CN106589178A - Vanadium-metallocene bimetallic catalyst and preparation method thereof - Google Patents
Vanadium-metallocene bimetallic catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a vanadium-metallocene bimetallic catalyst and a preparation method thereof. The catalyst is prepared from an inorganic supporter and a supported active component, wherein the inorganic carrier is inorganic oxide, and the active component is vanadium oxide and metallocene oxide. According to the vanadium-metallocene bimetallic catalyst and the preparation method thereof, a vanadium catalyst and a metallocene catalyst are compounded, the molecular weight of produced high-density polyethylene is increased, the distribution is widened, the content and distribution of comonomers can be improved, meanwhile, the catalyst has higher activity, is a high-performance supported vanadium-metallocene bimetallic catalyst and has better hydrogen regulation responsiveness through titanium dioxide modification.
Description
Technical field
The present invention relates to a kind of catalyst, and in particular to a kind of vanadium and metallocene bimetallic catalyst and preparation method thereof.
Background technology
It, by a kind of thermoplastic of vinyl monomer polymerization, is yield and consumption figure in the world today that polyethylene (PE) resin is
One of maximum general-purpose plastics product, mainly including Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), height
Density polyethylene (HDPE) and some there is the polyethylene of property.Polyethylene have excellent mechanical property, electrical insulating property,
Chemical resistance, lower temperature resistance and excellent processing characteristics.Polyethylene products are widely used in industry, agricultural, automobile, logical
The every field such as news and daily life.The polyethylene catalysts being currently known mainly have Ziegler-Natta catalyst, chromium system to urge
The catalyst of agent and metallocene catalyst and some other Nonmetallocene class.
EP339571 disclose it is a kind of by using by the catalyst system of following material composition producing with wide molecular weight distribution
Polyethylene method：Catalytic component (A), has the silica carrier of titanium or chromium compound comprising deposition thereon；Catalytic component (B),
Comprising transistion metal compound；With catalytic component (c), such as a kind of aikyiaiurnirsoxan beta, MAO.
A kind of new supported chrome/vanadium metal oxide double activity center second is reported in number of patent application 201210118427.2
Alkene polymerization catalyst, represents as the third generation Phillips catalyst with chromium/vanadium double activity center, it is characterized in that in Phillips
The vanadium active component that load is introduced on chromium-based catalysts becomes the Chromium-polyethylencatalyst catalyst with chromium, two kinds of active center of vanadium.
The content of the invention
It is an object of the invention to provide a kind of vanadium and metallocene bimetallic catalyst and preparation method thereof, by metallocene catalyst and
Vanadium metal catalyst is combined so as to which the high density polyethylene (HDPE) molecule quantitative change of production is big, and distribution broadens, and can improve copolymerization
The content of monomer and its distribution, while catalyst also has greater activity, it is a kind of high-performance supported type vanadium and metallocene bimetallic
Catalyst and preparation method thereof, and the catalyst makes catalyst that there is more preferable hydrogen to adjust response by titania modified.
A kind of vanadium/cyclopentadienyl bimetallic catalyst of the present invention, the catalyst include the active component of inorganic carrier and load, and inorganic carrier is
Inorganic oxide, active component are barium oxide and metallocene compositionss.
Barium oxide of the barium oxide for low-oxidation-state；Inorganic carrier is the particulate inorganic oxide of porous, the ratio of inorganic carrier
Surface area is 50～500m2/ g, preferably 100～300m2/ g, the pore volume of inorganic carrier is 0.1～5.0cm3/ g, preferably 0.5～3.0
cm3/g；Metallocene is one or more of luxuriant zirconium metal, luxuriant hafnium metal or metallocene-titanium metal；The presoma of barium oxide be containing vanadic salts,
Water or organic solvent can be dissolved in containing vanadic salts, barium oxide presoma is hexafluoro ammonium vanadate, nitric acid vanadium, vanadyl oxalate, inclined vanadium
Sour ammonium, vanadium oxysulfate, sulfuric acid oxidation vanadium hydrate, Sulfovanadic acid, three chloro vanadium oxides, vanadic acid sodium, sodium metavanadate, biacetyl
Acetone oxidation vanadium, Triisopropoxyvanadium(V) oxide, three propanol vanadium oxides, vanadium acetylacetonate, oxidation triethoxy vanadium, divanadyl tetrachloride or silicon
Change one or more in three vanadium, the presoma of the barium oxide is more preferably ammonium metavanadate.In the presoma of barium oxide,
0.01～10wt%, preferably 0.05～5wt%, by the weight of vanadium in terms of of the vanadium load capacity for total catalyst weight.
