CN108017740A - Spherical porous mesoporous composite material and loaded catalyst and preparation method thereof - Google Patents
Spherical porous mesoporous composite material and loaded catalyst and preparation method thereof Download PDFInfo
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- CN108017740A CN108017740A CN201610944124.4A CN201610944124A CN108017740A CN 108017740 A CN108017740 A CN 108017740A CN 201610944124 A CN201610944124 A CN 201610944124A CN 108017740 A CN108017740 A CN 108017740A
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- 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
Abstract
The present invention relates to mesoporous materials field, discloses a kind of spherical porous mesoporous composite material and loaded catalyst and preparation method thereof.The spherical porous mesoporous composite material contains the meso-porous molecular sieve material with one-dimensional straight channels structure and the meso-porous molecular sieve material with hexagonal hole road structure, the average grain diameter of the spherical porous mesoporous composite material is 21 29 microns, specific surface area is 200 650 meters squared per grams, pore volume is 0.5 1.8 mls/g, and aperture is in tri-modal distribution.The meso-hole structure of spherical porous mesoporous composite material provided by the invention is stablized, particle diameter distribution is uniform, it is non-breakable as catalyst carrier intensity height, and the support type polyethylene catalysts being prepared by it are used for having high catalytic activity when catalyzed ethylene polymerization reacts, and can obtain heap density and the relatively low and non-breakable polyethylene product of melt index.
Description
Technical field
The present invention relates to mesoporous materials field, and in particular, to a kind of spherical porous mesoporous composite material, this is spherical porous
The preparation method of mesoporous composite material, the spherical porous mesoporous composite material prepared by this method, a kind of loaded catalyst, one
The preparation method of kind loaded catalyst, and the loaded catalyst prepared by this method.
Background technology
Since the regular mesoporous material of Mobile companies synthesis duct high-sequential in 1992, since it is with high ratio table
Face, regular pore passage structure and narrow pore-size distribution so that mesoporous material is applied in catalysis, separation, medicine and other fields
Very big concern is arrived.Zhao east member in 1998 et al. synthesizes a kind of new material-mesoporous material SBA-15, which has height
Spend orderly aperture (6-30nm), big pore volume (1.0cm3/ g), thicker hole wall (4-6nm), keep high mechanical properties
And good catalytic adsorption performance is (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, mesoporous material made from this method
Material is used as heterogeneous reaction catalyst carrier, the separation of catalyst and product easy to implement.
But conventional ordered mesoporous material SBA-15 microscopic appearances are bar-shaped, itself mobility is poor, its big ratio
Surface area and high pore volume cause to make it have stronger water suction, moisture absorption ability, this has been further exacerbated by the group of ordered mesoporous material
It is poly-, limit the storage of ordered mesoporous material, transport, post-processing and application.
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
Homogeneous polyethylene catalyst reach needed for high activity catalyst amount is big, production cost is high, and obtained polymer is without grain
Shape, can not use on widely used slurry process or gas phase polymerization technique.The effective way for overcoming the above problem is exactly handle
Soluble poly catalyst for ethylene carries out supported processing.At present, the supported research report of related polyethylene catalysts is very more.For
Further investigate new support/catalyst/co-catalyst system, it is necessary to study different carriers, with promote carried catalyst and
The further development of polyolefin industry.
The mesoporous material for the load polyethylene catalysts reported at present on document is MCM-41, is loaded again after being handled with MAO
Catalytic activity is 10 after the MCM-41 of polyethylene catalysts carries out vinyl polymerization6gPE/(mol Zr h).Mesoporous silica MCM 41
Hole wall structure heat endurance and the hydro-thermal that the reason for ethylene polymerization activity is relatively low mainly MCM-41 is carried out after supported catalyst are steady
It is qualitative poor, just there is part to cave in loading process hole wall, load effect is have impact on, so that have impact on catalytic activity.
Therefore, seek the mesoporous material that a kind of meso-hole structure is stablized, still can keep orderly after load active component
Meso-hole structure and be still a technical problem urgently to be resolved hurrily with the loaded catalyst of higher catalytic activity.
The content of the invention
The purpose of the present invention is overcome the defects of meso-hole structure is unstable in the prior art, there is provided a kind of spherical porous Jie
Hole composite material and the loaded catalyst containing the composite material, the particle diameter of the spherical porous mesoporous composite material it is small and
It is evenly distributed, meso-hole structure is stablized.Heap can be obtained using the loaded catalyst containing the spherical porous mesoporous composite material
Density and the relatively low and non-breakable polyethylene product of melt index.
Specifically, in a first aspect, the present invention provides a kind of spherical porous mesoporous composite material, this is spherical porous mesoporous multiple
Condensation material contains the meso-porous molecular sieve material with one-dimensional straight channels structure and the mesopore molecular sieve with hexagonal hole road structure
Material, the average grain diameter of the spherical porous mesoporous composite material are 21-29 micron, specific surface area is 200-650 square metres/
Gram, pore volume is 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size, second most respectively
Can several apertures and the 3rd most probable pore size, and first most probable pore size is 1-10 nanometers, and second most probable pore size is
20-35 nanometers, the 3rd most probable pore size is 40-50 nanometers.
Second aspect, the present invention provides a kind of preparation method of spherical porous mesoporous composite material, this method include with
Lower step：
(1) meso-porous molecular sieve material with one-dimensional straight channels structure is provided or is prepared with one-dimensional straight channels knot
The filter cake of the meso-porous molecular sieve material of structure, as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or is prepared with the mesoporous of hexagonal hole road structure
The filter cake of molecular screen material, as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, as component b；
(4) by the component a1, the component a2 and the component b is mixed and the first ball milling, will obtain first
Ball milling slurry and water mixed pulp, then carry out the second ball milling and obtain the second ball milling slurry, the second ball milling slurry is sprayed
Screened after mist drying using Cyclone Separation Technology；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical porous mesoporous composite material is 21-29 microns, compare surface
Product is 200-650 meters squared per grams, and pore volume is 0.5-1.8 mls/g, 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, and first most probable pore size is 1-10 nanometers, it is described
Second most probable pore size is 20-35 nanometers, and the 3rd most probable pore size is 40-50 nanometers.
The third aspect, the present invention provides the spherical porous mesoporous composite material prepared by the above method.
Fourth aspect, the present invention provides a kind of loaded catalyst, which contains carrier and is supported on the load
Magnesium salts and/or titanium salt on body, wherein, the carrier is spherical porous mesoporous composite material provided by the invention.
5th aspect, the preparation method the present invention provides a kind of loaded catalyst and the load by this method preparation
Type catalyst, this method include：In the presence of an inert gas, carrier is contacted with the mother liquor containing magnesium salts and/or titanium salt；Its
In, the carrier is spherical porous mesoporous composite material provided by the invention.
