CN105330768B - A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application - Google Patents
A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application Download PDFInfo
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- CN105330768B CN105330768B CN201410264707.3A CN201410264707A CN105330768B CN 105330768 B CN105330768 B CN 105330768B CN 201410264707 A CN201410264707 A CN 201410264707A CN 105330768 B CN105330768 B CN 105330768B
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Abstract
The invention discloses a kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application.The support type polyethylene catalyst includes spherical complex carrier and the magnesium salts and titanium salt that are supported on the spherical complex carrier, wherein, the spherical complex carrier contains the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, meso-porous molecular sieve material and silica gel with two-dimentional hexagonal hole road distributed architecture, the average grain diameter of the spherical complex carrier is 30 60 microns, specific surface area is 150 600 meters squared per grams, pore volume is 0.5 1.5 mls/g, aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size respectively, second most probable pore size and the 3rd most probable pore size, first most probable pore size is 24 nanometers, second most probable pore size is 5 15 nanometers, 3rd most probable pore size is 10 40 nanometers.The loaded catalyst that the present invention is provided has higher catalytic efficiency during catalyzed ethylene polymerization.
Description
Technical field
The present invention relates to a kind of support type polyethylene catalyst, the preparation side of the support type polyethylene catalyst
Method, the support type polyethylene catalyst prepared by this method, the support type polyethylene catalysts comprising the catalytic component,
And application of the catalyst in vinyl polymerization.
Background technology
Meso-porous molecular sieve material has the advantages that duct is orderly, aperture is adjustable, specific surface area and pore volume are larger, is good
Catalyst and carrier material.In recent years, the multiphases such as the solid acid, the heteropoly acid that are prepared using meso-porous molecular sieve material as template are urged
Agent not only has higher ethylene polymerization catalytic activity, and side reaction is less, it is relatively simple to post-process.
The development and application of polyethylene catalysts are the olefinic polymerization catalysis after traditional Ziegler-Natta catalyst
The another important breakthrough in agent field, this causes the research of polyethylene catalysts to enter the stage of a fast development.Due to
Catalyst amount needed for homogeneous polyethylene catalyst reaches high activity is big, and production cost is high, and obtained polymer is without grain
Shape, it is impossible to used on widely used slurry process or gas phase polymerization technique, the effective way for overcoming above mentioned problem is exactly handle
Soluble poly catalyst for ethylene carries out supported processing.At present, the supported research report of relevant polyethylene catalysts is very more.For
New support/catalyst/the co-catalyst system of further investigation, it is necessary to attempt different carriers, with promote carried catalyst and
The further development of polyolefin industry.
Mesoporous material is with its big surface area (500-2000m2/ g), spacious duct and big and adjustable aperture size
The advantage of (3-50nm) is used to prepare support type polyethylene catalysts by researcher, and by the support type polyethylene catalysts of gained
For ethylene polymerization.It is used for the mesoporous of load active component in the support type polyethylene catalysts reported on current document
Material is MCM-41, after being handled using MAO again load active component MCM-41 carry out vinyl polymerization after catalytic activity as 106gPE/
(mol Zr h).The reason for ethylene polymerization activity is relatively low is carried out after Mesoporous silica MCM 41 load active component and is mainly MCM-41
Hole wall structure heat endurance and hydrothermal stability it is poor, loading process hole wall just have part cave in, have impact on load effect,
So that reducing the catalytic efficiency of support type polyethylene catalysts.
The content of the invention
It is an object of the present invention to overcome the supported catalyst that meso-porous molecular sieve material of the prior art is made
The relatively low defect of agent catalytic efficiency in ethylene polymerisation process provides a kind of new support type polyethylene catalyst and its system
Preparation Method.
It is a further object to provide the support type polyethylene catalysts comprising above-mentioned catalytic component and its
Application in vinyl polymerization.
In order to achieve the above object, the present inventor after research by having found, will contain has one-dimensional hexagonal hole road
The meso-porous molecular sieve material of distributed architecture, the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture and silica gel it is mesoporous
Is not susceptible to reunite spherical is made in composite, can so retain the high-specific surface area of meso-porous molecular sieve material, big pore volume,
Large aperture and the features such as be distributed with one-dimensional hexagonal hole road distributed architecture and two-dimentional hexagonal hole road, can reduce mesopore molecular sieve again
The reunion of material, increases its mobility so that the loaded catalyst being made of the mesoporous composite material is poly- for ethene
The catalytic efficiency significantly improved can be obtained when closing reaction, so as to complete the present invention.
The present invention provides a kind of support type polyethylene catalyst, and the support type polyethylene catalyst includes ball
Shape complex carrier and the magnesium salts and titanium salt being supported on the spherical complex carrier, wherein, the spherical complex carrier contains
Meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, the mesopore molecular sieve with two-dimentional hexagonal hole road distributed architecture
Material and silica gel, the average grain diameter of the spherical complex carrier is 30-60 microns, and specific surface area is 150-600 meters squared per grams,
Pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and corresponding first most probable pore size, second most may be used respectively at three peaks
Several apertures and the 3rd most probable pore size, first most probable pore size are less than second most probable pore size, and described second most may be used
Several apertures are less than the 3rd most probable pore size, and first most probable pore size is 2-4 nanometers, and second most probable pore size is
5-15 nanometers, the 3rd most probable pore size is 10-40 nanometers.
The present invention also provides a kind of preparation method of support type polyethylene catalyst, and this method is included in inert gas
Under protection, spherical complex carrier is contacted with the solution containing magnesium salts and the compounded organic solvent of titanium salt, wherein, it is described spherical multiple
Close carrier and contain the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, with two-dimentional hexagonal hole road distributed architecture
Meso-porous molecular sieve material and silica gel, the average grain diameter of the spherical complex carrier is 30-60 microns, and specific surface area is 150-600
Meters squared per gram, pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable hole respectively
Footpath, 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, institute
The second most probable pore size is stated less than the 3rd most probable pore size, first most probable pore size is 2-4 nanometers, and described second most
Can several apertures be 5-15 nanometer, the 3rd most probable pore size be 10-40 nanometers.
The present invention also provides support type polyethylene catalyst prepared by a kind of above method.
Present invention also offers a kind of support type polyethylene catalysts, wherein, the support type polyethylene catalysts include
Above-mentioned support type polyethylene catalyst and alkyl aluminum compound.
Present invention also offers application of the above-mentioned support type polyethylene catalysts in vinyl polymerization.
