CN102453154B - Organic chromium catalyst for ethylene polymerization and preparation method thereof - Google Patents
Organic chromium catalyst for ethylene polymerization and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides an organic chromium catalyst for ethylene polymerization and a preparation method thereof. The catalyst comprises a main active catalyst, an inorganic oxide carrier, a modifier and a cocatalyst, wherein the main active catalyst is a chromium salt, and the content of the main active catalyst in the catalyst is 0.01-5% by mass; technical requirements of the carrier inorganic oxide comprise that the surface area is about 200-700m<2>/g, the pore volume is about 1-4cc/g, the aperture is about 60-700 and the particle dimension is about 10-200mum; the modifier is a recovery liquid for the preparation of an alkylsilane chromate catalyst; and the cocatalyst is an alkyl compound of Al, Li, B and Zn. The organic chromium catalyst for the ethylene polymerization provided in the invention has the advantages of high activity, proper induction time, and suitableness of the production of wide molecular weight distribution range polyethylene products; and the preparation method provided in the invention has the advantages of simple synthetic technology and low preparation cost.
Description
Technical field
The present invention is a kind of ethylene polymerization organic chromium Catalysts and its preparation method.Belong to ethylene rolymerization catalyst.Be particularly related to loading type organic chromium catalyst for ethylene polymerization and preparation method thereof.
Background technology
Chromium-based catalysts is applied in the poly production the earliest as an important kind of ethylene rolymerization catalyst.From initial at silica gel (Si0
2) or silica gel-aluminum oxide (SiO
2-Al
2O
3) upward the research of supported chromium is successful so far, people have found the preparation method of silica gel and the relative molecular mass (being designated hereinafter simply as molecular weight) that the activation method behind the load chromium-based catalysts can change product.The supported chrome series catalysts has been widely used in solution method, slurry process, the vapor phase process PE production technique.The PE resin that chromium-based catalysts makes can make in slush molding fields such as bottle, jar that shape is complicated, the processing rotatory better, cut bad mouth and melting the thicker product of part, this is because this resin contains long-chain branch component and a small amount of ultra-high molecular weight (about 10
7) component, thereby make its processing characteristics more superior.
In the PE production process, traditional chromium oxide catalyst is owing to exist that induction time is long, the product melting index is low, copolymerization performance is poor, hydrogen is transferred shortcomings such as insensitive, thereby more and more can not satisfy in the application people to the products made thereby performance demands.For this reason, at 20th century the mid-1970s, UCC, chemical companies such as Phillips actively improve chromium-based catalysts.
USP2,825,721 disclosed loading type chromium oxide catalysts are chromium trioxide or at least can partial oxygen under the high temperature oxidation condition change into the compound of chromium trioxide, load to prepare on the silica gel in the aqueous solution.This catalyzer has overcome the shortcoming of active ingredient synthesis technique complexity, has reduced the catalyzer cost, but narrower with the product molecular weight distribution of this Preparation of Catalyst.
USP3,324,095 disclosed loading type silane chromate ester catalysts, carrier is an inorganic oxide, and active ingredient is the silane chromate ester, and promotor is a kind ofly to have at least 1 or be no more than 2 organo-aluminium compounds that are connected in the alkoxyl group on the aluminium atom; Molecular weight is higher, the extrusion molding level product of molecular weight distribution broad though this catalyzer can be used for preparing, and the synthesis technique complexity of this catalyst activity component costs an arm and a leg catalyzer.
Have high reactivity, certain induction time by the polyethylene catalysts of chromic oxide preparation, can produce polymkeric substance with high molecular and intermediate molecular weight distribution.Catalyst activity based on silyl chromate is lower, but can produce the polymkeric substance than wide molecular weight distribution.Silyl chromate Catalyst Production cost is higher than the chromium oxide catalyst price usually.
Summary of the invention
The objective of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of active height, induction time to suit, be applicable to the ethylene polymerization organic chromium catalyzer of the polyethylene product of producing the broad range of molecular weight distributions.
