CN107417812A - Spherical double meso-hole structure composites and support type polyethylene catalysts and their preparation method - Google Patents
Spherical double meso-hole structure composites and support type polyethylene catalysts and their preparation method Download PDFInfo
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- CN107417812A CN107417812A CN201610348274.9A CN201610348274A CN107417812A CN 107417812 A CN107417812 A CN 107417812A CN 201610348274 A CN201610348274 A CN 201610348274A CN 107417812 A CN107417812 A CN 107417812A
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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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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/645—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44, not provided for in a single group of groups C08F4/642 - C08F4/643
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Abstract
The present invention relates to catalyst field, specifically, it is related to a kind of spherical double meso-hole structure composites, the preparation method of spherical double meso-hole structure composites, the spherical double meso-hole structure composites 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 double meso-hole structure composites disclosed by the invention contain the meso-porous molecular sieve material with hollow ball-shape structure, meso-porous molecular sieve material and silica gel with three-dimensional cubic cage structure.The meso-hole structure of spherical double meso-hole structure composites 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 double meso-hole structure composites,
The preparation method of spherical double meso-hole structure composites, the spherical double meso-hole structures prepared by this method are answered
Condensation material, a kind of support type polyethylene catalysts, the preparation method of the support type polyethylene catalysts, with
And the support type polyethylene catalysts prepared by this method.
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 are spherical double meso-hole structure composites of high activity during ethylene polymerization.
In order to realize foregoing invention purpose, on the one hand, the invention provides a kind of spherical double meso-hole structures to answer
Condensation material, wherein, the composite contain the meso-porous molecular sieve material with hollow ball-shape structure, with
The meso-porous molecular sieve material and silica gel of three-dimensional cubic cage structure, the pore volume of the composite are
0.3-1.8mL/g, specific surface area 50-650m2/ g, average grain diameter are 20-60 μm, and aperture is in three peaks point
Cloth, and three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size respectively,
First most probable pore size is less than second most probable pore size, and second most probable pore size is less than institute
State the 3rd most probable pore size, and first most probable pore size is 1-9nm, second most probable pore size
For 10-17nm, the 3rd most probable pore size is 20-50nm.
Second aspect, should the invention provides a kind of method for preparing spherical double meso-hole structure composites
Method comprises the following steps：
(1) meso-porous molecular sieve material with hollow ball-shape structure is provided or prepared with hollow ball-shape
The filter cake of the meso-porous molecular sieve material of structure, as component a；
(2) 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 b；
(3) provide silica gel or prepare the filter cake of silica gel, as component c；
(4) by the component a, the component b, the component c and binding agent is mixed and ball milling,
And the solid powder water slurrying that will be obtained after ball milling, then obtained slurry is spray-dried；
Wherein, above-mentioned steps make it that the pore volume of the composite is 0.3-1.8mL/g, and specific surface area is
50-650m2/ g, average grain diameter are 20-60 μm, and aperture is in tri-modal distribution, and three peaks correspond to first respectively
Most probable pore size, the second most probable pore size and the 3rd most probable pore size, first most probable pore size are less than
Second most probable pore size, second most probable pore size are less than the 3rd most probable pore size, and institute
It is 1-9nm to state the first most probable pore size, and second most probable pore size is 10-17nm, and the described 3rd most
Can several apertures be 20-50nm.
The third aspect, the invention provides the spherical double meso-hole structures being prepared by above-mentioned preparation method to answer
Condensation material.
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 double meso-hole structure composites.
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 be spray-dried successively；Wherein, the carrier is provided by the invention above-mentioned spherical double
Meso-hole structure composite.
6th aspect, the invention provides the support type polyethylene catalysts for having the above method to prepare.
The meso-hole structure of spherical double meso-hole structure composites provided by the invention is stablized, in supported active group
Orderly meso-hole structure is maintained to after point, and the support type polyethylene being prepared by it is urged
Agent is used for having high catalytic activity when catalyzed ethylene polymerization reacts, while can obtain heap density and melting
The relatively low and non-breakable polyethylene product of index, specifically, the heap density of the polyethylene product of preparation is
Below 0.42g/mL, melt index are below 0.55g/10min, break powder rate and are less than 3%.