In the supported catalyst component of the present invention, spherical complex carrier not only remains ordered mesoporous material
The characteristics of high-specific surface area, big pore volume, big aperture and narrowly distributing, and unique tri-modal distribution is presented in its pore-size distribution so that
Including containing the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, Jie with two-dimentional hexagonal hole road distributed architecture
The loaded catalyst of the spherical complex carrier of porous molecular sieve material and silica gel has higher during catalyzed ethylene polymerization
Catalytic efficiency.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the X-ray diffracting spectrum of the spherical complex carrier according to the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical complex carrier according to the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph of the support type polyethylene catalyst according to the present invention；
Fig. 4 is the pore size distribution curve figure of the spherical complex carrier according to the present invention.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of support type polyethylene catalyst, and the support type polyethylene catalyst includes ball
Shape complex carrier and the magnesium salts and titanium salt being supported on the spherical complex carrier, wherein, the spherical complex carrier contains
Meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, the mesopore molecular sieve with two-dimentional hexagonal hole road distributed architecture
Material and silica gel, the average grain diameter of the spherical complex carrier is 30-60 microns, and specific surface area is 150-600 meters squared per grams,
Pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and corresponding first most probable pore size, second most may be used respectively at three peaks
Several apertures and the 3rd most probable pore size, first most probable pore size are less than second most probable pore size, and described second most may be used
Several apertures are less than the 3rd most probable pore size, and first most probable pore size is 2-4 nanometers, and second most probable pore size is
5-15 nanometers, the 3rd most probable pore size is 10-40 nanometers.
Spherical complex carrier according to the present invention has the two-dimentional pore size distribution structure of hexagonal hole road three of a distinctive peacekeeping,
The average grain diameter of its particle is measured using laser fineness gage, and specific surface area, pore volume and most probable pore size are inhaled according to nitrogen
Attached method is measured.
Spherical complex carrier according to the present invention, by the way that the particle size of spherical complex carrier is controlled in above-mentioned model
Within enclosing, it can be ensured that the spherical complex carrier is not susceptible to reunite, and the supported catalyst component being made using it
Catalytic efficiency can be improved in catalyzed ethylene polymerization.When the specific surface area of the spherical complex carrier is less than 150 meters squared per grams
And/or pore volume be less than 0.5 ml/g when, be used as the catalytic efficiency meeting for the support type polyethylene catalysts that carrier is made
Significantly reduce；When the specific surface area of the spherical complex carrier be more than 600 meters squared per grams and/or pore volume be more than 1.5 milliliters/
Gram when, be used as the support type polyethylene catalysts that carrier is made and easily reunite in ethylene polymerisation process, so that shadow
Ring the catalytic efficiency of the polyethylene catalysts containing the catalytic component.
In the preferred case, the average grain diameter of the spherical complex carrier is 30-50 microns, and specific surface area is 180-600
Meters squared per gram, pore volume is 0.9-1.2 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable hole respectively
Footpath, 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, institute
The second most probable pore size is stated less than the 3rd most probable pore size, and first most probable pore size is 2-4 nanometers, described second
Most probable pore size is 5-10 nanometers, and the 3rd most probable pore size is 10-25 nanometers.
According to the present invention, on the basis of the total amount of the catalytic component, the total content of the magnesium salts and titanium salt can be
1-50 weight %, the content of the spherical complex carrier can be 50-99 weight %, and the weight ratio of the magnesium salts and titanium salt can be with
For 1：0.1-2；Preferably, on the basis of the total amount of the catalytic component, the total content of the magnesium salts and titanium salt is 15-30 weights
% is measured, the content of the spherical complex carrier is 70-85 weight %, and the weight ratio of the magnesium salts and titanium salt is 1：0.1-1.5.
According to the present invention, the magnesium salts and the titanium salt can be offer activity conventional in ethylene rolymerization catalyst field
The magnesium salts and titanium salt of component.Preferably, the magnesium salts can be magnesium chloride；The titanium salt titanium tetrachloride and/or titanium trichloride.
According to the present invention, relative to the mesopore molecular sieve described in 100 parts by weight with one-dimensional hexagonal hole road distributed architecture
The total amount of material and meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, the content of the silica gel is 1-200 weights
Measure part, preferably 50-150 parts by weight；The meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture and the tool
The weight ratio for having the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture is 1：0.1-10, preferably 1：0.5-2.
In the present invention, the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture and described there is two dimension
The meso-porous molecular sieve material of hexagonal hole road distributed architecture can be each meso-porous molecular sieve material commonly used in the art, and
It can prepare according to the conventional method.
In the present invention, the various silica gel that the silica gel can be commonly used for support type polyethylene catalysts field, Er Qieke
To prepare according to the conventional method.
The present invention also provides a kind of preparation method of support type polyethylene catalyst, and this method is included in inert gas
Under protection, spherical complex carrier is contacted with the solution containing magnesium salts and the compounded organic solvent of titanium salt, wherein, it is described spherical multiple
Close carrier and contain the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, with two-dimentional hexagonal hole road distributed architecture
Meso-porous molecular sieve material and silica gel, the average grain diameter of the spherical complex carrier is 30-60 microns, and specific surface area is 150-600
Meters squared per gram, pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable hole respectively
Footpath, 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, institute
The second most probable pore size is stated less than the 3rd most probable pore size, first most probable pore size is 2-4 nanometers, and described second most
Can several apertures be 5-15 nanometer, the 3rd most probable pore size be 10-40 nanometers.
Spherical complex carrier according to the present invention has the two-dimentional pore size distribution structure of hexagonal hole road three of a distinctive peacekeeping,
The average grain diameter of its particle is measured using laser fineness gage, and specific surface area, pore volume and most probable pore size are inhaled according to nitrogen
Attached method is measured.
Spherical complex carrier according to the present invention, by the way that the particle size of spherical complex carrier is controlled in above-mentioned model
Within enclosing, it can be ensured that the spherical complex carrier is not susceptible to reunite, and the supported catalyst component being made using it
Catalytic efficiency can be improved in catalyzed ethylene polymerization.When the specific surface area of the spherical complex carrier is less than 150 meters squared per grams
And/or pore volume be less than 0.5 ml/g when, being used as the catalytic efficiency for the loaded catalyst that carrier is made can significantly drop
It is low；, will when the specific surface area of the spherical complex carrier is more than 600 meters squared per grams and/or pore volume is more than 1.5 mls/g
It easily reunites as the loaded catalyst that carrier is made in ethylene polymerisation process, so as to influence to contain the catalyst
The catalytic efficiency of the polyethylene catalysts of component.