The present invention also aims to provide the ethylene polymerization organic chromium Preparation of catalysts method that a kind of synthesis technique is simple, manufacturing cost is lower.
Purpose of the present invention can reach by following measure:
Ethylene polymerization organic chromium catalyzer of the present invention comprises main body active catalyst, inorganic oxide carrier, properties-correcting agent and promotor, wherein:
A. described main body active catalyst is a chromic salts, and its content in the catalyzer total mass is 0.01-5%
The described carrier of B is that the technical requirements of inorganic oxide is:
A. surface-area is about 200-700m
2/ g;
B. pore volume is about 1-4cc/g;
C. the aperture is about 60-700
D. particle size is about 10-200 μ m;
C. described properties-correcting agent is that preparation alkyl silane chromate ester catalyst reclaims liquid;
D. described promotor is the alkylate of aluminium, lithium, boron, zinc.
Described chromic salts is selected from oxide compound, acetate, carboxylate salt, dichromate, the chromic salt of chromium.Can be one or more organic or inorganic chromic salts, wherein the oxidation valence state of chromium be 0-6.Chromic salts in the present invention also comprises chromium metal.Generally, the chemical formula of chromic salts is CrXn, and X can be with can be different in the formula, can be any organic or inorganic group, n be an integer, and its value is the typical organic radical of 1-6., each group can contain about 1-20 carbon atom, can be alkyl alkoxy, ester group, ketone group and/or amide group.Organic radical can be: straight chain base or contain the base of side chain, and cyclic group or acyclic radical, aryl or aliphatic group, and can constitute by blended aliphatic group, aryl and/or cyclic aliphatic base.Typical inorganic chromium compound has: the nitrate of the acetate of chromium, dichromate, chromic salt, chromium and the oxide compound of chromium etc.The oxide compound of the acetate of preferred chromium, the nitrate of chromium and chromium, the more preferably acetate of chromium.
The catalyst recovery liquid that described properties-correcting agent produces on the inorganic, metal oxide carrier for the alkyl silane chromate loads to.The properties-correcting agent main component is alkylsilanol and unreactive hydrocarbons solvent.The alkylsilanol structural formula is R
3SiOH.Wherein, R represents the alkyl in the alkylsilanol, alkyl can be identical also can be different, and should have 1-14 carbon atom.Alkylsilanol can include but not limited to trimethyl silicane alkanol, triethyl silicane alcohol, tributyl silanol, triisopentyl silanol, three-2-ethylhexyl silanol, three decyl silanols, three (14) base silane alcohol, tribenzyl silanol, triphen ethylsilane alcohol, triphenyl silanol, trimethylphenyl silanol etc. among the present invention, especially preferred triphenyl silanol.The alkylsilanol strength of solution is 1 * 10
-6-100mol/L, preferred 1 * 10
-5-10mol/L, more preferably 1 * 10
-4-1mol/L.
Described promotor is the alkyl organometallic compound, and alkyl metal cpd can be the alkylate of aluminium, lithium, boron, zinc, preferred alkyl aluminum compound among the present invention.
Adoptable organo-aluminium compound is alkylaluminium cpd and alkoxy aluminum compound, and alkylaluminium cpd has: trialkyl aluminium compound, aluminum alkyl halide and alkyl aluminum hydride.Usually, the alkyl of aluminum alkyls can be identical also can be different, and should have 1-14 carbon atom, halogen then is fluorine, chlorine, bromine and iodine.Concrete alkylaluminium cpd includes but not limited to, trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, dibutyl aluminum bromide and close compound.Usually, alkoxy aluminum compound has general formula R
2-Al-0R, wherein alkyl can be identical also can be different, and should have 1-14 carbon atom, the example includes but not limited to, oxyethyl group diethyl aluminum, methoxyl group diethyl aluminum, oxyethyl group dimethyl aluminium, oxyethyl group di-isopropyl aluminium, propoxy-diethyl aluminum, oxyethyl group diisobutyl aluminum and ethoxyl methyl aluminium triethyl.Select triethyl aluminum among the embodiment for use, not should be appreciated that the present invention is so limited.
