CN107417821A - Spherical composite and support type polyethylene catalysts and their preparation method - Google Patents
Spherical composite and support type polyethylene catalysts and their preparation method Download PDFInfo
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- CN107417821A CN107417821A CN201610349142.8A CN201610349142A CN107417821A CN 107417821 A CN107417821 A CN 107417821A CN 201610349142 A CN201610349142 A CN 201610349142A CN 107417821 A CN107417821 A CN 107417821A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to catalyst field, specifically, it is related to a kind of spherical composite, the preparation method of the spherical composite, the spherical composite prepared by this method, a kind of support type polyethylene catalysts, the preparation method of the support type polyethylene catalysts, and the support type polyethylene catalysts prepared by this method.Spherical composite disclosed by the invention contains meso-porous molecular sieve material and silica gel with three-dimensional cubic cage structure.The meso-hole structure of spherical composite provided by the invention is stable, orderly meso-hole structure is maintained to after load active component, and by the support type polyethylene catalysts being prepared by it for there is high catalytic activity during catalyzed ethylene polymerization reaction.
Description
Technical field
The present invention relates to catalyst field, in particular it relates to a kind of spherical composite, this is spherical compound
The preparation method of material, the spherical composite prepared by this method, a kind of support type polyethylene catalysts,
The preparation method of the support type polyethylene catalysts, and the support type polyethylene prepared by this method are catalyzed
Agent.
Background technology
Since the regular mesoporous material of Mobile companies synthesis duct high-sequential in 1992, due to its tool
Have high ratio surface, regular pore passage structure and narrow pore-size distribution so that mesoporous material catalysis,
Separation, the application of medicine and other fields have obtained very big concern.Zhao east member in 1998 et al. synthesizes one kind
New material-mesoporous material SBA-15, the material have the aperture (6-30nm), big of high-sequential
Pore volume (1.0cm3/ g), thicker hole wall (4-6nm), the high mechanical properties kept and good urge
Change absorption property (see D.Y.Zhao, J.L.Feng, Q.S.Huo, et al Science 279 (1998)
548-550).CN1341553A discloses a kind of preparation method of mesonic pore molecular sieve carrier material, the party
Mesoporous material made from method easily realizes point of catalyst and product as heterogeneous reaction catalyst carrier
From.
But conventional ordered mesoporous material SBA-15 microscopic appearances are bar-shaped, itself mobility is poor,
Its big specific surface area and high pore volume cause to make it have stronger water suction, moisture absorption ability, and this further adds
The acute reunion of ordered mesoporous material, limit the storage of ordered mesoporous material, transport, post-processing and should
With.
The development and application of polyethylene catalysts are that alkene gathers after traditional Ziegler-Natta catalyst
Close catalyst field another important breakthrough, this cause the research of polyethylene catalysts entered one it is fast
Hail the stage of exhibition.The catalyst amount reached due to homogeneous polyethylene catalyst needed for high activity is big, raw
It is high to produce cost, and obtained polymer can not gather without particle shape in widely used slurry process or vapor phase method
Close and used in technique.The effective way for overcoming above mentioned problem is exactly that soluble poly catalyst for ethylene is born
Loadization processing.At present, the supported research report of relevant polyethylene catalysts is very more.It is new to further investigate
Support/catalyst/co-catalyst system, it is necessary to different carriers is studied, to promote carried catalyst
With the further development of polyolefin industry.
The mesoporous material for the load polyethylene catalysts reported at present on document is MCM-41, with aluminium methyl
It is catalyzed after loading the MCM-41 progress vinyl polymerizations of polyethylene catalysts after oxygen alkane (MAO) processing again
Activity is 106gPE/(mol Zr h).Vinyl polymerization work is carried out after Mesoporous silica MCM 41 supported catalyst
Property it is relatively low the reason for be mainly MCM-41 hole wall structure heat endurance and hydrothermal stability it is poor, negative
Load process hole wall just has part to cave in, and load effect is have impact on, so that have impact on catalytic activity.Therefore,
It is necessary to seek a kind of stable mesoporous material of meso-hole structure, can still keeps orderly mesoporous after load
Material.
The content of the invention
The purpose of the present invention is the defects of overcoming prior art, there is provided a kind of meso-hole structure is stable, is loading
It is maintained to orderly mesoporous material after active component, and in load polyethylene catalysts to be catalyzed
There is the spherical composite of high activity during ethylene polymerization.
In order to realize foregoing invention purpose, in a first aspect, the invention provides a kind of spherical composite,
Wherein, the composite contains meso-porous molecular sieve material and silica gel with three-dimensional cubic cage structure, institute
The pore volume for stating composite is 0.5-1.8mL/g, specific surface area 200-650m2/ g, average grain diameter are
20-60 μm, aperture is in bimodal distribution, and bimodal corresponds to the first most probable pore size and the second most probable respectively
Aperture, first most probable pore size are less than second most probable pore size, and the first most probable hole
Footpath is 1-10nm, and second most probable pore size is 10-50nm.
Second aspect, the invention provides a kind of method for preparing spherical composite, this method include with
Lower step：
(1) meso-porous molecular sieve material with three-dimensional cubic cage structure is provided or prepared with three-dimensional
The filter cake of the meso-porous molecular sieve material of cube cage structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) by the component a, the component b and binding agent is mixed and ball milling, and by after ball milling
Obtained slurry, is then spray-dried by the water slurrying of obtained solid powder；
Wherein, above-mentioned steps make it that the pore volume of the spherical composite is 0.5-1.8mL/g, compare surface
Product is 200-650m2/ g, average grain diameter are 20-60 μm, and aperture is in bimodal distribution, and bimodal right respectively
The first most probable pore size and the second most probable pore size are answered, first most probable pore size is less than described second most
Can several apertures, and first most probable pore size is 1-10nm, and second most probable pore size is
10-50nm。
The third aspect, the invention provides the spherical composite being prepared by above-mentioned preparation method.