Present invention employs the Cyclone Separation Technology in secondary ball milling technology and spray drying technology, secondary ball milling technology makes
Obtained slurry is finer and smoother, the spheroidal particle stable structure obtained after being spray-dried, can be with as catalyst carrier
Recycle, intensity height is non-breakable, and the preparation of the spherical porous mesoporous composite material of the present invention need not be used and bonded
Agent, can thus be destroyed to avoid the structure of the sample during high temperature removal binding agent.Using Cyclone Separation Technology,
The particle diameter of obtained spherical porous mesoporous composite material is small, particle diameter distribution is uniform and grading curve is narrow, can be to avoid making
The reunion of ordered mesoporous material during, improves its mobility, storage to ordered mesoporous material, transport, post-processing and
Using bringing convenience.
In addition, the meso-hole structure of spherical porous mesoporous composite material provided by the invention is stablized, after load active component
Orderly meso-hole structure is maintained to, the loaded catalyst good fluidity that will be prepared by it.The support type is urged
When agent is used for ethylene polymerization, heap density and the relatively low and non-breakable polyethylene product of melt index, tool can be obtained
Body, the flour rate of the polyethylene product of preparation is less than 3 weight %.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, 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 diffraction pattern (XRD spectra) of the spherical porous mesoporous composite material in embodiment 1, abscissa 2
θ, ordinate are intensity；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the spherical porous mesoporous composite material microscopic appearance in embodiment 1；
Fig. 3 is the size distribution curve of the spherical porous mesoporous composite material in embodiment 1；
Fig. 4 is the graph of pore diameter distribution of the spherical porous mesoporous composite material in embodiment 1.
Embodiment
The embodiment of the present invention is described in detail below.It is 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 endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of spherical porous mesoporous composite material, which contains with one
The meso-porous molecular sieve material of straight channels structure and the meso-porous molecular sieve material with hexagonal hole road structure are tieed up, it is described spherical porous
The average grain diameter of mesoporous composite material is 21-29 microns, and specific surface area is 200-650 meters squared per grams, pore volume 0.5-1.8
Ml/g, aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size respectively, the second most probable pore size and the 3rd most may be used
Several apertures, and first most probable pore size be 1-10 nanometer, second most probable pore size be 20-35 nanometers, the described 3rd
Most probable pore size is 40-50 nanometers.
A kind of preferred embodiment according to the present invention, the average grain diameter of the spherical porous mesoporous composite material are
22-28 microns, specific surface area is 220-300 meters squared per grams, and pore volume is 1.1-1.7 mls/g, and aperture is in tri-modal distribution, and
Three peaks correspond to 6-9 nanometers of the first most probable pore size, 22-32 nanometers of the second most probable pore size and the 3rd most probable pore size 42- respectively
50 nanometers；
A kind of preferred embodiment according to the present invention, the average grain diameter of the spherical porous mesoporous composite material are
23-27 microns, specific surface area is 220-275 meters squared per grams, and pore volume is 1.2-1.5 mls/g, and aperture is in tri-modal distribution, and
Three peaks correspond to 7-8 nanometers of the first most probable pore size, 24-31 nanometers of the second most probable pore size and the 3rd most probable pore size 45- respectively
50 nanometers.
In the present invention, the average grain diameter of the spherical porous mesoporous composite material is measured using laser fineness gage,
Specific surface area, pore volume and most probable pore size are measured according to nitrogen adsorption methods, the surface of the spherical porous mesoporous composite material
Pattern is measured by scanning electron microscope instrument (SEM).In the present invention, the average grain diameter is average particulate diameter.
In the present invention, the meso-porous molecular sieve material with one-dimensional straight channels structure and described with hexagonal hole road
The ratio of the meso-porous molecular sieve material of structure can be in interior variation in a big way, for example, Jie with one-dimensional straight channels structure
Porous molecular sieve material and with hexagonal hole road structure meso-porous molecular sieve material weight ratio can be 1：0.1-10, is preferably 1：
0.5-2。
In the present invention, the spherical porous mesoporous composite material does not contain binding agent such as polyvinyl alcohol or polyethylene glycol
Deng.
In the present invention, the spherical porous mesoporous composite material can also contain the silica introduced by silica gel.
" silica being introduced into by silica gel " refers in the preparation process of the spherical porous mesoporous composite material, by silica gel conduct
Preparing raw material brings the silica component in the spherical porous mesoporous composite material finally prepared into.Described spherical porous mesoporous
In composite material, relative to the meso-porous molecular sieve material described in 100 parts by weight with one-dimensional straight channels structure and the tool
There is the total amount of the meso-porous molecular sieve material of hexagonal hole road structure, the content of the silica introduced by silica gel can be 1-
200 parts by weight, are preferably 20-180 parts by weight, more preferably 50-150 parts by weight.
Present invention also offers a kind of preparation method of spherical porous mesoporous composite material, this method comprises the following steps：
(1) meso-porous molecular sieve material with one-dimensional straight channels structure is provided or is prepared with one-dimensional straight channels knot
The filter cake of the meso-porous molecular sieve material of structure, as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or is prepared with the mesoporous of hexagonal hole road structure
The filter cake of molecular screen material, as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, as component b；
(4) by the component a1, the component a2 and the component b is mixed and the first ball milling, will obtain first
Ball milling slurry and water mixed pulp, then carry out the second ball milling and obtain the second ball milling slurry, the second ball milling slurry is sprayed
Screened after mist drying using Cyclone Separation Technology；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical porous mesoporous composite material is 21-29 microns, compare surface
Product is 200-650 meters squared per grams, and pore volume is 0.5-1.8 mls/g, 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, and first most probable pore size is 1-10 nanometers, it is described
Second most probable pore size is 20-35 nanometers, and the 3rd most probable pore size is 40-50 nanometers.
A kind of preferred embodiment according to the present invention, the average grain diameter of the spherical porous mesoporous composite material are
22-28 microns, specific surface area is 220-300 meters squared per grams, and pore volume is 1.1-1.7 mls/g, and aperture is in tri-modal distribution, and
Three peaks correspond to 6-9 nanometers of the first most probable pore size, 22-32 nanometers of the second most probable pore size and the 3rd most probable pore size 42- respectively
50 nanometers；
A kind of preferred embodiment according to the present invention, the average grain diameter of the spherical porous mesoporous composite material are
23-27 microns, specific surface area is 220-275 meters squared per grams, and pore volume is 1.2-1.5 mls/g, and aperture is in tri-modal distribution, and
Three peaks correspond to 7-8 nanometers of the first most probable pore size, 24-31 nanometers of the second most probable pore size and the 3rd most probable pore size 45- respectively
50 nanometers.
In the present invention, by by the control of the particle size of spherical porous mesoporous composite material within the above range, can be with
Ensure that the spherical porous mesoporous composite material is not susceptible to reunite, and be used as loaded catalyst made of carrier can
To improve the reaction raw materials conversion ratio during ethylene polymerization.
