CN108623720A - Spherical mesoporous composite material and loaded catalyst and preparation method thereof - Google Patents
Spherical mesoporous composite material and loaded catalyst and preparation method thereof Download PDFInfo
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- CN108623720A CN108623720A CN201710166707.3A CN201710166707A CN108623720A CN 108623720 A CN108623720 A CN 108623720A CN 201710166707 A CN201710166707 A CN 201710166707A CN 108623720 A CN108623720 A CN 108623720A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to mesoporous materials field, a kind of spherical porous mesoporous composite material and loaded catalyst and preparation method thereof are disclosed.The average grain diameter of the spherical mesoporous composite material is 20 30 microns, and specific surface area is 100 300 meters squared per grams, and pore volume is 0.5 1.8 mls/g, and aperture is in bimodal distribution, and bimodal corresponding most probable pore size is 1 10 nanometers and 20 55 nanometers.The meso-hole structure of spherical 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 when catalyzed ethylene polymerization reaction for having high catalytic activity, 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 fields, and in particular, to a kind of spherical mesoporous composite material, this is spherical mesoporous compound
The preparation method of material, the spherical mesoporous composite material prepared by this method, a kind of loaded catalyst, a kind of supported catalyst
The preparation method of agent, and the loaded catalyst by this method preparation.
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
Prodigious 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.
However conventional ordered mesoporous material SBA-15 microscopic appearances are rodlike, itself mobility is poor, big ratio
Surface area and high hole, which hold, causes 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-, it limits 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 makes the research of polyethylene catalysts 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.It is exactly handle to overcome the effective way of the above problem
Soluble poly catalyst for ethylene carries out supported processing.Currently, the related supported research report of polyethylene catalysts is very more.For
Further investigate new support/catalyst/co-catalyst system, it is necessary to study different carriers, with push carried catalyst and
The further development of polyolefin industry.
The mesoporous material for the load polyethylene catalysts reported on document at present 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 thermal stability that the relatively low reason of ethylene polymerization activity is mainly MCM-41 is carried out after supported catalyst and hydro-thermal is steady
It is qualitative poor, just there is part to cave in loading process hole wall, load effect is affected, so that affecting catalytic activity.
Therefore, seek a kind of mesoporous material that 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.
Invention content
The purpose of the present invention is overcoming the defect that meso-hole structure is unstable in the prior art, provide a kind of spherical mesoporous multiple
Condensation material and loaded catalyst containing the composite material, the grain size of the spherical mesoporous composite material is small and distribution is equal
Even, meso-hole structure is stablized.Heap density and melting can be obtained using the loaded catalyst containing the spherical mesoporous composite material
The relatively low and non-breakable polyethylene product of index.
Specifically, in a first aspect, the present invention provides a kind of spherical mesoporous composite material, the spherical mesoporous composite material
Average grain diameter is 20-30 microns, and specific surface area is 100-300 meters squared per grams, and pore volume is 0.5-1.8 mls/g, and aperture is in
Bimodal distribution, and bimodal corresponding most probable pore size is 1-10 nanometers and 20-55 nanometers.
Second aspect, the present invention provides a kind of preparation method of spherical mesoporous composite material, this method includes following step
Suddenly：
(1) it provides meso-porous molecular sieve material or prepares the filter cake of meso-porous molecular sieve material, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a and the component b are subjected to mixing and the first ball milling, the first ball milling slurry and water that will be obtained
Then mixed pulp carries out the second ball milling and obtains the second ball milling slurry, used after the second ball milling slurry is spray-dried
Cyclone Separation Technology is screened；
Wherein, above-mentioned steps so that the average grain diameter of the spherical mesoporous composite material is 20-30 microns, and specific surface area is
100-300 meters squared per grams, pore volume are 0.5-1.8 mls/g, and aperture is in bimodal distribution, and bimodal corresponding most probable
Aperture is 1-10 nanometers and 20-55 nanometers.
The third aspect, the present invention provides the spherical mesoporous composite materials 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 on body and/or titanium salt, wherein the carrier is spherical mesoporous composite material provided by the invention.
5th aspect, the load prepared the present invention provides a kind of preparation method of loaded catalyst and by this method
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 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
It recycles, intensity height is non-breakable, and the preparation of the spherical mesoporous composite material of the present invention need not use binder, this
Sample can be destroyed to avoid the structure of sample during high temperature removal binder.Using Cyclone Separation Technology, obtain
Spherical mesoporous composite material grain size it is small, particle diameter distribution is uniform and grading curve is narrow, can be to avoid in use
The reunion of ordered mesoporous material improves its mobility, to ordered mesoporous material storage, transport, post-processing and application bring
It is convenient.
