CN106632760A - Spherical aluminum-containing mesoporous composite material and supported catalyst and preparation method and application thereof and ethylene polymerization method - Google Patents
Spherical aluminum-containing mesoporous composite material and supported catalyst and preparation method and application thereof and ethylene polymerization method Download PDFInfo
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Abstract
The invention relates to a spherical aluminum-containing mesoporous composite material, a preparation method of the aluminum-containing mesoporous composite material, a spherical aluminum-containing mesoporous composite material prepared the method, and a supported catalyst containing the spherical aluminum-containing mesoporous composite material, a preparation method of the supported catalyst, the supported catalyst, an application of the supported catalyst in ethylene polymerization, and a method for ethylene polymerization by using the supported catalyst, wherein the spherical aluminum-containing mesoporous composite material contains an aluminum component and a mesoporous molecular sieve material having a three-dimensional cubic tunnel structure. The supported catalyst prepared by taking the spherical aluminum-containing mesoporous composite material as a carrier has high catalytic activity during ethylene polymerization.
Description
Technical field
The present invention relates to a kind of spherical mesoporous composite material containing aluminum, the spherical system containing aluminum mesoporous composite material
Preparation Method, the spherical mesoporous composite material containing aluminum prepared by the method is spherical composite mesoporous containing aluminum containing this
The loaded catalyst of material, the preparation method of the loaded catalyst, the support type prepared by the method
Catalyst, application of the loaded catalyst in ethylene polymerization, and using the supported catalyst
The method that agent carries out vinyl polymerization.
Background technology
The development and application of polyethylene catalysts are that after traditional Ziegler-Natta catalyst, alkene gathers
Close catalyst field another important breakthrough, this cause the research of polyethylene catalysts entered into one it is fast
Hail the stage of exhibition.The catalyst amount reached due to homogeneous polyethylene catalyst needed for high activity is big, raw
High cost is produced, and the polymer for obtaining is without particle shape, it is impossible to it is poly- in widely used slurry process or vapor phase method
Close and used in technique, the effective way for overcoming the problems referred to above is exactly that soluble poly catalyst for ethylene is born
Loadization process.At present, the supported research report of relevant polyethylene catalysts is very more.It is new for further investigation
Support/catalyst/co-catalyst system, it is necessary to different carriers are attempted, to promote carried catalyst
With the further development of polyolefin industry.Mesoporous material with its big surface area (500-2000m2/g),
Spacious duct and the advantage of big and adjustable aperture size (3-50nm) is used for polyethylene by researcher
Catalyst is loaded and for ethylene polymerization.
The mesoporous material of the load polyethylene catalysts reported on document at present is MCM-41, with MAO
It is 10 to load the MCM-41 of polyethylene catalysts after process again and carry out catalysis activity after vinyl polymerization6
gPE/(mol Zr h).Ethylene polymerization activity is carried out after Mesoporous silica MCM 41 supported catalyst relatively low
The hole wall structure heat stability and hydrothermal stability that reason is mainly MCM-41 is poor, in loading process hole
Wall just has part to cave in, and load effect is have impact on, so that have impact on catalysis activity.Therefore, one is sought
The stable mesoporous material of meso-hole structure is planted, can still keep orderly meso-hole structure to be very must after load
Want.
The present invention using by high alumina ceramic ball milling and using spray drying method synthesize high intensity contain aluminum it is big
Hole diplopore mesoporous composite material, carries out obtaining the composite wood of polyethylene catalysts after polyethylene catalysts load
Material, and use it for ethylene polymerization and obtain the reaction process of polyethylene product.
The content of the invention
The invention aims to overcome poly- in ethylene using loaded catalyst made by existing carrier
Close the relatively low defect of catalysis activity in reaction, there is provided a kind of to be suitable as the spherical composite mesoporous containing aluminum of carrier
Material, and the spherical preparation method containing aluminum mesoporous composite material, by the spherical containing aluminum of the method preparation
Mesoporous composite material, containing the spherical loaded catalyst containing aluminum mesoporous composite material, the support type is urged
The preparation method of agent, the loaded catalyst prepared by the method, loaded catalyst is poly- in ethylene
Close the application in reaction, and the method for carrying out ethylene polymerization using the loaded catalyst.