Purpose of the present invention can also reach by following measure:
Ethylene polymerization organic chromium catalyzer of the present invention is characterized in that
A. described main body active catalyst is a chromic salts, and its content in the catalyzer total mass is 0.1-1.5%
The described carrier of B is that the technical requirements of inorganic oxide is:
A. surface-area is about 245-500m
2/ g;
B. pore volume is about 1.5-3cc/g;
C. the aperture is about 100-300
D. particle size is about 40-150 μ m;
C. described properties-correcting agent is that the alkyl silane chromate loads to the recovery liquid that produces in the support of the catalyst process;
But the alkylate of D. described promotor aluminium, lithium, boron, zinc.
Ethylene polymerization organic chromium catalyzer of the present invention, inorganic oxide carrier described in the B is any one that chooses from silica gel, aluminum oxide, aluminum phosphate, titanium oxide, perhaps its any two or more combinations.
Ethylene polymerization organic chromium catalyzer of the present invention, the effective constituent of properties-correcting agent described in the C is alkylsilanol.
Ethylene polymerization organic chromium catalyzer of the present invention, described in the D in the promotor metallic element and main body active catalyst chromium element mol ratio be 0.1-50.
Ethylene polymerization organic chromium catalyzer of the present invention, promotor described in the D can join in the catalyzer before the polymerization catalyst reaction, also can add in the polymerization system on the spot in polymerization process.
A kind of ethylene polymerization organic chromium Preparation of catalysts method of the present invention is provided below the present invention, comprises the steps:
A. dipping, prebake
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 0.5-48 hour;
C. roasting
Through the dried catalyzer of step B, under 300-950 ℃ of temperature, in the oxidizing atmosphere, roasting 0.5-48 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection, add modifier solution, under 45 ℃ of temperature, lucifuge reaction 0.5-20 hour, described modifier solution, the organic solvent of employing are iso-pentane, pentane, hexane, heptane, pure kerosene and other similar alkane; Saturated naphthenic hydrocarbon is as hexanaphthene, pentamethylene, dimethylcyclopentane, methylcyclohexane and other loop-like alkane; Aromatic hydrocarbons is as in the benzene,toluene,xylene any one.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, described alkyl metal cpd solution, the organic solvent of employing are iso-pentane, pentane, hexane, heptane, pure kerosene and other similar alkane; Saturated naphthenic hydrocarbon is as hexanaphthene, pentamethylene, dimethylcyclopentane, methylcyclohexane and other loop-like alkane; Aromatic hydrocarbons is as in the benzene,toluene,xylene any one.
Be a kind of ethylene polymerization organic chromium catalyzer preferred manufacturing procedure of the present invention below, it is characterized in that comprising the steps:
A. flood
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 1-24 hour;
C. roasting
Through the dried catalyzer of step B, under 300-850 ℃ of temperature, in the oxidizing atmosphere, roasting 1-24 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection; add modifier solution, under 45 ℃ of temperature, lucifuge reaction 1-15 hour; described modifier solution, the organic solvent of employing are any one in iso-pentane, pentane, normal hexane, the heptane.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, described alkyl metal cpd solution, the organic solvent of employing are any one in iso-pentane, pentane, normal hexane, the heptane.
Be another kind of ethylene polymerization organic chromium catalyzer preferred manufacturing procedure of the present invention below, it is characterized in that comprising the steps:
A. flood
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 1-12 hour;
C. roasting
Through the dried catalyzer of step B, under 300-850 ℃ of temperature, in the oxidizing atmosphere, roasting 4-12 hour;
In this step, the compound of chromium is oxidized to the oxide compound of high valence state; During hyperthermic treatment, remain unchanged after can once rising to a certain temperature, also can temperature-gradient method, promptly after rising to a certain temperature maintenance certain hour, continue to be warming up to another temperature maintenance certain hour, process is kept in this intensification one can be divided into several times as required.
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection, adds modifier solution, under 45 ℃ of temperature, and lucifuge reaction 2-10 hour, described modifier solution, the organic solvent of employing is an iso-pentane.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, described alkyl metal cpd solution, the organic solvent of employing is an iso-pentane.