Fourth aspect, the invention provides a kind of support type polyethylene catalysts, the catalyst contains carrier
With load magnesium salts and/or titanium salt on the carrier, wherein, the carrier is provided by the invention above-mentioned
Spherical composite.
5th aspect, the invention provides a kind of preparation method of support type polyethylene catalysts, this method
Including：In the presence of an inert gas, carrier is impregnated in the mother liquor containing magnesium salts and/or titanium salt,
Then filtered and dried successively；Wherein, the carrier is above-mentioned spherical composite wood provided by the invention
Material.
6th aspect, the invention provides the support type polyethylene catalysts for having the above method to prepare.
The meso-hole structure of spherical composite provided by the invention is stable, still can after load active component
Orderly meso-hole structure is enough kept, and the support type polyethylene catalysts being prepared by it are used to urge
There is high catalytic activity when changing ethylene polymerization.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing be for providing a further understanding of the present invention, and a part for constitution instruction, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is the X-ray diffracting spectrum of the spherical composite C1 described in the embodiment of the present invention 1；
Fig. 2 is the x-ray diffraction pattern of the support type polyethylene catalysts D1 described in the embodiment of the present invention 1
Spectrum；
Fig. 3 is the SEM scannings of the microscopic appearance of the spherical composite C1 described in the embodiment of the present invention 1
Electron microscope；
Fig. 4 is the graph of pore diameter distribution of the spherical composite C1 described in the embodiment of the present invention 1.
Embodiment
The embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, this
A little scopes or value should be understood to comprising the value close to these scopes or value.For number range, respectively
Between the endpoint value of individual scope, between the endpoint value of each scope and single point value, and single point
Can be combined with each other between value and obtain one or more new number ranges, these number ranges should by regarding
For specific disclosure herein.
In a first aspect, the invention provides a kind of spherical composite, wherein, the composite contains tool
There are the meso-porous molecular sieve material and silica gel of three-dimensional cubic cage structure, the pore volume of the composite is
0.5-1.8mL/g, specific surface area 200-650m2/ g, average grain diameter are 20-60 μm, and aperture is in bimodal
Distribution, and bimodal the first most probable pore size corresponding respectively and the second most probable pore size, first most probable
Aperture is less than second most probable pore size, and first most probable pore size is 1-10nm, and described
Two most probable pore sizes are 10-50nm.
In the present invention, the average grain diameter of the spherical composite is measured using laser fineness gage,
Specific surface area, pore volume and most probable pore size measure according to nitrogen adsorption methods, the spherical composite
Surface topography is measured by ESEM instrument (SEM).In the present invention, the average grain diameter is flat
Equal particle diameter.
In the present invention, can by the way that the particle size of spherical composite is controlled within above range
To ensure that the spherical composite is not susceptible to reunite, and it is used as support type made of carrier and urges
Agent can improve the reaction raw materials conversion ratio during ethylene polymerization.When the spherical composite
Specific surface area be less than 200m2When/g and/or pore volume are less than 0.5mL/g, it is used as made of carrier
The catalytic activity of loaded catalyst can significantly reduce；When the specific surface area of the spherical composite is more than
650m2When/g and/or pore volume are more than 1.8mL/g, it is used as loaded catalyst made of carrier and exists
Easily reunite during ethylene polymerization, so as to influence turning for monomer during ethylene polymerization
Rate.
In the preferred case, the pore volume of the spherical composite is 0.6-1.6mL/g, and specific surface area is
200-450m2/ g, average grain diameter are 30-55 μm, and the first most probable pore size is 3-8nm, the second most probable
Aperture is 20-45nm.
It is further preferred that the pore volume of the spherical composite is 1.0-1.2mL/g, specific surface area is
200-300m2/ g, average grain diameter are 50-55 μm, and the first most probable pore size is 6-8nm, the second most probable
Aperture is 25-42nm.
According to the present invention, the present invention is to having the molecular sieve of three-dimensional cubic cage structure in spherical composite
The content of material and silica gel is not particularly limited, as long as meeting the microscopic dimensions of spherical composite
State condition.In situations where it is preferred, relative to having three-dimensional cubic caged described in 100 parts by weight
The meso-porous molecular sieve material of structure, the content of the silica gel can be 1-200 parts by weight, from further carrying
The angle of the performance of high density polyethylene product, it is highly preferred that three-dimensional relative to having described in 100 parts by weight
The meso-porous molecular sieve material of cube cage structure, the content of the silica gel is 50-200 parts by weight.
Second aspect, the invention provides a kind of method for preparing spherical composite, this method can wrap
Include following steps：
(1) meso-porous molecular sieve material with three-dimensional cubic cage structure is provided or prepared with three-dimensional
The filter cake of the meso-porous molecular sieve material of cube cage structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) by the component a, the component b and binding agent is mixed and ball milling, and by after ball milling
Obtained slurry, is then spray-dried by the water slurrying of obtained solid powder；
Wherein, above-mentioned steps make it that the pore volume of the spherical composite is 0.5-1.8mL/g, compare surface
Product is 200-650m2/ g, average grain diameter are 20-60 μm, and aperture is in bimodal distribution, and bimodal right respectively
The first most probable pore size and the second most probable pore size are answered, first most probable pore size is less than described second most
Can several apertures, and first most probable pore size is 1-10nm, and second most probable pore size is
10-50nm。
In the preferred case, the pore volume of the spherical composite is 0.6-1.6mL/g, and specific surface area is
200-450m2/ g, average grain diameter are 30-55 μm, and the first most probable pore size is 3-8nm, the second most probable
Aperture is 20-45nm.