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：
The X-ray that Fig. 1 is spherical double meso-hole structure composite D1 described in the embodiment of the present invention 1 is spread out
Penetrate collection of illustrative plates；
Fig. 2 is the microscopic appearance of spherical double meso-hole structure composite D1 described in the embodiment of the present invention 1
SEM scanning electron microscope (SEM) photographs；
Fig. 3 is the pore-size distribution of spherical double meso-hole structure composite D1 described in the embodiment of the present invention 1
Figure.
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 double meso-hole structure composites, wherein, this is compound
Material contains the meso-porous molecular sieve material with hollow ball-shape structure, Jie with three-dimensional cubic cage structure
Porous molecular sieve material and silica gel, the pore volume of the composite is 0.3-1.8mL/g, and specific surface area is
50-650m2/ g, average grain diameter are 20-60 μm, and aperture is in tri-modal distribution, and three peaks correspond to first respectively
Most probable pore size, the second most probable pore size and the 3rd most probable pore size, first most probable pore size are
1-9nm, second most probable pore size are 10-17nm, and the 3rd most probable pore size is 20-50nm.
In the present invention, the average grain diameter of spherical double meso-hole structure composites is using laser particle size point
Cloth instrument measures, and specific surface area, pore volume and most probable pore size measure according to nitrogen adsorption methods, described spherical
The surface topography of double meso-hole structure composites is measured by ESEM instrument (SEM).In the present invention,
The average grain diameter is average particulate diameter.
In the present invention, by the way that the particle size of spherical double meso-hole structure composites is controlled in above-mentioned model
Within enclosing, it can be ensured that spherical double meso-hole structure composites are not susceptible to reunite, and are used
Reaction raw materials conversion during ethylene polymerization can be improved by making loaded catalyst made of carrier
Rate.When the specific surface area of spherical double meso-hole structure composites is less than 50m2/ g and/or pore volume are small
When 0.3mL/g, being used as the catalytic activity of loaded catalyst made of carrier can significantly reduce；
When the specific surface area of spherical double meso-hole structure composites is more than 650m2/ g and/or pore volume are more than
During 1.8mL/g, it is easy during ethylene polymerization to be used as loaded catalyst made of carrier
Reunite, so as to influence the conversion ratio of monomer during ethylene polymerization.
In the preferred case, the pore volume of spherical double meso-hole structure composites is 0.3-1.5mL/g,
Specific surface area is 60-500m2/ g, average grain diameter are 40-60 μm, and the first most probable pore size is 2-8nm,
Second most probable pore size is 10-16nm, and the 3rd most probable pore size is 20-45nm.
It is further preferred that the pore volume of spherical double meso-hole structure composites is 0.3-0.9mL/g,
Specific surface area is 70-200m2/ g, average grain diameter are 45-55 μm, and the first most probable pore size is 3-8nm,
Second most probable pore size is 10-16nm, and the 3rd most probable pore size is 20-40nm.
According to the present invention, the present invention is to having hollow ball-shape structure in spherical double meso-hole structure composites
The content of molecular screen material and silica gel is not particularly limited, as long as making spherical double meso-hole structure composites
Microscopic dimensions meet above-mentioned condition.It is in situations where it is preferred, described with hollow ball-shape structure
The weight ratio of meso-porous molecular sieve material, the meso-porous molecular sieve material with three-dimensional cubic cage structure and silica gel
For 1：0.5-2：0.5-2, preferably 1：0.5-1.5：0.5-1.5.
Second aspect, should the invention provides a kind of method for preparing spherical double meso-hole structure composites
Method may comprise steps of：
1) meso-porous molecular sieve material with hollow ball-shape structure is provided or prepared with hollow ball-shape knot
The filter cake of the meso-porous molecular sieve material of structure, as component a；
(2) 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 b；
(3) provide silica gel or prepare the filter cake of silica gel, as component c；
(4) by the component a, the component b, the component c and binding agent is mixed and ball milling,
And the solid powder water slurrying that will be obtained after ball milling, then obtained slurry is spray-dried；
Wherein, above-mentioned steps make it that the pore volume of the composite is 0.3-1.8mL/g, and specific surface area is
50-650m2/ g, average grain diameter are 20-60 μm, and aperture is in tri-modal distribution, and three peaks correspond to first respectively
Most probable pore size, the second most probable pore size and the 3rd most probable pore size, first most probable pore size are
1-9nm, second most probable pore size are 10-17nm, and the 3rd most probable pore size is 20-50nm.