Catalyzer of the present invention both can be used for the alkene homopolymerization, also can be used for the copolymerization of alkene.Described homopolymerization is meant is not having to make alkene such as ethene carry out polymerization under the situation of comonomer.Described copolymerization is meant by olefinic monomer such as ethene and contains the linearity of 3-20 carbon atom or the monomeric polyreaction of high alpha-olefin of branching.Wherein, the high alpha-olefin monomer of Shi Heing includes, but not limited to propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene and 3,5,5-trimethylammonium-1-hexene etc.
The present invention is applicable to known devices and reaction conditions, by any suspension, solution, slurry or gas phase process olefin polymerization and it is not limited to the polymerization system of any particular type.Slurry polymerization system generally includes the reactor that adds olefinic monomer and catalyst composition, and described reactor contains and is useful on the dissolving or the polyolefinic liquid reaction medium that suspends.Liquid reaction medium can be made up of for non-reacted inert liquid hydrocarbon down a large amount of liquid monomers or employed polymerizing condition.Although described inert liquid hydrocarbon needn't act on catalyst composition or the effect of the polymer solvent that obtained by this method, its is usually with act on the monomeric solvent that uses in polyreaction.The unreactive hydrocarbons that are suitable for this purpose are Trimethylmethane, iso-pentane, hexane, hexanaphthene, heptane, benzene, toluene etc.Olefinic monomer contacts with reactivity between the catalyst composition and should or stir and keep by continuously stirring.To contain the monomeric reaction medium of olefin polymer product and unreacted alkene extracts from reactor continuously.Separate olefin polymer product, and unreacted alkene monomer and liquid reaction medium are recycled in the reactor.
The present invention is equally applicable to gas phase polymerization system.Usually, conventional gas fluidized-bed process is under reaction conditions, under the catalyzer existence condition, the air-flow of one or more olefinic monomers is passed through fluidized-bed reactor continuously being enough to the solids bed is remained under the speed of suspended state.The air-flow that will contain unreacted monomer takes out continuously from reactor, compresses, cooling, optional part or total condensation and be recycled to reactor.Product taken out from reactor and add monomer join in the recirculated air.Temperature control for polymerization system is needed, also can exist for catalyzer and any gas of reactant inert at gas flow.
The disclosed technical scheme of ethylene polymerization organic chromium Catalysts and its preparation method of the present invention has following positively effect compared to existing technology:
1. provide a kind of active height, induction time to suit, be applicable to the ethylene polymerization organic chromium catalyzer of the polyethylene product of producing the broad range of molecular weight distributions.
2. the ethylene polymerization organic chromium Preparation of catalysts method that a kind of synthesis technique is simple, manufacturing cost is lower is provided.
3. the relative chromium oxide catalyst of catalyzer of the present invention has clear improvement in performances such as polyvinyl resin product molecular weight distribution, copolymerization performance, hydrogen accent susceptibilitys.
4. adopt two (tri-phenyl-silane) chromate/SiO 2 catalysts of the inventive method preparation with low cost, economic benefit is obvious.The cost of catalyst preparation described in the present invention is saved more than 50% than traditional double (tri-phenyl-silane) chromate/SiO 2 catalyst, and cost is lower.