It is further preferred that the pore volume of the spherical composite is 1.0-1.2mL/g, specific surface area is
200-300m2/ g, average grain diameter are 50-55 μm, and the first most probable pore size is 6-8nm, the second most probable
Aperture is 25-42nm.
In step (1), the filter cake of the meso-porous molecular sieve material with three-dimensional cubic cage structure is prepared
Process can include：In acidic aqueous solution, in the presence of potassium sulfate, template and silicon source are entered
Row contact, and the mixture obtained after contact is subjected to crystallization and filtering.
In step (1), the dosage mol ratio of template and silicon source can be 1：20-200, it is preferably
1：100-200.It is highly preferred that the dosage mol ratio of template and potassium sulfate can be 1：100-800,
More preferably 1：200-400.
In the present invention, the template can be various templates commonly used in the art.Preferably,
The template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, and the template can lead to
Cross and be commercially available (for example, Fuka companies, trade name can be purchased fromF108, point
Minor is EO132PO60EO132, molecular weight Mn is that 14600), can also pass through existing various methods
It is prepared.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the template
Molal quantity calculates to obtain according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene.
In the present invention, the silicon source can be various silicon sources commonly used in the art, preferably described silicon
Source is at least one in tetraethyl orthosilicate, methyl silicate, positive silicic acid propyl ester, sodium metasilicate and Ludox
Kind, more preferably tetraethyl orthosilicate.
In the present invention, the acidic aqueous solution can be that various acidity commonly used in the art are water-soluble
Liquid, for example, can be at least one of hydrochloric acid, sulfuric acid, the nitric acid and hydrobromic acid aqueous solution, it be preferably
Aqueous hydrochloric acid solution.
In the present invention, the condition that template contacts with silicon source can include：Temperature is 25-60 DEG C, when
Between be 10-72h, pH value 1-7；Preferably, the condition that template contacts with silicon source can include：Temperature
Spend for 35-45 DEG C, time 20-30h.In order to be more beneficial for the uniform mixing between each material, the mould
Plate agent contacts with silicon source preferably to be carried out under agitation.The dosage of the acidic aqueous solution is preferably so that mould
The pH value of the haptoreaction system of plate agent and silicon source is 1-7.
In the present invention, the condition of the crystallization can include：Temperature is 90-150 DEG C, and the time is
10-40h；Preferably, temperature is 90-120 DEG C, time 20-30h.It is further preferred that the crystalline substance
Change is implemented by hydrothermal crystallization method.
In the present invention, there is the meso-porous molecular sieve material of three-dimensional cubic cage structure in above-mentioned preparation
During filter cake, it can be included with obtaining the process of filter cake by filtering：After filtration, spend from
Sub- water washs (washing times can be 2-10) repeatedly, is then filtered.
In step (1), the meso-porous molecular sieve material of three-dimensional cubic cage structure " provide with " can be with
It is the product for directly weighing or choosing the meso-porous molecular sieve material with three-dimensional cubic cage structure, can also
It is to prepare the meso-porous molecular sieve material with three-dimensional cubic cage structure.It is described that there is three-dimensional cubic caged knot
The preparation method of the meso-porous molecular sieve material of structure can be implemented according to the conventional method, for example, its preparation side
Method can include：Meso-porous molecular sieve material with three-dimensional cubic cage structure is prepared according to the above method
Filter cake, then by gained filtration cakes torrefaction.
In step (2), preparing the process of the filter cake of silica gel can include：In the presence of a mineral acid,
Waterglass is contacted with polyalcohol, and the mixture obtained after contact is filtered.
According to the present invention, there is no particular limitation to the polyalcohol by the present invention, and preferably described polyalcohol is
At least one of ethylene glycol, propane diols and glycerine, preferably ethylene glycol and/or glycerine, more preferably
For glycerine.
According to the present invention, there is no particular limitation for the condition that the present invention contacts to waterglass with polyalcohol, can
With according to suitably being determined in the common process for preparing silica gel.Under preferable case, the condition bag of the contact
Include：Temperature is 10-60 DEG C, preferably 30-45 DEG C；Time is 1-5h, preferably 1-3h；PH value is
2-4, preferably 2.5-3.5.
In order to be more beneficial for the uniform mixing between each material, waterglass and the catalytic process of polyalcohol are excellent
Choosing is carried out under agitation.
Preferably, the weight ratio of the waterglass, inorganic acid and polyalcohol is 3-6：2-3：1；It is more excellent
Elect 3-5 as：1：1.
The waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 3-20 weight %, preferably 10-20
Weight %.
The inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulfuric acid,
At least one of nitric acid and hydrochloric acid.The inorganic acid can use in pure form, can also be with it
The form of the aqueous solution uses.The dosage of the inorganic acid is preferably so that the haptoreaction of waterglass and polyalcohol
The pH value of system is 2-4.
In step (2), " offer silica gel " can directly weigh or choose silica gel product, can also
It is to prepare silica gel.Preparing the method for silica gel can implement according to the conventional method, such as can include：Root
The filter cake of silica gel is prepared according to the above method, then by gained filtration cakes torrefaction.
According to the present invention, in step (3), the present invention does not have to the dosage and species of the binding agent
Special limitation, in order to improve the intensity of spherical composite, and then the performance of polyethylene product is improved,
Relative to the component a of 100 parts by weight, the dosage of the component b can be 1-200 parts by weight,
The dosage of the binding agent can be 1-10 parts by weight；Preferably, the dosage of the component b is 50-200
Parts by weight, the dosage of the binding agent is 2-8 parts by weight.It is highly preferred that the binding agent is polyethylene
Alcohol and/or polyethylene glycol, most preferably polyvinyl alcohol.