In order to achieve the above object, the invention provides a kind of spherical mesoporous composite material containing aluminum, wherein,
The spherical mesoporous composite material containing aluminum contains al composition and mesoporous point with three-dimensional cubic duct structure
Son sieves material, and the spherical mean diameter containing aluminum mesoporous composite material for 10-80 microns, specific surface
Product is 100-180 meters squared per grams, and pore volume is 0.5-2 ml/g, and aperture is in bimodal distribution, and described
Bimodal corresponding most probable pore size is respectively 4-8 nanometers and 30-40 nanometers.
Present invention also offers a kind of spherical preparation method containing aluminum mesoporous composite material, the method include with
Lower step：
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure is provided or is prepared and there is three-dimensional
The filter cake of the meso-porous molecular sieve material of cube pore passage structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) mixed being incorporated in high alumina ceramic tank of component a and component b is carried out into ball milling, and
By the pressed powder obtained after ball milling water slurrying, then the slurry for obtaining is spray-dried；
Wherein, it is 10-80 that component a causes the spherical mean diameter containing aluminum mesoporous composite material
Micron, specific surface area is 100-180 meters squared per grams, and pore volume is 0.5-2 ml/g, and aperture is in bimodal
Distribution, and the bimodal corresponding most probable pore size is respectively 4-8 nanometers and 30-40 nanometers.
Present invention also offers the spherical mesoporous composite material containing aluminum prepared by said method.
Present invention also offers a kind of loaded catalyst, the catalyst contains carrier and is supported on the load
Magnesium component and titanium component on body, wherein, the carrier for the present invention provide it is above-mentioned spherical mesoporous containing aluminum
Composite.
Present invention also offers a kind of preparation method of loaded catalyst, the method includes：In indifferent gas
Under atmosphere, carrier is impregnated in the catalyst mother solution containing magnesium component and/or titanium component, then carried out
Filter and be dried, wherein, the above-mentioned spherical mesoporous composite material containing aluminum that the carrier is provided for the present invention,
The catalyst mother solution is the combined organic solution containing magnesium component and/or titanium component.
Present invention also offers the loaded catalyst prepared by said method.
Present invention also offers application of the above-mentioned loaded catalyst in ethylene polymerization.
Present invention also offers a kind of method of vinyl polymerization, the method includes：In the presence of a catalyst,
Under conditions of polyreaction, make ethylene that polyreaction to occur, wherein, the catalyst is carried for the present invention
For loaded catalyst.
The present inventor has found through in-depth study, containing with above-mentioned spherical composite mesoporous containing aluminum
The catalysis activity of the catalyst of material is higher, can catalyzed ethylene polymerization react and obtain higher activity.
Reason is likely due to：On the one hand, as a rule, although mesoporous point with three-dimensional cubic duct structure
The bigger serface and high pore volume of son sieve material can make it have higher catalysis activity, but while also can
Stronger water suction, moisture absorption ability are made it have, therefore, when mesoporous point with three-dimensional cubic duct structure
Son sieve material for it is bar-shaped when, agglomeration traits will be aggravated, to storing, transport, afterwards process and application brings not
Just.And the spherical mesoporous composite material containing aluminum that the present invention is provided is spherical, spheroid intensity is big, can reduce
The agglomeration traits and Crushing Problem of powder body simultaneously improve its mobility；Further, since in mechanical milling process aluminum
Introduce and spheroid intensity is increased, reduce the spheroid in catalyst loading process is carried out and crush；Finally,
The characteristics of carrier not only remains the high-specific surface area of ordered mesoporous material, big pore volume, also add
Aperture is big and advantage of narrowly distributing, and its pore-size distribution is presented unique bimodal distribution, more conducively activity
The load of component.It follows that the spherical mesoporous composite material containing aluminum that the present invention is provided is dexterously by microsphere
Structure in combination with the ordered mesoporous material that aperture has the advantages that bimodal distribution, so as to spherical contain for described
The application of aluminum mesoporous composite material provides more preferable platform, and has expanded its application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with
Detailed description below is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is according to the spherical X-ray diffracting spectrum containing aluminum mesoporous composite material of the present invention
(XRD spectrum)；
Fig. 2 is the scanning electron microscope according to the spherical microscopic appearance containing aluminum mesoporous composite material of the present invention
Figure (SEM figures).