In addition, the meso-hole structure of spherical mesoporous composite material provided by the invention is stablized, after load active component still
Orderly meso-hole structure can be kept, the loaded catalyst good fluidity that will be prepared by it.By the loaded catalyst
When for ethylene polymerization, heap density and the relatively low and non-breakable polyethylene product of melt index can be obtained, specifically,
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.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and 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 mesoporous composite material in embodiment 1, and abscissa is 2 θ, is indulged
Coordinate is intensity；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the spherical mesoporous composite material microscopic appearance in embodiment 1；
Fig. 3 is the size distribution curve of the spherical mesoporous composite material in embodiment 1；
Fig. 4 is the graph of pore diameter distribution of the spherical mesoporous composite material in embodiment 1.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of spherical mesoporous composite material, the average grain diameter of the spherical mesoporous composite material is 20-30
Micron, specific surface area are 100-300 meters squared per grams, and pore volume is 0.5-1.8 mls/g, and aperture is in bimodal distribution, and bimodal
Corresponding most probable pore size is 1-10 nanometers and 20-55 nanometers.
According to a preferred embodiment of the present invention, the average grain diameter of the spherical mesoporous composite material is 21-29
Micron, specific surface area are 210-290 meters squared per grams, and pore volume is 0.8-1.8 mls/g, and aperture is in bimodal distribution, and bimodal
Corresponding most probable pore size is 1-8 nanometers and 30-52 nanometers.
The average grain diameter of a kind of preferred embodiment according to the present invention, the spherical mesoporous composite material is 22-
28 microns, specific surface area is 220-280 meters squared per grams, and pore volume is 1-1.7 mls/g, and aperture is in bimodal distribution, and bimodal
Corresponding most probable pore size is 1-5 nanometers and 40-50 nanometers.
In the present invention, the average grain diameter of the spherical mesoporous composite material is measured using laser fineness gage, compares table
Area, pore volume and most probable pore size are measured according to nitrogen adsorption methods, and the surface topography of the spherical mesoporous composite material passes through
Scanning electron microscope instrument (SEM) measures.In the present invention, the average grain diameter is average particle diameter.
In the present invention, the spherical mesoporous composite material is without containing binder such as polyvinyl alcohol or polyethylene glycol etc..
In addition, " the flour rate of spherical mesoporous composite material is less than 3 weight % " refers to using described spherical mesoporous
When the loaded catalyst that composite material is prepared is used for the preparation of polyethylene, the flour rate of obtained polyethylene product is small
In 3 weight %.
In the present invention, the spherical mesoporous composite material can also contain the silica introduced by silica gel." pass through
The silica that silica gel is introduced into " refers to being used as by silica gel in the preparation process of the spherical mesoporous composite material and preparing raw material
Bring the silica component in the spherical mesoporous composite material finally prepared into.In the spherical mesoporous composite material, relatively
It can be heavy for 1-200 in the content of the meso-porous molecular sieve material of 100 parts by weight, the silica introduced by silica gel
Measure part, preferably 20-180 parts by weight, more preferably 50-150 parts by weight.
The present invention also provides a kind of preparation methods of spherical mesoporous composite material, and this approach includes the following steps：
(1) it provides meso-porous molecular sieve material or prepares the filter cake of meso-porous molecular sieve material, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a and the component b are subjected to mixing and the first ball milling, the first ball milling slurry and water that will be obtained
Then mixed pulp carries out the second ball milling and obtains the second ball milling slurry, used after the second ball milling slurry is spray-dried
Cyclone Separation Technology is screened；
Wherein, above-mentioned steps so that the average grain diameter of the spherical mesoporous composite material is 20-30 microns, and specific surface area is
100-300 meters squared per grams, pore volume are 0.5-1.8 mls/g, and aperture is in bimodal distribution, and bimodal corresponding most probable
Aperture is 1-10 nanometers and 20-55 nanometers.
According to a preferred embodiment of the present invention, the average grain diameter of the spherical mesoporous composite material is 21-29
Micron, specific surface area are 210-290 meters squared per grams, and pore volume is 0.8-1.8 mls/g, and aperture is in bimodal distribution, and bimodal
Corresponding most probable pore size is 1-8 nanometers and 30-52 nanometers.
The average grain diameter of a kind of preferred embodiment according to the present invention, the spherical mesoporous composite material is 22-
28 microns, specific surface area is 220-280 meters squared per grams, and pore volume is 1-1.7 mls/g, and aperture is in bimodal distribution, and bimodal
Corresponding most probable pore size is 1-5 nanometers and 40-50 nanometers.
In the present invention, by controlling within the above range the particle size of spherical mesoporous composite material, it can be ensured that
The spherical mesoporous composite material is not susceptible to reunite, and is used as loaded catalyst made of carrier and can improve second
Reaction raw materials conversion ratio in alkene polymerization process.
In the preparation process of above-mentioned spherical mesoporous composite material, mainly by control mesoporous material filter cake (component a's)
The pore-size distribution control of the spherical mesoporous composite material is bimodal distribution by composition, and mainly by controlling forming method
(that is, the component a and the component b are first carried out mixing and the first ball milling, the first obtained ball milling slurry is mixed into system with water
Slurry, then carries out the second ball milling and obtains the second ball milling slurry, the second ball milling slurry is spray-dried) spherical shape is situated between
The microscopic appearance control of hole composite material is spherical shape.
According to the present invention, in step (1), the process for preparing the filter cake of meso-porous molecular sieve material may include：By template
Agent, sour agent and silicon source carry out first and are mixed, and obtained mixture is carried out crystallization and filtering.Described first is mixed
Sequence there is no particular limitation, template, sour agent and silicon source can be carried out at the same time mixing, arbitrary two kinds can also be mixed
It closes, adds other components and be uniformly mixed.According to a kind of preferred embodiment, first template and sour agent are uniformly mixed, so
After add silicon source be uniformly mixed.