In the preferred case, the average grain diameter of the spherical complex carrier is 30-50 microns, and specific surface area is 180-600
Meters squared per gram, pore volume is 0.9-1.2 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable hole respectively
Footpath, 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, institute
The second most probable pore size is stated less than the 3rd most probable pore size, and first most probable pore size is 2-4 nanometers, described second
Most probable pore size is 5-10 nanometers, and the 3rd most probable pore size is 10-25 nanometers.
According to the present invention, the weight of the magnesium salts, the titanium salt and the spherical complex carrier is than can be in wider model
Interior variation is enclosed, usually, the weight ratio of the magnesium salts, the titanium salt and the spherical complex carrier consumption can be 1：0.1-2：
0.02-2, preferably 1：0.1-1.5：0.2-2.
According to the present invention, the magnesium salts and titanium salt are consistent with being described above, and will not be repeated here.
According to the present invention, the compounded organic solvent can be that can dissolve the magnesium salts and titanium salt and readily removed
Various solvents, it is preferable that the compounded organic solvent is tetrahydrofuran and isopropanol.
According to the present invention, the volume ratio of tetrahydrofuran and isopropanol can be 1：1-3, preferably 1:1-1.5.
According to the present invention, the inert gas can be various chemically interactive not with carrier and active component generation
Various gases.For example, the inert gas can be carried by the one or more in zero group gas in nitrogen and the periodic table of elements
For.
According to the present invention, there is no particular limitation for the condition contacted for the magnesium salts and titanium salt with the ball type carrier,
As long as making the content of the magnesium in the catalytic component of acquisition and titanium meet expected use requirement.Usually, the contact
Condition can include：Temperature is 25-100 DEG C, and the time is 1-12 hours.Preferably, the condition of the contact includes：Temperature is
35-75 DEG C, the time is 2-9 hours.
The present invention is not particularly limited for the method for the contact, for example can be using dipping, spraying.Due to dipping
Method is easier to make the solution containing magnesium salts and titanium salt enter in the duct of the carrier, therefore, present invention preferably employs
The method of dipping carries out the contact.
According to the present invention, the preparation method of the supported catalyst component also includes magnesium salts and titanium salt being combined with spherical
Gains after carrier is contacted are filtered, washed and dried.The filtering is preferred to use suction filtration method, and the washing is excellent
Choosing is washed using tetrahydrofuran.
The condition of the drying includes：Dry temperature is 25-100 DEG C, and the dry time is 1-12h, it is preferable that described
Dry condition includes：Dry temperature is 35-85 DEG C, and the dry time is 2-9h.
According to the present invention, the spherical complex carrier is prepared by following method：
(1) providing the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture or preparing has one-dimensional hexagonal hole
The filter cake of the meso-porous molecular sieve material of road distributed architecture, is used as component a1；
(2) providing the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparing has two-dimentional hexagonal hole
The filter cake of the meso-porous molecular sieve material of road distributed architecture, is used as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(4) the component a1, the component a2 and the component b are mixed and ball milling, and will be obtained after ball milling
Obtained slurry, is then spray-dried by solid powder water slurrying；
Wherein, the component a1 and the component a2 cause the average grain diameter of the spherical complex carrier to be 30-60 microns,
Specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is distinguished in tri-modal distribution, and three peaks
The first most probable pore size of correspondence, the second most probable pore size and the 3rd most probable pore size, first most probable pore size is less than described
Second most probable pore size, second most probable pore size is less than the 3rd most probable pore size, and first most probable pore size
For 2-4 nanometers, second most probable pore size is 5-15 nanometers, and the 3rd most probable pore size is 10-40 nanometers.
Under preferable case, the component a1 and the component a2 cause the average grain diameter of the spherical complex carrier to be 30-
50 microns, specific surface area is 180-600 meters squared per grams, and pore volume is 0.9-1.2 mls/g, and first most probable pore size is small
In second most probable pore size, second most probable pore size is less than the 3rd most probable pore size, and described first most may be used
Several apertures are 2-4 nanometers, and second most probable pore size is 5-10 nanometers, and the 3rd most probable pore size is 10-25 nanometers.
In step (1), the preparation of the filter cake of the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture is prepared
Process includes：In the presence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with sour agent, and will
The mixture obtained after contact carries out crystallization and filtering.
According to the present invention, the template, ethanol, the consumption of trimethylpentane and tetramethoxy-silicane are not limited particularly
It is fixed, it can be changed in wider scope, usually, the template, ethanol, trimethylpentane and tetramethoxy-silicane rub
Your ratio can be 1：100-500：200-500：50-200, preferably 1：200-400：250-400：70-150.
The template can be various templates commonly used in the art.Most preferably, the template is three embedding
Section copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, the template can be commercially available (for example, can be purchased from
Aldrich, trade name P123, molecular formula is EO20PO70EO20), it can also be prepared into by existing various methods
Arrive.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template according to polyoxyethylene-
The mean molecule quantity of polyoxypropylene polyoxyethylene is calculated and obtained.
The sour agent can be used for the material or mixture (such as solution) for adjusting pH value for various routines.The sour agent
It is preferred that using in form of an aqueous solutions.Preferably, the sour agent is the acetic acid and sodium acetate that pH value is 1-6 (more preferably 3-5)
Cushioning liquid.
The condition that tetramethoxy-silicane is contacted with the sour agent can include：Temperature is 10-60 DEG C, preferably 15-40 DEG C；When
Between be 10-72 hours, preferably 20-45h；PH value is 1-7.In order to be more beneficial for the uniform mixing between each material, four methoxy
Base silane is contacted with sour agent and preferably carried out under agitation.The consumption of the sour agent is preferably so that tetramethoxy-silicane and sour agent
Haptoreaction system pH value be 1-7.
The condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.It is described under preferable case
The condition of crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
During the filter cake of meso-porous molecular sieve material in above-mentioned preparation with one-dimensional hexagonal hole road distributed architecture, pass through
Filtering can be included with the process for obtaining filter cake：After filtration, with deionized water cyclic washing, (washing times can be 2-
10) suction filtration, is then carried out.