In the preparation process of above-mentioned spherical porous mesoporous composite material, mainly by controlling mesoporous material filter cake (component
A1 and component a2) composition, be tri-modal distribution by the control of the pore-size distribution of the spherical porous mesoporous composite material, and mainly lead to
Control forming method is crossed (that is, the component a1 and component a2 and the component b first to be carried out mixing and the first ball milling, will obtained
The first ball milling slurry and water mixed pulp, then carry out the second ball milling and obtain the second ball milling slurry, by the second ball milling slurry
It is spray-dried) microscopic appearance of the spherical porous mesoporous composite material is controlled to be spherical.
According to the present invention, in step (1), the filter cake of the meso-porous molecular sieve material with one-dimensional straight channels structure is prepared
Process can include：Template, silicon source, ethanol, trimethylpentane and sour agent are carried out first to be mixed, and first is mixed
The mixture that splice grafting touches carries out crystallization and filtering；There is no particular limitation for first order being mixed, Ke Yixian
Template, silicon source, ethanol, trimethylpentane and sour agent are carried out at the same time mixing, any two or three can also be mixed, then
Other components are added to be uniformly mixed.A kind of preferred embodiment according to the present invention, first mixes template, ethanol and sour agent
Uniformly, then add trimethylpentane to be uniformly mixed, it is equal then to add silicon source (such as can be tetramethoxy-silicane) mixing
It is even.
In the present invention, the dosage of the template, ethanol, trimethylpentane and silicon source can be in interior change in a big way
It is dynamic, for example, template, ethanol, the molar ratio of trimethylpentane and silicon source can be 1：100-500：200-500：50-200, more
Preferably 1：180-400：250-400：70-150.
In the present invention, the template can be the various templates of this area routine, as long as the ball enabled to
The pore structure of the porous mesoporous composite material of shape meets the requirements.For example, the template can be triblock copolymer polyoxy
Ethene-polyoxypropylene polyoxyethylene.Wherein, which can be commercially available (for example, it is public to be purchased from Aldrich
Department, trade name P123, molecular formula EO20PO70EO20, molecular weight Mn is that 5800), can also pass through existing various method systems
It is standby to obtain.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxy
The number-average molecular weight of ethene-polyoxypropylene polyoxyethylene is calculated.
In the present invention, the silicon source can be various silicon sources commonly used in the art.For example, the silicon source can be
At least one in ethyl orthosilicate, methyl orthosilicate (also known as tetramethoxy-silicane), positive silicic acid propyl ester, sodium metasilicate and Ludox
Kind, it is preferably tetramethoxy-silicane.
In the present invention, the sour agent can be various acidic aqueous solutions commonly used in the art, it is preferable that the acid
Agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6.There is no particular limitation for the dosage of the acid agent, can be in larger model
Enclose interior variation, it is preferable that the first pH value being mixed is 1-7.
To first condition being mixed there is no particular limitation by the present invention, for example, described first is mixed
Condition generally includes：Temperature can be 10-60 DEG C, be preferably 10-20 DEG C；It is preferably 10-30 when time can be 10-72 small
Hour；PH value can be 1-7, be preferably 3-6.It is a kind of excellent according to the present invention in order to be more advantageous to the uniform mixing between each material
The embodiment of choosing, described first is mixed and carries out under agitation.
In the present invention, the condition of the crystallization of first mixture being mixed includes：Temperature can be 30-
150 DEG C, be preferably 40-80 DEG C；When time can be 10-72 small, when being preferably 20-30 small.According to a kind of preferable embodiment party
Formula, the crystallization are implemented by hydrothermal crystallization method.
In step (1), there is the mistake of the filter cake of the meso-porous molecular sieve material of one-dimensional straight channels structure in above-mentioned preparation
Cheng Zhong, can be included by filtering with the process for obtaining filter cake：After filtration, (washing times are washed repeatedly with deionized water
Can be 2-10), then filtered.
In step (1), " providing the meso-porous molecular sieve material with one-dimensional straight channels structure " can directly be weighed
Or choose the product of the meso-porous molecular sieve material with one-dimensional straight channels structure or prepare with one-dimensional straight channels
The meso-porous molecular sieve material of structure.The preparation method of the meso-porous molecular sieve material with one-dimensional straight channels structure can root
Implement according to conventional method, for example, its preparation method can include：Being prepared according to the above method has one-dimensional straight channels structure
Meso-porous molecular sieve material filter cake, then by gained filtration cakes torrefaction.
According to the present invention, in step (2), the mistake of the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure is prepared
Journey can include：Ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia progress second is mixed, and second is mixed
Obtained mixture is contacted to be filtered.
According to the present invention, during the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure is prepared, each thing
The content of matter can also make choice and adjust in a wider scope, for example, the ethyl orthosilicate, cetyl trimethyl
The molar ratio of ammonium bromide and ammonia can be 1：0.1-1：0.1-5, is preferably 1：0.2-0.5：1.5-3.5.
In the present invention, the ammonia adds preferably in the form of ammonium hydroxide.The ammonium hydroxide of the present invention can be that concentration is 10-
25 weight %.
In the present invention, the second of ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia is mixed process in water
In the presence of carry out.Preferably, part water is introduced in the form of ammonium hydroxide, and part water is added in the form of deionized water.In positive silicon
Acetoacetic ester, the second of cetyl trimethylammonium bromide and ammonia are mixed in system, and the molar ratio of ethyl orthosilicate and water can
Think 1:100-200, is preferably 1:120-180.
There is no particular limitation to second condition being mixed by the present invention, such as can include：The temperature of contact
It it is preferably 50-90 DEG C for 25-100 DEG C；When the time of contact is 2-8 small, when being preferably 3-7 small, pH value can be 7.5-11,
Preferable ph is 8-10.Preferably, second it is mixed and carries out under agitation, in favor of the uniform mixing between each material.
During the filter cake in above-mentioned preparation with the meso-porous molecular sieve material of hexagonal hole road structure, obtained by filtering
Obtaining the process of filter cake can include：After filtration, (washing times can be 2-10), Ran Houjin are washed repeatedly with deionized water
Row filters.
According to the present invention, in step (2), " providing the meso-porous molecular sieve material with hexagonal hole road structure " can be straight
Connect the product for weighing or choosing the meso-porous molecular sieve material with hexagonal hole road structure or prepare with hexagonal hole road knot
The meso-porous molecular sieve material of structure.The preparation method of the meso-porous molecular sieve material with hexagonal hole road structure can be according to routine
Method implement, for example, its preparation method can include：Mesoporous molecular with hexagonal hole road structure is prepared according to the above method
The filter cake of material is sieved, then by gained filtration cakes torrefaction.
According to the present invention, in step (3), preparing the process of the filter cake of silica gel can include：By waterglass, polyalcohol and
Inorganic acid carries out the 3rd and is mixed, and the 3rd mixture being mixed is filtered.
In the present invention, there is no particular limitation for the 3rd condition being mixed, can be according to preparing the normal of silica gel
Rule technique suitably determines.For example, the 3rd condition being mixed includes：Temperature can be 10-60 DEG C, be preferably 20-
40℃；When time can be 1-5 small, when being preferably 1-3 small；PH value is 2-4.It is uniformly mixed between each material in order to be more advantageous to
Close, the 3rd process being mixed preferably carries out under agitation.