In the present invention, the template is preferably cetyl trimethylammonium bromide (CTAB) and polyethylene glycol octyl benzene
Base ether, the acid agent is hydrochloric acid.
According to the present invention, there is no particular limitation for the silicon source, can be various silicon sources commonly used in the art.Example
Such as, the silicon source can be at least one in ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and Ludox
Kind, preferably ethyl orthosilicate.
In the present invention, the dosage of the template, silicon source and sour agent can change in wide range.For example, massage
You are than meter, silicon source：Triton X-100：Cetyl trimethylammonium bromide (CTAB)：Hydrogen chloride：Water=1：0.1-
0.5：0.1-0.6：5-50：100-500, preferably 1：0.2-0.5：0.2-0.4：10-20：200-300.Wherein, polyethylene glycol
The molal quantity of octyl phenyl ether calculates to obtain according to the average molecular weight of Triton X-100.
The Triton X-100 can be the various Triton X-100s that may be used as template, example
Such as triton x-100.In addition, since triton x-100 is usually liquid, so can also be by volume.For example, relative to
The volume of the silicon source of 1mol, the Triton X-100 (pure triton x-100) can be 72-179ml.
There is no particular limitation for the condition that the present invention is mixed to described first, for example, described first is mixed
Condition includes：Temperature can be 10-60 DEG C, preferably 25-60 DEG C；Time can be 10-72 hours, preferably 10-30 hours；
PH value can be 1-7, preferably 3-6.In order to be more advantageous to the uniform mixing between each substance, described first is mixed and preferably exists
It is carried out under stirring condition.
According to a kind of preferred embodiment of the present invention, the described first process for being mixed includes：(1) by cetyl
Trimethylammonium bromide (CTAB), Triton X-100 (triton x-100) and hydrochloric acid stirred at a temperature of 25-60 DEG C to
Dissolving；(2) step (1) acquired solution and esters of silicon acis are stirred 10-72 hours at a temperature of 25-60 DEG C, stands 10-72 hours.
In the present invention, there is no particular limitation for the condition of the crystallization, can be the conventional selection of this field.Such as institute
The condition for stating crystallization includes：Temperature can be 25-60 DEG C, preferably 30-50 DEG C；Time can be 10-40 hours, preferably
15-35 hours.According to a kind of preferred embodiment, the crystallization is implemented by hydrothermal crystallization method.
In the present invention, during the above-mentioned filter cake for preparing meso-porous molecular sieve material, filter cake is obtained by filtering
Process may include：After filtration, it washs (washing times can be 2-10) repeatedly with deionized water, is then taken out
Filter.
In step (1), " providing meso-porous molecular sieve material " can directly weigh or choose meso-porous molecular sieve material
Product can also be to prepare meso-porous molecular sieve material.The preparation method of the meso-porous molecular sieve material can be according to conventional side
Method is implemented, for example, preparation method may include：The filter cake of meso-porous molecular sieve material is prepared according to the above method, then by institute
Obtain filtration cakes torrefaction.
According to the present invention, in step (2), the process for preparing the filter cake of silica gel includes：By waterglass, polyalcohol and inorganic
Acid carries out second and is mixed, and obtained mixture is filtered.
In the present invention, there is no particular limitation for the described second condition being mixed, can be according to preparing the normal of silica gel
Rule technique suitably determines.For example, the described second condition for being mixed includes：Temperature can be 10-60 DEG C, preferably 20-
40℃；Time can be 1-5 hours, preferably 1-3 hours；PH value is 2-4.It is uniform mixed between each substance in order to be more advantageous to
It closes, the described second process being reacted in a mixed contact manner preferably carries out under agitation.
In the present invention, the dosage of the waterglass, inorganic acid and polyalcohol can change in wide range.For example,
The weight ratio of the waterglass, inorganic acid and polyalcohol can be 1-8：0.1-5：1, 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, and concentration can be 3-20 weight %, preferably
10-20 weight %.The inorganic acid can be various inorganic acids commonly used in the art, such as can be sulfuric acid, nitric acid and
It is 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 being 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 type of the polyalcohol, such as can be glycerine and/or second two
Alcohol.
According to the present invention, in step (2), " providing silica gel " can directly weigh or choose silica gel product, can also
It is to prepare silica gel.The method for preparing silica gel can be implemented according to the conventional method, such as may include：It is prepared according to the above method
The filter cake of silica gel, then by gained filtration cakes torrefaction.
During the above-mentioned filter cake for preparing silica gel, may include with the process for obtaining filter cake by filtering：It is filtering
Later, the content of washing to sodium ion is 0.2 weight % hereinafter, preferably 0.01-0.03 weight %, is then filtered.It washes
The mode washed is the conventional selection of this field, can be that washing and/or alcohol are washed, actual conditions are ripe for those skilled in the art
Know, details are not described herein.