In step (1), " providing the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture " can be direct
Weigh or choose the product of the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture or prepare with one-dimensional
The meso-porous molecular sieve material of hexagonal hole road distributed architecture.The meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture
Preparation method can implement according to the conventional method, for example, its preparation method can include：Being prepared according to the above method has
The filter cake of the meso-porous molecular sieve material of one-dimensional hexagonal hole road distributed architecture, then by gained filtration cakes torrefaction, and will be obtained after drying
Product in template removal.The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80
Hour.
In step (2), preparing the process of the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure includes：Will just
Silester, cetyl trimethylammonium bromide and ammonia haptoreaction, and the mixture obtained after haptoreaction is subjected to crystallization
And filtering.
According to the present invention, the mol ratio of the tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can be wider
In the range of change, as long as the meso-porous molecular sieve material filter cake with two-dimentional hexagonal hole road structure can be formed, usually,
The mol ratio of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can be 1：0.1-1：0.1-5, preferably 1：0.2-
0.5：1.5-3.5.
According to the present invention, ammonia is added preferably in the form of ammoniacal liquor.
According to the present invention, haptoreaction process the depositing in water of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia
Carried out lower.Preferably, part water is introduced in the form of ammoniacal liquor, and part water is added in the form of deionized water.In positive silicic acid second
In the haptoreaction system of ester, cetyl trimethylammonium bromide and ammonia, the mol ratio of tetraethyl orthosilicate and water can be 1：
100-200, preferably 1：120-180.
According to the present invention, the catalytic condition of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia is without spy
It is other to limit, as long as the meso-porous molecular sieve material filter cake with hexagonal hole road structure can be formed, usually, positive silicic acid second
The catalytic condition of ester, cetyl trimethylammonium bromide and ammonia can include：Temperature is 25-100 DEG C, preferably 40-80
℃；Time is 10-72 hours, preferably 24-72 hours.Preferably, the haptoreaction is carried out under agitation, in favor of between each material
Uniform mixing.
According to the present invention, there is no particular limitation for condition of the present invention to the crystallization, and the condition of the crystallization can be
The conventional selection in this area, for example, the condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.
Under preferable case, the condition of the crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40 hours.The crystallization passes through hydro-thermal
Crystallization method is implemented.
During the filter cake of meso-porous molecular sieve material in above-mentioned preparation with two-dimentional hexagonal hole road structure, pass through filtering
It can be included with the process for obtaining filter cake：After filtration, with deionized water cyclic washing (washing times can be 2-10 times),
Then suction filtration is carried out.
In step (2), " providing the meso-porous molecular sieve material with two-dimentional hexagonal hole road structure " can directly be weighed
Or choose the product of the meso-porous molecular sieve material with two-dimentional hexagonal hole road structure or prepare with two-dimentional hexagonal hole road
The meso-porous molecular sieve material of structure.The preparation method of the meso-porous molecular sieve material with two-dimentional hexagonal hole road structure can root
Implement according to conventional method, for example, its preparation method can include：Being prepared according to the above method has two-dimentional hexagonal hole road structure
Meso-porous molecular sieve material filter cake, then by gained filtration cakes torrefaction.
In step (3), preparing the process of the filter cake of silica gel can include：Waterglass is contacted with inorganic acid, and
The mixture obtained after contact is filtered.
There is no particular limitation for the weight ratio of the consumption of waterglass and inorganic acid, can be according to the conventional work for preparing silica gel
The appropriate determination of skill.Under preferable case, the weight ratio of the waterglass and inorganic acid can be 3-6:1.It should be noted that on
Stating the weight of waterglass includes the content of its reclaimed water.When the inorganic acid is as a solution in use, the weight of above-mentioned inorganic acid
Amount includes the content of its reclaimed water.
According to the present invention, there is no particular limitation for the condition that waterglass is contacted with inorganic acid, can be according to preparing silica gel
Suitably determined in common process.Under preferable case, the condition that waterglass is contacted with inorganic acid can include：Temperature is 10-60
DEG C, preferably 20-40 DEG C；Time is 1-5 hours, preferably 1.5-3 hours；PH value is 2-4.In order to be more beneficial between each material
Uniform mixing, waterglass preferably carries out under agitation with the catalytic process of inorganic acid.
The waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 weight %, preferably 12-30 weight %.
According to the present invention, the inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulphur
At least one of acid, nitric acid and hydrochloric acid.The inorganic acid can be used in pure form, can also be with the shape of its aqueous solution
Formula is used.The consumption of the inorganic acid is preferably so that the pH value of the haptoreaction system of waterglass and inorganic acid is 2-4.
In step (3), " offer silica gel " can directly be weighed or choose silica gel product or prepare silica gel.
Preparing the method for silica gel can implement according to the conventional method, for example, can include：The filter cake of silica gel is prepared according to the above method,
Then by gained filtration cakes torrefaction.
It is above-mentioned prepare the filter cake of silica gel during, can be included with the process for obtaining filter cake by filtering：In filtering
Afterwards, it is 0.01-0.03 weight % with the content of distilled water cyclic washing to sodium ion, then carries out suction filtration.
In step (4), relative to the component a1 and the component a2 of 100 parts by weight total consumption, the component b
Consumption can be 1-200 parts by weight, preferably 50-150 parts by weight；The weight of the component a1 and the component a2 consumption
Than that can be 1：0.1-10, preferably 1：0.5-2.
In step (4), the ball milling can be carried out in ball mill, and the inwall of ball grinder is preferably in the ball mill
The diameter of abrading-ball in polytetrafluoroethyllining lining, ball mill can be 2-3mm；The quantity of abrading-ball can be according to the size of ball grinder
Reasonably selected, for the ball grinder that size is 50-150ml, can generally use 1 abrading-ball；The material of the abrading-ball
Can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling can include：The rotating speed of abrading-ball can be
Temperature in 300-500r/min, ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hours.
In step (4), the process of the solid powder water slurrying obtained after ball milling can be entered at 25-60 DEG C
OK.In pulping process, the weight ratio of the consumption of solid powder and water can be 1：0.1-2, preferably 1：0.3-0.9.