Embodiment
The present invention will now be described in further detail by the embodiment:
Embodiment 1
Taking by weighing concentration is the chromium acetate aqueous solution 0.87g of 50wt%, and its chromium content is 11.5wt%, adds deionized water 56ml.The chromium acetate aqueous solution for preparing is joined in 20g Davison 955 silica gel, mixed the back dipping 6 hours, 60-120 ℃ of oven dry more than 12 hours in air atmosphere then.The bottom that then that drying is good catalyst Precursors is put into Φ 30 * 500mm is welded with the silica tube activator of sintered quartz grid distributor, and the high pure nitrogen that feeds through dehydration and deoxidation makes catalyst fluidization.Intensification heated quarty tube activator, kept 2 hours at 200 ℃, make catalyzer further remove moisture, be warming up to 325 ℃, switch to the dry air of dehydration, be warming up to 600 ℃, kept 4 hours, again switchback high pure nitrogen at last, device to be activated is cooled to room temperature, takes out chromium oxide catalyst and places nitrogen atmosphere to store for future use.Get the 1g chromium oxide catalyst and place the catalyst preparation bottle, adding TPS concentration is 3.84 * 10
-3The PS properties-correcting agent 12.5ml of mol/L, 45 ℃ of lucifuges were reacted 2.5 hours.Press Al/Cr=20 and add triethyl aluminum, stirred 1 hour, blow down solvent with high purity nitrogen then, make chromium content 0.5wt%, Al/Cr=20, the PS0.5 catalyzer of TPS: Cr=0.5 (mol ratio).
Embodiment 2-5
Embodiment 2-5 and embodiment 1 similar process, difference is PS properties-correcting agent dosage difference.Among the embodiment 2, PS properties-correcting agent dosage 25ml, TPS: Cr=1.0; Among the embodiment 3, PS properties-correcting agent dosage 18.75ml, TPS: Cr=1.5; Among the embodiment 4, PS properties-correcting agent dosage 25ml, TPS: Cr=2.0; Among the embodiment 5, PS properties-correcting agent 20.83ml, TPS: Cr=3.0.
Comparative Examples 1
Get Davidson 955 silica gel 20g, the bottom of putting into Φ 30 * 500mm is welded with the silica tube activator of sintered quartz grid distributor, and the high pure nitrogen that feeds through dehydration and deoxidation makes catalyst fluidization.Intensification heated quarty tube activator was kept 2 hours at 200 ℃, made catalyzer further remove moisture, continued to be warming up to 600 ℃, kept 4 hours, and device to be activated then is cooled to room temperature, and 955 good silica gel place nitrogen atmosphere to store for future use to take out activation.Take out 955 good silica gel 1g of activation, place the catalyst preparation bottle, add the 30ml iso-pentane, be warming up to 45 ℃, add two (tri-phenyl-silane) chromate 0.06g, lucifuge reaction 2.5 hours.Press Al/Cr=20 and add triethyl aluminum, stirred 1 hour, blow down solvent with high purity nitrogen then, make chromium content 0.5wt%, two (tri-phenyl-silane) chromate (BC) catalyzer of Al/Cr=20.
Embodiment 1-5, Comparative Examples 1 are carried out the polymerization evaluation, and experimental result sees Table 1,2:
Table 1 polymerizing condition: 85 ℃, pressure: normal pressure, polymerization time: 1 hour
Illustrate:
Modifier concentration 3.84 * 10 among the embodiment 1,2
-3Mol/L;
Modifier concentration 7.68 * 10 among the embodiment 3,4
-3Mol/L;
Modifier concentration 1.15 * 10 among the embodiment 5
-2Mol/L.
Table 2 polymerizing condition: 85 ℃, pressure: normal pressure, polymerization time: 1 hour
Embodiment 6
Taking by weighing concentration is the chromium acetate aqueous solution 0.87g of 50wt%, and its chromium content is 11.5wt%, adds deionized water 56ml.The chromium acetate aqueous solution for preparing is joined in 20g Davison 955 silica gel, mixed the back dipping 6 hours, 60-120 ℃ of oven dry more than 12 hours in air atmosphere then.The bottom that then that drying is good catalyst Precursors is put into Φ 30 * 500mm is welded with the silica tube activator of sintered quartz grid distributor, and the high pure nitrogen that feeds through dehydration and deoxidation makes catalyst fluidization.Intensification heated quarty tube activator, kept 2 hours at 200 ℃, make catalyzer further remove moisture, be warming up to 325 ℃, switch to the dry air of dehydration, be warming up to 600 ℃, kept 4 hours, again switchback high pure nitrogen at last, device to be activated is cooled to room temperature, takes out chromium oxide catalyst and places nitrogen atmosphere to store for future use.Get the 1g chromium oxide catalyst and place the catalyst preparation bottle, adding TPS concentration is 7.68 * 10
-3The PS properties-correcting agent 18.75ml of mol/L, 45 ℃ of lucifuges were reacted 2.5 hours.Press Al/Cr=20 and add triethyl aluminum, stirred 1 hour, blow down solvent with high purity nitrogen then, make chromium content 0.5wt%, Al/Cr=15, the PS1.5 catalyzer of TPS: Cr=1.5 (mol ratio).