In the present invention, the dosage of the waterglass, inorganic acid and polyalcohol can be in interior variation in a big way.For example,
The weight ratio of the waterglass, inorganic acid and polyalcohol can be 1-8：0.1-5：1, it is preferably 3-6：0.5-4：1, more preferably
3-6：1-3：1.
In the present invention, the waterglass is the aqueous solution of sodium metasilicate, its concentration can be 3-20 weight %, is preferably
10-20 weight %.The inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulfuric acid, nitric acid and
One or more in hydrochloric acid.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution,
It is preferred that used in the form of the aqueous solution of 3-20 weight %.The dosage of the inorganic acid is preferably so that contact of the waterglass with inorganic acid
The pH value of reaction system is 2-4.
In the present invention, there is no particular limitation for the species of the polyalcohol, such as can be glycerine and/or second two
Alcohol, is preferably glycerine.
According to the present invention, 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：Prepared according to the above method
The filter cake of silica gel, 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：Filtering
Afterwards, it is below 0.2 weight % to wash to the content of sodium ion, is preferably 0.01-0.03 weight %, is then filtered.Wash
The mode washed is the conventional selection of this area, can be that washing and/or alcohol are washed, actual conditions is ripe for those skilled in the art
Know, details are not described herein.
According to the present invention, in step (4), the dosage of the component a1, component a2 and component b can be interior in a big way
Change, for example, total dosage of the component a1 and the component a2 relative to 100 parts by weight, the dosage of the component b can be with
For 1-200 parts by weight, it is preferably 20-180 parts by weight, is more preferably 50-150 parts by weight；The component a1 and component a2
Dosage weight ratio can be 1:0.1-10, is preferably 1:0.5-2.
The present invention improves prepared polyethylene production to improve the intensity of the spherical porous mesoporous composite material
The performance of product, is realized using to the secondary ball milling method of slurry.
According to the present invention, in step (4), first ball milling and the second ball milling can carry out in the ball mill, described
The inner wall of ball grinder is preferably agate liner in ball mill, and the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball
It can reasonably be selected according to the size of ball grinder, for the ball grinder that size is 50-150mL, can usually use 1
Abrading-ball；The material of the abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., be preferably agate.First ball milling and the second ball milling
Condition can be identical or different, the condition of first ball milling and the second ball milling includes independently of one another：The rotating speed of abrading-ball can
Think 200-800r/min, the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100h；It is preferred that
Ground, the rotating speed of abrading-ball are 300-500r/min, and the temperature in ball grinder is 25-50 DEG C, and the time of ball milling is 5-20h.
According to the present invention, in step (4), the temperature by obtained the first ball milling slurry and water mixed pulp can be
25-60 DEG C, the weight ratio of the dosage of the first ball milling slurry and water can be 1：0.1-5, is preferably 1：0.5-3.5.
According to the present invention, in step (4), the spray drying can be implemented according to conventional mode, can be selected from pressure
At least one of gentle flow type spray seasoning of power spray drying process, centrifugal spray drying method.It is a kind of preferred according to the present invention
Embodiment, the spray drying uses centrifugal spray drying method.The spray drying can carry out in atomizer.It is described
The condition of spray drying can include：Temperature is 150-600 DEG C, rotating speed 10000-15000r/min；It is described under preferable case
The condition of spray drying includes：Temperature is 150-250 DEG C, and rotating rotating speed is 11000-13000r/min.
According to the present invention, the step of being screened after the second ball milling slurry is spray-dried using Cyclone Separation Technology
Including：The second ball milling slurry is spray-dried, the gas containing powder of discharge is subjected to cyclonic separation to collect
The powder.Specifically, powder contained in discharge gas is separated using Cyclone Separation Technology, the powder of recycling falls into collection powder
Cylinder, for exhaust gas by separator outlet to centrifugal blower, cyclone separator lower part is provided with butterfly valve, and when work opens butterfly valve, obtains
Sample has the particle diameter being evenly distributed.
According to the present invention, in step (4), when the component a1 is the mesopore molecular sieve with one-dimensional straight channels structure
The filter cake of material, the component a2 is the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure, and the component b is silicon
During the filter cake of glue, namely when step (1) is the mistake of the filter cake of meso-porous molecular sieve material of the preparation with one-dimensional straight channels structure
Journey, for step (2) to prepare the process of the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure, step (3) is to prepare silicon
During the process of the filter cake of glue, the preparation method of the spherical porous mesoporous composite material can also include：Spraying in step (4)
After drying process, the removed template method from the powder collected by cyclonic separation.The condition of the removed template method includes：Temperature
Degree can be 90-600 DEG C, be preferably 300-600 DEG C；It is preferably 10-24h when time can be 10-80 small.
Present invention also offers the spherical porous mesoporous composite material prepared by the above method.
Present invention also offers a kind of loaded catalyst, which contains the magnesium of carrier and load on the carrier
Salt and/or titanium salt, wherein, the carrier is spherical porous mesoporous composite material provided by the invention.
According to the present invention, the content of the magnesium salts, titanium salt and the carrier can be in interior variation in a big way.For example, with
On the basis of the gross weight of the catalyst, the sum of content in terms of magnesium elements and titanium elements can be respectively for the magnesium salts and titanium salt
1-10 weight %, the content of the carrier can be 90-99 weight %.Preferably, the magnesium salts and titanium salt are respectively with magnesium elements
It is 1.5-9.5 weight % with the sum of the content of titanium elements meter, the content of the carrier is 90.5-98.5 weight %.It is highly preferred that
The sum of content in terms of magnesium elements and titanium elements is 4-9 weight % respectively for the magnesium salts and titanium salt, and the content of the carrier is 91-
96 weight %.
A kind of preferred embodiment according to the present invention, the dosage weight ratio of the magnesium salts and titanium salt is 1：0.1-2, it is excellent
Elect 1 as：0.5-2.
In the present invention, there is no particular limitation for the species of the magnesium salts and titanium salt, can be the conventional selection of this area.
For example, the magnesium salts can be the one or more in magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium bromide, it is preferably magnesium chloride；Institute
It can be titanium tetrachloride and/or titanium trichloride to state titanium salt.
In the present invention, the content of each element can use X-ray fluorescence spectra analytic approach to survey in the catalytic component
.
In the present invention, the loaded catalyst can be prepared according to various methods commonly used in the art, as long as
Magnesium salts and/or titanium salt are loaded on the carrier.
Present invention also offers a kind of preparation method of loaded catalyst, in the presence of an inert gas, by carrier with containing
There is the contact of the mother liquor of magnesium salts and/or titanium salt；Wherein, the carrier is spherical porous mesoporous composite material provided by the invention.
In the present invention, the mother liquor containing magnesium salts and/or titanium salt can be organic molten containing magnesium salts and/or titanium salt
Agent, the organic solvent can be isopropanol and tetrahydrofuran, and the volume ratio of tetrahydrofuran and isopropanol can be 1：1-3,
Preferably 1：1-1.5.