In the preferred case, the pore volume of spherical double meso-hole structure composites is 0.3-1.5mL/g,
Specific surface area is 60-500m2/ g, average grain diameter are 40-60 μm, and the first most probable pore size is 2-8nm,
Second most probable pore size is 10-16nm, and the 3rd most probable pore size is 20-45nm.
It is further preferred that the pore volume of spherical double meso-hole structure composites is 0.3-0.9mL/g,
Specific surface area is 70-200m2/ g, average grain diameter are 45-55 μm, and the first most probable pore size is 3-8nm,
Second most probable pore size is 10-16nm, and the 3rd most probable pore size is 20-40nm.
In step (1), the mistake of the filter cake of the meso-porous molecular sieve material with hollow ball-shape structure is prepared
Journey can include：In acidic aqueous solution, in the presence of trimethylpentane and ethanol, by template with
Silicon source is contacted, and the mixture obtained after contact is carried out into crystallization and filtering.
In step (1), template, ethanol, the mol ratio of trimethylpentane and silicon source are 1：100-500：
200-500：50-200, preferably 1：180-400：250-400：70-150.
In step (1), the template can be various templates commonly used in the art.It is excellent
Selection of land, the template are triblock copolymer polyethylene glycol glycerine-polyethylene glycol, the template
It can be commercially available (for example, Aldrich, trade name P123, molecular formula can be purchased from
For EO20PO70EO202, molecular weight Mn is that 5800), can also be prepared into by existing various methods
Arrive.When the template is polyethylene glycol glycerine-polyethylene glycol, the molal quantity of the template
Calculate to obtain according to the mean molecule quantity of polyethylene glycol glycerine-polyethylene glycol.
In step (1), the silicon source can be various silicon sources commonly used in the art, preferably institute
It is tetramethoxy-silicane to state silicon source.
In step (1), the acidic aqueous solution can be various acid waters commonly used in the art
Solution, it is preferable that the acidic aqueous solution is the acetic acid and sodium acetate buffer solution that pH value is 1-6.
In step (1), the condition that template contacts with silicon source can include：Temperature is 10-60 DEG C,
Time is 10-72h, pH value 1-7；Preferably, the condition that template contacts with silicon source can include：
Temperature is 10-20 DEG C, time 10-30h.It is described in order to be more beneficial for the uniform mixing between each material
Template contacts with silicon source preferably to be carried out under agitation.The dosage of the acidic aqueous solution preferably so that
The pH value of the haptoreaction system of template and silicon source is 1-7.
In step (1), the condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is
10-40h；Preferably, temperature is 40-80 DEG C, time 20-30h.It is further preferred that the crystalline substance
Change is implemented by hydrothermal crystallization method.
In step (1), there is the filter of the meso-porous molecular sieve material of hollow ball-shape structure in above-mentioned preparation
During cake, it can be included with obtaining the process of filter cake by filtering：After filtration, deionization is used
Water washs (washing times can be 2-10) repeatedly, is then filtered.
In step (1), " providing the meso-porous molecular sieve material with hollow ball-shape structure " can be straight
Connect the product for weighing or choosing the meso-porous molecular sieve material with hollow ball-shape structure or prepare tool
There is the meso-porous molecular sieve material of hollow ball-shape structure.The mesopore molecular sieve material with hollow ball-shape structure
The preparation method of material can be implemented according to the conventional method, for example, its preparation method can include：According to
The above method prepares the filter cake of the meso-porous molecular sieve material with hollow ball-shape structure, then by gained filter cake
Dry.
In step (2), 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 (2), 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 step (2), the template can be various templates commonly used in the art.It is excellent
Selection of land, the template are triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, the template
It can be commercially available (for example, Fuka companies, trade name can be purchased fromF108,
Molecular formula is EO132PO60EO132, molecular weight Mn is that 14600), can also pass through existing various sides
Method is prepared.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the template
Molal quantity calculate to obtain according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene.
In step (2), the silicon source can be various silicon sources commonly used in the art, preferably institute
State silicon source in tetraethyl orthosilicate, methyl silicate, positive silicic acid propyl ester, sodium metasilicate and Ludox extremely
Few one kind, more preferably tetraethyl orthosilicate.
