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CN108203476A - Supported polyethylene catalyst and preparation method thereof - Google Patents

Supported polyethylene catalyst and preparation method thereof Download PDF

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Publication number
CN108203476A
CN108203476A CN201611187535.XA CN201611187535A CN108203476A CN 108203476 A CN108203476 A CN 108203476A CN 201611187535 A CN201611187535 A CN 201611187535A CN 108203476 A CN108203476 A CN 108203476A
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China
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support type
organic
chromium
catalyst
type polyethylene
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Inventor
李冬霞
王文燕
张瑞
杨琦
高宇新
宋磊
王立娟
杨国兴
王�华
赵兴龙
任鹤
孙彬彬
王斯晗
姜进宪
和树立
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Petrochina Co Ltd
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Petrochina Co Ltd
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Publication of CN108203476A publication Critical patent/CN108203476A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02Ethene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention relates to a supported polyethylene catalyst, which comprises a porous inorganic carrier and active components, wherein the active components are an organic chromium source, an inorganic chromium source and an organic molybdenum source; the total load of Cr and Mo in the active component is 0.01-20 wt% of the total weight of the catalyst; the molar ratio of Cr to Mo is 0.01: 0.99-0.99: 0.01; the molar ratio of the organic chromium source to Cr in the inorganic chromium source is 1: 9-9: 1. The invention also relates to a preparation method of the supported polyethylene catalyst. In the catalyst, the active site of Mo can improve the loading of the organic chromium source of the catalyst, and improve the content of the polyethylene polymerization monomer and the distribution uniformity of the comonomer.

Description

A kind of support type polyethylene catalysts and preparation method thereof
Technical field
The present invention relates to a kind of support type polyethylene catalysts and preparation method thereof, and specifically a kind of support type contains chrome molybdenum Polyethylene catalysts and preparation method thereof.
Background technology
An important kind of the chromium-based catalysts as ethylene rolymerization catalyst, earliest applied in the production of polyethylene. From initial in silica gel (SiO2) or silica gel-aluminium oxide (SiO2-Al2O3) on supported chromium research success so far, It has been discovered that the activation method after the preparation method of silica gel and load chromium-based catalysts can change the average molecular matter of product It measures (hereinafter referred to as molecular weight).Supported chrome series catalysts are had been widely used in solwution method, slurry process, vapor phase method PE production works In skill.The Hogan and Banks of Phillips companies are found that ethylene polymerization CrO in nineteen fifty-one3/SiO2Catalyst, Unide- Carbide companies develop foremost Cp on the basis of Phillips companies2Cr type catalyst is urged so as to start chromium system A very important field of the agent as ethylene rolymerization catalyst.
USP2825721 is being sent out about Chromium-polyethylencatalyst catalyst for Phillips oil companies first acquisition in 1958 Bright patent, which, which reports for the first time after chromium oxide is supported on silica gel or alumina carrier surface, has very high vinyl polymerization Activity, the patent realized industrialization production high density polyethylene (HDPE) by Phillips oil companies later, gathered for its what slurry endless tube Ethylene process, the load chromium content of catalyst is 1% (weight percent).By the development of more than 50 years, carried out series modification and It improves, has shared 600 multinomial patents (Phillips oil companies possess wherein 300 multinomial patents) so far, wherein so far should There is titanium to be modified with wider patented technology and be modified Phillips chromium-based catalysts patented technologies with aluminium.
USP4049896 describes a kind of aluminium and is modified Phillips chromium-based catalysts patented technologies, by USI/Equistar public affairs Department reported first in 1977, mainly by introducing Metal aluminum salt in catalyst preparation process (during roast finally It is converted into aluminium oxide) Phillips chromium-based catalysts are modified, aluminium modification can improve polymerization catalyst activity, reduce and gather Adduct molecule amount is so as to enhance Molecular weight regulation means, broadening molecular weight distribution to improve processing performance and the physical property of product, enhancing Polymer anti-stress cracking intensity etc..Relevant improvement patent has USP4052544 etc..