In step (3), the ball milling can be carried out in ball mill, ball grinder in the ball mill
Inwall be preferably agate liner, the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball
Can reasonably it be selected according to the size of ball grinder, the ball grinder for size for 50-150mL,
1 abrading-ball can generally be used；The material of the abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., preferably
For agate.The condition of the ball milling can include：The rotating speed of abrading-ball is 200-800r/min, in ball grinder
Temperature be 15-100 DEG C, the time of ball milling is 0.1-100h；Preferably, the rotating speed of abrading-ball is
300-500r/min, the temperature in ball grinder is 25-50 DEG C, and the time of ball milling is 5-20h.
In step (3), the process by the solid powder water slurrying obtained after ball milling can be at 25-60 DEG C
Lower progress.In pulping process, the weight ratio of the dosage of solid powder and water can be 1:0.1-5, it is excellent
Elect 1 as：0.5-3.5.
In step (3), the spray drying can be implemented according to the mode of routine, such as can be
Carried out in atomizer.The condition of the spray drying can include：Temperature is 150-600 DEG C, rotation
Rotating speed can be 10000-15000r/min；Under preferable case, the condition of the spray drying includes：Temperature
Spend for 150-250 DEG C, the rotating speed of rotation is 11000-13000r/min.
In step (3), when the component a is the mesopore molecular sieve with three-dimensional cubic cage structure
The filter cake of material, when the component b is the filter cake of silica gel, namely when step (1) has three to prepare
The process of the filter cake of the meso-porous molecular sieve material of cube cage structure is tieed up, step (2) is to prepare silica gel
During the process of filter cake, the preparation method of the spherical composite can also include：In step (3)
After spray-drying process, removed template method in the product obtained from spray drying.Preferably, it is described de-
The condition of template agent removing includes：Temperature is 90-600 DEG C, more preferably 400-600 DEG C；Time is 10-80
Hour, more preferably 10-24h.
The third aspect, present invention also offers the spherical composite prepared by the above method.
Fourth aspect, present invention also offers a kind of support type polyethylene catalysts, the catalyst contains load
The magnesium salts and/or titanium salt of body and load on the carrier, wherein, the carrier is ball provided by the invention
Shape composite.
According to the present invention, in the loaded catalyst, the present invention is to the magnesium salts and/or titanium salt
There is no particular limitation for content, can be carried out according to the conventional loaded catalyst in this area suitably true
Fixed, for example, on the basis of the gross weight of the catalyst, the content of the carrier is 90-99 weight %,
The magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 1-10 weight %；It is preferred that
Ground, the content of the carrier is 94-96 weight %, and the magnesium salts and titanium salt are respectively with magnesium elements and titanium member
The content sum of element meter is 4-6 weight %；It is further preferred that the content of the carrier is 94.5-95
Weight %, the magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 5-5.5 weights
Measure %.
In the present invention, the catalyst can be prepared according to various methods commonly used in the art, only
Magnesium salts and/or titanium salt are loaded on the spherical composite.
5th aspect, present invention also offers a kind of preparation method of support type polyethylene catalysts, the party
Method includes：In the presence of an inert gas, carrier is impregnated in the mother liquor containing magnesium salts and/or titanium salt,
Then filtered and dried successively；Wherein, the carrier is spherical composite provided by the invention.
According to the present invention, the condition of the dipping can include：Temperature is 25-100 DEG C, time 0.1-5h；
Preferably, the condition of the dipping includes：Temperature is 40-60 DEG C, time 1-3h.
In the present invention, to the dosage of the magnesium salts and titanium salt, there is no particular limitation, in the preferred case,
The dosage of the carrier, magnesium salts and titanium salt causes in the support type polyethylene catalysts being prepared, with
On the basis of the gross weight of the catalyst, the content of the carrier is 90-99 weight %, the magnesium salts and
Titanium salt is respectively using the content sum that magnesium elements and titanium elements are counted as 1-10 weight %；It is highly preferred that the load
The content of body is 94-96 weight %, the magnesium salts and the titanium salt content in terms of magnesium elements and titanium elements respectively
Sum is 4-6 weight %；It is further preferred that the content of the carrier is 94.5-95 weight %, it is described
Magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 5-5.5 weight %.
In a kind of preferred embodiment of the present invention, the dosage weight ratio of the magnesium salts and titanium salt is 1：
0.1-2, preferably 1：0.5-2.
In the present invention, the magnesium salts can be various magnesium salts commonly used in the art, for example, can be with
For the one or more in magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium bromide, preferably magnesium chloride.
In the present invention, the titanium salt can be various titanium salts commonly used in the art, for example, can be with
For titanium tetrachloride and/or titanium trichloride.
In the present invention, the content of element can use X-ray fluorescence spectra analytic approach in the catalyst
Measure.
In situations where it is preferred, the mother liquor can also contain the organic solvent of dissolving magnesium salts and titanium salt, this
Invention has no particular limits to the organic solvent, if magnesium salts and titanium salt can be dissolved, such as
Can be isopropanol and tetrahydrofuran, the volume ratio of isopropanol and tetrahydrofuran can be 1：1-3, preferably
For 1：1-1.5.
In the present invention, the drying condition of preparation of the present invention to the catalyst has no particular limits,
Can be various conditions commonly used in the art；The preparation of preferred catalyst is additionally included in after filtering and dry
Washing process before dry, and/or process of lapping after drying.Those skilled in the art can basis
Practice situation is selected the condition of the washing and grinding, will not be repeated here.