In step (2), the acidic aqueous solution can be various acid waters commonly used in the art
Solution, for example, can be at least one of hydrochloric acid, sulfuric acid, the nitric acid and hydrobromic acid aqueous solution, preferably
For aqueous hydrochloric acid solution.
In step (2), the condition that template contacts with silicon source can include：Temperature is 25-60 DEG C,
Time is 10-72h, pH value 1-7；Preferably, the condition that template contacts with silicon source can include：
Temperature is 35-45 DEG C, time 20-30h.It is described in order to be more beneficial for the uniform mixing between each material
Template contacts with silicon source preferably to be carried out under agitation.The dosage of the acidic aqueous solution preferably so that
The pH value of the haptoreaction system of template and silicon source is 1-7.
In step (2), 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 step (2), there is the meso-porous molecular sieve material of three-dimensional cubic cage structure in above-mentioned preparation
Filter cake during, can be included with obtaining the process of filter cake by filtering：After filtration, spend
Ionized water washs (washing times can be 2-10) repeatedly, is then filtered.
In step (2), 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 (3), 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.
In step (3), there is no particular limitation to the polyalcohol by the present invention, preferably described polynary
Alcohol is at least one of ethylene glycol, propane diols and glycerine, preferably ethylene glycol and/or glycerine, more
Preferably glycerine.
In step (3), there is no particular limitation for the condition that the present invention contacts to waterglass with polyalcohol,
Can suitably it be determined according in the common process for preparing silica gel.Under preferable case, the condition of the contact
Including：Temperature is 10-60 DEG C, preferably 30-45 DEG C；Time is 1-5h, preferably 1-3h；PH value
For 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 (3), " 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 (4), 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 double meso-hole structure composites, and then improve polyethylene production
The performance of product, relative to the component a of 100 parts by weight, the dosage of the component b can be 50-150
Parts by weight, the dosage of the component c can be 50-150 parts by weight, and the dosage of the binding agent can be
1-10 parts by weight.Preferably, the binding agent is polyvinyl alcohol and/or polyethylene glycol, is more preferably gathered
Vinyl alcohol.
In step (4), 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 (4), 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 (4), 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 (4), when the component a is the meso-porous molecular sieve material with hollow ball-shape structure
Filter cake, the component b be silica gel filter cake when, namely when step (1) for prepare there is hollow ball
The process of the filter cake of the meso-porous molecular sieve material of shape structure, step (2) are the mistake for the filter cake for preparing silica gel
Cheng Shi, the preparation method of spherical double meso-hole structure composites can also include：In step (3)
Spray-drying process after, the removed template method from spray drying obtained product.Preferably, it is described
The condition of removed template method 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 double meso-hole structure composite woods prepared by the above method
Material.
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
The double meso-hole structure composites of shape.
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 91-98 weight %, and the magnesium salts and titanium salt are respectively with magnesium elements and titanium member
The content sum of element meter is 2-9 weight %；It is further preferred that the content of the carrier is 91.5-95
Weight %, the magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 5-8.5 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 spherical double meso-hole structure composites.
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 double meso-hole structures provided by the invention
Composite.
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 91-98 weight %, the magnesium salts and the titanium salt content in terms of magnesium elements and titanium elements respectively
Sum is 2-9 weight %；It is further preferred that the content of the carrier is 91.5-95 weight %, it is described
Magnesium salts and titanium salt are respectively using the content sum that magnesium elements and titanium elements are counted as 5-8.5 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, polyethylene glycol glycerine-polyethylene glycol is purchased from Aldrich
Company, trade name P123, molecular formula EO20PO70EO202, molecular weight Mn is 5800.
Polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Fuka companies, trade name
F108, molecular formula EO132PO60EO132, it is abbreviated as F108, average molecular mass Mn 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.
Polyethylene flour rate：Sieved and determined by 800 eye mesh screens.
Embodiment 1
The present embodiment is used for the spherical double meso-hole structure composites and loaded catalyst for illustrating the present invention
And their preparation method.
