodiment 15

Weigh composite catalyst 150mg in embodiment 2 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature is controlled at 80 DEG C.After the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor Refined heptane is as solvent, the refined 1- hexenes after dehydration and deoxidation processing, using triisobutyl aluminium (TiBA) as co-catalyst, its The concentration of middle co-catalyst is 0.986mmol/mL, dosage 0.072mL, i.e. Al/Cr=5, is eventually adding composite catalyst and opens Beginning polymerisation.The dosage of wherein 1- hexenes is 2.8mL, i.e., 1- hexenes are 4vol% with the volume ratio for polymerizeing solvent for use.Instead Should during online acquisition monomer ethylene instantaneous consumption and by computer record, after 80 DEG C of reactions are carried out 1 hour, add salt Acid/alcohol mixed solution terminating reaction, weigh and analyze after polymer vacuum drying.

Embodiment 16

Weigh composite catalyst 150mg in embodiment 3 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance to add Heat, high pure nitrogen is then replaced into, is operated three times repeatedly, then with the displacement of a small amount of monomer ethylene once, will finally filled in reactor Expire ethene to pressure-fired.Polymerization temperature is controlled at 80 DEG C.After the processing of 70mL or so dehydration and deoxidations is sequentially added into reactor Refined heptane is as solvent, the refined 1- hexenes after dehydration and deoxidation processing, using triisobutyl aluminium (TiBA) as co-catalyst, its The concentration of middle co-catalyst is 0.986mmol/mL, dosage 0.072mL, i.e. Al/Cr=5, is eventually adding composite catalyst and opens Beginning polymerisation.The dosage of wherein 1- hexenes is 2.8mL, i.e., 1- hexenes are 4vol% with the volume ratio for polymerizeing solvent for use.Instead Should during online acquisition monomer ethylene instantaneous consumption and by computer record, after 80 DEG C of reactions are carried out 1 hour, add salt Acid/alcohol mixed solution terminating reaction, weigh and analyze after polymer vacuum drying.

Comparative example 1

By 10g silica gel, (pore volume is 1.5~1.7cm³/ g, surface area are 250~300m²/ g) it is immersed in alkali formula vinegar In the aqueous solution of sour chromium (chromium load capacity is 0.5wt%), 4h is continuously stirred at room temperature until reaction is complete.Then in 120 DEG C of oil Bath is lower to dry 6h, is transferred to 120 DEG C of dry 8h in air dry oven, obtained sample is then carried out into high temperature roasting in fluid bed Burn, 600 DEG C of insulation 4h in high pure air, then Temperature fall cools down under a nitrogen, and above-mentioned roasting process is as shown in Figure 1.Finally Obtained unmodified supported chrome catalysts are transferred in glove box under nitrogen protection and saved backup.

Comparative example 2

By 10g silica gel, (pore volume is 1.5~1.7cm³/ g, surface area are 250~300m²/ g) it is immersed in ammonium dichromate water In solution (chromium load capacity is 0.5wt%), after dipping 4h is stirred at room temperature, 120 DEG C of dry 6h are warming up to, baking oven is then transferred to and does Dry 6h；Dry sample is placed in quartzy fluid bed, 600 DEG C of calcination activation 4h in high pure air, obtains Phillips catalysis Agent.Upper 10g second silica gels are immersed in ammonium metatungstate aqueous solution (tungsten load amount is 1.77wt%), stirring dipping 4h at 50 DEG C Afterwards, drying is then transferred to oven drying 6h；Dry sample is placed in quartzy fluid bed in high pure air and carries out 600 DEG C Calcination activation 4h, natural cooling, obtains supported tungsten oxide catalysts under nitrogen protection.By Phillips catalyst obtained above and Supported tungsten oxide catalysts under nitrogen protection, according to Cr/W mol ratios 1:1 machinery mixes, and obtains mixed catalyst and saves backup.

Comparative example 3

Composite catalyst 150mg in comparative example 1 is weighed respectively carries out polymerization experiment.Polymerization reaction kettle is carried out in advance Heating in vacuum, high pure nitrogen is then replaced into, is operated three times repeatedly, then once most backward reactor is replaced with a small amount of monomer ethylene Micro refined ethene is inside filled to 0.12MPa.Then the refined normal heptane solvents of 40mL are added into reactor successively, are separately added into Dosage makees co-catalyst for the triisobutyl aluminium (TiBA) of Al/Cr=5,10,15,20 and (corresponds to comparative example 3-1,3- respectively 2nd, 3-3,3-4), add the normal heptane solvent after 30mL dehydration and deoxidations refine.Ethylene pressure is adjusted to 0.15MPa, is finally added Enter composite catalyst and start polymerisation, the instantaneous consumption of online acquisition monomer ethylene and by computer record in course of reaction, After 80 DEG C of reactions are carried out 1 hour, hydrochloric acid/alcohol mixed solution terminating reaction is added, weighs and divides after polymer vacuum drying Analysis.