According to the present invention, in step (3), the dosage of the component a and component b can change in wide range.Example
Such as, the dosage of the dosage relative to the component a of 100 parts by weight, the component b can be 1-200 parts by weight, preferably
20-180 parts by weight, more preferably 50-150 parts by weight.
The present invention realizes to improve the intensity of the carrier using to the secondary ball milling method of slurry.
According to the present invention, in step (3), 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., 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 each independently：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
The rotating speed on ground, abrading-ball is 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 (3), the temperature by obtained the first ball milling slurry and water mixed pulp can be
25-60 DEG C, preferably 25-50 DEG C；The weight ratio of the dosage of the first ball milling slurry and water can be 1：0.1-5, preferably
1：0.5-3.5.
According to the present invention, in step (3), 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.According to of the invention a kind of preferred
Embodiment, it is described spray drying use centrifugal spray drying method.The spray drying can carry out in atomizer.It is described
The condition of spray drying may 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 the rotating speed of rotation is 11000-13000r/min.
According to the present invention, the step of screening using Cyclone Separation Technology after the second ball milling slurry is spray-dried
May include：：The second ball milling slurry is spray-dried, by gas of the discharge containing powder carry out cyclonic separation with
Collect the powder.Specifically, powder contained in discharge gas is detached using Cyclone Separation Technology, the powder of recycling falls into collection
Powder drum, for exhaust gas by separator outlet to centrifugal blower, cyclone separator lower part is equipped with butterfly valve, and when work opens butterfly valve, obtains
Sample there is the grain size that is evenly distributed.
According to the present invention, in step (3), when the filter cake that the component a is meso-porous molecular sieve material, the component b is
When the filter cake of silica gel, namely when the process that step (1) is the filter cake for preparing meso-porous molecular sieve material, step (2) is to prepare silica gel
Filter cake process when, the preparation method of the carrier can also include：After the spray-drying process of step (3), from logical
Cross removed template method in the powder that whirlwind separates and collects.The condition of the removed template method includes：Temperature can be 250-800
DEG C, preferably 300-600 DEG C；Time can be 10-40 hours, preferably 20-30h.
The present invention also provides the spherical mesoporous composite materials prepared by the above method.
The present invention also provides 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 mesoporous composite material provided by the invention.
According to the present invention, the content of the magnesium salts, titanium salt and the carrier can change in wide range.For example, with
On the basis of the total 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
The content of 1-10 weight %, 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 %.
According to a preferred embodiment of the present invention, the dosage weight ratio of the magnesium salts and titanium salt is 1：0.1-2, it is excellent
It is selected as 1：0.5-2.
In the present invention, there is no particular limitation for the type of the magnesium salts and titanium salt, can be the conventional selection of this field.
For example, the magnesium salts can be one or more in magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium bromide, preferably magnesium chloride；Institute
It can be titanium tetrachloride and/or titanium trichloride to state titanium salt.
In the present invention, the survey of X-ray fluorescence spectra analytic approach may be used in the content of each element 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.
The present invention also provides a kind of preparation methods of loaded catalyst, in the presence of an inert gas, by carrier with contain
There is the contact of the mother liquor of magnesium salts and/or titanium salt；Wherein, the carrier is spherical 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 mesoporous
Composite material is excessive.For example, the magnesium salts, the titanium salt and the dosage of the carrier make the loaded catalyst being prepared
In, on the basis of the total weight of the catalyst, the magnesium salts and titanium salt the sum of the content in terms of magnesium elements and titanium elements respectively
Can be 1-10 weight %, the content of the carrier can be 90-99 weight %.Preferably, the magnesium salts and titanium salt respectively with
The sum of content of magnesium elements and titanium elements meter is 1.5-9.5 weight %, and the content of the carrier is 90.5-98.5 weight %.More
Preferably, 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 carrier contains
Amount is 91-96 weight %.
Preferably, the condition that the carrier is contacted with the mother liquor containing magnesium salts and/or titanium salt includes：Temperature is 25-100
DEG C, preferably 40-60 DEG C；Time is 0.1-5h, 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, by load there is the carrier of magnesium salts and/or titanium salt to be filtered and dry.The condition of the drying is without spy
Other limitation can be the conventional drying mode and condition of this field.It is preferred that the preparation of loaded catalyst further includes in mistake
Washing process after filter and before the drying, and/or process of lapping after drying.Those skilled in the art can basis
Practice situation selects 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, preferably nitrogen in the nitrogen or the periodic table of elements of domain routine.
The present invention also provides the loaded catalysts prepared by the above method.
The present invention is described in detail with reference to embodiments.
In the following Examples and Comparative Examples, cetyl trimethylammonium bromide (CTAB) is purchased from lark prestige (J＆K), average
Molecular weight 364, CAS：57-09-0；Triton X-100 (triton x-100) is limited purchased from Shanghai life work bioengineering
Company, article No. TB0198.
In following embodiment and comparative example, X-ray diffraction analysis is in the model purchased from German Bruker AXS companies
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from Kang Ta companies of the U.S.
It is carried out on attached instrument, wherein before being tested, sample is deaerated 4 hours at 200 DEG C；X-ray fluorescence analysis is in dutch company
It is carried out on the x-ray fluorescence analyzer of model Axios-Advanced；Size distribution curve is surveyed by Malvern laser particle analyzer
.
The heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
Melt index：It is measured according to ASTM D1238-99.
The flour rate of polyethylene particle powder：It is sieved and is measured by 800 mesh screens, specifically, by the polyethylene particle
Powder is sieved by 800 mesh, and flour rate is the weight of polyethylene particle powder sieve through 800 mesh and the polyethylene tested
The percentage of the weight of grain powder.
Embodiment 1
The present embodiment is used to illustrate spherical mesoporous composite material and loaded catalyst of the present invention and preparation method thereof
(1) spherical mesoporous composite material is prepared
By the Triton X-100 of 1.5 grams of CTAB (cetyl trimethylammonium bromide) and 1.5ml (Qula is logical-
X100 it) is added in the concentrated hydrochloric acid of 29.6 grams of 37 weight % and the hydrochloric acid of 75 grams of water composition, is mixed at 40 DEG C
CTAB is completely dissolved；4.35 grams of ethyl orthosilicates are added in above-mentioned solution again, at a temperature of 40 DEG C, in mechanical agitation rate
To be stirred 15 hours under 340r/min, 24 hours are stood at 40 DEG C；Acquired solution is transferred to the reaction of polytetrafluoroethyllining lining
In kettle, by being filtered, washed, obtaining mesoporous material filter cake A1 after 50 DEG C of crystallization 24 hours.
It is with weight ratio by the sulfuric acid solution and glycerine of the waterglass of a concentration of 15 weight % and a concentration of 12 weight %
5：1：1 carries out mixing and haptoreaction 1.5 hours at 30 DEG C, then with the sulfuric acid of a concentration of 98 weight % adjustment pH value to 3,
Then obtained reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains silica gel
Filter cake B1.
The 20g filter cake A1 and 10g filter cakes B1 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein ball grinder
Material 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.Close ball milling
Tank carries out the first ball milling in ball grinder, and temperature is 25 DEG C, and the time is 5 hours.By the first obtained ball milling slurry and 15g water
Then the mixed pulp at 25 DEG C carries out the second ball milling, temperature is 25 DEG C, and the time is 5 hours.The the second ball milling slurry that will be obtained
It is then screened using Cyclone Separation Technology to be spray-dried under 12000r/min in rotating speed at 200 DEG C, screening is obtained
Product 10h is calcined at 550 DEG C in Muffle furnace, removed template method obtains spherical mesoporous composite material C1.
Spherical 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 mesoporous composite material C1 has mesoporous material is specific to be situated between
Pore structure.
Fig. 2 is the microscopic appearance SEM figures of spherical mesoporous composite material C1, as seen from the figure, spherical mesoporous composite material C1's
Microscopic appearance is the microballoon that grain size is 20-30 μm, and its good dispersion property.
Fig. 3 is the size distribution curve of spherical mesoporous composite material C1, it can be seen from the figure that spherical mesoporous composite material
C1 has uniform size distribution.
Fig. 4 is the graph of pore diameter distribution of spherical mesoporous composite material C1, as seen from the figure, spherical mesoporous composite material C1 tools
There is double-pore structure distribution, and duct is uniform.
The pore structure parameter of spherical mesoporous composite material C1 is as shown in table 1 below.
Table 1
First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma, teases
It is the second most probable pore size after number.
(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 mesoporous composite material C1 of 1g at 45 DEG C
It is added in mother liquor and impregnates 1h, then filter, be used in combination n-hexane to carry out washing 4 times, in 75 DEG C of dryings, and be ground, obtain
Catalyst D1.
It is obtained by x-ray fluorescence analysis, in the obtained catalyst D1 of the present embodiment, based on the element, magnesium elements
Content is 7.5 weight %, and the content of titanium elements is 2 weight %.
Embodiment 2
The present embodiment is used to illustrate spherical mesoporous composite material and loaded catalyst of the present invention and preparation method thereof
(1) spherical mesoporous composite material is prepared
By the Triton X-100 (Qula of 1.125 grams of CTAB (cetyl trimethylammonium bromide) and 3.75ml
Logical-X100) it is added in 20.6 grams of the concentrated hydrochloric acid of 37 weight % and the hydrochloric acid of 62.2 grams of water composition, it is mixed at 40 DEG C
It is completely dissolved to CTAB；4.35 grams of ethyl orthosilicates are added in above-mentioned solution again, by mistake after 30 DEG C of crystallization 35 hours
It filters, wash, obtaining mesoporous material filter cake A2.
It is with weight ratio by the sulfuric acid solution and glycerine of the waterglass of a concentration of 20 weight % and a concentration of 12 weight %
3：2：1 carries out mixing and the haptoreaction 3h at 40 DEG C, then adjusts pH value to 4, then with the sulfuric acid of a concentration of 98 weight %
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.