Embodiment 7-11
Embodiment 7-11 is substantially the same manner as Example 6, has just added comonomer 1-hexene in polymerization process, and 1-hexene adding proportion is respectively 1,3,5,8,10 by volume among the embodiment 7-11.Embodiment 6-11 is carried out the polymerization evaluation response, and experimental result sees Table 3:
Table 3 polymerizing condition: 85 ℃, pressure: normal pressure, polymerization time: 1 hour
Illustrate:
The description of analytical methods that adopts among the embodiment is as follows:
The dsc analysis method is as follows among the embodiment: adopt Pyris Diamond differential scanning calorimeter polymer samples to be carried out mensuration such as fusing point.Temperature range :-100～300 ℃; Temperature accuracy: 0.01 ℃; Dynamic range: 0.2uw～800mw; Calorimetric precision: 0.1%.
Molecular weight determination is measured as follows among the embodiment: molecular weight of polyethylene adopts viscosimetry to measure, and makes solvent with perhydronaphthalene, 135 ℃ of temperature, and Ubbelohde viscometer records intrinsic viscosity.Calculate molecular weight according to formula.
Mn＝5.37×10
4×[η]
1.37
The catalyst experiment chamber is estimated and is adopted the polymerization of normal pressure slurry polymerization reactor, and the built-in magnetic agitation of reactor uses the oil bath system that polymerization reactor is heated.Polyreaction is carried out as follows: reactor heating, charge into high pure nitrogen, and get rid of then, vacuumize again, so the repeated treatments polymerization reactor is 10 times.Charge into ethene, in reactor, add catalyzer then, the beginning polyreaction.Calculate polymer yield as follows:
W
PE＝(Q·60)/(t
poly·w
cat)
Wherein Q is polymerization time t
Poly(minute) productive rate (g) of interpolymer, w
CatBe catalyst levels.Polyreaction adds a certain amount of ethanol after finishing in polymer, termination reaction emits reaction gas, reclaims polyethylene product.
Claims (8)
1. an ethylene polymerization organic chromium Preparation of catalysts method is characterized in that comprising main body active catalyst, inorganic oxide carrier, properties-correcting agent and promotor, wherein:
A. described main body active catalyst is a chromic salts, and its content in the catalyzer total mass is 0.1-1.5%;
The described carrier of B is that the technical requirements of inorganic oxide is:
A. surface-area is 245-500m
2/ g;
B. pore volume is 1.5-3cc/g;
C. the aperture is
D. particle size is 40-150 μ m;
C. described properties-correcting agent is that the alkyl silane chromate loads to the recovery liquid that produces in the support of the catalyst process;
D. described promotor is the alkylate of aluminium, lithium, boron, zinc;
Described preparation method comprises the steps:
A. dipping, prebake
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.1-1.5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 0.5-48 hour;
C. roasting
Through the dried catalyzer of step B, under 300-950 ℃ of temperature, in the oxidizing atmosphere, roasting 0.5-48 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection, add modifier solution, under 45 ℃ of temperature, lucifuge reaction 0.5-20 hour, described modifier solution, the organic solvent of employing are iso-pentane, pentane, hexane, heptane, pure kerosene and other similar alkane; Hexanaphthene, pentamethylene, dimethylcyclopentane, methylcyclohexane and other loop-like alkane; In the benzene,toluene,xylene any one;
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, described alkyl metal cpd solution, the organic solvent of employing are iso-pentane, pentane, hexane, heptane, pure kerosene and other similar alkane; Hexanaphthene, pentamethylene, dimethylcyclopentane, methylcyclohexane and other loop-like alkane; In the benzene,toluene,xylene any one.