In the present invention, the inert gas is the gas not reacted with raw material and product, such as can
Think at least one of group 0 element gas in this area conventional nitrogen or the periodic table of elements, preferably
For nitrogen.
6th aspect, present invention also offers the support type polyethylene catalysts prepared by the above method.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is public purchased from Fuka
Department, trade nameF108, molecular formula EO132PO60EO132, F108 is abbreviated as,
Average molecular mass Mn is 14600.
In following examples and comparative example, X-ray diffraction analysis are purchased from German Bruker AXS companies
Model D8Advance X-ray diffractometer on carry out；Scanning electron microscope analysis is purchased from U.S. FEI
Carried out in the model XL-30 of company SEM；Pore structure parameter is analyzed purchased from the U.S.
Carried out on the model Autosorb-1 of Kang Ta companies nitrogen adsorption desorption instrument, wherein, before being tested,
Sample is deaerated 4 hours at 200 DEG C；Model of the x-ray fluorescence analysis in dutch company
Carried out on Axios-Advanced x-ray fluorescence analyzer.
The heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
Melt index：Determined according to ASTM D1238-99.
Embodiment 1
The present embodiment be used for illustrate the present invention spherical composite and loaded catalyst and they
Preparation method.
(1) spherical composite is prepared
By 1.46g (0.0001mol) templates F108,5.24g (0.03mol) K2SO4Work as with 60g
The hydrochloric acid solution that amount concentration is 2 is stirred to F108 at 38 DEG C to be completely dissolved；
4.2g (0.02mol) tetraethyl orthosilicate is added in above-mentioned solution, 15min is stirred at 38 DEG C,
24h is stood at 38 DEG C；
It is then transferred in the reactor of agate liner, the crystallization 24h at 100 DEG C, then carries out
Filter and be washed with deionized 4 times, then filter and obtain mesoporous point with three-dimensional cubic cage structure
The filter cake A1 of son sieve material.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine with
Weight ratio is 5：1：1 is mixed and the haptoreaction 1.5h at 30 DEG C, is then 98 weights with concentration
The sulfuric acid for measuring % adjusts pH value to 3, then obtained reaction mass is filtered, and use distilled water
Washing is 0.02 weight % to sodium ions content, obtains the filter cake B1 of silica gel.
10g filter cake A1,10g filter cake B1 and 0.5g polyvinyl alcohol of above-mentioned preparation is put into 100mL together
Ball grinder in, wherein, the material of ball grinder is agate, and Material quality of grinding balls is agate, abrading-ball it is a diameter of
3mm, quantity are 1, rotating speed 400r/min.Ball grinder is closed, temperature is 25 DEG C in ball grinder
Lower ball milling 5 hours, obtains solid powder；The solid powder is dissolved in 25g deionized waters, at 200 DEG C
Under in rotating speed be 12000r/min under be spray-dried；By the product obtained after spray drying in Muffle furnace in
10h is calcined at 550 DEG C, removing F108 (template), obtains spherical composite C1.
Spherical composite C1 is characterized with XRD, ESEM and nitrogen adsorption instrument.
Spherical composite C1 pore structure parameter is as shown in table 1 below.
Table 1
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.1g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in 10mL tetrahydrofuran and answering for isopropanol
(volume ratio of tetrahydrofuran and isopropanol is 1 in bonding solvent：1.2) catalyst mother liquor, is formed.At 45 DEG C
The lower spherical composite C1 of 1g are added in mother liquor impregnates 1h, then filters, and entered with n-hexane
Row washing 4 times, in 75 DEG C of dryings, and is ground, obtains catalyst D1.
Fig. 1 is X-ray diffracting spectrum, and as seen from the figure, spherical composite C1 has mesoporous material institute
Distinctive three-dimensional cubic cage structure.
Fig. 2 is X-ray diffracting spectrum, and as seen from the figure, support type polyethylene catalysts D1 has mesoporous
Three-dimensional cubic cage structure specific to material.
Fig. 3 is spherical composite C1 microscopic appearance SEM figures, as seen from the figure, spherical composite
C1 microscopic appearance is the microballoon that particle diameter is 20-60 μm, and its good dispersion property.
Fig. 4 is spherical composite C1 graph of pore diameter distribution, as seen from the figure, spherical composite
C1 has double-pore structure distribution, and duct is uniform.
Drawn by x-ray fluorescence analysis, in the catalyst D1 described in the present embodiment, in terms of element,
The content of magnesium elements is 4 weight %, and the content of titanium elements is 1.3 weight %.
Comparative example 1
Commercially available ES955 silica gel (GRACE companies) is calcined into 10h for 400 DEG C under nitrogen protection,
With eliminating hydroxide and Residual water, so as to obtain the ES955 silica gel through thermal activation.
Method according to the step of embodiment 1 (2) prepares catalyst, except that, using identical heavy
The ES955 silica gel for measuring the above-mentioned activation of part replaces spherical composite C1, so as to which comparative catalyst be made
DD1。
Drawn by x-ray fluorescence analysis, in comparative catalyst DD1, in terms of element, magnesium elements
Content be 3 weight %, the content of titanium elements is 1.2 weight %.
Comparative example 2
Spherical composite and catalyst are prepared according to method same as Example 1, wherein different
It is, in step (1) prepares spherical composite material, by 10g filter cake A1 and 10g filter cakes B1
It is put into together in 100mL ball grinder, i.e., does not add binding agent polyvinyl alcohol.Urged so as to which contrast be made
Agent DD2.
Drawn by x-ray fluorescence analysis, in comparative catalyst DD2, in terms of element, magnesium elements
Content be 2.3 weight %, the content of titanium elements is 0.7 weight %.
Embodiment 2
The present embodiment be used for illustrate the present invention spherical composite and loaded catalyst and they
Preparation method.