In step (4), the spray drying can be implemented according to conventional mode, for example, can enter in atomizer
OK.The condition of the spray drying can include：Temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/
min；Under preferable case, the condition of the spray drying includes：Temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-
13000r/min。
In step (4), when the component a1 is the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture
Filter cake, the component a2 is the filter cake of the meso-porous molecular sieve material with two-dimentional hexagonal hole road structure, and the component b is silica gel
Filter cake when, namely when step (1) to prepare the filter cake of the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture
Process, step (2) is the process of the filter cake of meso-porous molecular sieve material of the preparation with two-dimentional hexagonal hole road distributed architecture, step
(3) when for the process for the filter cake for preparing silica gel, the preparation method of the spherical chlorite mesoporous composite material can also include：
After the spray drying of step (4), removed template method in the product obtained from spray drying.The condition of the removed template method can
With including：Temperature is 300-600 DEG C, and the time is 10-80 hours.
Present invention also offers the support type polyethylene catalyst prepared by the above method.
Present invention also offers a kind of support type polyethylene catalysts, wherein, the support type polyethylene catalysts include
Above-mentioned support type polyethylene catalyst and alkyl aluminum compound.
According to the present invention, the alkyl aluminum compound can be various alkyl aluminum chemical combination conventional in ethylene rolymerization catalyst
Thing.Usually, the alkyl in the alkyl aluminum compound is C1-C5Alkyl, it is preferable that the alkyl aluminum be triethyl aluminum.
In the present invention, the C1-C5Alkyl can for methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
One or more in isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
According to the present invention, there is no particular limitation for the consumption of the alkyl aluminum compound, under preferable case, the alkyl aluminum
The mol ratio of aluminium and the titanium in the catalytic component in compound can be 1-150：1, preferably 1-100：1.
Present invention also offers application of the above-mentioned support type polyethylene catalysts in vinyl polymerization.The method of concrete application
Prior art progress is referred to, be will not be repeated here.
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 purchased from Aldrich, writes a Chinese character in simplified form
For P123, molecular formula is EO20PO70EO20, the material for being 9003-11-6 in the registration number of U.S. chemical abstract, mean molecule
Measure as 5800.
In following examples and comparative example, X-ray diffraction analysis are in the model purchased from German Bruker AXS companies
Carried out on D8Advance X-ray diffractometer；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on electron microscope；Pore structure parameter analysis inhales de- in the nitrogen of the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on attached instrument, wherein, before being tested, sample is deaerated 4 hours at 200 DEG C；Type of the average grain diameter in Malvern company
Number for Mastersizer2000 laser fineness gage on carry out, sample is dissolved in ethanol；X-ray fluorescence analysis is in Holland
Carried out on the model Axios-Advanced of company x-ray fluorescence analyzer.
The heap density of polyolefine powder is measured using method as defined in GB/T1636-2008.
Melt index：Determined according to ASTM D1238-99.
Embodiment 1
The present embodiment is used to illustrate support type polyethylene catalyst of the present invention and preparation method thereof.
(1) spherical complex carrier is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 2.76g (0.06mol) ethanol is added to
28ml, pH value in 4 acetic acid and the buffer solution of sodium acetate, to stir to P123 and being completely dissolved at 15 DEG C, obtain backward
6g (0.053mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then adds 2.13g (0.014mol) four thereto
Methoxy silane, stirs 20h under conditions of 15 DEG C, pH value is 4.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reactor of lining, the crystallization 24h at 60 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is had
There is the filter cake X1 of the meso-porous molecular sieve material of one-dimensional hexagonal hole road distributed architecture；
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is rubbing for ammonia in 10g, tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor and water
You are than being 1：0.37：2.8：142, and stir at 80 DEG C 24h, then the hydro-thermal process 24h at 100 DEG C again, was then carried out
Filter and and be washed with deionized 4 times, then suction filtration obtains the filter of the meso-porous molecular sieve material with two-dimentional hexagonal hole road structure
Cake Y1.
The sulfuric acid solution that the waterglass and concentration for being 15 weight % by concentration are 12 weight % is using weight ratio as 5:1 is mixed
Merge haptoreaction 2 hours at 30 DEG C, then adjust pH value to 3 with concentration for 98 weight % sulfuric acid, then to obtaining
Reaction mass carries out suction filtration, and is washed with distilled water to sodium ions content for 0.02 weight %, obtains the filter cake B1 of silica gel.
5g filter cake X1,5g filter cake Y1 and 10g filter cakes B1 of above-mentioned preparation is put into 100ml ball grinders together, wherein, ball
The material of grinding jar is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, and rotating speed is 400r/
min.Ball grinder is closed, temperature is ball milling 1 hour at 60 DEG C in ball grinder, obtains 20g solid powders；The solid powder is molten
Solution is spray-dried in 18 grams of deionized waters at 200 DEG C in the case where rotating speed is 12000r/min；The production that will be obtained after spray drying
Thing is calcined 24 hours in Muffle furnace at 500 DEG C, and removed template method obtains 18 grams of spherical complex carrier C1.
(2) support type polyethylene catalyst is prepared
In N2Under protection, by 1g MgCl2With 1g TiCl4It is dissolved in 500mL tetrahydrofuran and the double solvents of isopropanol
(volume ratio of tetrahydrofuran and isopropanol is 1：1.2) in, the catalyst mother liquor of the component containing Mg and Ti is formed.Then in 75 DEG C of temperature
The lower above-mentioned spherical complex carrier C1 of 1g that add of degree are impregnated, dipping 4h.It is cooled to after room temperature, is then filtered, removes liquid
Obtain solid product after body, and with tetrahydrofuran cyclic washing solid product 4 times, it is finally that obtained solid product is true at 75 DEG C
Sky is dried 4 hours, obtains the powdery support type polyethylene catalyst Cat-1 with good flow performance.
It is glimmering with XRD, ESEM, U.S. Kang Ta companies Atsorb-1 type nitrogen adsorptions instrument, Particle Size Analyzer and X-ray
Light analysis is characterized to the supported catalyst component.
Fig. 1 is the X-ray diffracting spectrum of the spherical complex carrier C1 according to the present invention.The low-angle occurred by XRD spectra
Spectral peak understands that the spherical complex carrier has the hexagonal hole road structure of peacekeeping two dimension specific to mesoporous material.
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of the spherical complex carrier C1 according to the present invention.As seen from the figure, ball
Shape complex carrier C1 microscopic appearance is the Mesoporous Spheres that particle diameter is 30-60 μm.
Fig. 3 is the scanning electron microscope (SEM) photograph of support type polyethylene catalyst Cat-1 microscopic appearance.As seen from the figure, load
Type polyethylene catalyst Cat-1 microscopic appearance remains unchanged keeps spherical substantially, and particle diameter is 30-60 μm.
Fig. 4 is spherical complex carrier C1 pore size distribution curve figure.