(1) spherical double meso-hole structure composites are prepared
1g (0.00017mol) template P123 and 1.69g (0.037mol) ethanol is added to 28mL
PH=4.4 acetic acid and sodium acetate buffer solution in, at 15 DEG C stirring be completely dissolved to template, will
6g (0.05mol) trimethylpentane is added in above-mentioned solution, after stirring 8h at 15 DEG C, then by 2.13g
(0.014mol) tetramethoxy-silicane is added in above-mentioned solution, after stirring 20h at 15 DEG C, by solution
Be transferred in the reactor of agate liner, after 60 DEG C of baking oven crystallization 24h, then filtered and spend from
Sub- water washing 4 times, then filter the filter cake for the meso-porous molecular sieve material for obtaining having hollow ball-shape structure
A1。
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；By 4.2g (0.02mol)
Tetraethyl orthosilicate is added in above-mentioned solution, and 15min is stirred at 38 DEG C, and 24h is stood at 38 DEG C；Then
Transfer them in the reactor of agate liner, the crystallization 24h at 100 DEG C, then filtered and be used in combination
Deionized water is washed 4 times, is then filtered and is obtained the meso-porous molecular sieve material with three-dimensional cubic cage structure
Filter cake B1.
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 C1 of silica gel.
By 10g filter cake A1,10g filter cake B1,10g filter cake C1 and 0.5g polyethylene of above-mentioned preparation
Alcohol is put into 100mL ball grinder together, wherein, the material of ball grinder is agate, and Material quality of grinding balls is
Agate, a diameter of 3mm of abrading-ball, quantity are 1, rotating speed 400r/min.Ball grinder is closed,
Temperature is ball milling 5h at 25 DEG C in ball grinder, obtains solid powder；The solid powder is dissolved in 25g
In deionized water, at 200 DEG C in rotating speed be 12000r/min under be spray-dried；It will be obtained after spray drying
To product calcine 10h at 550 DEG C in Muffle furnace, removed template method, obtain spherical double mesoporous knots
Structure composite D1.
Table is carried out to spherical double meso-hole structure composite D1 with XRD, ESEM and nitrogen adsorption instrument
Sign.
Fig. 1 is X-ray diffracting spectrum, and as seen from the figure, spherical double meso-hole structure composite D1 have
Hollow ball-shape structure specific to mesoporous material.
Fig. 2 is spherical double meso-hole structure composite D1 microscopic appearance SEM figures, as seen from the figure,
Spherical double meso-hole structure composite D1 microscopic appearance is the microballoon that particle diameter is 20-60 μm, and its point
Dissipate functional.
Fig. 3 is spherical double meso-hole structure composite D1 graph of pore diameter distribution, as seen from the figure, ball
The double meso-hole structure composite D1 of shape have three pore size distribution$s, and duct is uniform.
Spherical double meso-hole structure composite D1 pore structure parameter is as shown in table 1 below.
Table 1
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with 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 double meso-hole structure composite D1 of 1g are added in mother liquor impregnates 1h, then filters, and
Washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and is ground, obtains catalyst E1.
Drawn by x-ray fluorescence analysis, in the catalyst E1 described in the present embodiment, in terms of element,
The content of magnesium elements is 7.17 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 double meso-hole structure composite D1, so as to be made
Comparative catalyst DE1.
Drawn by x-ray fluorescence analysis, in comparative catalyst DE1, in terms of element, magnesium elements
Content be 3.0 weight %, the content of titanium elements is 1.2 weight %.
Comparative example 2
Spherical double meso-hole structure composites and catalyst are prepared according to method same as Example 1, its
In except that, in step (1) prepares spherical double meso-hole structure composite materials, by 10g
Filter cake A1,10g filter cake B1 and 10g filter cake C1 is put into 100mL ball grinder together, i.e., does not add
Enter binding agent polyvinyl alcohol.So as to which comparative catalyst DE2 be made.
Drawn by x-ray fluorescence analysis, in comparative catalyst DE2, in terms of element, magnesium elements
Content be 2.1 weight %, the content of titanium elements is 1.3 weight %.
Embodiment 2
The present embodiment is used for the spherical double meso-hole structure composites and loaded catalyst for illustrating the present invention
And their preparation method.
(1) spherical double meso-hole structure composites are prepared
1g (0.00017mol) template P123 and 1.4g (0.03mol) ethanol is added to 28mL
PH=4.4 acetic acid and sodium acetate buffer solution in, at 10 DEG C stirring be completely dissolved to template, will
4.56g (0.04mol) trimethylpentane is added in above-mentioned solution, after stirring 8h at 10 DEG C, then will
1.83g (0.012mol) tetramethoxy-silicane is added in above-mentioned solution, will after stirring 30h at 10 DEG C
Solution is transferred in the reactor of agate liner, after 80 DEG C of baking oven crystallization 20h, is then filtered and is used in combination
Deionized water is washed 6 times, then filters the filter for the meso-porous molecular sieve material for obtaining having hollow ball-shape structure
Cake A2.