USP3780011 describes a kind of titanium and is modified Phillips chromium-based catalysts patented technologies, the technology by Chemplex/Equistar companies reported first in 1971, mainly by introducing Titanium in catalyst preparation process Salt (titanium oxide is eventually converted into during roast) is modified Phillips chromium-based catalysts, and titanium modification can be improved and be urged Agent polymerization activity, reduction polymer molecular weight are processed so as to enhance Molecular weight regulation means, broadening molecular weight distribution with improving Performance and the physical property of product, enhancing polymer anti-stress cracking intensity and die swell etc..Relevant improvement patent has USP4053436 etc..
EP563274 describes a kind of fluorine richness chromium-based catalysts technology, and inorganic fluorine is to be added to chromium oxide before activation to urge In agent.Add in inorganic fluorine (such as HF, (NH4)2SiF6, (NH4)3BF6Deng), thus it is possible to vary the hydrogen tune of chromium oxide catalyst is sensitive Property, obtain the HDPE products of Narrow Molecular Weight Distribution.The chromium oxide catalyst of dipping titanium is further improved with fluorine, it is single that copolymerization can be improved The addition rate of body, improves the copolymerization performance of polymer, and with the increase of fluorine content, the low molecular weight part of copolymer and molten Melting index reduces.Fluorine is because fluorine reacts release water outlet with surface silanol groups to the facilitation of chrome catalysts, forms surface Si-F keys.Find out from CO low temperature infrared spectrograms, fluorine processing reduces the cloud density of chromium atom, changes active sites Distribution, so as to improve the physical property of PE products.
USP5032651 describes a kind of method, and the compounding of zirconium metallocene catalyst and chromium-containing catalyst, which has been synthesized, to be had The polyvinyl resin of high rigidity, good environmental stress crack resistance, this resin are particularly suitable for production film-grade product.
CN1350007A describes Cr catalysts for ethylene polymerization that a kind of nickel is modified and preparation method thereof, prepared by this method Catalyst have high polymerization activity and preferable copolymerization performance, the polymer produced have higher molecular weight.
CN1296020A describes a kind of titanium, Cr catalysts for ethylene polymerization that nickel is modified and preparation method thereof, this method The catalyst of preparation has high polymerization activity and preferable copolymerization performance, and the polymer produced has higher melt flows speed Rate and wider molecular weight distribution, after overactivation, already oxidised object form exists for described chromium, nickel, titanium.
CN1858072 describes carrier type chromium-series catalyst that a kind of titanium is modified and preparation method thereof, the catalyst Carrier is silica gel, and titanium compound and chromium compound are supported on the silica-gel carrier, and catalyst hydrogen tune ability obtained is strong, can be used for High fusion index polymer is produced, polymeric shear response (HLMI/MI ratios) is low, is suitable for production for manufacturing film and tubing Wide molecular weight distribution Alathon and copolymer.
The present invention contains for a kind of support type there are two types of chromium source and a kind of polyethylene catalysts of organic molybdenum source, using this method Catalyst copolymerization performance can be improved, there is presently no the relevant reports using this method.
Invention content
The object of the present invention is to provide a kind of support type polyethylene catalysts and preparation method thereof, are prepared using the present invention The characteristics of active central negative carrying capacity of catalyst is high, and catalyst copolymerization performance is good.
In order to achieve the above objectives, the present invention provides a kind of support type polyethylene catalysts, including porous inorganic carrier and work Property component, the active component be Organic Chromium source, inorganic chromium source and organic molybdenum source;The total load of Cr, Mo in the active component Measure 0.01wt%~20wt% for the total catalyst weight, preferably 0.05wt%~15wt%, more preferable 0.1wt%~ 10wt%;The molar ratio of Cr, Mo are 0.01:0.99~0.99:0.01, preferably 0.25:0.75~0.75:0.25, more preferably 0.4:0.6~0.6:0.4;The molar ratio of the Organic Chromium source and Cr in the inorganic chromium source are 1:9~9:1, preferably 2:8~8: 2, more preferable 3:6~6:3.