In the preparation process of the catalyst, the dosage of the magnesium salts and the titanium salt is preferably relative to spherical porous
Mesoporous composite material is excessive.For example, the support type that the dosage of the magnesium salts, the titanium salt and the carrier to be prepared is urged
In agent, on the basis of the gross weight of the catalyst, the magnesium salts and the titanium salt content in terms of magnesium elements and titanium elements respectively
The sum of can be 1-10 weight %, the content of the carrier can be 90-99 weight %.Preferably, the magnesium salts and titanium salt point
The sum of content not in terms of magnesium elements and titanium elements is 1.5-9.5 weight %, and the content of the carrier is 90.5-98.5 weights
Measure %.It is highly preferred that the sum of content in terms of magnesium elements and titanium elements is 4-9 weight % respectively for the magnesium salts and titanium salt, it is described
The content of carrier is 91-96 weight %.
Preferably, the carrier includes with the condition that the mother liquor containing magnesium salts and/or titanium salt contacts：Temperature is 25-100
DEG C, it is preferably 40-60 DEG C；Time is 0.1-5h, is preferably 1-3h.
In the present invention, the preparation method of the loaded catalyst further includes：In carrier and contain magnesium salts and/or titanium salt
Mother liquor contact after, the carrier for being loaded with magnesium salts and/or titanium salt is filtered and dried.The condition of the drying is without spy
Other limitation, can be the conventional drying mode and condition of this area.It is preferred that the preparation of loaded catalyst was additionally included in
Washing process after filter and before the drying, and/or process of lapping after drying.Those skilled in the art can basis
Practice situation makes choice the condition of the washing and grinding, and details are not described herein.
In the present invention, the inert gas is the gas not reacted with raw material and product, such as can be ability
At least one of group 0 element gas in the nitrogen or the periodic table of elements of domain routine, is preferably nitrogen.
Present invention also offers the loaded catalyst prepared by the above method.
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 EO20PO70EO20, the material for being 9003-11-6 in the registration number of U.S. chemical abstract, number-average molecular weight
Mn is 5800.
In following embodiments and comparative example, X-ray diffraction analysis are in the model D8 purchased from German Bruker AXS companies
Carried out on the X-ray diffractometer of Advance；Scanning electricity of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on sub- microscope；Pore structure parameter analyzes the nitrogen adsorption desorption in the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on instrument, wherein, before being tested, by sample when 200 DEG C of degassings 4 are small；Type of the x-ray fluorescence analysis in dutch company
Number for Axios-Advanced x-ray fluorescence analyzer on carry out；Size distribution curve is measured by Malvern laser particle analyzer.
The heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
Melt index：Measured according to ASTM D1238-99.
The flour rate of polyethylene particle powder：By 800 mesh sieve mesh screen point measure, specifically, by the polyethylene particle
For powder by 800 mesh sieves, flour rate is the weight and the polyethylene tested through the polyethylene particle powder of 800 mesh sieves
The percentage of the weight of grain powder.
Embodiment 1
The present embodiment is used for spherical porous mesoporous composite material and loaded catalyst and its preparation side for illustrating the present invention
Method
(1) spherical porous mesoporous composite material is prepared
1g (0.00017mol) template P123 and 1.69g (0.037mol) ethanol is added to the pH=4.4's of 28mL
In acetic acid and sodium acetate buffer solution, stirring to template is completely dissolved at 15 DEG C, and 6g (0.05mol) trimethylpentane is added
Into above-mentioned solution, after stirring 8h at 15 DEG C, then 2.13g (0.014mol) tetramethoxy-silicane is added in above-mentioned solution,
After stirring 20h at 15 DEG C, transfer the solution into the reaction kettle of agate liner, after 60 DEG C of baking oven crystallization 24h, then filtered
And be washed with deionized 4 times, then filter the filter cake for the meso-porous molecular sieve material for obtaining having one-dimensional straight channels structure
A11。
At 80 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein, the addition of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1：0.37：2.8：142, and when stirring 4 is small at a temperature of 80 DEG C, then will be molten
Liquid is filtered and is washed with distilled water four times, obtains the filter cake A12 with the meso-porous molecular sieve material of hexagonal hole road structure.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as
4：1：1 is mixed and when haptoreaction 1 is small at 40 DEG C, then adjusts pH value to 3 with the sulfuric acid that concentration is 98 weight %, so
Obtained reaction mass is filtered afterwards, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains silica gel
Filter cake B1.
5g filter cake A11,5g filter cake A12 and 10g filter cakes B1 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, its
In, the material of ball grinder is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 400r/
min.Ball grinder is closed, the first ball milling is carried out in ball grinder, temperature is 25 DEG C, when the time is 5 small.The first ball milling that will be obtained
Slurry and 40g water mixed pulp at 25 DEG C, then carry out the second ball milling, and temperature is 25 DEG C, when the time is 5 small.By what is obtained
Second ball milling slurry is to be spray-dried under 12000r/min in rotating speed at 200 DEG C, is then sieved using Cyclone Separation Technology
Choosing, calcines 10h, removing P123 (template), obtains spherical porous Jie in Muffle furnace by the product that screening obtains at 550 DEG C
Hole composite material C1.
Spherical porous mesoporous composite material C1 is characterized with XRD, scanning electron microscope and nitrogen adsorption instrument.
Fig. 1 is X-ray diffracting spectrum, and as seen from the figure, spherical porous mesoporous composite material C1 is peculiar with mesoporous material institute
Meso-hole structure.
Fig. 2 is the microscopic appearance SEM figures of spherical porous mesoporous composite material C1, it can be seen from the figure that spherical porous Jie
The microscopic appearance of hole composite material C1 is the microballoon that particle diameter is 21-29 μm, and its good dispersion property.
Fig. 3 is the size distribution curve of spherical porous mesoporous composite material C1, it can be seen from the figure that spherical porous mesoporous
Composite material C1 has uniform size distribution.
Fig. 4 is the graph of pore diameter distribution of spherical porous mesoporous composite material C1, it can be seen from the figure that spherical porous mesoporous multiple
Condensation material C1 is distributed with loose structure, and duct is uniform.
The pore structure parameter of spherical porous mesoporous composite material C1 is as shown in table 1 below.
Table 1
*：First most probable pore size, the second most probable pore size and the 3rd most probable pore size are separated with comma：According to by it is left extremely
Right order is the first most probable pore size, the second most probable pore size and the 3rd most probable pore size successively.
(2) catalyst is prepared
0.1g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in (four in the tetrahydrofuran of 10mL and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.2) catalyst mother liquor, is formed.By the spherical porous composite mesoporous materials of 1g at 45 DEG C
Material C1, which is added in mother liquor, impregnates 1h, then filters, and carries out washing 4 times with n-hexane, in 75 DEG C of dryings, and is ground,
Obtain catalyst D1.