Table 1 is spherical complex carrier C1 pore structure parameter.
Table 1
Spherical complex carrier C1 is three pore size distributions it can be seen from the data of upper table 1.
Elementary analysis result shows that the content of titanium is 2.0% in catalytic component, and the content of chlorine is 10.1%, Mg contents
For 3.5%.It is computed learning, on the basis of the total amount of catalytic component, the total content of magnesium chloride and titanium tetrachloride is 22 weights
% is measured, the content of carrier is 78 weight %.
Comparative example 1
Commercially available ES955 silica gel (GRACE companies) is calcined 10 hours 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 catalytic component, except that, using identical weight part
ES955 silica gel replaces spherical complex carrier C1.So as to which reference catalyst component DCat-1 is made.
Elementary analysis result shows that the content of titanium is 1.2% in reference catalyst component, and the content of chlorine contains for 6.8%, Mg
Measure as 1.8%.
Embodiment 2
The present embodiment is used to illustrate support type polyethylene catalyst of the present invention and preparation method thereof.
(1) spherical complex carrier is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethanol is added to
28ml, pH value in 5 acetic acid and the buffer solution of sodium acetate, to stir to P123 and being completely dissolved at 15 DEG C, obtain backward
9.12g (0.08mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then adds 3.04g (0.02mol) thereto
Tetramethoxy-silicane, stirs 45h under conditions of 25 DEG C, pH value is 5.5, obtained solution then is transferred into polytetrafluoroethylene (PTFE)
In the reactor of liner, the crystallization 20h at 100 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is obtained
To the filter cake X2 of the meso-porous molecular sieve material with one-dimensional hexagonal hole road single hole distributed architecture.
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is rubbing for ammonia in 10g, tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor and water
You are than being 1：0.2：3.5：120, and stir at 60 DEG C 48h, then the hydro-thermal process 20h at 80 DEG C again, is then filtered
With and be washed with deionized 4 times, then suction filtration obtains the filter cake of the meso-porous molecular sieve material with two-dimentional hexagonal hole road structure
Y2。
The sulfuric acid solution that the waterglass and concentration for being 15 weight % by concentration are 12 weight % is using weight ratio as 4:1 is mixed
Merge haptoreaction 1.5 hours at 40 DEG C, then pH value is adjusted to 2 with concentration for 98 weight % sulfuric acid, then to obtaining
Reaction mass carry out suction filtration, and be washed with distilled water to sodium ions content for 0.02 weight %, obtain the filter cake B2 of silica gel.
13g filter cake X2,7g filter cake Y2 and 10g filter cakes B2 of above-mentioned preparation is put into 100ml ball grinders together, wherein,
The material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, and rotating speed is 300r/
min.Ball grinder is closed, temperature is ball milling 0.5 hour at 80 DEG C in ball grinder, obtains 30g solid powders；By the solid powder
It is dissolved in 15 grams of deionized waters, is spray-dried at 250 DEG C in the case where rotating speed is 11000r/min；By what is obtained after spray drying
Product is calcined 15 hours in Muffle furnace at 550 DEG C, and removed template method obtains 28 grams of spherical complex carrier C2.
(2) supported catalyst component is prepared
In N2Under protection, by 1g MgCl2And 0.1gTiCl4It is dissolved in 500mL tetrahydrofuran and the double solvents of isopropanol
(volume ratio of tetrahydrofuran and isopropanol is 1：1.5) in, the catalyst mother liquor of the component containing Mg and Ti is formed.Then in 35 DEG C of temperature
The lower above-mentioned spherical complex carrier C2 of 2g that add of degree are impregnated, dipping 9h.It is cooled to after room temperature, is then filtered, removes liquid
Obtain solid product after body, and with tetrahydrofuran cyclic washing solid product 4 times, it is finally that obtained solid product is true at 75 DEG C
Sky is dried 4 hours, obtains the powdery support type polyethylene catalyst Cat-2 with good flow performance.
Table 2 is spherical complex carrier C2 pore structure parameter.
Table 2
Spherical complex carrier C2 is three pore size distributions it can be seen from the data of upper table 2.
Elementary analysis result shows that the content of titanium is 0.1% in catalytic component, and the content of chlorine is for 1.0%, Mg contents
3.7%.It is computed learning, on the basis of the total amount of catalytic component, the total content of magnesium chloride and titanium tetrachloride is 16 weight %,
The content of carrier is 84 weight %.
Embodiment 3
The present embodiment is used to illustrate loaded catalyst of the present invention and preparation method thereof.
(1) spherical complex carrier is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethanol is added to
28ml, pH value in 3 acetic acid and the buffer solution of sodium acetate, to stir to P123 and being completely dissolved at 15 DEG C, obtain backward
5.7g (0.05mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then adds 4.56g (0.03mol) four thereto
Methoxy silane, stirs 10h under conditions of 40 DEG C, pH value is 3.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reactor of lining, the crystallization 40h at 40 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is had
There is the filter cake X3 of the meso-porous molecular sieve material of one-dimensional hexagonal hole road single hole distributed architecture.
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is rubbing for ammonia in 10g, tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor and water
You are than being 1：0.5：1.5：180, and stir at 40 DEG C 72h, then the hydro-thermal process 40h at 40 DEG C again, is then filtered
With and be washed with deionized 4 times, then suction filtration obtains the filter cake of the meso-porous molecular sieve material with two-dimentional hexagonal hole road structure
Y3。
The sulfuric acid solution that the waterglass and concentration for being 15 weight % by concentration are 12 weight % is using weight ratio as 6:1 is mixed
Merge haptoreaction 3 hours at 20 DEG C, then adjust pH value to 4 with concentration for 98 weight % sulfuric acid, then to obtaining
Reaction mass carries out suction filtration, and is washed with distilled water to sodium ions content for 0.02 weight %, obtains the filter cake B3 of silica gel.
5g filter cake X3,10g filter cake Y3 and 22.5g filter cakes B3 of above-mentioned preparation is put into 100ml ball grinders together, its
In, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, and rotating speed is
500r/min.Ball grinder is closed, temperature is ball milling 10 hours at 40 DEG C in ball grinder, obtains 37.5g solid powders；This is consolidated
Body powder is dissolved in 11.5 grams of deionized waters, is spray-dried at 150 DEG C in the case where rotating speed is 13000r/min；Will spray drying
The product obtained afterwards is calcined 70 hours in Muffle furnace at 450 DEG C, and removed template method obtains 35 grams of spherical chlorite mesoporous multiple
Condensation material C3.