The preparation method of described vanadium/cyclopentadienyl bimetallic catalyst, comprises the following steps：
(1) barium oxide presoma is attached on inorganic carrier to obtain a kind of catalyst precarsor；
(2) gained catalyst precarsor is carried out barium oxide that high-temperature roasting obtains oxidation state under oxidative conditions；
(3) sample is reacted under the reducing conditions, is obtained the barium oxide of the low-oxidation-state of prereduction；
(4) will be the barium oxide of the low-oxidation-state of prereduction enterprising in inorganic carrier with metallocene compositionss or metallocene compositionss
Catalyst contact after row load obtains final load-type vanadium and metallocene bimetallic catalyst and preparation method thereof.
In above-mentioned steps (1), inorganic carrier is any of the IIth A, III B, IV B, I B, II B, III A and IV A races metal
Oxide.
Inorganic carrier is silicon dioxide, aluminium sesquioxide, titanium dioxide, zirconium oxide, magnesium oxide, calcium oxide, silica gel or inorganic
Clay.It is preferred that silica gel, more preferably particularly unformed Bio-sil, 955 silica gel of Davison, the life of 955 silica gel of Davison
Product producer is Grace companies.
Catalyst such as titanium dioxide titanium mode such as be modified by way of inorganic carrier is modified is further optimized so as to obtained
Preferably hydrogen adjusts response and copolymerization performance.
Inorganic carrier is titania modified inorganic carrier；The titanium compound raw material for preparing titania modified inorganic carrier is acetyl
Acetone oxygen titanium, titanous chloride., titanium tetrachloride, tert-butyl alcohol titanium, tetra-n-butyl titanate, titanyl sulfate, titanium sulfate, hexafluorotitanic acid
One or more in ammonium, isopropyl titanate or tetraethyl titanate.
Step (2) high temperature roasting is divided into two stages of cold stage and hot stage to be carried out, and cold stage enters at 100～300 DEG C
OK, hot stage is carried out at 300～900 DEG C；Cold stage continues 1～10 hour, and hot stage continues 1～10 hour.It is described
Preferably 2～8 hours cold stage persistent period.Preferably 2～9 hours hot stage persistent period, more preferably 3～8 hours.
The mechanical water adsorbed in the cold stage carrier is removed, and the part of hydroxyl on the hot stage inorganic carrier is removed
Go.
The cold stage is carried out under noble gases or air atmosphere；The hot stage roasting is in air or Oxygen Condition
Under carry out.The cold stage is carried out under noble gases or air atmosphere, is preferably carried out under an inert gas, the inertia
The gas such as atmosphere such as nitrogen, helium, argon, is preferably carried out in a nitrogen atmosphere.According to an embodiment, the high temperature
Stage roasting is carried out under air or Oxygen Condition, is carried out preferably under the conditions of dry air.After the roasting terminates, will
The catalyst for obtaining is cooled down from hot stage.According to an embodiment, 300～400 DEG C of temperature is cooled to after high-temperature roasting
When spending, atmosphere is converted, for example, is changed into noble gases, such as nitrogen etc. from air.According to an embodiment, this is cooled to certainly
Right cooling down.The catalyst for obtaining is saved backup under inert gas atmosphere.
When 300～400 DEG C of temperature is cooled to after high-temperature roasting, atmosphere is converted, is changed into noble gases from air.
In step (3), reducing agent is organo-aluminum compound, preferred trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, three isobutyls
Base aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, dibutyl aluminum bromide, diethylaluminium ethoxide, methyl
One or more in aikyiaiurnirsoxan beta, ethylaluminoxane, butyla-luminoxane；Reducing agent use ratio is controlled
1～100: 1, preferably 6～50:1, the addition reducing agent recovery time is 1min～4h, preferably 0.5～2h.
The combination of the presoma and inorganic carrier of barium oxide is referred to as loading process, and load step is：Before containing barium oxide
Drive body component solution impregnation is on inorganic carrier and is dried.The solution of the presoma component of barium oxide is by barium oxide
Presoma be dissolved in water or organic solvent, wherein organic solvent can be arbitrarily can to dissolve the presoma of barium oxide
Solvent, preferred alcohol.