The 10g filter cake A2 and 10g filter cakes B2 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein ball grinder
Material is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 500r/min.Close ball milling
Tank carries out the first ball milling in ball grinder, and temperature is 35 DEG C, and the time is 20 hours.By the first obtained ball milling slurry and 20g water
Then the mixed pulp at 35 DEG C carries out the second ball milling, temperature is 25 DEG C, and the time is 10 hours.The second obtained ball milling is starched
Material is to be spray-dried under 13000r/min in rotating speed at 150 DEG C, is then screened, will be screened using Cyclone Separation Technology
To product 15h is calcined at 600 DEG C in Muffle furnace, removed template method obtains spherical mesoporous composite material C2.
The pore structure parameter of spherical mesoporous composite material C2 is as shown in table 2 below.
Table 2
First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma, teases
It is the second most probable pore size after number.
(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 mesoporous composite material C2 of 1g
It is added in mother liquor and impregnates 1h, then filter, be used in combination n-hexane to carry out washing 4 times, in 75 DEG C of dryings, and be ground, obtain
Catalyst D2.
It is obtained by x-ray fluorescence analysis, in the obtained catalyst D2 of the present embodiment, based on the element, magnesium elements
Content is 7.0 weight %, and the content of titanium elements is 0.8 weight %.
Embodiment 3
The present embodiment is used to illustrate spherical mesoporous composite material and loaded catalyst of the present invention and preparation method thereof
(1) spherical mesoporous composite material is prepared
By the Triton X-100 (Qula of 0.75 gram of CTAB (cetyl trimethylammonium bromide) and 2.25ml
Logical-X100) it is added in 41.2 grams of the concentrated hydrochloric acid of 37 weight % and the hydrochloric acid of 93.3 grams of water composition, it is mixed at 60 DEG C
It is completely dissolved to CTAB；4.35 grams of ethyl orthosilicates are added in above-mentioned solution again, at a temperature of 60 DEG C, in mechanical agitation speed
Rate is to be stirred 10 hours under 340r/min, and 20 hours are stood at 60 DEG C；Acquired solution is transferred to the anti-of polytetrafluoroethyllining lining
It answers in kettle, by being filtered, washed, obtaining mesoporous material filter cake A3 after 40 DEG C of crystallization 30 hours.
It is with weight ratio by the sulfuric acid solution and ethylene glycol of the waterglass of a concentration of 10 weight % and a concentration of 12 weight %
6：3：1 carries out mixing and haptoreaction 1 hour at 45 DEG C, then adjusts pH value to 2, so with the sulfuric acid of a concentration of 98 weight %
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.
The 10g filter cake A3 and 15g filter cakes B3 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein ball grinder
Material 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.Close ball milling
Tank carries out the first ball milling in ball grinder, and temperature is 50 DEG C, and the time is 10 hours.The the first ball milling slurry and 87.5g that will be obtained
Then water mixed pulp at 50 DEG C carries out the second ball milling, temperature is 40 DEG C, and the time is 5 hours.The second obtained ball milling is starched
Material is to be spray-dried under 11000r/min in rotating speed at 250 DEG C, is then screened, will be screened using Cyclone Separation Technology
To product calcined for 24 hours at 400 DEG C in Muffle furnace, removed template method obtains spherical mesoporous composite material C3.
The pore structure parameter of obtained spherical mesoporous composite material C3 is as shown in table 3 below.
Table 3
First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma, teases
It is the second most probable pore size after number.
(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.The spherical mesoporous composite material C3 of 1g are added at 40 DEG C
Enter and impregnate 3h into mother liquor, then filter, is used in combination n-hexane to carry out washing 4 times, in 75 DEG C of dryings, and is ground, is urged
Agent D3.
It is obtained by x-ray fluorescence analysis, in the obtained catalyst D3 of the present embodiment, based on the element, magnesium elements
Content is 6.6 weight %, and the content of titanium elements is 1.2 weight %.
Embodiment 4
The present embodiment is used to illustrate spherical mesoporous composite material and loaded catalyst of the present invention and preparation method thereof
Spherical mesoporous composite material and loaded catalyst are prepared in the same manner as shown in Example 1, unlike,
During the filter cake for preparing silica gel, glycerine is not added, obtains spherical mesoporous composite material C4 and catalyst D4.
The pore structure parameter of spherical mesoporous composite material C4 is as shown in table 4 below.
Table 4
First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma, teases
It is the second most probable pore size after number.
It is obtained by xrf analysis, in the catalyst D4 described in the present embodiment, based on the element, the content of magnesium elements is 6.2
The content of weight %, titanium elements are 0.8 weight %.
Comparative example 1
This comparative example is for illustrating 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, to obtain the ES955 silica gel through thermal activation.
Catalyst is prepared according to the method for 1 step of embodiment (2), the difference is that using the above-mentioned work of identical weight part
The ES955 silica gel of change replaces spherical mesoporous composite material C1, to which comparative catalyst DD1 be made.
Comparative example 2
This comparative example is for illustrating carrier and loaded catalyst of reference and preparation method thereof
Spherical mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1.Unlike, only carry out the
One ball milling, without the second ball milling.Specifically, the 10g filter cake A1 and 10g filter cakes B1 of above-mentioned preparation is put into togerther 100mL's
In ball grinder.Ball grinder is closed, the first ball milling is carried out in ball grinder, temperature is 25 DEG C, and the time is 5 hours.Will obtained
Obtained slurry at 200 DEG C in rotating speed is to be sprayed under 12000r/min by one ball milling slurry and 40g water mixed pulp at 25 DEG C
Mist is dried.Spherical mesoporous composite material DC2 and loaded catalyst DD2 is made.