Support type polyethylene catalysts of the present invention, wherein, the inorganic chromium source is preferably chromium trioxide, nitric acid At least one of chromium, chromic acetate, chromium chloride, chromium sulfate, ammonium chromate, ammonium dichromate and alkali formula chromic acetate.
Support type polyethylene catalysts of the present invention, wherein, the Organic Chromium source is preferably selected from double-triphenyl first silicon Alkyl chromate, two luxuriant at least one of chromium and organosilan chromate.
Support type polyethylene catalysts of the present invention, wherein, organic molybdenum source is preferably dialkyl dithio phosphorus Sour oxygen molybdenum, nitrogenous dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, molybdenum amine complex, molybdenum naphthenate and At least one of alkyl salicylate molybdenum.
Support type polyethylene catalysts of the present invention, wherein, the Organic Chromium source is preferably using organic calorize Close the Organic Chromium of object processing.
Support type polyethylene catalysts of the present invention, wherein, organic molybdenum source is preferably using organic calorize Close the organic-molybdenum of object processing.
Support type polyethylene catalysts of the present invention, these, it is preferred to, the organo-aluminum compound is alkyl aluminum Compound, and meet general formula R1-Al-OR2, in formula, R1And R2It is identical or different, it is independently the alkyl of C1~12.It is more excellent Organo-aluminum compound is selected as triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, triisopropylaluminiuand, methyl diethyl aluminum, trimethyl Aluminium, ethoxide (DEAlE), methoxylation diethyl aluminum, ethoxyquin dimethyl aluminium, ethoxyquin diisopropyl aluminium, the third oxygen Change one kind in diethyl aluminum, ethoxyquin diisobutyl aluminum and ethoxylated methyl aluminium ethide.
Support type polyethylene catalysts of the present invention, these, it is preferred to, the porous inorganic carrier is by changing Property inorganic carrier obtains.
Support type polyethylene catalysts of the present invention, wherein, the inorganic carrier is preferably selected from silica, three oxygen Change at least one of two aluminium, titanium dioxide, zirconium oxide, magnesia, calcium oxide, inorganic clay and montmorillonite.
Support type polyethylene catalysts of the present invention, wherein, the average grain diameter of the inorganic carrier is preferably 1 micron ~100 microns, more preferable 20 microns~80 microns;Pore volume is preferably 0.5cm3/ g~10.0cm3/ g, more preferable 2cm3/ g~ 8.0cm3/g;Surface area is preferably 50m2/ g~1000m2/ g, more preferable 200m2/ g~700m2/g。
Support type polyethylene catalysts of the present invention, wherein, the modification is preferably that aluminium is modified:Using aluminum salt solution The inorganic carrier is impregnated, the aluminium salt is selected from Al (NO3)3、AlC13And Al2(SO4)3In one kind.
Support type polyethylene catalysts of the present invention, wherein, the modification is preferably that titanium is modified, using infusion process or Cogel methods are modified.
Support type polyethylene catalysts of the present invention, wherein, the modification is preferably fluorine richness:The inorganic carrier With fluorine component co-impregnation.
The present invention also provides a kind of preparation methods of support type polyethylene catalysts, are that above-mentioned support type polyethylene is urged The preparation method of agent, includes the following steps:
(1) porous inorganic carrier is immersed in the aqueous solution containing inorganic chromate salt, dip time 1-12h, dipping temperature It it is 25-100 DEG C, then the dry 5-20h at 100-300 DEG C, 1-12h is roasted in 300 DEG C of -1000 DEG C of air atmospheres;
(2) step (1) products therefrom is immersed in the organic solution of Organic Chromium source and organic molybdenum source, dip time 1- 12h, dipping temperature are 25-100 DEG C, then dry 5-20h in nitrogen atmosphere between 100-300 DEG C, finally obtain support type Polyethylene catalysts.
Support type polyethylene catalysts preparation method of the present invention, it is organic in the organic solution in step (2) Solvent is preferably ethyl alcohol, propyl alcohol, butanol, octanol, ethylene glycol, propylene glycol, butanediol, ethohexadiol, pentane, hexane, heptane, pungent The isomer of alkane, benzene,toluene,xylene or substance described above.