(1) spherical composite is prepared
By 1.46g (0.0001mol) templates F108,6.96g (0.04mol) K2SO4Work as with 60g
The hydrochloric acid solution that amount concentration is 2 is stirred to F108 at 38 DEG C to be completely dissolved；
3.1g (0.015mol) tetraethyl orthosilicate is added in above-mentioned solution, 15min is stirred at 45 DEG C,
30h is stood at 45 DEG C；
It is then transferred in the reactor of agate liner, the crystallization 30h at 120 DEG C, then carries out
Filter and be washed with deionized 4 times, then filter and obtain mesoporous point with three-dimensional cubic cage structure
The filter cake A2 of son sieve material.
By the waterglass that concentration is 20 weight % and the sulfuric acid solution that concentration is 12 weight % and propane diols with
Weight ratio is 4：1：1 is mixed and the haptoreaction 3h at 40 DEG C, is then 98 weight % with concentration
Sulfuric acid adjust pH value to 4, then obtained reaction mass is filtered, and with distilling water washing
It is 0.02 weight % to sodium ions content, obtains the filter cake B2 of silica gel.
10g filter cake A2,5g filter cake B2 and 0.2g polyvinyl alcohol of above-mentioned preparation is put into 100mL together
Ball grinder in, wherein, the material of ball grinder is agate, and Material quality of grinding balls is agate, abrading-ball it is a diameter of
3mm, quantity are 1, rotating speed 500r/min.Ball grinder is closed, temperature is 30 DEG C in ball grinder
Lower ball milling 10h, obtains solid powder；The solid powder is dissolved in 100g deionized waters, at 150 DEG C
Under in rotating speed be 13000r/min under be spray-dried；By the product obtained after spray drying in Muffle furnace in
15h is calcined at 600 DEG C, removing F108 (template), obtains spherical composite C2.
Spherical composite C2 pore structure parameter is as shown in table 2 below.
Table 2
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.1g magnesium chlorides and 0.2g titanium tetrachlorides are dissolved in 10mL tetrahydrofuran and answering for isopropanol
(volume ratio of tetrahydrofuran and isopropanol is 1 in bonding solvent：1.5) catalyst mother liquor, is formed.At 60 DEG C
Under, the spherical composite C2 of 1g are added in mother liquor and impregnate 1h, are then filtered, and use n-hexane
Washing 4 times is carried out, in 75 DEG C of dryings, and is ground, obtains catalyst D2.
Drawn by xrf analysis, in the catalyst D2 described in the present embodiment, in terms of element, magnesium member
The content of element is 3.4 weight %, and the content of titanium elements is 2 weight %.
Embodiment 3
The present embodiment be used for illustrate the present invention spherical composite and loaded catalyst and they
Preparation method.
(1) spherical composite is prepared
By 1.46g (0.0001mol) templates F108,3.48g (0.02mol) K2SO4Work as with 60g
The hydrochloric acid solution that amount concentration is 2 is stirred to F108 at 38 DEG C to be completely dissolved；
2.1g (0.01mol) tetraethyl orthosilicate is added in above-mentioned solution, 15min is stirred at 35 DEG C,
20h is stood at 35 DEG C；
It is then transferred in the reactor of agate liner, the crystallization 20h at 90 DEG C, then carried out
Filter and be washed with deionized 4 times, then filter and obtain the mesoporous molecular with three-dimensional cubic cage structure
Sieve the filter cake A3 of material.
By the waterglass that concentration is 10 weight % and the sulfuric acid solution that concentration is 12 weight % and ethylene glycol with
Weight ratio is 3：1：1 is mixed and the haptoreaction 1h at 45 DEG C, is then 98 weight % with concentration
Sulfuric acid adjust pH value to 2, then obtained reaction mass is filtered, and with distilling water washing
It is 0.02 weight % to sodium ions content, obtains the filter cake B3 of silica gel.
10g filter cake A3,20g filter cake B3 and 0.8g polyethylene glycol of above-mentioned preparation is put into 100mL together
Ball grinder in, wherein, the material of ball grinder is agate, and Material quality of grinding balls is agate, abrading-ball it is a diameter of
3mm, quantity are 1, rotating speed 300r/min.Ball grinder is closed, temperature is 50 DEG C in ball grinder
Lower ball milling 20h, obtains solid powder；The solid powder is dissolved in 50g deionized waters, at 250 DEG C
Under in rotating speed be 11000r/min under be spray-dried；By the product obtained after spray drying in Muffle furnace in
24h is calcined at 400 DEG C, removing F108 (template), obtains spherical composite C3.
Spherical composite C3 pore structure parameter is as shown in table 3 below.
Table 3
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.2g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in 10mL tetrahydrofuran and answering for isopropanol
(volume ratio of tetrahydrofuran and isopropanol is 1 in bonding solvent：1) catalyst mother liquor, is formed.At 40 DEG C
The lower spherical composite C3 of 1g are added in mother liquor impregnates 3h, then filters, and entered with n-hexane
Row washing 4 times, in 75 DEG C of dryings, and is ground, obtains catalyst D3.
Drawn by xrf analysis, in the catalyst D3 described in the present embodiment, in terms of element, magnesium member
The content of element is 3.1 weight %, and the content of titanium elements is 1.9 weight %.
Embodiment 4
The present embodiment be used for illustrate the present invention spherical composite and loaded catalyst and they
Preparation method.
Spherical composite and catalyst are prepared according to method same as Example 1, wherein different
It is, in step (1) prepares spherical composite material, during the filter cake of silica gel is prepared,
Glycerine is not added, obtains spherical composite C4 and catalyst D4.
Spherical composite C4 pore structure parameter is as shown in table 4 below.