The pore structure parameter of spherical mesoporous composite material DC2 is as shown in table 5 below.
Table 5
It is obtained by xrf analysis, in the catalyst DD2 described in this comparative example, based on the element, the content of magnesium elements is
The content of 6.8 weight %, titanium elements are 1.1 weight %.
Comparative example 3
This comparative example is for illustrating spherical mesoporous composite material and loaded catalyst of reference and preparation method thereof
Spherical mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1.Unlike, rotation is not used
Wind isolation technics is screened, specifically, by the second obtained ball milling slurry at 200 DEG C in rotating speed be 12000r/min under spray
Mist is dried, and the product obtained after spray drying is then calcined 10h in Muffle furnace at 550 DEG C, removed template method obtains ball
Shape mesoporous composite material DC3 and loaded catalyst DD3.
The pore structure parameter of spherical mesoporous composite material DC3 is as shown in table 6 below.
Table 6
It is obtained by xrf analysis, in the catalyst DD3 described in this comparative example, based on the element, the content of magnesium elements is
The content of 6.0 weight %, titanium elements are 0.8 weight %.
Comparative example 4
This comparative example is for illustrating spherical mesoporous composite material and loaded catalyst of reference and preparation method thereof
Spherical mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1.
Unlike, it only carries out the first ball milling and does not also use Cyclone Separation Technology to be screened without the second ball milling.
Specifically, the 10g filter cake A1 and 10g filter cakes B1 of above-mentioned preparation is put into togerther in 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 5 hours.By the first obtained ball milling slurry and 40g water at 25 DEG C
Lower mixed pulp, by obtained slurry at 200 DEG C in rotating speed be 12000r/min under be spray-dried, then will spray drying after
Obtained product calcines 10h in Muffle furnace at 550 DEG C, and removed template method obtains spherical mesoporous composite material DC4 and load
Type catalyst DD4.
The pore structure parameter of spherical mesoporous composite material DC4 is as shown in table 7 below.
Table 7
It is obtained by xrf analysis, in the catalyst DD4 described in this comparative example, based on the element, the content of magnesium elements is
The content of 5.4 weight %, titanium elements are 1.0 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used to illustrate the application of loaded catalyst provided by the invention.
In the stainless steel polymerization autoclave of 2L, with nitrogen and ethylene, respectively three times, 200mL hexanes are then added in displacement, will
Kettle temperature rises to 80 DEG C, adds 800mL hexanes, and with the addition of hexane, the triethyl aluminum of a concentration of 1mol/L of 2mL is added
(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
It holds as 1.0MPa, separation is filtered after being reacted 1 hour at 70 DEG C, obtains 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 to illustrate the application of loaded catalyst provided by the invention.
In the stainless steel polymerization autoclave of 2L, with nitrogen and ethylene, respectively three times, 200mL hexanes are then added in displacement, will
Kettle temperature rises to 75 DEG C, adds 900mL hexanes, and with the addition of hexane, the triethyl aluminum of a concentration of 1mol/L of 2mL is added
(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, separation is filtered after being reacted 1.5 hours at 75 DEG C, obtains 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 to illustrate the application of loaded catalyst provided by the invention.
In the stainless steel polymerization autoclave of 2L, with nitrogen and ethylene, respectively three times, 200mL hexanes are then added in displacement, will
Kettle temperature rises to 85 DEG C, adds 700mL hexanes, and with the addition of hexane, the triethyl aluminum of a concentration of 1mol/L of 2mL is added
(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 filters separation, obtains polyethylene particle powder after being reacted 2 hours at 85 DEG C.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 to illustrate the application of loaded catalyst provided by the invention.
The polymerization of ethylene 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
The application of loaded catalyst of this Experimental comparison example for illustrating reference
The polymerization of ethylene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the comparison 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
The result compared from the above EXPERIMENTAL EXAMPLE 1-4 and Experimental comparison's example 1-4 can be seen that ball provided by the invention
When shape mesoporous composite material and loaded catalyst are used for ethylene polymerization, catalyst has higher catalytic activity, and
It can obtain heap density and the relatively low and non-breakable polyethylene product of melt index, specifically, the polyethylene product of preparation
Heap density is 0.5g/mL hereinafter, melt index is 0.5g/10min hereinafter, flour rate is less than 3 weight %.And the present invention is not used
The obtained polyethylene product of method, flour rate is more than 5 weight %.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, 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 also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of spherical mesoporous composite material, which is characterized in that the average grain diameter of the spherical mesoporous composite material is that 20-30 is micro-
Rice, specific surface area are 100-300 meters squared per grams, and pore volume is 0.5-1.8 mls/g, and aperture is in bimodal distribution, and bimodal point
Not corresponding most probable pore size is 1-10 nanometers and 20-55 nanometers.
2. spherical mesoporous composite material according to claim 1, wherein the average grain diameter of the spherical mesoporous composite material
It is 21-29 microns, specific surface area is 210-290 meters squared per grams, and pore volume is 0.8-1.8 mls/g, and aperture is in bimodal distribution,
And bimodal corresponding most probable pore size is 1-8 nanometers and 30-52 nanometers.