In step (4), metallocene is preferably zirconocene, the metallocene compound with following molecular formula：Cp2ZrR′R″。
Wherein Cp is represented selected from unsubstituted cyclopentadienyl；By including the unsubstituted and substituted straight chain containing 1-20 carbon atom, prop up
The cyclopentadienyl replaced by group in the group of the alkyl group and condensed ring group of chain, ring-type or part cyclic；Or selectivity contains
Heteroatomic unsubstituted and substituted monocyclic or polycyclic aromatic groups；And the cyclopentadienyl that aralkyl replaces.Substituent group shape on luxuriant ring
Into the condensed cyclic structure containing heteroatomic benzene, naphthalene or hexamethylene ring condensed containing one or more." substituent group can be identical for R ' and R
Or it is different, " substituent group includes the alkyl with 1-6 carbon atom, unsubstituted or substituted benzyl and by with l-6 to R ' with R
In the group of the alkyl-substituted phenoxy group of individual carbon atom.Preferred R ' and R " be include methyl, benzyl or Phenoxymethyl and they
With reference to group in.R ' or R " or be halogen, preferred chlorine.
The catalyst that step (3) is obtained is contacted with the metallocene catalyst of metallocene compound or support type, it is preferred to use I.
Contacted in the form of dry powder；II. contacted under conditions of solvent, and be dried removing solvent under inert conditions and obtained
Obtain the preferable catalyst of mobility.
Final obtained vanadium and metallocene bimetallic catalyst and preparation method thereof contain two kinds of metal active centres vanadium and metallocene,
Vanadium active center ratio is not relatively low obvious to resin interference, and vanadium ratio is too high to cause final resin relative molecular mass too high, make
Processing characteristics is reduced.V element and the preferred mol ratio of metallocene are 0.05:1 to 20:1, more preferably 0.5:1 to 5:1.
Vanadium and metallocene bimetallic catalyst of the present invention and preparation method thereof, titanium load capacity are total catalyst weight
0.1～10wt%, preferably 0.2～8wt%, based on the weight of Ti.
The catalyst carries out olefinic polyreaction to be carried out in the reactor of common type, including batch (-type) or continuous reaction
Device, is slurry mode or vapor mode.
Present invention preferably employs vapor phase polymerizer.
The catalyst possesses vanadium active center and metallocene active center Liang Zhong active center, for synthesizing ethylene homopolymer and ethylene
With alpha olefin copolymer.The catalyst has higher activity simultaneously.
The polymerization of ethylene, the preparation method of the polymer of the ethylene being especially distributed with bimodal or broad peak.This catalyst
Compositionss contain vfanadium compound component and metallocenes, and they are combined into bimetallic active center catalyst with different modes.
Using the present invention catalyst preparation Natene and copolymer, MFR (21.6kg) 0.01～120g/10min of scope,
Relative molecular mass distribution 1～10.
The preparation process of catalyst preferably adopts following steps：
(1) 955 silica gel of Davison is added in 955 silica gel of undressed Davison and is prepared as inorganic carrier
Barium oxide presoma, being slowly stirred at 50 DEG C～60 DEG C makes solution be uniformly dispersed in whole system, static dipping 4-6
Individual hour, makes active component well into in silica gel micropore, and the loaded article for having impregnated is dried at a temperature of 120 DEG C, takes off
Except mechanical water therein, the pressed powder of the drying with good fluidity is obtained.
(2) pressed powder of above-mentioned drying is carried out into 100-900 DEG C of high-temperature activation under conditions of air presence, makes vanadium metal oxygen
Chemical conversion high-valence state.
(3) reduced using alkyl aluminum and then in an inert atmosphere, eventually pass intensification and be dried desolvation to obtain mobility good
The catalyst of the low-oxidation-state barium oxide of good prereduction.
955 silica gel of Davison is carried out into high-temperature activation, mechanical water and part chemical water in carrier is removed, is subsequently adding MAO
(MAO) processes catalyst carrier, and after the carrier to processing is washed, load metallocene compound is (such as Cp2ZrCl2),
It is scrubbed again to remove unsupported metallocene compound, then it is dried prepared carried metallocene catalyst, i.e. metallocene compositionss
Catalyst after being loaded on inorganic carrier.
(4) in an inert atmosphere, finished catalyst contact load type metallocene catalyst is mixed or under solvent condition
Carry out being mixed to prepare the double center catalyst slurries of vfanadium compound/metallocene, then be dried and obtain catalyst dry powder.
The preparation process of catalyst preferably adopts following steps：
(1) 955 silica gel of Davison is added in 955 silica gel of undressed Davison and is prepared as inorganic carrier
Barium oxide presoma, being slowly stirred at 50 DEG C～60 DEG C makes solution be uniformly dispersed in whole system, static dipping 4-6
Individual hour, makes active component well into in silica gel micropore, and the loaded article for having impregnated is dried at a temperature of 120 DEG C, takes off
Except mechanical water therein, the pressed powder of the drying with good fluidity is obtained.
(2) pressed powder of above-mentioned drying is carried out into 100-900 DEG C of high-temperature activation under conditions of air presence, makes vanadium metal oxygen
Chemical conversion high-valence state.