Table 4
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
Drawn by xrf analysis, in the catalyst D4 described in the present embodiment, in terms of element, magnesium member
The content of element is 3.5 weight %, and the content of titanium elements is 1.8 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for the application for illustrating loaded catalyst provided by the invention.
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds
200mL hexanes, kettle temperature is risen to 80 DEG C, adds 800mL hexanes, with the addition of hexane, is added
The hexane solution for the triethyl aluminum (TEA) that the concentration for entering 2mL is 1mol/L, is subsequently added into 0.5g's
Catalytic component D1, is passed through ethylene gas, and pressure is risen into 1.0MPa and is maintained 1.0MPa,
70 DEG C reaction 1 hour after filter separation, obtain polyethylene particle powder.Polyethylene particle powder is carried out
Measure, the heap density (BD) of polyethylene particle powder are 0.38g/mL, melt index
MI2.16=0.5g/10min.It is computed determining, the efficiency of catalyst is 2300gPE/gcath.
Experimental comparison's example 1
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, using identical weight part
The comparative catalyst DD1 for preparing of comparative example 1 replace the catalyst D1 that is prepared by embodiment 1.
The heap density (BD) of gained polyethylene particle powder is 0.4g/mL, melt index MI2.16=
0.87g/10min.It is computed determining, the efficiency of catalyst is 1767g PE/gcath.
Experimental comparison's example 2
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, using identical weight part
The comparative catalyst DD2 for preparing of comparative example 2 replace the catalyst D1 that is prepared by embodiment 1.
The heap density (BD) of gained polyethylene particle powder is 0.69g/mL, melt index
MI2.16=0.77g/10min.It is computed determining, the efficiency of catalyst is 1300g PE/gcath.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for the application for illustrating loaded catalyst provided by the invention.
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds
200mL hexanes, kettle temperature is risen to 75 DEG C, adds 900mL hexanes, with the addition of hexane, is added
The hexane solution for the triethyl aluminum (TEA) that the concentration for entering 2mL is 1mol/L, is subsequently added into 0.1g's
Catalytic component D2, is passed through ethylene gas, and pressure is risen into 1MPa and is maintained 1MPa, at 75 DEG C
Reaction filters separation after 1.5 hours, obtains polyethylene particle powder.The heap of gained polyethylene particle powder
Density (BD) is 0.2g/mL, melt index MI2.16=0.7g/10min.It is computed determining, catalyst
Efficiency be 2100g PE/gcath.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for the application for illustrating loaded catalyst provided by the invention.
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds
200mL hexanes, kettle temperature is risen to 85 DEG C, adds 700mL hexanes, with the addition of hexane, is added
The hexane solution for the triethyl aluminum (TEA) that the concentration for entering 2mL is 1mol/L, is subsequently added into urging for 1g
Agent component D3, is passed through ethylene gas, and pressure is risen into 1MPa and is maintained 1MPa, anti-at 85 DEG C
Separation is filtered after answering 2 hours, obtains polyethylene particle powder.The heap density of gained polyethylene particle powder
(BD) it is 0.4g/mL, melt index MI2.16=0.5g/10min.It is computed determining, the effect of catalyst
Rate is 2050g PE/gcath.
EXPERIMENTAL EXAMPLE 4
This EXPERIMENTAL EXAMPLE is used for the application for illustrating loaded catalyst provided by the invention.
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, using identical weight part
The comparative catalyst D4 for preparing of embodiment 4 replace the catalyst D1 that is prepared by embodiment 1.Institute
The heap density (BD) for obtaining polyethylene particle powder is 0.42g/mL, melt index MI2.16
=0.33g/10min.It is computed determining, the efficiency of catalyst is 1950g PE/gcath.
It can be seen that from the above EXPERIMENTAL EXAMPLE 1-4 and comparative example 1-2 results contrasted and put forward the present invention
When spherical the composite and loaded catalyst supplied is used for ethylene polymerization, catalyst has higher
Catalytic activity, and the polyethylene product of heap density and the relatively low function admirable of melt index can be obtained.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality
The detail in mode is applied, can be to the technical side of the present invention in the range of the technology design of the present invention
Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Sign, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention no longer separately illustrate to various combinations of possible ways.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of spherical composite, it is characterised in that the composite contains with three-dimensional cubic cage
The meso-porous molecular sieve material and silica gel of shape structure, the pore volume of the composite is 0.5-1.8mL/g, than
Surface area is 200-650m2/ g, average grain diameter are 20-60 μm, and aperture is in bimodal distribution, and bimodal point
Not Dui Ying the first most probable pore size and the second most probable pore size, first most probable pore size is less than described the
Two most probable pore sizes, and first most probable pore size is 1-10nm, second most probable pore size is
10-50nm。
2. composite according to claim 1, wherein, relative to described in 100 parts by weight
Meso-porous molecular sieve material with three-dimensional cubic cage structure, the content of the silica gel is 1-200 parts by weight；
Preferably, the content of the silica gel is 50-200 parts by weight.
3. a kind of method for preparing spherical composite, this method comprise the following steps：
(1) meso-porous molecular sieve material with three-dimensional cubic cage structure is provided or prepared with three-dimensional
The filter cake of the meso-porous molecular sieve material of cube cage structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) by the component a, the component b and binding agent is mixed and ball milling, and by after ball milling
Obtained slurry, is then spray-dried by the water slurrying of obtained solid powder；
Wherein, above-mentioned steps make it that the pore volume of the spherical composite is 0.5-1.8mL/g, compare surface
Product is 200-650m2/ g, average grain diameter are 20-60 μm, and aperture is in bimodal distribution, and bimodal right respectively
The first most probable pore size and the second most probable pore size are answered, first most probable pore size is less than described second most
Can several apertures, and first most probable pore size is 1-10nm, and second most probable pore size is
10-50nm。
4. the method according to claim 11, wherein, in step (3), relative to 100 weights
Measure the component a of part, the dosage of the component b is 1-200 parts by weight, the dosage of the binding agent
For 1-10 parts by weight；Preferably, the dosage of the component b is 50-200 parts by weight, the binding agent
Dosage be 2-8 parts by weight；
It is highly preferred that the binding agent is polyvinyl alcohol and/or polyethylene glycol, most preferably polyvinyl alcohol.