3. spherical mesoporous composite material according to claim 1, wherein the spherical mesoporous composite material is without containing bonding
The flour rate of agent, the spherical mesoporous composite material is less than 3 weight %.
4. a kind of preparation method of spherical mesoporous composite material, which is characterized in that this approach includes the following steps：
(1) it provides meso-porous molecular sieve material or prepares the filter cake of meso-porous molecular sieve material, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a and the component b are subjected to mixing and the first ball milling, the first obtained ball milling slurry is mixed with water
Then slurrying carries out the second ball milling and obtains the second ball milling slurry, whirlwind is used after the second ball milling slurry is spray-dried
Isolation technics is screened；
Wherein, above-mentioned steps so that the average grain diameter of the spherical mesoporous composite material is 20-30 microns, specific surface area 100-
300 meters squared per grams, pore volume are 0.5-1.8 mls/g, and aperture is in bimodal distribution, and bimodal corresponding most probable pore size
For 1-10 nanometers and 20-55 nanometers.
5. preparation method according to claim 4, wherein in step (3), the component a relative to 100 parts by weight
Dosage, the dosage of the component b is 1-200 parts by weight, preferably 20-180 parts by weight, more preferably 50-150 parts by weight.
6. preparation method according to claim 4, wherein in step (1), prepare the filter cake of meso-porous molecular sieve material
Process includes：Template, sour agent and silicon source are carried out first to be mixed, and obtained mixture is subjected to crystallization and filtering；
Preferably, the template is cetyl trimethylammonium bromide and Triton X-100, and the acid agent is salt
Acid, the silicon source are at least one of ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and Ludox；
Preferably, according to the molar ratio, silicon source：Triton X-100：Cetyl trimethylammonium bromide：Hydrogen chloride：Water
=1：0.01-0.5：0.1-0.6：5-50：100-500；
Preferably, the described first condition for being mixed includes：Temperature is 10-60 DEG C, and the time is 10-72 hours, pH value 1-
7；The condition of the crystallization includes：Temperature is 25-60 DEG C, and the time is 10-72 hours；
Preferably, in step (2), the process for preparing the filter cake of silica gel includes：Waterglass, polyalcohol and inorganic acid are carried out the
Two are mixed, and obtained mixture is filtered；
Preferably, the described second condition for being mixed includes：Temperature is 10-60 DEG C, and the time is 1-5 hours, pH value 2-4；
Preferably, the weight ratio of the waterglass, inorganic acid and polyalcohol is 1-8：0.1-5：1；
Preferably, the inorganic acid is one or more in sulfuric acid, nitric acid and hydrochloric acid；The polyalcohol be glycerine and/or
Ethylene glycol.
7. according to the preparation method described in any one of claim 4-6, wherein in step (3), first ball milling and
The condition of second ball milling is identical or different, and the condition of first ball milling and the second ball milling includes each independently：Abrading-ball turns
Speed is 200-800r/min, and the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hours；
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；
Preferably, the step of being screened using Cyclone Separation Technology after the second ball milling slurry being spray-dried include：It will
The second ball milling slurry is spray-dried, and the gas containing powder of discharge is carried out cyclonic separation to collect the powder
Grain；
Preferably, the component a is the filter cake of meso-porous molecular sieve material, and the component b is the filter cake of silica gel；The method is also wrapped
It includes：After the spray-drying process of step (3), the removed template method from the powder collected by cyclonic separation；
Preferably, the condition of the removed template method includes：Temperature is 250-800 DEG C, and the time is 10-40 hours.
8. the spherical mesoporous composite material prepared by the method described in any one of claim 4-7.
9. a kind of loaded catalyst, which contains the magnesium salts and/or titanium salt of carrier and load on the carrier, special
Sign is that the carrier is the spherical mesoporous composite material described in any one of claim 1-3 and 8.
10. catalyst according to claim 9, wherein on the basis of the total 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, which is characterized in that this method includes：In the presence of an inert gas, it will carry
Body is contacted with the mother liquor containing magnesium salts and/or titanium salt；Wherein, the carrier is described in any one of claim 1-3 and 8
Spherical 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 total weight of the loaded catalyst, the content of the carrier is 90-99
The sum of content in terms of magnesium elements and titanium elements is 1-10 weight % respectively for weight %, 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 by the method described in claim 11 or 12.
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| CN106467579A (en) * | 2015-08-17 | 2017-03-01 | 中国石油化工股份有限公司 | Macropore two dimension double hole channel spherical complex carrier and the composite containing polyethylene catalysts and their preparation method and application |
| CN106467582A (en) * | 2015-08-17 | 2017-03-01 | 中国石油化工股份有限公司 | Macropore two dimension the spherical complex carrier of straight channels and the composite containing polyethylene catalysts with and its preparation method and application |
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| WO2022078492A1 (en) * | 2020-10-15 | 2022-04-21 | 中国石油化工股份有限公司 | Magnesium-based solid and catalyst component having multimodal pore distribution, and preparation methods therefor |
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