(2) supported catalyst component is prepared
In N2Under protection, by 1g MgCl2With 1.5g TiCl4It is dissolved in 500mL tetrahydrofuran and isopropanol double solvents
(volume ratio of tetrahydrofuran and isopropanol is 1：1) in, the catalyst mother liquor of the component containing Mg and Ti is formed.Then in 60 DEG C of temperature
The above-mentioned spherical complex carrier C1 of lower addition 0.2g are impregnated, and impregnate 2h.It is cooled to after room temperature, is then filtered, removes liquid
Obtain solid product after body, and with tetrahydrofuran cyclic washing solid product 4 times, it is finally that obtained solid product is true at 75 DEG C
Sky is dried 4 hours, obtains the powdery support type polyethylene catalyst Cat-3 with good flow performance.
Table 3 is spherical complex carrier C3 pore structure parameter.
Table 3
Spherical complex carrier C3 is three pore size distributions it can be seen from the data of upper table 3.
Elementary analysis result shows that the content of titanium is 3% in catalytic component, and the content of chlorine is for 15%, Mg contents
4%.It is computed learning, on the basis of the total amount of catalytic component, the total content of magnesium chloride and titanium tetrachloride is 28 weight %, is carried
The content of body is 72 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity of the support type polyethylene catalysts according to the present invention.
In 2 liters of stainless steel polymerization autoclave, with nitrogen and ethene respectively displacement three times, 200 milliliters of hexanes are then added,
Kettle temperature is risen to 80 DEG C, 800 milliliters of hexanes are added, with the addition of hexane, the concentration for adding 2 milliliters is the three of 1 mol/L
Aluminium ethide (TEA) hexane solution, is subsequently added into 0.1g support type polyethylene catalyst Cat-1, ethene is passed through, by pressure
Rise to 1.0MPa and be maintained 1.0MPa, reacted 1 hour at 70 DEG C.Polyethylene particle powder is obtained, the polyethylene particle powder
Heap density (BD) be 0.37g/ml, melt index MI2.16=1.28g/10min.It is computed determining, the efficiency of catalyst is
3043g PE/gcat.h。
Experimental comparison's example 1
Polymerizeing for ethene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 1, unlike, using pair of identical weight part
DCat-1 prepared by ratio 1 replaces catalytic component Cat-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/gcat.h.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating the application according to the loaded catalyst of the present invention in vinyl polymerization.
In 2 liters of stainless steel polymerization autoclave, with nitrogen and ethene respectively displacement three times, 200 milliliters of hexanes are then added,
Kettle temperature is risen to 80 DEG C, 800 milliliters of hexanes are added, with the addition of hexane, the concentration for adding 2 milliliters is the three of 1 mol/L
Aluminium ethide (TEA) hexane solution, is subsequently added into 0.1 gram of polyethylene catalyst Cat-2, is passed through ethene, pressure is risen to
1.0MPa is simultaneously maintained 1.0MPa, is reacted 1 hour at 70 DEG C.The heap density (BD) of the polyethylene particle powder is 0.39g/ml,
Melt index MI2.16=1.53g/10min.It is computed determining, the efficiency of catalyst is 3101g PE/gcat.h.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for illustrating the application according to the loaded catalyst of the present invention in vinyl polymerization.
In 2 liters of stainless steel polymerization autoclave, with nitrogen and ethene respectively displacement three times, 200 milliliters of hexanes are then added,
Kettle temperature is risen to 80 DEG C, 800 milliliters of hexanes are added, with the addition of hexane, the concentration for adding 2 milliliters is the three of 1 mol/L
Aluminium ethide (TEA) hexane solution, is subsequently added into 0.1 gram of polyethylene catalyst Cat-3, is passed through ethene, pressure is risen to
1.0MPa is simultaneously maintained 1.0MPa, is reacted 1 hour at 80 DEG C.The heap density (BD) of the polyethylene particle powder is 0.35g/ml,
Melt index MI2.16=1.31g/10min.It is computed determining, the efficiency of catalyst is 2908g PE/gcat.h.
It can be seen from EXPERIMENTAL EXAMPLE 1-3 more than in ethylene polymerisation process, the catalyst containing embodiment 1-3
The catalyst of component has higher catalytic efficiency.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (30)
1. a kind of support type polyethylene catalyst, the support type polyethylene catalyst include spherical complex carrier with
And it is supported on magnesium salts and titanium salt on the spherical complex carrier, it is characterised in that the spherical complex carrier contains with one
Tie up the meso-porous molecular sieve material of hexagonal hole road distributed architecture, the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture and
Silica gel, the average grain diameter of the spherical complex carrier is 30-60 microns, and specific surface area is 150-600 meters squared per grams, pore volume
For 0.5-1.5 mls/g, aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size, the second most probable pore size respectively
With the 3rd most probable pore size, first most probable pore size is less than second most probable pore size, second most probable pore size
Less than the 3rd most probable pore size, first most probable pore size is 2-4 nanometers, and second most probable pore size is received for 5-15
Rice, the 3rd most probable pore size is 10-40 nanometers.
2. catalytic component according to claim 1, wherein, on the basis of the total amount of the catalytic component, the magnesium
The total content of salt and titanium salt is 1-50 weight %, and the content of the spherical complex carrier is 50-99 weight %, the magnesium salts and titanium
The weight ratio of salt is 1：0.1-2.
3. catalytic component according to claim 1 or claim 2, wherein, on the basis of the total amount of the catalytic component, the magnesium
The total content of salt and titanium salt is 40-50 weight %, and the content of the spherical complex carrier is 50-60 weight %, the magnesium salts and
The weight ratio of titanium salt is 1：0.1-1.5.
4. catalytic component according to claim 1, wherein, relative to having one-dimensional hexagonal hole described in 100 parts by weight
The total amount of the meso-porous molecular sieve material of road distributed architecture and meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, institute
The content for stating silica gel is 1-200 parts by weight；The meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture with it is described
The weight ratio of meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture is 1：0.1-10.
5. the catalytic component according to claim 1 or 4, wherein, relative to having one-dimensional six side described in 100 parts by weight
The total amount of the meso-porous molecular sieve material of pore distribution structure and meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture,
The content of the silica gel is 50-150 parts by weight；The meso-porous molecular sieve material and institute with one-dimensional hexagonal hole road distributed architecture
The weight ratio for stating the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture is 1：0.5-2.