(3) reduced using alkyl aluminum and then in an inert atmosphere, eventually pass intensification and be dried desolvation to obtain mobility good
The catalyst of the low-oxidation-state barium oxide of good prereduction.
(4) catalyst of the low-oxidation-state barium oxide of above-mentioned prereduction is made into serosity state in normal hexane or in technical white oil,
In an inert atmosphere, the solution of metallocene catalyst is dropped in catalyst, stirring is obtained the double centers of vfanadium compound/metallocene and urges
Agent.
The preparation method of described titania modified inorganic carrier is as follows：
I) will stir after titanium compound and organic solvent mixing, sour back flow reaction is added, inorganic carrier is added and is reacted, reaction
Afterwards product is dried；
II) by the product for obtaining roasting at 300～900 DEG C of high temperature, obtain the titania modified inorganic carrier.
Polymer is prepared using the gas phase polymerization of the catalyst of the present invention, step is as follows：
Polymeric kettle is processed under high temperature, vacuum state first, and supplementary high pure nitrogen is standby, and dry powder catalyst is after metering in height
Polymeric kettle is added under purity nitrogen gas shielded, is stirred after evacuation, kettle temperature is raised to assigned temperature by the logical hot water of chuck, is slowly added to ethylene
Gas starts polyreaction to reaction pressure.Polymerization pressure keeps permanent by control system by mass flowmenter and pressure transducer
Fixed, polymerization temperature adjusts on-line heating device by control system by combination type water-bath and water circulating pump is controlled.Comonomer and
The addition of hydrogen is added by independent pipeline or after distribution tank distribution.After polymerization starts timing, constant temperature and pressure reaction.
Polymer is prepared using the gas phase polymerization of the catalyst of the present invention, step is as follows：
It is first by polymeric kettle evacuation, multiple with high pure nitrogen displacement, solvent is then added under vacuum conditions.High pure nitrogen is protected
Lower addition alkyl aluminum, stirring.In the lower catalyst fines for adding of nitrogen protection, comonomer and hydrogen are added, is warmed up to specified
Temperature, is passed through ethylene to the polymerization pressure for setting, starts polyreaction.Polymerization pressure is led to by mass flowmenter and pressure transducer
Cross control system and keep constant, polymerization temperature adjusts on-line heating device and water circulating pump by control system by combination type water-bath and carries out
Control.After polymerization starts timing, constant temperature and pressure reaction.
Preparation method is not limited to both the above.
The method of testing and condition of the characteristic performance of obtained polymer is as follows：
1) high temperature gel chromatograph (HT-GPC)
The average weight-molecular mass and relative molecular mass distribution high temperature gel chromatographic determination of polyethylene product：This experiment is adopted
PL-220 type high-temperature gel permeation chromatography instrument (Polymer Laboratories companies) come determine polyethylene relative molecular mass and its
Relative molecular mass distribution.With 1 in experiment, 2,4- trichloro-benzenes are solvent, are determined at 160 DEG C.Using Narrow distribution polystyrene
As the universal calibration method processing data of standard specimen.
2) melt mass flow rate (MFR)
Using Italian 6942/000 Melt Flow Rate Measurer of CEAST companies, carry out by GB/T 3682-2000,190 DEG C of temperature.
Compared with prior art, the invention has the advantages that：
Vanadium of the present invention and metallocene bimetallic catalyst and preparation method thereof, metallocene catalyst and vanadium metal catalyst are carried out multiple
Close so as to which the high density polyethylene (HDPE) molecule quantitative change of production is big, and distribution broadens, and can improve content and its distribution of comonomer,
Simultaneously catalyst also has greater activity, is a kind of high-performance supported type vanadium and metallocene bimetallic catalyst and preparation method thereof,
And the catalyst makes catalyst that there is more preferable hydrogen to adjust response by titania modified.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Methods described is conventional method if no special instructions.The material is commercial if no special instructions.
Embodiment 1-1
955 silica gel of commercially available Davison is selected as inorganic carrier；0.11g ammonium metavanadates are dissolved in 36ml at 60 DEG C to steam
In distilled water (vanadium load capacity is 0.30wt%), then 20g silica gel is immersed in ammonium metavanadate solution, 1h is impregnated at 60 DEG C
Make active component uniform adsorption in silica gel micropore, whole process belongs to physical adsorption process.Turn after 20h is dried at 120 DEG C
Roasting is carried out in moving on to fluid bed, roasting process 200 DEG C of low-temperature bakes first in nitrogen are incubated 1h, then in high pure air
600 DEG C of insulation 4h, then Temperature fall cooling under a nitrogen.Using normal hexane as solvent, diethylaluminium ethoxide is added to enter
Row reduction, Al/V mol ratios are 12: 1, reduce 30min.Then heat to 70 DEG C and be dried 4h, obtain mobility preferably pre-
The catalyst containing low-oxidation-state barium oxide of reduction is standby.