Drawn by x-ray fluorescence analysis, in the obtained catalyst D1 of the present embodiment, based on the element, magnesium elements
Content is 7.0 weight %, and the content of titanium elements is 1.6 weight %.
Embodiment 2
The present embodiment is used for spherical porous mesoporous composite material and loaded catalyst and its preparation side for illustrating the present invention
Method
(1) spherical porous mesoporous composite material is prepared
1g (0.00017mol) template P123 and 1.4g (0.03mol) ethanol is added to the second of the pH=4.4 of 28mL
Stir in acid and sodium acetate buffer solution, at 10 DEG C and be completely dissolved to template, 4.56g (0.04mol) trimethylpentane is added
Enter into above-mentioned solution, after stirring 8h at 10 DEG C, then 1.83g (0.012mol) tetramethoxy-silicane is added to above-mentioned solution
In, after stirring 30h at 10 DEG C, transfer the solution into the reaction kettle of agate liner, after 80 DEG C of baking oven crystallization 20h, then carry out
Filter and be washed with deionized 6 times, then filter and obtain the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure
Filter cake A21.
At 50 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein, the addition of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1：0.5：1.5：180, and when stirring 7 is small at a temperature of 50 DEG C, then by solution
Filter and be washed with distilled water four times, obtain the filter cake A22 with the meso-porous molecular sieve material of hexagonal hole road structure；
By the waterglass that concentration is 20 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as
3：2：1 is mixed and the haptoreaction 3h at 20 DEG C, then adjusts pH value to 4 with the sulfuric acid that concentration is 98 weight %, then
Obtained reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter of silica gel
Cake B2.
6.7g filter cake A21,3.3g filter cake A22 and 15g filter cakes B2 of above-mentioned preparation is put into togerther the ball grinder of 100mL
In, wherein, the material of ball grinder is agate, 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, the first ball milling is carried out in ball grinder, temperature is 35 DEG C, when the time is 20 small.To obtain
One ball milling slurry and 87.5g water mixed pulp at 35 DEG C, then carry out the second ball milling, and temperature is 25 DEG C, when the time is 10 small.
By the second obtained ball milling slurry at 150 DEG C in rotating speed be 13000r/min under be spray-dried, then using cyclonic separation skill
Art is screened, and the product that screening obtains is calcined 15h in Muffle furnace at 600 DEG C, removing P123 (template), obtains ball
The porous mesoporous composite material C2 of shape.
The pore structure parameter of spherical porous mesoporous composite material C2 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 (four in the tetrahydrofuran of 10mL and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.5) catalyst mother liquor, is formed.At 60 DEG C, by the spherical porous composite mesoporous materials of 1g
Material C2, which is added in mother liquor, impregnates 1h, then filters, and carries out washing 4 times with n-hexane, in 75 DEG C of dryings, and is ground,
Obtain catalyst D2.
Drawn by x-ray fluorescence analysis, in the obtained catalyst D1 of the present embodiment, based on the element, magnesium elements
Content is 6.9 weight %, and the content of titanium elements is 1.1 weight %.
Embodiment 3
The present embodiment is used for spherical porous mesoporous composite material and loaded catalyst and its preparation side for illustrating the present invention
Method
(1) spherical porous mesoporous composite material is prepared
1g (0.00017mol) template P123 and 3.13g (0.068mol) ethanol is added to the pH=4.4's of 28mL
In acetic acid and sodium acetate buffer solution, stirring to template is completely dissolved at 20 DEG C, by 7.75g (0.068mol) trimethylpentane
It is added in above-mentioned solution, after stirring 8h at 20 DEG C, then 3.8g (0.025mol) tetramethoxy-silicane is added to above-mentioned solution
In, after stirring 10h at 20 DEG C, transfer the solution into the reaction kettle of agate liner, after 40 DEG C of baking oven crystallization 30h, then carry out
Filter and be washed with deionized 6 times, then filter and obtain the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure
Filter cake A31.
At 90 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein, the addition of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1：0.2：3.5：120, and when stirring 3 is small at a temperature of 90 DEG C, then by solution
Filter and be washed with distilled water four times, obtain the filter cake A32 with the meso-porous molecular sieve material of hexagonal hole road structure.
By the waterglass that concentration is 10 weight % and the sulfuric acid solution that concentration is 12 weight % and ethylene glycol using weight ratio as
6：3：1 is mixed and the haptoreaction 1.5h at 30 DEG C, then adjusts pH value to 2 with the sulfuric acid that concentration is 98 weight %, so
Obtained reaction mass is filtered afterwards, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains silica gel
Filter cake B3.
7g filter cake A31,14g filter cake A32 and 10g filter cakes B3 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, its
In, the material of ball grinder is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 300r/
min.Ball grinder is closed, the first ball milling is carried out in ball grinder, temperature is 50 DEG C, when the time is 10 small.The first ball that will be obtained
Defibrination material and 15g water mixed pulp at 50 DEG C, then carry out the second ball milling, and temperature is 40 DEG C, when the time is 5 small.It will obtain
The second ball milling slurry at 250 DEG C in rotating speed be 11000r/min under be spray-dried, then carried out using Cyclone Separation Technology
Screening, calcines 24h, removing P123 (template), obtains spherical porous in Muffle furnace by the product that screening obtains at 300 DEG C
Mesoporous composite material C3.
The pore structure parameter of obtained spherical porous mesoporous composite material C3 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 (four in the tetrahydrofuran of 10mL and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1) catalyst mother liquor, is formed.By the spherical porous mesoporous composite materials of 1g at 40 DEG C
C3, which is added in mother liquor, impregnates 3h, then filters, and carries out washing 4 times with n-hexane, in 75 DEG C of dryings, and is ground, obtains
To catalyst D3.
Drawn by x-ray fluorescence analysis, in the obtained catalyst D1 of the present embodiment, based on the element, magnesium elements
Content is 6.6 weight %, and the content of titanium elements is 0.8 weight %.
Embodiment 4
The present embodiment is used for spherical porous mesoporous composite material and loaded catalyst and its preparation side for illustrating the present invention
Method
Spherical porous mesoporous composite material and loaded catalyst are prepared in the same manner as shown in Example 1, it is different
It is during the filter cake of silica gel is prepared, not add glycerine, obtains spherical porous mesoporous composite material C4 and catalyst
D4。
The pore structure parameter of spherical porous mesoporous composite material C4 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 D4 described in the present embodiment, based on the element, the content of magnesium elements is 7.5
Weight %, the content of titanium elements is 0.8 weight %.
Comparative example 1
This comparative example is used to illustrate carrier and loaded catalyst of reference and preparation method thereof
Commercially available ES955 silica gel (GRACE companies) is calcined into 10h for 400 DEG C under nitrogen protection, with eliminating hydroxide and remaining
Moisture, so as to obtain the ES955 silica gel through thermal activation.
Method according to 1 step of embodiment (2) prepares catalyst, the difference is that the above-mentioned work using identical weight part
The ES955 silica gel of change replaces spherical porous mesoporous composite material C1, so that comparative catalyst DD1 be made.