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of spherical mesoporous composite material containing aluminum, wherein, it is described spherical mesoporous multiple containing aluminum
Condensation material contains al composition and the meso-porous molecular sieve material with three-dimensional cubic duct structure, and this is spherical
Mean diameter containing aluminum mesoporous composite material be 10-80 microns, specific surface area be 100-180 square metre/
Gram, pore volume is 0.5-2 ml/g, and aperture is in bimodal distribution, and the bimodal corresponding most probable hole
Footpath is respectively 4-8 nanometers and 30-40 nanometers.
Under preferable case, the spherical mean diameter containing aluminum mesoporous composite material is 30-60 microns, compares table
Area is 100-170 meters squared per grams, and pore volume is 0.8-1.8 ml/g, and aperture is in bimodal distribution, and
The bimodal corresponding most probable pore size is respectively 4-8 nanometers and 32-39 nanometers.In this case,
Gratifying catalytic effect not only can be obtained, but also can be with reduces cost.
According to the present invention, the spherical mesoporous composite material containing aluminum has three-dimensional cubic duct structure, its
The mean diameter of grain is measured using laser fineness gage, specific surface area, pore volume and most probable pore size root
Measure according to nitrogen adsorption methods.
In the present invention, the mean diameter is average particulate diameter.
According to the present invention, by the way that the spherical particle size containing aluminum mesoporous composite material is controlled in above range
Within, it can be ensured that the spherical mesoporous composite material containing aluminum is not susceptible to reunite, and is used as carrying
With higher catalysis activity during loaded catalyst made by body.When described spherical containing the composite mesoporous material of aluminum
When the specific surface area of material is less than 0.5 ml/g less than 100 meters squared per grams and/or pore volume, it is used as
The catalysis activity of loaded catalyst made by carrier can be significantly reduced；When described spherical composite mesoporous containing aluminum
When the specific surface area of material is more than 2 mls/g more than 180 meters squared per grams and/or pore volume, it is used as
Loaded catalyst made by carrier is susceptible to reunite during ethylene polymerization, so as to affect second
Reaction raw materials conversion ratio in alkene polymerization process.
According to the present invention, relative to mesoporous point with three-dimensional cubic duct structure described in 100 weight portions
Son sieve material, the content of the al composition can be 1-20 weight portions, preferably 5-19 weight portions.
In the present invention, the spherical mesoporous composite material containing aluminum can also contain two introduced by silica gel
Silicon oxide." silicon dioxide introduced by silica gel " is referred to described spherical containing aluminum mesoporous composite material
In preparation process, brought in the spherical mesoporous composite material containing aluminum of final preparation as preparing raw material by silica gel
Silica component.In the spherical mesoporous composite material containing aluminum, relative to the institute of 100 weight portions
State the meso-porous molecular sieve material with three-dimensional cubic duct structure, the silicon dioxide introduced by silica gel
Content can be 1-200 weight portions, preferably 50-150 weight portions.
In the present invention, the meso-porous molecular sieve material with three-dimensional cubic duct structure can be ability
The conventional use of various meso-porous molecular sieve materials in domain, and can prepare according to the conventional method.
Present invention also offers a kind of spherical preparation method containing aluminum mesoporous composite material, the method include with
Lower step：
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure is provided or is prepared and there is three-dimensional
The filter cake of the meso-porous molecular sieve material of cube pore passage structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) mixed being incorporated in high alumina ceramic tank of component a and component b is carried out into ball milling, and
By the pressed powder obtained after ball milling water slurrying, then the slurry for obtaining is spray-dried；
Wherein, it is 10-100 that component a causes the spherical mean diameter containing aluminum mesoporous composite material
Micron, specific surface area is 80-200 meters squared per grams, and pore volume is 0.5-2 ml/g, and aperture is in bimodal
Distribution, and the bimodal corresponding most probable pore size is respectively 2-10 nanometers and 30-40 nanometers.
According to the present invention, in step (1), the mesoporous molecular with three-dimensional cubic duct structure is prepared
The process of the filter cake of sieve material includes：In the presence of template and butanol, by tetraethyl orthosilicate and sour agent
Contacted, and the mixture obtained after contact is carried out into successively crystallization, is filtered and is washed.
According to the present invention, in step (1), the template, butanol and tetraethyl orthosilicate and sour agent
In sour mol ratio be 1:10-100:10-90:100-500, preferably 1:30-80:40-80:300-500,
Most preferably 1:78:60:323.