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；By 3.1g (0.015mol)
Tetraethyl orthosilicate is added in above-mentioned solution, and 15min is stirred at 45 DEG C, and 30h is stood at 45 DEG C；Then
Transfer them in the reactor of agate liner, the crystallization 30h at 120 DEG C, then filtered and be used in combination
Deionized water is washed 4 times, is then filtered and is obtained the meso-porous molecular sieve material with three-dimensional cubic cage structure
Filter cake B2.
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 C2 of silica gel.
By 10g filter cake A2,15g filter cake B2,15g filter cake C2 and 0.9g polyethylene of above-mentioned preparation
Alcohol is put into 100mL ball grinder together, wherein, the material of ball grinder is agate, and Material quality of grinding balls is
Agate, a diameter of 3mm of abrading-ball, quantity are 1, rotating speed 500r/min.Ball grinder is closed,
Temperature is ball milling 10h at 30 DEG C in ball grinder, obtains solid powder；The solid powder is dissolved in 100g
In deionized water, at 150 DEG C in rotating speed be 13000r/min under be spray-dried；It will be obtained after spray drying
To product calcine 15h at 600 DEG C in Muffle furnace, removed template method, obtain spherical double mesoporous knots
Structure composite D2.
Spherical double meso-hole structure composite D2 pore structure parameter is as shown in table 2 below.
Table 2
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with 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 double meso-hole structure composite D2 of 1g are added in mother liquor and impregnate 1h, are then filtered,
And washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and it is ground, obtains catalyst E2.
Drawn by xrf analysis, in the catalyst E2 described in the present embodiment, in terms of element, magnesium member
The content of element is 6.0 weight %, and the content of titanium elements is 1.7 weight %.
Embodiment 3
The present embodiment is used for the spherical double meso-hole structure composites and loaded catalyst for illustrating the present invention
And their preparation method.
(1) spherical double meso-hole structure composites are prepared
1g (0.00017mol) template P123 and 3.13g (0.068mol) ethanol is added to 28mL
PH=4.4 acetic acid and sodium acetate buffer solution in, at 20 DEG C stirring be completely dissolved to template, will
7.75g (0.068mol) trimethylpentane is added in above-mentioned solution, after stirring 8h at 20 DEG C, then will
3.8g (0.025mol) tetramethoxy-silicane is added in above-mentioned solution, will after stirring 10h at 20 DEG C
Solution is transferred in the reactor of agate liner, after 40 DEG C of baking oven crystallization 30h, is then filtered and is used in combination
Deionized water is washed 6 times, then filters the filter for the meso-porous molecular sieve material for obtaining having hollow ball-shape structure
Cake A3.
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；By 2.1g (0.01mol)
Tetraethyl orthosilicate is added in above-mentioned solution, and 15min is stirred at 35 DEG C, and 20h is stood at 35 DEG C；Then
Transfer them in the reactor of agate liner, crystallization 20h, is then filtered and spent at 90 DEG C
Ion water washing 4 times, then filter the meso-porous molecular sieve material that obtains there is three-dimensional cubic cage structure
Filter cake B3.
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 C3 of silica gel.
By 10g filter cake A3,5g filter cake B3,5g filter cake C3 and 0.2g polyethylene glycol of above-mentioned preparation
It is put into together in 100mL ball grinder, wherein, the material of ball grinder is agate, and Material quality of grinding balls is agate
Nao, a diameter of 3mm of abrading-ball, quantity are 1, rotating speed 300r/min.Ball grinder is closed, in ball
Temperature is ball milling 20h at 50 DEG C in grinding jar, obtains solid powder；The solid powder is dissolved in 50g
In ionized water, at 250 DEG C in rotating speed be 11000r/min under be spray-dried；It will be obtained after spray drying
Product 24h is calcined at 400 DEG C in Muffle furnace, removed template method, obtain spherical double meso-hole structures
Composite D3.
Spherical double meso-hole structure composite D3 pore structure parameter is as shown in table 3 below.