Comparative example 2
This comparative example is used to illustrate spherical porous mesoporous composite material and loaded catalyst of reference and preparation method thereof
Method according to embodiment 1 prepares spherical porous mesoporous composite material and loaded catalyst.Unlike, only into
The first ball milling of row, without the second ball milling.Specifically, by 5g filter cake A11,5g filter cake A12 and 10g filter cakes B1 mono- of above-mentioned preparation
Rise and be put into the ball grinder of 100mL.Ball grinder is closed, the first ball milling is carried out in ball grinder, temperature is 25 DEG C, and the time is small for 5
When.By the first obtained ball milling slurry and 40g water mixed pulp at 25 DEG C, it is in rotating speed at 200 DEG C by obtained slurry
It is spray-dried under 12000r/min.Spherical porous mesoporous composite material DC2 and loaded catalyst DD2 is made.
The pore structure parameter of spherical porous mesoporous composite material DC2 is as shown in table 5 below.
Table 5
*：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 DD2 described in this comparative example, based on the element, the content of magnesium elements is
6.1 weight %, the content of titanium elements is 0.7 weight %.
Comparative example 3
This comparative example is used to illustrate spherical porous mesoporous composite material and loaded catalyst of reference and preparation method thereof
Method according to embodiment 1 prepares spherical porous mesoporous composite material and loaded catalyst.Unlike, do not adopt
Screened with Cyclone Separation Technology, specifically, by the second obtained ball milling slurry at 200 DEG C in rotating speed be 12000r/min
Lower spray drying, then calcines 10h in Muffle furnace by the product obtained after spray drying at 550 DEG C, removes P123 (templates
Agent), obtain spherical porous mesoporous composite material DC3 and DD3.
The pore structure parameter of spherical porous mesoporous composite material DC3 is as shown in table 6 below.
Table 6
*：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 DD3 described in this comparative example, based on the element, the content of magnesium elements is
6.0 weight %, the content of titanium elements is 1.1 weight %.
Comparative example 4
This comparative example is used to illustrate spherical porous mesoporous composite material and loaded catalyst of reference and preparation method thereof
Method according to embodiment 1 prepares spherical porous mesoporous composite material and loaded catalyst.Unlike, only into
The first ball milling of row, without the second ball milling, does not also use Cyclone Separation Technology to be screened.Specifically, by the 5g of above-mentioned preparation
Filter cake A11,5g filter cake A12 and 10g filter cake B1 is put into togerther in the ball grinder of 100mL.Ball grinder is closed, is carried out in ball grinder
First ball milling, temperature are 25 DEG C, when the time is 5 small.By the first obtained ball milling slurry and 40g water mixed pulp at 25 DEG C,
By obtained slurry at 200 DEG C in rotating speed be 12000r/min under be spray-dried, the product that then will be obtained after spray drying
10h is calcined at 550 DEG C in Muffle furnace, removing P123 (template), obtains spherical porous mesoporous composite material DC4 and DD4.
The pore structure parameter of spherical porous mesoporous composite material DC2 is as shown in table 7 below.
Table 7
*：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 DD3 described in this comparative example, based on the element, the content of magnesium elements is
5.6 weight %, the content of titanium elements is 0.9 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for the application for illustrating loaded catalyst provided by the invention.
In the stainless steel polymerization autoclave of 2L, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 80 DEG C, adds 800mL hexanes, and with the addition of hexane, the concentration for adding 2mL is the triethyl aluminum of 1mol/L
(TEA) hexane solution, is subsequently added into the catalytic component D1 of 0.5g, is passed through ethylene gas, pressure is risen to 1.0MPa and is tieed up
Hold as 1.0MPa, when 70 DEG C of reactions 1 are small after filter separation, obtain polyethylene particle powder.Gained polyethylene particle powder
Heap density (BD), melt index MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for the application for illustrating loaded catalyst provided by the invention.
In the stainless steel polymerization autoclave of 2L, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 75 DEG C, adds 900mL hexanes, and with the addition of hexane, the concentration for adding 2mL is the triethyl aluminum of 1mol/L
(TEA) hexane solution, is subsequently added into the catalytic component D2 of 0.1g, is passed through ethylene gas, pressure is risen to 1MPa and is maintained
For 1MPa, when 75 DEG C of reactions 1.5 are small after filter separation, obtain polyethylene particle powder.The heap of gained polyethylene particle powder
Density (BD), melt index MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for the application for illustrating loaded catalyst provided by the invention.
In the stainless steel polymerization autoclave of 2L, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 85 DEG C, adds 700mL hexanes, and with the addition of hexane, the concentration for adding 2mL is the triethyl aluminum of 1mol/L
(TEA) hexane solution, is subsequently added into the catalytic component D3 of 1g, is passed through ethylene gas, pressure is risen to 1MPa and is maintained
1MPa, 85 DEG C reaction 2 it is small when after filter separation, obtain polyethylene particle powder.The heap density of gained polyethylene particle powder
(BD), melt index MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
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 the embodiment 4 of identical weight part
The catalyst D4 of preparation replaces the catalyst D1 being prepared by embodiment 1.The heap density (BD) of gained polyethylene particle powder,
Melt index MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
Experimental comparison's example 1-4
This Experimental comparison example is used for the application for illustrating the loaded catalyst of reference
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the contrast of identical weight part is respectively adopted
Comparative catalyst DD1-DD4 prepared by example 1-4 replaces the catalyst D1 being prepared by embodiment 1.Gained polyethylene particle powder
The heap density (BD) of material, melt index MI2.16, flour rate and catalyst efficiency be listed in Table 8 below.
Table 8
It can be seen that from the result of above EXPERIMENTAL EXAMPLE 1-4 and Experimental comparison's example 1-4 contrasts by ball provided by the invention
When the porous mesoporous composite material of shape and loaded catalyst are used for ethylene polymerization, catalyst has higher catalytic activity,
And heap density and the relatively low and non-breakable polyethylene product of melt index can be obtained, specifically, the polyethylene production of preparation
The heap density of product is below 0.5g/mL, and melt index is below 0.5g/10min, and flour rate is less than 3 weight %.And not using this
The polyethylene product that the method for invention obtains, flour rate is more than 5 weight %.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
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 (13)
1. a kind of spherical porous mesoporous composite material, it is characterised in that the spherical porous mesoporous composite material contains with one-dimensional
The meso-porous molecular sieve material of straight channels structure and the meso-porous molecular sieve material with hexagonal hole road structure, spherical porous Jie
The average grain diameter of hole composite material is 21-29 microns, and specific surface area is 200-650 meters squared per grams, and pore volume is 0.5-1.8 millis
Rise/gram, aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable respectively
Aperture, and first most probable pore size is 1-10 nanometers, second most probable pore size is 20-35 nanometers, and the described 3rd most
Can several apertures be 40-50 nanometers.