955 silica gel of Davison is selected as inorganic carrier；Toluene 20ml is added, is stirred, add 5mlMAO, then
Add Cp2ZrCl2Toluene solution, Al/Zr mol ratios are 120: 1, and after stirring 4h, washing is dried to obtain metallocene catalyst.
By vfanadium compound catalyst and metallocene catalyst with V/Zr mol ratios 1:1 carries out dry powder blend, and catalyst is obtained.
Gas-phase polymerization test is carried out using two ways
The first：Weighing above-mentioned three kinds of catalyst carries out gas-phase polymerization test.
1L vapor phase polymerizers are processed into 4h through heating, evacuation and high pure nitrogen first, the catalyst of above-mentioned preparation weighs 0.1g
Polymeric kettle is added under high pure nitrogen protection, kettle temperature is raised to into 92 DEG C, vinyl monomer is slowly added to reaction pressure 0.8Mpa, is opened
Beginning polyreaction, and keep pressure and temperature constant in polymeric kettle.Response time is 1h.Polyreaction cools out after terminating
Material, weighs, calculates activity, test polyvinyl resin performance.
Second：Hydrogen is carried out according to gas-phase polymerization mode using the catalyst of the first and adjusts aggregation test.In gas-phase polymerization processes
Add hydrogen 0.004MPa.
Embodiment 1-2
The present embodiment is same as Example 1, and difference is that just vfanadium compound catalyst and metallocene catalyst are rubbed with V/Zr
You compare 2:1 carries out dry powder blend, and catalyst is obtained.
Embodiment 1-3
The present embodiment is same as Example 1, and difference is that just vfanadium compound catalyst and metallocene catalyst are rubbed with V/Zr
You compare 3:1 carries out dry powder blend, and catalyst is obtained.
Embodiment 1-4
The present embodiment is same as Example 1, and difference is that just vfanadium compound catalyst and metallocene catalyst are rubbed with V/Zr
You compare 4:1 carries out dry powder blend, and catalyst is obtained.
Embodiment 2
Prepared according to the vanadium catalyst compound method in embodiment 1, except that Al/V mol ratios are 16: 1.
By the metallocene catalyst in the catalyst containing low-oxidation-state barium oxide of above-mentioned prereduction and embodiment 1 with 1:1 enters
Row dry powder blend, is obtained catalyst standby.
Gas-phase polymerization mode according to embodiment 1 carries out vinyl polymerization test.
Embodiment 3
Prepared according to the vanadium catalyst compound method in embodiment 1, except that Al/V mol ratios are 20: 1.
By the metallocene catalyst in the catalyst containing low-oxidation-state barium oxide of above-mentioned prereduction and embodiment 1 with 1:1 enters
Row dry powder blend, is obtained catalyst standby.
Gas-phase polymerization mode according to embodiment 1 carries out vinyl polymerization test.
Embodiment 4
Prepared according to the vanadium catalyst compound method in embodiment 1, except that using hexafluoro Ammonium Vanadate Solution as vanadium
Source.
By the metallocene catalyst in the catalyst containing low-oxidation-state barium oxide of above-mentioned prereduction and embodiment 1 with 1:1 enters
Row dry powder blend, is obtained catalyst standby.
Gas-phase polymerization mode according to embodiment 1 carries out vinyl polymerization test.
Embodiment 5
Prepared according to the vanadium catalyst compound method in embodiment 1, except that adopting vanadyl oxalate solution solution conduct
Vanadium source.
By the metallocene catalyst in the catalyst containing low-oxidation-state barium oxide of above-mentioned prereduction and embodiment 1 with 1:1 enters
Row dry powder blend, is obtained catalyst standby.
Gas-phase polymerization mode according to embodiment 1 carries out vinyl polymerization test.
Embodiment 6
Prepared according to the vanadium catalyst compound method in embodiment 1, except that adopting Cp2ZrMe2Toluene solution conduct
Metallocene active center.
By the vanadium catalyst in the catalyst containing low-oxidation-state barium oxide of above-mentioned prereduction and embodiment 1 according to 1:1 is carried out
Dry powder blend, is obtained catalyst.
Gas-phase polymerization mode according to embodiment 1 carries out vinyl polymerization test.
Embodiment 7
Prepared according to the vanadium catalyst compound method in embodiment 1, except that adopting Cp2ZrBz2Toluene solution conduct
Metallocene active center.