Porous inorganic carrier of the present invention be modified the specific steps are:
The Al is modified, and gel method may be used and prepare Al2O3Modified inorganic carrier can also use aluminum salt solution to impregnate The Al that inorganic carrier can also be realized2O3Modified, aluminum salt solution is selected from Al (NO3)3、AlC13And Al2(SO4)4At least one of. The suitable condition of its modified inorganic carrier process is:Aluminium salt is made into aqueous solution, a concentration of 10wt%~25wt% adds diluted acid tune PH to 1~1.8 is warming up to 40 DEG C~60 DEG C, adds in SiO2, the lower dipping 12h of strong stirring~for 24 hours, then with distilled water flushing extremely PH is 7, and drying, roasting obtain Al2O3Modified porous inorganic carrier;
The porous inorganic carrier that the titanium is modified can be prepared by infusion process or Cogel methods.Infusion process, Ji Jiangwu Airborne body is immersed in titanate esters or TiC14Organic solution in, titanate esters or TiC14Pass through the hydroxyl with carrier surface Learning reaction makes titanium be supported on carrier surface, and titanium modified carrier is prepared later using calcination.Usual hydrocarbon, which is used as, to be had Solvent, such as hexane or heptane.Cogel methods are that soluble titanium salt is dissolved in silicate, such as sodium metasilicate, improve solution PH value can form carrier and TiO2It is cogelled, estersil and titanium esters can also be dissolved in alcohol or acetone, added a small amount of Water prepares carrier and TiO2It is cogelled;
The porous inorganic carrier of the fluorine richness, the introducing of fluorine component can be prepared by the method for dipping, will be inorganic Carrier impregnation is to (NH4)2SiF6In solution, (NH4)2SiF6A concentration of 1%~10% molar fraction.
Support type polyethylene catalysts of the present invention, for producing Alathon and ethylene and alpha-olefin copolymer Object, the alpha-olefin are any one or more in 1- propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes and 1- decene.
The beneficial effects of the invention are as follows:The support type polyethylene catalysts of the present invention, it is same on same porous inorganic carrier The Mo active sites of the Cr active sites and organic molybdenum source in Shi Hanyou Organic Chromiums source and inorganic chromium source;Mo active sites can improve catalyst Active metal loading improves polyethylene polymerization content of monomer and comonomer distribution uniformity.
Specific embodiment
Following example is method in order to further illustrate the present invention, but be should not be limited thereto.
Evaluating catalyst mode is as follows in the present invention:It weighs composite catalyst 200mg and carries out polymerization experiment.In advance to polymerization Reaction kettle carries out heating in vacuum (100 DEG C), is then replaced into high pure nitrogen, operates three times repeatedly, then is put with a small amount of monomer ethylene It changes once, ethylene will be finally full of in reaction kettle to micro-positive pressure (0.15MPa).Polymerization temperature is controlled at 90 DEG C.Into reaction kettle 150mL or so dehydration and deoxidations are sequentially added treated refined heptane as solvent, add in organo-aluminum compound as co-catalysis Agent, cocatalyst concentration are 1.82mmol/mL (hexane solution), and dosage 0.30mL is eventually adding composite catalyst and starts Polymerisation.The instantaneous consumption of online acquisition monomer ethylene is (by the high-accuracy ethylene matter for connecting computer in reaction process Measure flowmeter) and by computer record.After 90 DEG C of reactions carry out 1 hour, add in hydrochloric acid/alcohol mixed solution and terminate reaction, gather Close simultaneously analysis product performance of weighing after object is dried in vacuo.