2. spherical porous mesoporous composite material according to claim 1, wherein, the spherical porous mesoporous composite material
Average grain diameter is 22-28 microns, and specific surface area is 220-300 meters squared per grams, and pore volume is 1.1-1.7 mls/g, and aperture is in
Tri-modal distribution, and three peaks correspond to 6-9 nanometers of the first most probable pore size, 22-32 nanometers of the second most probable pore size and the 3rd most respectively
Can be aperture 42-50 nanometers a few；
Preferably, the meso-porous molecular sieve material with one-dimensional straight channels structure and the mesopore molecular sieve with hexagonal hole road structure
The weight ratio of material is 1：0.1-10, is preferably 1：0.5-2.
3. a kind of preparation method of spherical porous mesoporous composite material, it is characterised in that this method comprises the following steps：
(1) meso-porous molecular sieve material with one-dimensional straight channels structure is provided or is prepared with one-dimensional straight channels structure
The filter cake of meso-porous molecular sieve material, as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or prepares the mesoporous molecular with hexagonal hole road structure
The filter cake of material is sieved, as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, as component b；
(4) by the component a1, the component a2 and the component b is mixed and the first ball milling, the first ball milling that will be obtained
Slurry and water mixed pulp, then carry out the second ball milling and obtain the second ball milling slurry, and it is dry that the second ball milling slurry is carried out spraying
Screened after dry using Cyclone Separation Technology；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical porous mesoporous composite material is 21-29 microns, and specific surface area is
200-650 meters squared per grams, pore volume are 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to first and most may be used respectively
Several apertures, the second most probable pore size and the 3rd most probable pore size, and first most probable pore size be 1-10 nanometers, described second
Most probable pore size is 20-35 nanometers, and the 3rd most probable pore size is 40-50 nanometers.
4. according to the method described in claim 3, wherein, in step (4), relative to 100 parts by weight the component a1 and
Total dosage of the component a2, the dosage of the component b is 1-200 parts by weight, is preferably 20-180 parts by weight, more preferably
50-150 parts by weight；
Preferably, the weight ratio of the component a1 and the component a2 are 1：0.1-10, more preferably 1：0.5-2.
5. according to the method described in claim 3, wherein, in step (1), prepare mesoporous with one-dimensional straight channels structure
The process of the filter cake of molecular screen material includes：Template, silicon source, ethanol, trimethylpentane and sour agent are carried out the first mixing to connect
Touch, and the mixture that first is mixed carries out crystallization and filtering；
Preferably, the template is triblock copolymer polyethylene glycol glycerine-polyethylene glycol；The silicon source is tetramethyl
Oxysilane；The acid agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6；
Preferably, the molar ratio of template, ethanol, trimethylpentane and silicon source is 1：100-500：200-500：50-200, more
Preferably 1：180-400：250-400：70-150；
Preferably, first condition being mixed includes：Temperature is 10-60 DEG C, when the time is 10-72 small, pH value 1-
7；The condition of the crystallization of first mixture being mixed includes：Temperature is 30-150 DEG C, and the time is small for 10-72
When；
Preferably, in step (2), preparing the process of the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure includes：
Ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia progress second is mixed, and second is mixed
Mixture is filtered；
Preferably, the molar ratio of ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia is 1：0.1-1：0.1-5, is preferably
1：0.2-0.5：1.5-3.5；
Preferably, second condition being mixed includes：Temperature is 25-100 DEG C, when the time is 2-8 small；
Preferably, in step (3), preparing the process of the filter cake of silica gel includes：Waterglass, polyalcohol and inorganic acid are carried out the
Three are mixed, and the 3rd mixture being mixed is filtered；
Preferably, the 3rd condition being mixed includes：Temperature is 10-60 DEG C, when the time is 1-5 small, pH value 2-4；
It is highly preferred that the weight ratio of the waterglass, inorganic acid and polyalcohol is 1-8：0.1-5：1；The inorganic acid for sulfuric acid,
One or more in nitric acid and hydrochloric acid；The polyalcohol is glycerine and/or ethylene glycol.
6. according to the method described in any one in claim 3-5, wherein, in step (4), first ball milling and second
The condition of ball milling is identical or different, and the condition of first ball milling and the second ball milling includes independently of one another：The rotating speed of abrading-ball is
200-800r/min, the temperature in ball grinder are 15-100 DEG C, time of ball milling for 0.1-100 it is small when；
Preferably, the weight ratio of the dosage of the first ball milling slurry and water is 1：0.1-5, the first ball milling slurry and water mixed pulp
Temperature is 25-60 DEG C；
Preferably, the condition of the spray drying includes：Temperature is 150-600 DEG C, rotating speed 10000-15000r/min.
7. the method according to claim 3 or 4, wherein, using whirlwind point after the second ball milling slurry is spray-dried
The step of being screened from technology includes：The second ball milling slurry is spray-dried, by the gas containing powder of discharge
Body carries out cyclonic separation to collect the powder；
Preferably, the component a1 be the meso-porous molecular sieve material with one-dimensional straight channels structure filter cake, the component a2
For the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure, the component b is the filter cake of silica gel；The method is also wrapped
Include：After the spray-drying process of step (4), the removed template method from the powder collected by cyclonic separation；
Preferably, the condition of the removed template method includes：Temperature is 90-600 DEG C, when the time is 10-80 small.
8. the spherical porous mesoporous composite material prepared as the method described in any one in claim 3-7.
9. a kind of loaded catalyst, which contains the magnesium salts and/or titanium salt of carrier and load on the carrier, it is special
Sign is that the carrier is the spherical porous mesoporous composite material described in any one in claim 1-2 and 8.
10. catalyst according to claim 9, wherein, on the basis of the gross weight of the loaded catalyst, the load
The content of body is 90-99 weight %, and the sum of content in terms of magnesium elements and titanium elements is 1-10 weights respectively for the magnesium salts and titanium salt
Measure %.
11. a kind of preparation method of loaded catalyst, it is characterised in that this method includes：In the presence of an inert gas, will carry
Body is contacted with the mother liquor containing magnesium salts and/or titanium salt；Wherein, the carrier is described in any one in claim 1-2 and 8
Spherical porous mesoporous composite material.
12. according to the method for claim 11, wherein, the magnesium salts, the titanium salt and the carrier dosage making
In standby obtained loaded catalyst, on the basis of the gross weight of the loaded catalyst, the content of the carrier is 90-99
Weight %, the sum of content in terms of magnesium elements and titanium elements is 1-10 weight % respectively for the magnesium salts and titanium salt；
Preferably, the condition of the contact includes：Temperature is 25-100 DEG C, time 0.1-5h.
13. the loaded catalyst prepared as the method described in claim 11 or 12.
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| CN112892582A (en) * | 2019-12-03 | 2021-06-04 | 中国石油化工股份有限公司 | Light gasoline cracking catalyst containing all-silicon three-hole spherical mesoporous composite material and preparation method and application thereof |
| CN113754798A (en) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | Spheroidal ultra-macroporous mesoporous material, polyolefin catalyst, preparation method of polyolefin catalyst and olefin polymerization method |
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