Comparative example 4

Weigh catalyst 150mg in comparative example 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction The refined normal heptane solvents of 40mL are added in kettle, the triethyl aluminum (TEA) that dosage is Al/Cr=5 is added and makees co-catalyst, then add Enter the normal heptane solvent after 30mL dehydration and deoxidations refine.Ethylene pressure is adjusted to 0.15MPa, treats that temperature in the kettle is constant at 80 DEG C Afterwards, catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by the height for connecting computer in course of reaction Accurate Ethylene mass flowmeter) and by computer record.Hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.Will after filtering Resulting polymers are weighed and analyzed after drying 4h at 60 DEG C in vacuum drying chamber.

Comparative example 5

Weigh catalyst 150mg in comparative example 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction 40mL is added in kettle and refines normal heptane solvent, adds triisobutyl aluminium (TIBA) co-catalyst that dosage is Al/Cr=5, respectively The 1- hexenes of the 2.8mL through dewater treatment are added, i.e. 1- hexenes are respectively 4vol% with the volume ratio for polymerizeing solvent for use, then are added Enter the normal heptane solvent after 30mL dehydration and deoxidations refine, regulation ethylene pressure to 0.15MPa.Treat that temperature in the kettle is constant at 80 DEG C Afterwards, catalyst is added to start to react.The instantaneous consumption of online acquisition monomer ethylene is (by the height for connecting computer in course of reaction Accurate Ethylene mass flowmeter) and by computer record.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.Filtering Weigh and analyze after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber afterwards.

Comparative example 6

Weigh catalyst 150mg in comparative example 1 and carry out polymerization under atmospheric pressure experiment.Polymerization reaction kettle heating in vacuum is removed It is miscellaneous, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to reaction The refined normal heptane solvents of 40mL are added in kettle, the triisobutyl aluminium (TiBA) that dosage is Al/Cr=5 is added and makees co-catalyst, The normal heptane solvent after 30mL dehydration and deoxidations refine is added, then adds 10mL H into kettle respectively₂.Adjust ethylene pressure to 0.15MPa, it is constant after 80 DEG C after temperature in the kettle, add catalyst and start to react.Online acquisition monomer ethylene in course of reaction Instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) and by computer record.After 1h add hydrochloric acid/ Alcohol mixed solution terminating reaction.Weigh and divide after resulting polymers are dried into 4h at 60 DEG C in vacuum drying chamber after filtering Analysis.

Comparative example 7

Catalyst 150mg in comparative example 1 is weighed respectively carries out polymerization under atmospheric pressure experiment.By polymerization reaction kettle heating in vacuum Removal of impurities, and, micro refined ethene is filled in most backward reactor to 0.12MPa with high pure nitrogen pump drainage three times.Then successively to anti- Answer and the refined normal heptane solvents of 40mL are added in kettle, add the triisobutyl aluminium (TIBA) that dosage is Al/Cr=5 and be used as co-catalysis Agent, add the normal heptane solvent after 30mL dehydration and deoxidations refine, regulation ethylene pressure to 0.15MPa.Polymerization temperature difference is steady Be scheduled on 60 DEG C, 70 DEG C, 90 DEG C (corresponding to comparative example 7-1,7-2,7-3 respectively) when, add catalyst start to react.Reacted The instantaneous consumption (by the high-accuracy Ethylene mass flowmeter for connecting computer) of online acquisition monomer ethylene and by electricity in journey Brain records.50mL hydrochloric acid/alcohol mixed solution terminating reaction is added after 1h.After filtering by resulting polymers in vacuum drying chamber Weigh and analyze after drying 4h at 60 DEG C.

Comparative example 8

Weigh composite catalyst 150mg in comparative example 2 and carry out polymerization experiment.Vacuum is carried out to polymerization reaction kettle in advance Heating, is then replaced into high pure nitrogen, operates repeatedly three times, then is once filled with the displacement of a small amount of monomer ethylene in most backward reactor Micro refined ethene is to 0.12MPa.Then the refined normal heptane solvents of 40mL are added into reactor successively, are separately added into dosage Make co-catalyst for Al/Cr=5 triisobutyl aluminium (TiBA), add the normal heptane solvent after 30mL dehydration and deoxidations refine. Ethylene pressure is adjusted to 0.15MPa, composite catalyst is eventually adding and starts polymerisation, online acquisition monomer second in course of reaction The instantaneous consumption of alkene and by computer record, after 80 DEG C of reactions are carried out 1 hour, add hydrochloric acid/alcohol mixed solution terminate it is anti- Should, weigh and analyze after polymer vacuum drying.