Embodiment 1:
Inorganic carrier silica, average grain diameter are 58 microns, pore volume 4.7cm3/ g, surface area 255m2/ g, is adopted Al is prepared with gel method2O3It is modified to obtain porous inorganic carrier.Modified silica is immersed to the aqueous solution of chromium oxide In, dip time 8h, dipping temperature is 65 DEG C, and then the dry 10h at 150 DEG C, 8h is roasted in 550 DEG C of air atmospheres; Products therefrom is immersed in the ethylene glycol solution containing two luxuriant chromium and dialkyl dithiophosphoric acid oxygen molybdenum, dip time 7h, Dipping temperature is 55 DEG C, then the dry 5-20h in 200 DEG C of nitrogen atmospheres.Measure the total of Cr, Mo metal on porous inorganic carrier Load capacity is the 8.5wt% of total catalyst weight, and the molar ratio of Cr, Mo are 0.88:0.12, Cr in inorganic chromium source and Organic Chromium source Molar ratio be 8:2.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisobutyl aluminium, polymerized monomer 1- fourths Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 4.7g/10min (5Kg counterweights), density 0.9480g/ 10min。
Embodiment 2:
Inorganic carrier magnesia, average grain diameter are 15 microns, pore volume 9.1cm3/ g, surface area 270m2/ g, passes through Titanium is modified to obtain porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of chromium sulfate, dip time 6h, dipping temperature It is 45 DEG C to spend, and then the dry 15h at 180 DEG C, 4h is roasted in 450 DEG C of air atmospheres;Products therefrom is immersed in containing two In the ethohexadiol solution of luxuriant chromium and molybdenum dialkyldithiocarbamacompositions, dip time 4h, dipping temperature is 80 DEG C, Ran Hou Dry 18h in 190 DEG C of nitrogen atmospheres.The total load amount for measuring Cr, Mo metal on porous inorganic carrier is total catalyst weight The molar ratio of 4.2wt%, Cr, Mo are 0.42:0.58, the molar ratio of Cr is 4 in inorganic chromium source and Organic Chromium source:6.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- penta Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 1.2g/10min (5Kg counterweights), density 0.9487g/ 10min。
Embodiment 3:
Inorganic carrier titanium dioxide, average grain diameter are 2 microns, pore volume 7.7cm3/ g, surface area 350m2/ g, passes through Aluminium is modified to obtain porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of ammonium dichromate, dip time 4h, dipping Temperature is 70 DEG C, and then the dry 9h at 240 DEG C, 12h is roasted in 600 DEG C of air atmospheres;By products therefrom be immersed in containing In the n-heptane solution of organosilan chromate and molybdenum amine complex, dip time 7h, dipping temperature is 70 DEG C, then 230 Dry 20h in DEG C nitrogen atmosphere.The total load amount for measuring Cr, Mo metal on porous inorganic carrier is total catalyst weight The molar ratio of 3.8wt%, Cr, Mo are 0.23:0.77, the molar ratio of Cr is 2 in inorganic chromium source and Organic Chromium source:8.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- oneself Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 3.5g/10min (5Kg counterweights), density 0.9459g/ 10min。
Embodiment 4:
Inorganic carrier montmorillonite, average grain diameter are 77 microns, pore volume 4.9cm3/ g, surface area 600m2/ g, passes through Fluorine richness obtains porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of chromium trioxide, dip time 10h, leaching Stain temperature is 55 DEG C, and then the dry 13h at 160 DEG C, 1h is roasted in 350 DEG C of air atmospheres;Products therefrom is immersed in and is contained In the toluene solution for having double-triphenyl silylchromate and nitrogenous dialkyl dithiophosphoric acid oxygen molybdenum, dip time 3h, Dipping temperature is 55 DEG C, then the dry 14h in 170 DEG C of nitrogen atmospheres.The total of Cr, Mo metal on porous inorganic carrier is measured to bear Carrying capacity is the 0.1wt% of total catalyst weight, and the molar ratio of Cr, Mo are 0.35:0.65, Cr in inorganic chromium source and Organic Chromium source Molar ratio is 8:2.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, the polymerized monomer 1- last of the ten Heavenly stems Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 9.2g/10min (5Kg counterweights), density 0.9481g/ 10min。
Embodiment 5:
Inorganic carrier calcium oxide, average grain diameter are 41 microns, pore volume 1.3cm3/ g, surface area 240m2/ g, passes through Fluorine richness obtains porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of chromium chloride, dip time 1h, dipping temperature It is 90 DEG C to spend, and then the dry 18h at 200 DEG C, 8h is roasted in 450 DEG C of air atmospheres;Products therefrom is immersed in containing having In the octanol solution of machine silane chromate ester and molybdenum dialkyldithiocarbamacompositions, dip time 12h, dipping temperature 35 DEG C, 17h is then dried in 270 DEG C of nitrogen atmospheres.The total load amount for measuring Cr, Mo metal on inorganic carrier is overall catalyst weight The molar ratio of the 20wt% of amount, Cr, Mo are 0.29:0.71, the molar ratio of Cr is 7 in inorganic chromium source and Organic Chromium source:3.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- fourths Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 8.7g/10min (5Kg counterweights), density 0.9421g/ 10min。
Embodiment 6:
Inorganic carrier inorganic clay, average grain diameter are 99 microns, pore volume 6.5cm3/ g, surface area 100m2/ g leads to Cross aluminium be modified it is porous.Porous inorganic carrier is immersed in the aqueous solution of ammonium chromate, dip time 3h, dipping temperature is 35 DEG C, then the dry 7h at 120 DEG C, 6h is roasted in 550 DEG C of air atmospheres;Products therefrom is immersed in containing two luxuriant chromium and In the propanol solution of molybdenum naphthenate, dip time 6h, dipping temperature is 50 DEG C, then dry in 150 DEG C of nitrogen atmospheres 12h.The total load amount for measuring Cr, Mo metal on inorganic carrier is the 13.1wt% of total catalyst weight, and the molar ratio of Cr, Mo are 0.51:0.49, the molar ratio of Cr is 1 in inorganic chromium source and Organic Chromium source:9.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- fourths Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 5.2g/10min (5Kg counterweights), density 0.9512g/ 10min。
Embodiment 7:
Inorganic carrier zirconium oxide, average grain diameter are 83 microns, pore volume 5.1cm3/ g, surface area 180m2/ g, passes through Aluminium is modified to obtain porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of alkali formula chromic acetate, dip time 2h, leaching Stain temperature is 100 DEG C, and then the dry 16h at 220 DEG C, 10h is roasted in 400 DEG C of air atmospheres;Products therefrom is immersed in In hexane solution containing double-triphenyl silylchromate and nitrogenous dialkyl dithiophosphoric acid oxygen molybdenum, dip time is 4h, dipping temperature are 65 DEG C, then the dry 2h in 210 DEG C of nitrogen atmospheres.Measure the total of Cr, Mo metal on porous inorganic carrier Load capacity is the 1.9wt% of total catalyst weight, and the molar ratio of Cr, Mo are 0.15:0.85, Cr in inorganic chromium source and Organic Chromium source Molar ratio be 5:5.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- penta Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 3.8g/10min (5Kg counterweights), density 0.9452g/ 10min。
Embodiment 8:
Inorganic carrier alundum (Al2O3), average grain diameter are 60 microns, pore volume 3.7cm3/ g, surface area 1000m2/ g, It is modified to obtain porous inorganic carrier by titanium.Porous inorganic carrier is immersed in the aqueous solution of chromic nitrate, dip time 12h, Dipping temperature is 25 DEG C, and then the dry 5h at 100 DEG C, 4h is roasted in 800 DEG C of air atmospheres;Products therefrom is immersed in and is contained In the octane solution for having double-triphenyl silylchromate and alkyl salicylate molybdenum, dip time 2h, dipping temperature 80 DEG C, 11h is then dried in 100 DEG C of nitrogen atmospheres.The total load amount of Cr, Mo metal on porous inorganic carrier is measured using ICP For the 4.1wt% of total catalyst weight, the molar ratio of Cr, Mo are 0.41:0.59, mole of Cr in inorganic chromium source and Organic Chromium source Than being 6:4.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- third Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 2.7g/10min (5Kg counterweights), density 0.9439g/ 10min。
Embodiment 9:
Inorganic carrier magnesia, average grain diameter are 35 microns, pore volume 0.5cm3/ g, surface area 50m2/ g, passes through titanium Modification obtains porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of chromic acetate, dip time 11h, dipping temperature It is 45 DEG C to spend, and then the dry 2h at 300 DEG C, 3h is roasted in 1000 DEG C of air atmospheres;Products therefrom is immersed in containing two In the octane solution of luxuriant chromium and dialkyl dithiophosphoric acid oxygen molybdenum, dip time 1h, dipping temperature is 30 DEG C, then 300 Dry 1h in DEG C nitrogen atmosphere.The total load amount for measuring Cr, Mo metal on porous inorganic carrier is total catalyst weight The molar ratio of 17.3wt%, Cr, Mo are 0.68:0.32, the molar ratio of Cr is 3 in inorganic chromium source and Organic Chromium source:7.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- fourths Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 0.9g/10min (5Kg counterweights), density 0.9508g/ 10min。
Embodiment 10:
Inorganic carrier calcium oxide, average grain diameter are 55 microns, pore volume 10.0cm3/ g, surface area 680m2/ g, passes through Titanium is modified to obtain porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of chromium sulfate, dip time 7h, dipping temperature It is 80 DEG C to spend, and then the dry 11h at 260 DEG C, 9h is roasted in 300 DEG C of air atmospheres;Products therefrom is immersed in containing two In the benzole soln of luxuriant chromium and molybdenum naphthenate, dip time 5h, dipping temperature is 40 DEG C, is then done in 190 DEG C of nitrogen atmospheres Dry 13h.The total load amount for measuring Cr, Mo metal on porous inorganic carrier is the 12.4wt% of total catalyst weight, and Cr, Mo's rubs You are than being 0.19:0.81, the molar ratio of Cr is 4 in inorganic chromium source and Organic Chromium source:6.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- oneself Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 7.7g/10min (5Kg counterweights), density 0.9438g/ 10min。
Comparative example 1:
Inorganic carrier silica, average grain diameter are 58 microns, pore volume 4.7cm3/ g, surface area 255m2/ g, is adopted Al is prepared with gel method2O3It is modified.Modified silica is immersed in the aqueous solution of chromium oxide, dip time 8h, Dipping temperature is 65 DEG C, and then the dry 10h at 150 DEG C, 8h is roasted in 550 DEG C of air atmospheres;It measures modified inorganic The total load amount of Cr metals is the 8.5wt% of total catalyst weight on carrier.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisobutyl aluminium, polymerized monomer 1- fourths Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 4.9g/10min (5Kg counterweights), density 0.9502g/ 10min。
Embodiment 2:
Inorganic carrier magnesia, average grain diameter are 15 microns, pore volume 9.1cm3/ g, surface area 270m2/ g, passes through Titanium is modified to obtain porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of chromium sulfate, dip time 6h, dipping temperature It is 45 DEG C to spend, and then the dry 15h at 180 DEG C, 4h is roasted in 450 DEG C of air atmospheres.Measure Cr gold on porous inorganic carrier The load capacity of category is the 4.2wt% of total catalyst weight.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- penta Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 1.0g/10min (5Kg counterweights), density 0.9513g/ 10min。
Embodiment 3:
Inorganic carrier titanium dioxide, average grain diameter are 2 microns, pore volume 7.7cm3/ g, surface area 350m2/ g, passes through Aluminium is modified to obtain porous inorganic carrier.Porous inorganic carrier is immersed in the aqueous solution of ammonium dichromate, dip time 4h, dipping Temperature is 70 DEG C, and then the dry 9h at 240 DEG C, 12h is roasted in 600 DEG C of air atmospheres.Measure Cr on porous inorganic carrier Total load amount be total catalyst weight 3.8wt%.
Using evaluating catalyst mode analysis of catalyst, wherein, co-catalyst is triisopropylaluminiuand, polymerized monomer 1- oneself Alkene, the polyethylene product performance of preparation are as follows:Melt flow rate (MFR) is 3.5g/10min (5Kg counterweights), density 0.9472g/ 10min。
It can be seen from above example and comparative example under same activated centre load capacity, what the present invention developed The density of the polyethylene product of catalyst preparation is relatively low, illustrates that the content of polymerized monomer is higher, and the copolymerization performance of catalyst is good.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art It should all belong to the scope of protection of the present invention.