By the vanadium catalyst in the catalyst containing low-oxidation-state barium oxide of above-mentioned prereduction and embodiment 1 according to 1:1 is carried out
Dry powder blend, is obtained catalyst.
Gas-phase polymerization mode according to embodiment 1 carries out vinyl polymerization test.
Embodiment 8
The catalyst containing low-oxidation-state barium oxide of the prereduction in embodiment 1 is suspended in technical white oil prepared weight to contain
The slurry catalyst for 10% is measured, 1 is respectively with the mol ratio of V/Zr with the metallocene catalyst in embodiment 1：1 (embodiment
8-1)、2：1 (embodiment 8-2), 3：Metallocene catalyst toluene solution Deca is entered and is mixed by the ratio of 1 (embodiment 8-3)
The double center catalyst of even prepared vfanadium compound/metallocene.
Aggregation test is carried out using two ways
The first：Measuring above-mentioned three kinds of catalyst respectively carries out slurry polymerization experiments.First by 2L polymeric kettle evacuation, High Purity Nitrogen is used
Gas is replaced 3 times, then adds the solvent for measuring under vacuum conditions.High pure nitrogen protection is lower to add 5ml alkyl aluminums, stirring
Certain hour.In the lower addition 2ml catalyst slurries of nitrogen protection, 10ml comonomer 1- hexenes are added, 75 DEG C are warmed up to,
Ethylene is passed through to the polymerization pressure 0.8Mpa for setting, starts polyreaction.Polymerization pressure is led to by mass flowmenter and pressure transducer
Cross control system and keep constant, polymerization temperature adjusts on-line heating device and water circulating pump by control system by combination type water-bath and carries out
Control.After polymerization starts timing, constant temperature and pressure reacts 1 hour.Polyreaction cools after terminating discharging, weighs, calculates
Activity, test polyvinyl resin performance.
Second：Gas-phase polymerization mode according to the first carries out hydrogen and adjusts aggregation test, except that in gas-phase polymerization processes
Add hydrogen 0.004MPa.
Embodiment 9
955 silica gel of inorganic carrier Davison is immersed in the hexane solution of tetra-n-butyl titanate (titanium load capacity is 2wt%),
After continuous stirring 4h, 80 DEG C of oil bath is dried 4h, and the solvent in silica-gel carrier duct is then further removed using vacuum drying 2h,
It is transferred in air dry oven 80 DEG C and is dried 8h；Then dried sample is carried out into calcination activation, Gao Chunkong in fluid bed
The lower 500 DEG C of insulations 6h of gas, silica gel finally Temperature fall cooling under a nitrogen, obtains titania modified silica gel obtained in infusion process.
0.11g ammonium metavanadates are dissolved in at 60 DEG C in 36ml distilled water (vanadium load capacity is 0.30wt%), then by 20g silicon
Glue is immersed in ammonium metavanadate solution, and 1h is impregnated at 60 DEG C makes active component uniform adsorption in above-mentioned titanium dioxide silica gel micropore
In, whole process belongs to physical adsorption process.Roasting, roasting are carried out during fluid bed is transferred to after 20h is dried at 120 DEG C
Cheng Shouxian 100 DEG C of low-temperature bakes in nitrogen are incubated 3h, 600 DEG C of insulation 4h in high pure air, then Temperature fall under a nitrogen
Cooling.Using normal hexane as solvent, diethylaluminium ethoxide is added to be reduced, Al/V mol ratios are 12: 1, reduce 30min.
Then heat to 70 DEG C and be dried 4h, obtain the preferable vfanadium compound catalyst of mobility standby.
955 silica gel of Davison is selected as inorganic carrier；Toluene 20ml is added, is stirred, add 5ml MAO, then
Add Cp2ZrCl2Toluene solution, Al/Zr mol ratios are 120: 1, and after stirring 4h, washing is dried to obtain metallocene catalyst.
By above-mentioned catalyst with V/Zr mol ratios 1:1 carries out dry powder blend, and catalyst is obtained.
Weighing above-mentioned three kinds of catalyst carries out gas-phase polymerization test.First by 1L vapor phase polymerizers through heating, evacuation and high-purity
Nitrogen treatment 4h, the catalyst of above-mentioned preparation weigh 0.1g or so and add polymeric kettle under high pure nitrogen protection, and kettle temperature is raised to
, vinyl monomer is slowly added to reaction pressure 0.8Mpa, start polyreaction, and keep pressure and temperature in polymeric kettle permanent by 92 DEG C
It is fixed.Response time is 1h.Polyreaction cools after terminating discharging, weighs, calculates activity, test polyvinyl resin performance.