The present invention is by chemical method by two kinds of different transition metal, and chromium source is inorganic chromium source, alkali formula chromic acetate, tungsten source I.e. acetic acid tungsten load prepares a kind of new chromium tungsten composite catalyst in same catalyst carrier.The catalyst is being applied With in the copolymerization experiments exemplified by ethylene homo and ethene/1- hexenes, can be produced in single-reactor has wide molecular weight distribution (MWD=20-40) Alathon and alpha olefin copolymer (polyvinyl resin).Simultaneously by changing compound proportion, polymerization Temperature, hydrogen such as adjust at preparation and the process conditions, using catalyst can adjust Alathon and alpha olefin copolymer molecular weight and Molecular weight distribution.

The ethylene polymerization activity of 1 each embodiment of table

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

(1) influence of co-catalyst dosage

The co-catalyst dosage of table 2 is to chromium tungsten bimetallic catalyst and the influence of monochrome center catalyst ethylene homopolymerization

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature=80 DEG C；Normal heptane=70mL； Catalyst amount=150mg；Carry chromium content=0.5wt%；Carry tungsten amount=1.77wt%；Co-catalyst=TiBA.

As known from Table 2, under conditions of using TiBA as co-catalyst (embodiment 5 and comparative example 3), with co-catalysis Agent dosage continues to increase, and the process successively decreased is presented in the activity of ethylene homo.During composite catalyst use, to reach poly- High activity is closed, the dosage of co-catalyst has suitable a value or scope, i.e., fully can removed in reaction system The impurity such as moisture, and can plays reduction to catalyst, but over reduction can cause number of active center to reduce and cause polymerization to be lived Property reduce, there is also similar rule for other co-catalysts in addition to TiBA.As can be drawn from Table 1, it is minimum in experiment Co-catalysis dosage has met that activation of catalyst acts on, and with the increase of dosage, the activated centre quantity of over reduction increases, activity Reduce.Under the conditions of different co-catalyst dosages, the fusing point of polymerizate is basically identical, and molecular weight is first raised and reduced afterwards, explanation The reducing degree in activated centre has a significant impact to the molecular weight of polymer.

(2) influence of the co-catalyst species to polymerization activity and product property

Table 3 gives under different co-catalysts (embodiment 4-1,5 and comparative example 3-1,5) vinyl polymerization result.From Table 3 understands that under the effect of different co-catalysts the ethylene homo activity of composite catalyst is different, when co-catalyst is TEA Active obvious reduction, is unfavorable for the homopolymerization of ethene.Under the conditions of two kinds of co-catalysts, instantaneous ethene consumption top occur when Between approach, but peak is variant, and its kinetics of polymerization curvilinear trend is roughly the same, all shows the rule for first raising and reducing afterwards Rule.Simultaneously when making co-catalyst with TEA, the fusing point of polymer melting point polymers of the TiBA obtained by when making co-catalyst that compare has Reduced.Molecular weight and molecualr weight distribution differs widely under the conditions of different co-catalysts, illustrates co-catalyst to catalyst activity Large effect is distributed with after the reducing degree at center and reduction.

Influence of the 3 different co-catalysts of table to ethylene homo

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature=80 DEG C；Normal heptane=70mL； Catalyst amount=150mg；Carry chromium content=0.5wt%；Carry tungsten amount=1.77wt%；Al/Cr=5.

(3) influence of polymerization temperature

Influence of the polymerization temperature of table 4 to ethylene homo

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Normal heptane=70mL；Catalyst amount= 150mg；Cr:W=1:1, Cr%=0.5% (wt)；Co-catalyst=TiBA, Al/Cr=5.

Table 4 is the vinyl polymerization result of chromium tungsten composite catalyst under different polymerization temperatures (embodiment 4-2 and embodiment 10). Under conditions of reaction pressure is certain, in 35 DEG C -80 DEG C of polymerization temperatures range, with the rise of reaction temperature, liquid-phase system The solubility of interior ethene reduces, on composite catalyst ethylene homo activity in the trend gradually reduced, illustrate polymerization activity with instead Answer in system that medium transfer rate is relevant, reaction temperature has a significant impact to reactivity.Further product analyze Arrive, the polyethylene product obtained under different polymerization temperatures has similar fusing point, its molecular weight (Molecule Weight, MW) With the rise of polymerization temperature, occur first raise the trend reduced afterwards, illustrate polymerization temperature and meanwhile to polymerisation chain tra nsfer with Chain, which increases, to be had an impact.Meanwhile reaction temperature is to producing the two of HMW and low molecule amount in composite catalyst activated centre Major class center has a certain impact, and with the rise of temperature, the molecular weight distribution of polyethylene product becomes narrow gradually.