Claims (15)

1. a kind of support type polyethylene catalysts, which is characterized in that including porous inorganic carrier and active component, the activearm It is divided into Organic Chromium source, inorganic chromium source and organic molybdenum source;The total load amount of Cr, Mo are the overall catalyst weight in the active component 0.01wt%~20wt% of amount;The molar ratio of Cr, Mo are 0.01:0.99~0.99:0.01;The Organic Chromium source and the nothing The molar ratio of Cr is 1 in machine chromium source:9~9:1.
2. support type polyethylene catalysts according to claim 1, which is characterized in that the inorganic chromium source is three oxidations At least one of chromium, chromic nitrate, chromic acetate, chromium chloride, chromium sulfate, ammonium chromate, ammonium dichromate and alkali formula chromic acetate.
3. support type polyethylene catalysts according to claim 1, which is characterized in that the Organic Chromium source is selected from double-three Phenyl silyl groups chromate, two luxuriant at least one of chromium and organosilan chromate.
4. support type polyethylene catalysts according to claim 1, which is characterized in that organic molybdenum source is dialkyl group two D2EHDTPA oxygen molybdenum, nitrogenous dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, molybdenum amine complex, cycloalkanes At least one of sour molybdenum and alkyl salicylate molybdenum.
5. support type polyethylene catalysts according to claim 1, which is characterized in that the Organic Chromium source is using having The Organic Chromium of machine aluminium compound processing.
6. support type polyethylene catalysts according to claim 1, which is characterized in that organic molybdenum source is using having The organic-molybdenum of machine aluminium compound processing.
7. support type polyethylene catalysts according to claim 5 or 6, which is characterized in that the organo-aluminum compound is Alkyl aluminum compound, and meet general formula R1-Al-OR2, in formula, R1And R2It is identical or different, it is independently the alkane of C1~12 Base.
8. support type polyethylene catalysts according to claim 1, which is characterized in that the porous inorganic carrier is to pass through Modified inorganic carrier obtains.
9. support type polyethylene catalysts according to claim 8, which is characterized in that the inorganic carrier is selected from titanium dioxide At least one of silicon, alundum (Al2O3), titanium dioxide, zirconium oxide, magnesia, calcium oxide, inorganic clay and montmorillonite.
10. support type polyethylene catalysts according to claim 8, which is characterized in that the average grain of the inorganic carrier Diameter is 1 micron~100 microns, pore volume 0.5cm3/ g~10.0cm3/ g, surface area 50m2/ g~1000m2/g。
11. support type polyethylene catalysts according to claim 8, which is characterized in that described to be modified as aluminium modification:Using Aluminum salt solution impregnates the inorganic carrier, and the aluminium salt is selected from Al (NO3)3、AlC13And Al2(SO4)3In one kind.
12. support type polyethylene catalysts according to claim 8, which is characterized in that it is described to be modified as titanium modification, it uses Infusion process or Cogel methods are modified.
13. support type polyethylene catalysts according to claim 8, which is characterized in that described to be modified as fluorine richness:It is described Inorganic carrier and fluorine component co-impregnation.
14. a kind of preparation method of support type polyethylene catalysts is that claim 1-13 any one of them support types gather The preparation method of catalyst for ethylene, which is characterized in that include the following steps:
(1) porous inorganic carrier is immersed in the aqueous solution containing inorganic chromate salt, dip time 1-12h, dipping temperature 25- 100 DEG C, then the dry 5-20h at 100-300 DEG C, 1-12h is roasted in 300 DEG C of -1000 DEG C of air atmospheres;
(2) step (1) products therefrom is immersed in the organic solution of Organic Chromium source and organic molybdenum source, dip time 1-12h, Dipping temperature is 25-100 DEG C, then dries 5-20h in nitrogen atmosphere between 100-300 DEG C, finally obtains the poly- second of support type Alkene catalyst.
15. the preparation method of support type polyethylene catalysts according to claim 14, which is characterized in that in step (2), Organic solvent in the organic solution is ethyl alcohol, propyl alcohol, butanol, octanol, ethylene glycol, propylene glycol, butanediol, ethohexadiol, penta Alkane, hexane, heptane, octane, benzene,toluene,xylene or substance described above isomer.
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