Comparative example 1
Gas-phase polymerization side of the catalyst containing low-oxidation-state barium oxide of the prereduction in selection embodiment 1 according to embodiment 1
Formula carries out aggregation test.
Comparative example 2
Metallocene catalyst in selection embodiment 1 carries out aggregation test according to the gas-phase polymerization mode of embodiment 1.
Table 1 is the catalysis activity and gather that embodiment 1-1 carries out that to embodiment 1-4 different composite comparison catalysts gas-phase polymerization obtains
Close product GPC test results.As a result show that vanadium/zirconium ratio is bigger, average weight-molecular mass is higher, and profile exponent is wider.
But after the increase to a certain extent of vanadium ratio, activity decreases.
Polymerization catalyst and product GPC result of 1 embodiment 1-1 of table to embodiment 1-4 different composite ratio
Table 2 is the catalyst gas-phase polymerization result under the conditions of 3 difference Al/V of embodiment 2- embodiment.As a result Al/V ratios are shown
Bigger, activity is reduced, and average weight-molecular mass is raised, and profile exponent broadens.
2 embodiment 2- embodiment of table, 3 difference Al/V is than polymerization catalyst and product GPC results
Table 3 is the catalyst gas-phase polymerization product property result under the conditions of 5 different vanadium sources of embodiment 4- embodiment.
3 embodiment 4- embodiment of table, 5 different vanadium source catalyst gas-phase polymerization product properties
Table 4 is the catalyst gas-phase polymerization product property result under the conditions of 7 different metallocene catalysts of embodiment 6- embodiment.
4 embodiment 6- embodiment of table, 7 different metallocene catalyst gas-phase polymerization product properties
Table 5 is the catalysis activity and gather that embodiment 8-1 carries out that to the different composite comparison catalysts of embodiment 8-3 slurry polymerization obtains
Close product GPC test results.
Catalyst slurry polymerization and product test result of 5 embodiment 8-1 of table to the different composite ratio of embodiment 8-3
Table 6 is comparative example 1, comparative example 2 and embodiment 1-3 different type polymerization catalyst and product property test result.Show
Composite catalyst polymerization activity is higher than monometallic activity, and relative molecular mass distribution is most wide.
6 comparative example 1,2 of table and embodiment 1-3 different type polymerization catalyst and product property test result
Table 7 is embodiment 9, the test result that embodiment 8 obtains second polymerization test, second polymerization of embodiment 1-1 is tested,
Be through titanium be modified catalyst homopolymerization and hydrogen debugging test and unmodified catalyst hydrogen adjusting data.
7 embodiment 9 of table, embodiment 8 obtain the test result of second polymerization test of second polymerization test and embodiment 1-1
Found out by 7 data of table, the catalyst molecule amount being modified through titanium decreases, after adding hydrogen, molecular distribution narrows,
More narrower than unmodified catalyst distribution under the conditions of same added hydrogen, molecular weight is lower, shows more sensitive to hydrogen.
Claims (10)
1. a kind of vanadium and metallocene bimetallic catalyst, it is characterised in that the catalyst includes the activearm of inorganic carrier and load
Point, inorganic carrier is inorganic oxide, and active component is barium oxide and metallocene compositionss.
2. vanadium according to claim 1 and metallocene bimetallic catalyst, it is characterised in that barium oxide is low-oxidation-state
Barium oxide；Inorganic carrier is the particulate inorganic oxide of porous, and the specific surface area of inorganic carrier is 50～500m2/ g, nothing
The pore volume of airborne body is 0.1～5.0cm3/g；Metallocene is one or more of luxuriant zirconium metal, luxuriant hafnium metal or metallocene-titanium metal；
Barium oxide presoma is hexafluoro ammonium vanadate, nitric acid vanadium, vanadyl oxalate, ammonium metavanadate, vanadium oxysulfate, the hydration of sulfuric acid oxidation vanadium
Thing, Sulfovanadic acid, three chloro vanadium oxides, vanadic acid sodium, sodium metavanadate, bis-acetylacetonate vanadium oxide, Triisopropoxyvanadium(V) oxide, 3 third
One or more in alcohol vanadium oxide, vanadium acetylacetonate, oxidation triethoxy vanadium, three vanadium of divanadyl tetrachloride or silication；Barium oxide
Presoma in, vanadium load capacity for total catalyst weight 0.01～10wt%, in terms of the weight of vanadium.