Table 3
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with 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 double meso-hole structure composite D3 of 1g are added in mother liquor impregnates 3h, then filters, and
Washing 4 times is carried out with n-hexane, in 75 DEG C of dryings, and is ground, obtains catalyst E3.
Drawn by xrf analysis, in the catalyst E3 described in the present embodiment, in terms of element, magnesium member
The content of element is 6.2 weight %, and the content of titanium elements is 1.32 weight %.
Embodiment 4
The present embodiment is used for the spherical double meso-hole structure composites and loaded catalyst for illustrating the present invention
And their preparation method.
Spherical double meso-hole structure composites and catalyst are prepared according to method same as Example 1, its
In except that, in step (1) prepares spherical double meso-hole structure composite materials, preparing
During the filter cake of silica gel, do not add glycerine, obtain spherical double meso-hole structure composite D4 and
Catalyst E4.
Spherical double meso-hole structure composite D4 pore structure parameter is as shown in table 4 below.
Table 4
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
Drawn by xrf analysis, in the catalyst E4 described in the present embodiment, in terms of element, magnesium member
The content of element is 5.9 weight %, and the content of titanium elements is 1.1 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 E1, 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 0.41g/mL, melt index
MI2.16=0.4g/10min, flour rate are less than 2%.It is computed determining, the efficiency of catalyst is
2715gPE/gcat·h。
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 DE1 for preparing of comparative example 1 replace the catalyst E1 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, flour rate are more than 8%.It is computed determining, the efficiency of catalyst is 1767g PE/
gcat·h。
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 DE2 for preparing of comparative example 2 replace the catalyst E1 that is prepared by embodiment 1.
The heap density (BD) of gained polyethylene particle powder is 0.45g/mL, melt index
MI2.16=0.67g/10min, flour rate are more than 8%.It is computed determining, the efficiency of catalyst is 1050g PE/
gcat·h。
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 E2, 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 0.4g/mL, melt index MI2.16=0.55g/10min, flour rate are less than 3%.Through
Calculate and determine, the efficiency of catalyst is 2150g 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 E3, 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 0.42g/mL, melt index MI2.16=0.47g/10min, flour rate are less than 3%.Through meter
Calculate and determine, the efficiency of catalyst is 2200g 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 E4 for preparing of embodiment 4 replace the catalyst E1 that is prepared by embodiment 1.Institute
The heap density (BD) for obtaining polyethylene particle powder is 0.4g/mL, melt index MI2.16=0.4g/10min,
Flour rate is less than 3%.It is computed determining, the efficiency of catalyst is 2050g PE/gcath.
It can be seen that from above EXPERIMENTAL EXAMPLE 1-4 and Experimental comparison's example 1-2 results contrasted and send out this
When spherical the double meso-hole structure composites and loaded catalyst of bright offer are used for ethylene polymerization, urge
Agent has higher catalytic activity, and can obtain heap density and melt index is relatively low and non-breakable
Polyethylene product, specifically, the heap density of the polyethylene product of preparation is below 0.42g/mL, melt
It is below 0.55g/10min to melt index, breaks powder rate and is less than 3%.
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 (19)
1. a kind of spherical double meso-hole structure composites, it is characterised in that the composite, which contains, to be had
The meso-porous molecular sieve material of hollow ball-shape structure, the meso-porous molecular sieve material with three-dimensional cubic cage structure
And silica gel, the pore volume of the composite is 0.3-1.8mL/g, specific surface area 50-650m2/ g, put down
Equal particle diameter is 20-60 μm, and aperture be in tri-modal distribution, and three peaks corresponding first most probable pore size, the respectively
Two most probable pore sizes and the 3rd most probable pore size, first most probable pore size are 1-9nm, described second
Most probable pore size is 10-17nm, and the 3rd most probable pore size is 20-50nm.
2. composite according to claim 1, wherein, it is described with hollow ball-shape structure
The weight ratio of meso-porous molecular sieve material, the meso-porous molecular sieve material with three-dimensional cubic cage structure and silica gel
For 1：0.5-1.5：0.5-1.5.