(4) influence of the hydrogen to polymerization

Influence of the hydrogen of table 5 to ethylene homo

Polymerizing condition：Ethylene pressure=0.14MPa；Polymerization time=1hr；Polymerization temperature=80 DEG C；Normal heptane=70mL； Catalyst amount=160mg；It is total to carry chromium content=0.5wt%；Co-catalyst=TiBA, Al/Cr=10.

The influence that hydrogen is adjusted during catalyst compounded polymerization as shown in table 5 (embodiment 4-1,11,8-1,12,9-1,13 and contrast Embodiment 3-1,6).As can be seen from the table, under different compound proportions the ethylene homo activity of composite catalyst respectively than not having All decreased under hydrogen existence condition, variation of melting point is little, but the molecular weight of polyethylene is greatly reduced, and illustrates hydrogen Play a part of an obvious chain-transferring agent, accelerate the transfer of chain, cause its molecular weight substantially to reduce.

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

Influence of the 1- hexenes addition of table 6 to ethene/1- hervene copolymers

The result that table 6 gives ethene/1- hervene copolymers of various catalyst compounded and pure Phillips catalyst (is implemented Example 4-1,14,8-1,15,9-1,16 and comparative example 3-1,5).As comonomer concentration raises, the second of composite catalyst Alkene/1- hervene copolymer activity shows the trend of reduction, with reference to the result of ethylene homo before, shows ethene/1- hervene copolymers Activity is below the activity of ethylene homo.Fusing point as the addition of copolymer-1-hexene monomers causes product polyethylene kind produces than homopolymerization Product decrease.And increasing with comonomer 1- hexene additions, the molecular weight and molecular weight point of its product polyethylene Cloth reduction all more obvious than equal dimerization product.Ethene/1- hervene copolymers activity, fusing point compare phase on the composite catalyst of different compound proportions The equal dimerization product answered has and slightly reduced, but molecular weight is all substantially reduced, and molecular weight distribution substantially narrows.Contrast different W contents Composite catalyst, the response to copolymerization is basically identical, and increasing with W content, and Copolymerization activity gradually increases, molecular weight point Cloth also gradually broadens.Compare homopolymerization products, and with the insertion of comonomer 1- hexenes, HMW and low molecular weight part are equal Reduce, molecular weight distribution substantially narrows.

The influence of (6) two kinds of transition metal compound proportions

The influence for the catalyst compounded ethylene homo that the co-catalyst dosage of table 7 matches to different activities center

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature=80 DEG C；Normal heptane=70mL； Catalyst amount=150mg；Carry chromium content=0.5wt%.

As known from Table 7, under conditions of using TiBA as co-catalyst (embodiment 8), it is continuous with co-catalyst dosage Increasing, the process successively decreased is presented in the activity of ethylene homo, and minimum in experiment helps the amount of urging to meet that activation of catalyst acts on, with The increase of dosage, the activated centre quantity of over reduction increase, and activity reduces, and this is consistent with the trend of example 5.

As known from Table 7, under conditions of using TiBA as co-catalyst (embodiment 9), it is continuous with co-catalyst dosage Increase, the activity of ethylene homo, which is presented, first increases the process successively decreased afterwards, illustrates the increase with W content, it is necessary to for reducing work The co-catalysis dosage at property center increases, but over reduction can make it that number of active center is reduced, so as to cause polymerization activity to reduce.Will Most highly active obtained by both catalyst obtains table 8 such as following table compared with the most highly active of catalyst of the present invention.

Influence of the proportional quantity in 8 two kinds of activated centres of table to ethylene homo

Polymerizing condition：Ethylene pressure=0.15MPa；Polymerization time=1hr；Polymerization temperature=80 DEG C；Normal heptane=70mL； Catalyst amount=150mg；Co-catalyst=TiBA, Al/Cr=10；Carry chromium content=0.5wt%.

Table 8 gives under different compound proportions (embodiment 4-1,8-1 and 9-3) vinyl polymerization result.In different W additions Under, do not change other reaction conditions, reactivity reduces with the increase of W content, illustrates that W is to Phillips in composite catalyst The ethylene polymerization activity of catalyst is unfavorable.Further by the analysis to the said goods polyethylene, with W additions Increase, the molecular weight increase of product polyethylene, the fusing point of product gradually rise, and illustrate different W additions to composite catalyst Polymerizate have a significant impact.