3. vanadium described in a kind of claim 1 and the preparation method of metallocene bimetallic catalyst, it is characterised in that including following
Step：
(1) barium oxide presoma is attached on inorganic carrier to obtain a kind of catalyst precarsor；
(2) gained catalyst precarsor is carried out barium oxide that high-temperature roasting obtains oxidation state under oxidative conditions；
(3) sample is reacted under the reducing conditions, is obtained the barium oxide of the low-oxidation-state of prereduction；
(4) will be the barium oxide of the low-oxidation-state of prereduction enterprising in inorganic carrier with metallocene compositionss or metallocene compositionss
Catalyst contact after row load obtains final load-type vanadium/metallocene composite polyethylene catalyst.
4. the preparation method of vanadium according to claim 1 and metallocene bimetallic catalyst, it is characterised in that above-mentioned steps
(1) in, inorganic carrier is any oxide of the IIth A, III B, IV B, I B, II B, III A and IV A races metal.
5. vanadium according to claim 1 or 4 and the preparation method of metallocene bimetallic catalyst, it is characterised in that inorganic
Carrier is silicon dioxide, aluminium sesquioxide, titanium dioxide, zirconium oxide, magnesium oxide, calcium oxide, silica gel or inorganic clay.
6. the preparation method of vanadium according to claim 1 and metallocene bimetallic catalyst, it is characterised in that inorganic carrier
For titania modified inorganic carrier；Prepare titania modified inorganic carrier titanium compound raw material be acetylacetone,2,4-pentanedione oxygen titanium, three
Titanium chloride, titanium tetrachloride, tert-butyl alcohol titanium, tetra-n-butyl titanate, titanyl sulfate, titanium sulfate, ammonium hexa-fluorotitanate, metatitanic acid isopropyl
One or more in ester or tetraethyl titanate.
7. the preparation method of vanadium according to claim 1 and metallocene bimetallic catalyst, it is characterised in that step (2)
High temperature roasting is divided into two stages of cold stage and hot stage to be carried out, and cold stage is carried out at 100～300 DEG C, hot stage
Carry out at 300～900 DEG C；Cold stage continues 1～10 hour, and hot stage continues 1～10 hour.
8. the preparation method of vanadium according to claim 7 and metallocene bimetallic catalyst, it is characterised in that the low temperature
Stage is carried out under noble gases or air atmosphere；The hot stage roasting is carried out under air or Oxygen Condition.
9. the preparation method of vanadium according to claim 7 and metallocene bimetallic catalyst, it is characterised in that roast in high temperature
When 300～400 DEG C of temperature is cooled to after burning, atmosphere is converted, is changed into noble gases from air.
10. the preparation method of vanadium according to claim 7 and metallocene bimetallic catalyst, it is characterised in that step (3)
Middle reducing agent be trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride,
In dibutyl aluminum chloride, dibutyl aluminum bromide, diethylaluminium ethoxide, MAO, ethylaluminoxane, butyla-luminoxane
One or more；Reducing agent use ratio control Al/V mol ratios be 1～100: 1, add the reducing agent recovery time be
1min～4h.
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| CN110878130A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Supported chromium and metallocene bimetallic catalyst, preparation method and application thereof |
| CN116212852A (en) * | 2023-03-10 | 2023-06-06 | 青岛科技大学 | A kind of vanadium catalyst and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1564830A (en) * | 2001-09-11 | 2005-01-12 | 埃克森美孚化学专利公司 | Method for preparing polyolefins |
| CN102627710A (en) * | 2012-04-16 | 2012-08-08 | 华东理工大学 | Preparation method and application of novel supported double-center composite polyethylene catalyst |
| CN106554440A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | For preparing the catalyst of polyvinyl resin and its polyvinyl resin of preparation |
-
2015
- 2015-10-15 CN CN201510665759.6A patent/CN106589178B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1564830A (en) * | 2001-09-11 | 2005-01-12 | 埃克森美孚化学专利公司 | Method for preparing polyolefins |
| CN102627710A (en) * | 2012-04-16 | 2012-08-08 | 华东理工大学 | Preparation method and application of novel supported double-center composite polyethylene catalyst |
| CN106554440A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | For preparing the catalyst of polyvinyl resin and its polyvinyl resin of preparation |
Non-Patent Citations (1)
| Title |
|---|
| 黄仲涛: "《工业催化剂手册》", 30 October 2004 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878130A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Supported chromium and metallocene bimetallic catalyst, preparation method and application thereof |
| CN110878130B (en) * | 2018-09-06 | 2023-04-07 | 中国石油化工股份有限公司 | Supported chromium and metallocene bimetallic catalyst, preparation method and application thereof |
| CN116212852A (en) * | 2023-03-10 | 2023-06-06 | 青岛科技大学 | A kind of vanadium catalyst and its preparation method and application |
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