3. a kind of method for preparing spherical double meso-hole structure composites, this method comprise the following steps：
(1) meso-porous molecular sieve material with hollow ball-shape structure is provided or prepared with hollow ball-shape
The filter cake of the meso-porous molecular sieve material of structure, as component a；
(2) 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 b；
(3) provide silica gel or prepare the filter cake of silica gel, as component c；
(4) by the component a, the component b, the component c and binding agent is mixed and ball milling,
And the solid powder water slurrying that will be obtained after ball milling, then obtained slurry is spray-dried；
Wherein, above-mentioned steps make it that the pore volume of the composite is 0.3-1.8mL/g, and specific surface area is
50-650m2/ g, average grain diameter are 20-60 μm, and aperture is in tri-modal distribution, and three peaks correspond to first respectively
Most probable pore size, the second most probable pore size and the 3rd most probable pore size, first most probable pore size are
1-9nm, second most probable pore size are 10-17nm, and the 3rd most probable pore size is 20-50nm.
4. the method according to claim 11, wherein, in step (4), relative to 100 weights
Measure the component a of part, the dosage of the component b is 50-150 parts by weight, the dosage of the component c
For 50-150 parts by weight, the dosage of the binding agent is 1-10 parts by weight；
Preferably, the binding agent is polyvinyl alcohol and/or polyethylene glycol, more preferably polyvinyl alcohol.
5. according to the method for claim 3, wherein, in step (1), prepare with hollow
The process of the filter cake of the meso-porous molecular sieve material of chondritic includes：In acidic aqueous solution, in trimethyl
In the presence of pentane and ethanol, template is contacted with silicon source, and the mixture that will be obtained after contact
Carry out crystallization and filtering.
6. according to the method for claim 5, wherein, template, ethanol, trimethylpentane and
The mol ratio of silicon source is 1：100-500：200-500：50-200, preferably 1：180-400：250-400：
70-150；
Preferably, the template is triblock copolymer polyethylene glycol glycerine-polyethylene glycol；Institute
It is tetramethoxy-silicane to state silicon source；The acidic aqueous solution is that the acetic acid that pH value is 1-6 and sodium acetate delay
Rush solution；
Preferably, the condition of the contact includes：Temperature is 10-60 DEG C, and the time is 10-72 hours,
PH value is 1-7；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is 10-72 hours.
7. according to the method for claim 3, wherein, in step (2), 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 mould
In the presence of plate agent and potassium sulfate, template is contacted with silicon source, and the mixing that will be obtained after contact
Thing carries out crystallization and filtering.
8. according to the method for claim 7, wherein, in step (2), the template with
The dosage mol ratio of silicon source is 1：20-200；
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.
9. according to the method for claim 3, wherein, in step (3), 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.
10. the method according to claim 11, wherein, in step (3), the polyalcohol
For at least one of ethylene glycol, propane diols and glycerine, preferably ethylene glycol and/or glycerine；It is more excellent
Selection of land, the weight ratio of the waterglass, inorganic acid and polyalcohol is 3-6：2-3：1.
11. the method according to claim 11, wherein, in step (3), the contact
Condition includes：Temperature is 10-60 DEG C, and the time is 1-5 hours, pH value 2-4；The inorganic acid is
At least one of sulfuric acid, nitric acid and hydrochloric acid.
12. the method according to claim 11, wherein, in step (4), 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。
13. the method according to claim 3 or 4, wherein, the component a is with hollow ball
The filter cake of the meso-porous molecular sieve material of shape structure, the component b are Jie with three-dimensional cubic cage structure
The filter cake of porous molecular sieve material, the component c are the filter cake of silica gel, and methods described also includes：In step
(3) after spray-drying process, removed template method in the product obtained from spray drying；Preferably,
The condition of the removed template method includes：Temperature is 90-600 DEG C, and the time is 10-80 hours.
14. answered as spherical double meso-hole structures prepared by the method described in any one in claim 3-13
Condensation material.
15. 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 14 in any one
Described spherical double meso-hole structure composites.
16. catalyst according to claim 15, 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 %.
17. 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
Spray drying；Wherein, the carrier is spherical double described in any one in claim 1-2 and 14
Meso-hole structure composite.
18. according to the method for claim 17, 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 %.
19. the support type polyethylene catalysts prepared as the method described in claim 17 or 18.
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| CN110614112A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being spherical aluminum-containing mesoporous molecular sieve silica gel composite material, and preparation method 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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| 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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| CN110614112A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being spherical aluminum-containing mesoporous molecular sieve silica gel composite material, and preparation method and application thereof |
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