5. according to the method for claim 3, wherein, in step (1), preparing has three-dimensional
The process of the filter cake of the meso-porous molecular sieve material of cube cage structure includes：In acidic aqueous solution, in sulphur
In the presence of sour potassium, template is contacted with silicon source, and the mixture obtained after contact is subjected to crystalline substance
Change and filter.
6. the method according to claim 11, wherein, the dosage of template, potassium sulfate and silicon source
Mol ratio is 1：100-800：20-200；
Preferably, the template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；Institute
State silicon source in tetraethyl orthosilicate, methyl silicate, positive silicic acid propyl ester, sodium metasilicate and Ludox extremely
Few one kind；The acidic aqueous solution is at least one of hydrochloric acid, sulfuric acid, the nitric acid and hydrobromic acid aqueous solution；
Preferably, the condition of the contact includes：Temperature is 25-60 DEG C, and the time is 10-72 hours,
PH value is 1-7；The condition of the crystallization includes：Temperature is 90-150 DEG C, and the time is 10-40 hours.
7. according to the method for claim 3, wherein, in step (2), prepare the filter of silica gel
The process of cake includes：In the presence of a mineral acid, waterglass is contacted with polyalcohol, and by after contact
Obtained mixture is filtered.
8. according to the method for claim 7, wherein, in step (2), the polyalcohol is
At least one of ethylene glycol, propane diols and glycerine, preferably ethylene glycol and/or glycerine；More preferably
Ground, the weight ratio of the waterglass, inorganic acid and polyalcohol is 3-6：2-3：1.
9. the method according to claim 11, wherein, in step (2), the bar of the contact
Part includes：Temperature is 10-60 DEG C, and the time is 1-5 hours, pH value 2-4；The inorganic acid is sulphur
At least one of acid, nitric acid and hydrochloric acid.
10. the method according to claim 11, wherein, in step (3), the ball milling
Condition includes：The rotating speed of abrading-ball is 300-500r/min, and the temperature in ball grinder is 15-100 DEG C, ball milling
Time be 0.1-100 hours；The condition of the spray drying includes：150-600 DEG C of temperature, rotating speed are
10000-15000r/min。
11. the method according to claim 3 or 4, wherein, the component a is vertical with three-dimensional
The filter cake of the meso-porous molecular sieve material of square cage structure, the component b be silica gel filter cake, methods described
Also include：After the spray-drying process of step (3), removed in the product obtained from spray drying
Template；Preferably, the condition of the removed template method includes：Temperature is 90-600 DEG C, and the time is
10-80 hours.
12. the spherical composite prepared as the method described in any one in claim 3-11.
13. a kind of support type polyethylene catalysts, the catalyst contains carrier and load on the carrier
Magnesium salts and/or titanium salt, it is characterised in that the carrier be claim 1-2 and 12 in any one
Described spherical composite.
14. catalyst according to claim 13, wherein, using the gross weight of the catalyst as
Benchmark, the content of the carrier is 90-99 weight %, and the magnesium salts and titanium salt are respectively with magnesium elements and titanium
The content sum of element meter is 1-10 weight %.
15. a kind of preparation method of support type polyethylene catalysts, this method include：Deposited in inert gas
Under, carrier is impregnated in the mother liquor containing magnesium salts and/or titanium salt, then carry out successively filtering and
Dry；Wherein, the carrier is the spherical composite wood described in any one in claim 1-2 and 12
Material.
16. according to the method for claim 15, wherein, the condition of the dipping includes：Temperature
For 25-100 DEG C, time 0.1-5h；
Preferably, the dosage of the carrier, magnesium salts and titanium salt causes in the support type polyethylene being prepared
In catalyst, on the basis of the gross weight of the catalyst, the content of the carrier is 90-99 weight %,
The magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 1-10 weight %.
17. the support type polyethylene catalysts prepared as the method described in claim 15 or 16.
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| CN110734511A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Polyolefin catalyst with spherical double-mesoporous composite material as carrier, polyolefin and preparation methods of polyolefin catalyst and polyolefin |
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| US7691773B2 (en) * | 2004-03-23 | 2010-04-06 | Samsung Sdi Co., Ltd. | Supported catalyst and method for preparing the same |
| CN105175586A (en) * | 2014-06-13 | 2015-12-23 | 中国石油化工股份有限公司 | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method |
| CN105330768A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
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| US7691773B2 (en) * | 2004-03-23 | 2010-04-06 | Samsung Sdi Co., Ltd. | Supported catalyst and method for preparing the same |
| CN105175586A (en) * | 2014-06-13 | 2015-12-23 | 中国石油化工股份有限公司 | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method |
| CN105330768A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
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| CN110734511A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Polyolefin catalyst with spherical double-mesoporous composite material as carrier, polyolefin and preparation methods of polyolefin catalyst and polyolefin |
| CN110734511B (en) * | 2018-07-19 | 2022-07-12 | 中国石油化工股份有限公司 | Polyolefin catalyst with spherical double-mesoporous composite material as carrier, polyolefin and preparation methods of polyolefin catalyst and polyolefin |
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