2. according to the ethylene polymerization organic chromium Preparation of catalysts method of claim 1, it is characterized in that inorganic oxide carrier described in the B is any one that chooses from silica gel, aluminum oxide, aluminum phosphate, titanium oxide, perhaps its any two or more combinations.
3. according to the ethylene polymerization organic chromium Preparation of catalysts method of claim 1, the effective constituent that it is characterized in that properties-correcting agent described in the C is alkylsilanol.
4. according to the ethylene polymerization organic chromium Preparation of catalysts method of claim 1, it is characterized in that described in the D that metallic element and main body active catalyst chromium element mol ratio are 0.1-50 in the promotor.
5. according to the ethylene polymerization organic chromium Preparation of catalysts method of claim 1, it is characterized in that promotor described in the D can join in the catalyzer, also can add in the polymerization system on the spot in polymerization process before the polymerization catalyst reaction.
6. according to the ethylene polymerization organic chromium Preparation of catalysts method of claim 1, it is characterized in that comprising the steps:
A. flood
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.1-1.5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 1-24 hour;
C. roasting
Through the dried catalyzer of step B, under 300-850 ℃ of temperature, in the oxidizing atmosphere, roasting 1-24 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection, add modifier solution, under 45 ℃ of temperature, lucifuge reaction 1-15 hour, described modifier solution, the organic solvent of employing are any one in iso-pentane, pentane, normal hexane, the heptane;
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, described alkyl metal cpd solution, the organic solvent of employing are any one in iso-pentane, pentane, normal hexane, the heptane.
7. according to the ethylene polymerization organic chromium Preparation of catalysts method of claim 1, it is characterized in that comprising the steps:
A. flood
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.1-1.5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 1-12 hour;
C. roasting
Through the dried catalyzer of step B, under 300-850 ℃ of temperature, in the oxidizing atmosphere, roasting 4-12 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection, adds modifier solution, under 45 ℃ of temperature, and lucifuge reaction 2-10 hour, described modifier solution, the organic solvent of employing is an iso-pentane;
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, described alkyl metal cpd solution, the organic solvent of employing is an iso-pentane.
8. according to the ethylene polymerization organic chromium catalyst prod of the described ethylene polymerization organic chromium of claim 1 Preparation of catalysts method preparation.
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| CN106749786A (en) * | 2016-07-20 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of polyethylene catalysts |
| CN108690150B (en) * | 2017-04-07 | 2020-11-10 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and olefin polymerization method |
| CN109160963B (en) * | 2018-08-28 | 2021-05-04 | 吉化集团吉林市天龙催化剂有限公司 | Magnesium modified chromium catalyst for ethylene polymerization and preparation method thereof |
| CN112409514B (en) * | 2019-08-23 | 2023-04-28 | 中国石油化工股份有限公司 | Chromium-based polyethylene catalyst and preparation method thereof |
| CN114621368B (en) * | 2020-12-10 | 2023-11-28 | 中国石油天然气股份有限公司 | Ethylene gas phase polymerization grade switching agent and preparation method thereof |
| CN114621371B (en) * | 2020-12-10 | 2023-11-28 | 中国石油天然气股份有限公司 | On-line rapid switching method from gas-phase polyethylene metallocene catalyst to chromium catalyst |
| CN115536767A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Supported chromium-based polyethylene catalyst and preparation method thereof |
Citations (3)
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| US3324095A (en) * | 1965-05-14 | 1967-06-06 | Union Carbide Corp | Polymerization process |
| CN1753729A (en) * | 2003-02-26 | 2006-03-29 | 尤尼威蒂恩技术有限责任公司 | Production of broad molecular weight polyethylene |
| CN101173013A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3324095A (en) * | 1965-05-14 | 1967-06-06 | Union Carbide Corp | Polymerization process |
| CN1753729A (en) * | 2003-02-26 | 2006-03-29 | 尤尼威蒂恩技术有限责任公司 | Production of broad molecular weight polyethylene |
| CN101173013A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same |
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