Claims

1. a kind of supported chrome tungsten bimetallic catalyst, it is characterised in that chromated oxide and tungsten including inorganic carrier and load Oxide.

2. a kind of supported chrome tungsten bimetallic catalyst according to claim 1, it is characterised in that the chromated oxide Raw material sources be selected from chromium trioxide, chromic nitrate, chromic acetate, chromium chloride, chromium sulfate, ammonium chromate, ammonium dichromate, alkali formula chromic acetate, Other chromium soluble-salts and combinations thereof, preferably chromic acetate and alkali formula chromic acetate；The raw material sources choosing of the tungsten oxide From tungstic acid, ammonium tungstate, sodium phosphotungstate, sodium tungstate, potassium tungstate, tungstosilicic acid, water-insoluble Tungstenic compound and they Combination, preferably tungsten acid and tungstosilicic acid；The inorganic carrier be selected from silica, alundum (Al2O3), titanium dioxide, zirconium oxide, Magnesia, calcium oxide, inorganic clay and combinations thereof, and silica gel that is unmodified or being modified through Ti, Al or F, preferably without fixed Shape Bio-sil.

3. a kind of supported chrome tungsten bimetallic catalyst according to claim 1 or 2, it is characterised in that in inorganic carrier On Cr total load amounts be total catalyst weight 0.01-5wt%, preferably 0.05-4wt%, more preferably 0.1-2wt%, press Cr weight meter；W total load amounts on inorganic carrier are the 0.01-5wt%, preferably 0.05- of total catalyst weight 4wt%, more preferably 0.1-2wt%, based on W weight.

4. a kind of supported chrome tungsten bimetallic catalyst according to claim 1 or 2, it is characterised in that described without airborne The pore volume of body is 0.5-5cm³/ g, preferably 1.0-3.0cm³/ g, more preferably 1.3-2.5cm³/ g, further preferred 1.5- 1.8cm³/g；The surface area of the inorganic carrier is 100-600m²/ g, preferably 150-500m²/ g, more preferably 220-400m²/ g, Further preferred 250-350m²/g；The average grain diameter of the inorganic carrier is 1-100 microns, preferably 5-80 microns, more preferably 10-60 microns.

5. a kind of preparation method of the supported chrome tungsten bimetallic catalyst as described in claim 1-4 any one, its feature exist In comprising the following steps：

6. the preparation method of supported chrome tungsten bimetallic catalyst according to claim 5, it is characterised in that dip time is 1~12h, preferably 4~8h, dipping temperature are 10~80 DEG C, preferably 20~70 DEG C, are then dried between 90~250 DEG C, preferably 100~200 DEG C, 6~20h of drying time, preferably 8~15h；Roasting work is carried out in inert gas either oxygen or air To change, sintering temperature is 300~900 DEG C, and preferably 400~800 DEG C, the time is 1~10h, preferably 3~8h, is then cooled down, Inert gas is switched to when being cooled to 300~400 DEG C, natural cooling, the catalyst is obtained and saves backup；Preferably, it is described Roasting is carried out with two stages of cold stage and hot stage, and cold stage is carried out at 100~300 DEG C, continues 1~10 hour, It is preferred that 2~9 hours, hot stage is carried out at 300~900 DEG C, continues 1~10 hour, preferably 2~9 hours, more preferably 3~8 hours.

7. according to the preparation method of the supported chrome tungsten bimetallic catalyst of claim 5 or 6, it is characterised in that also include Following steps：In step II under inert atmosphere) organic metal co-catalyst is added in obtained catalyst carries out prereduction activation Processing, dry, preserve stand-by；Preferably, 2-8 hours are dried between 60-120 DEG C, are then preserved under an inert gas stand-by.

8. the preparation method of supported chrome tungsten bimetallic catalyst according to claim 7, it is characterised in that organic gold Belong to co-catalyst and be selected from organo-aluminum compound, organo-lithium compound, organoboron compound either combinations thereof.

9. a kind of supported chrome tungsten bimetallic catalyst as described in claim 1-4 any one is in olefin polymer is produced Using, it is characterised in that it is preferred for producing Alathon and ethylene copolymer.

10. application of the supported chrome tungsten bimetallic catalyst in olefin polymer is produced according to claim 9, its feature It is, alkene is contacted with catalyst compounded under polymerization conditions, it is described catalyst compounded including the double gold of the supported chrome tungsten Metal catalyst and at least one co-catalyst；Preferably, the co-catalyst is in aluminium compound, zinc alkyl and tin alkyl It is one or more kinds of.