6. a kind of preparation method of support type polyethylene catalyst, this method is included under inert gas shielding, will be spherical
Complex carrier is contacted with the solution containing magnesium salts and the compounded organic solvent of titanium salt, it is characterised in that the spherical complex carrier
Mesoporous point containing the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, with two-dimentional hexagonal hole road distributed architecture
Son sieve material and silica gel, the average grain diameter of the spherical complex carrier is 30-60 micron, specific surface area for 150-600 square metres/
Gram, pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size, second respectively
Most probable pore size and the 3rd most probable pore size, first most probable pore size are 2-4 nanometers, and second most probable pore size is 5-
15 nanometers, the 3rd most probable pore size is 10-40 nanometers.
7. method according to claim 6, wherein, the magnesium salts, the titanium salt and the spherical complex carrier consumption
Weight ratio is 1：0.1-2：0.02-2.
8. method according to claim 7, wherein, the magnesium salts, the titanium salt and the spherical complex carrier consumption
Weight ratio is 1：0.1-1.5：0.2-2.
9. the method according to any one in claim 6-8, wherein, the magnesium salts is magnesium chloride；The titanium salt is four
Titanium chloride and/or titanium trichloride.
10. method according to claim 6, wherein, the compounded organic solvent is tetrahydrofuran and isopropanol.
11. method according to claim 6, wherein, the condition of the contact includes：Temperature is 25-100 DEG C, and the time is
1-12 hours.
12. the method according to any one in claim 6-8, wherein, the spherical complex carrier passes through following side
It is prepared by method：
(1) providing the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture or preparing has one-dimensional hexagonal hole road point
The filter cake of the meso-porous molecular sieve material of cloth structure, is used as component a1；
(2) providing the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparing has two-dimentional hexagonal hole road point
The filter cake of the meso-porous molecular sieve material of cloth structure, is used as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(4) the component a1, the component a2 and the component b are mixed and ball milling, and the solid that will be obtained after ball milling
Obtained slurry, is then spray-dried by powder water slurrying；
Wherein, the component a1 and the component a2 make it that the average grain diameter of the spherical complex carrier is 30-60 microns, compare table
Area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is corresponded to respectively in tri-modal distribution, and three peaks
First 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 described second
Most probable pore size, second most probable pore size is less than the 3rd most probable pore size, and first most probable pore size is 2-4
Nanometer, second most probable pore size is 5-15 nanometers, and the 3rd most probable pore size is 10-40 nanometers.
13. method according to claim 12, wherein, in step (4), relative to the component a1 of 100 parts by weight
With total consumption of the component a2, the consumption of the component b is 1-200 parts by weight；The component a1 and the component a2 weight
Amount is than being 1：0.1-10.
14. method according to claim 13, wherein, in step (4), relative to the component a1 of 100 parts by weight
With total consumption of the component a2, the consumption of the component b is 50-150 parts by weight；The component a1 and the component a2 weight
Amount is than being 1：0.5-2.
15. method according to claim 12, wherein, it is described that there is one-dimensional hexagonal hole road distributed architecture in step (1)
The preparation process of filter cake of meso-porous molecular sieve material include：In the presence of template, trimethylpentane and ethanol, by tetramethyl
TMOS is contacted with sour agent, and the mixture obtained after contact is carried out into crystallization and filtering.
16. method according to claim 15, wherein, the template, ethanol, trimethylpentane and tetramethoxy-silicane
Mol ratio be 1：100-500：200-500：50-200.
17. method according to claim 16, wherein, the template, ethanol, trimethylpentane and tetramethoxy-silicane
Mol ratio be 1：200-400：250-400：70-150.
18. method according to claim 15, wherein, the template is triblock copolymer polyoxyethylene-polyoxy third
Alkene-polyoxyethylene；The sour agent is the cushioning liquid of the acetic acid that pH value is 1-6 and sodium acetate；Tetramethoxy-silicane and the acid
The condition of agent contact includes：Temperature is 10-60 DEG C, and the time is 10-72 hours, and pH value is 1-7；The condition of the crystallization includes：
Temperature is 30-150 DEG C, and the time is 10-72 hours.
19. method according to claim 12, wherein, in step (2), prepare Jie with two-dimentional hexagonal hole road structure
The process of the filter cake of porous molecular sieve material includes：By tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia haptoreaction, and
The mixture obtained after haptoreaction is subjected to crystallization and filtering.
20. method according to claim 19, wherein, tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia rub
You are than being 1：0.1-1：0.1-5.
21. method according to claim 20, wherein, tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia rub
You are than being 1：0.2-0.5：1.5-3.5.
22. method according to claim 19, wherein, the catalytic condition includes：Temperature is 25-100 DEG C, when
Between be 10-72 hours；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is 10-72 hours.
23. method according to claim 12, wherein, in step (3), preparing the process of the filter cake of silica gel includes：Will
Waterglass is contacted with inorganic acid, and the mixture obtained after contact is filtered.
24. method according to claim 23, wherein, the condition that waterglass is contacted with inorganic acid includes：Temperature is 10-60
DEG C, the time is 1-5 hours, and pH value is 2-4；The inorganic acid is the one or more in sulfuric acid, nitric acid and hydrochloric acid.
25. method according to claim 12, wherein, in step (4), the condition of the ball milling includes：Turn of abrading-ball
Speed is that the temperature in 300-500r/min, ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hours；The spraying is dry
Dry condition includes：100-300 DEG C of temperature, rotating speed is 10000-15000r/min.
26. method according to claim 12, wherein, the component a1 is Jie with one-dimensional hexagonal hole road distributed architecture
The filter cake of porous molecular sieve material, the component a2 is the filter of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture
Cake, the component b is the filter cake of silica gel, and methods described also includes：It is dry from spraying after the spray-drying process of step (4)
Removed template method in dry obtained product.
27. method according to claim 26, wherein, the condition of the removed template method includes：Temperature is 300-600
DEG C, the time is 10-80 hours.
28. support type polyethylene catalyst prepared by the method in claim 6-27 described in any one.
29. a kind of support type polyethylene catalysts, it is characterised in that the support type polyethylene catalysts include claim 1-
Catalytic component and alkyl aluminum compound in 5 and 28 described in any one.
30. application of the support type polyethylene catalysts in vinyl polymerization described in claim 29.
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| CN107417832A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of ethene polymerization method and polyethylene |
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