In the present invention, to the template, there is no particular limitation, can be commonly used in the art
Various template, it is preferable that the template is triblock copolymer PULLRONIC F68-polyoxy
Ethylene, the template can be commercially available (for example, can be purchased from Aldrich, trade name
For P123, molecular formula is EO20PO70EO20), it is also possible to prepared by existing various methods.
When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template according to
The mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene is calculated and obtained.
In the present invention, the sour agent can be that various routines can be used for adjusting the material of pH value or mixed
Compound (such as solution).Preferably, the sour agent is hydrochloric acid.As sour agent hydrochloric acid preferably with aqueous solution
Form use.The pH value of aqueous hydrochloric acid solution can be 1-6.
The butanol is preferably n-butyl alcohol.
In the present invention, the condition that tetraethyl orthosilicate is contacted with sour agent can include：Temperature is 10-60 DEG C,
Time is 10-72 hours, and pH value is 1-6.It is described for the uniform mixing being more beneficial between each material
Tetraethyl orthosilicate is contacted with sour agent and preferably carried out under agitation.The consumption of the sour agent is preferably so that just
Silester is 1-6 with the pH value of the haptoreaction system of sour agent.
Further, the present invention is to the template, between butanol, tetraethyl orthosilicate and acidic aqueous solution
The way of contact be not particularly limited, for example, above-mentioned four kinds of materials can be mixed contact simultaneously,
The mixture relaying that several materials therein can be first mixed contact, again obtain the addition of remaining material
Continuous mixing contact.Under preferable case, the way of contact is first by the template, butanol and acid water
Solution mix homogeneously, and the mixture for obtaining is placed in 30-45 DEG C of water-bath, then keeping temperature is not
Become, then tetraethyl orthosilicate is slowly dropped in said mixture, and stirring reaction 20-40 hour.With
On the basis of the template of 1g, the drop rate of the tetraethyl orthosilicate can be 0.1-1g/min.
In the present invention, the condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72
Hour.Under preferable case, the condition of the crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40
Hour.The crystallization is implemented by hydrothermal crystallization method.
In the present invention, there is the filter of the meso-porous molecular sieve material of three-dimensional cubic duct structure in above-mentioned preparation
During cake, can be included by the process filtered to obtain filter cake：After filtration, deionization is used
Water cyclic washing (washing times can be 2-10 time), then carries out sucking filtration.
In the present invention, in step (1), " mesoporous molecular with three-dimensional cubic duct structure is provided
Sieve material " can directly weigh or choose the meso-porous molecular sieve material with three-dimensional cubic duct structure
The meso-porous molecular sieve material of product, or preparation with three-dimensional cubic duct structure.It is described to have three
The preparation method of the meso-porous molecular sieve material of dimension cube pore passage structure can be implemented according to the conventional method, example
Such as, its preparation method can include：Prepared according to said method mesoporous with three-dimensional cubic duct structure
The filter cake of molecular screen material, then by gained filtration cakes torrefaction, and the template in the product that will be obtained after drying
Agent is removed.The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80
Hour.
According to the present invention, in step (2), preparing the process of the filter cake of silica gel can include：By water
Glass is contacted with mineral acid and n-butyl alcohol, and the mixture obtained after contact is filtered and washed
Wash.
According to the present invention, in step (2), the condition of the contact can be the conventional choosing in this area
Select, for example, the waterglass can include with the condition of the contact of mineral acid and n-butyl alcohol：Temperature is
10-60 DEG C, the time is 1-5 hours, and pH value is 2-4.For the uniform mixing being more beneficial between each material,
Waterglass is preferably carried out under agitation with the catalytic process of mineral acid.
In situations where it is preferred, the waterglass can be with the weight ratio of mineral acid and n-butyl alcohol
3-6:1:1。
In the present invention, the waterglass is the aqueous solution of sodium silicate, and its concentration can be 10-50 weights
Amount %, preferably 12-30 weight %.The mineral acid can be commonly used in the art various inorganic
Acid, can be at least one in sulphuric acid, nitric acid and hydrochloric acid for example.The mineral acid can be with pure state
Form use, it is also possible to used in the form of its aqueous solution.The consumption of the mineral acid is preferably so that water
Glass is 2-4 with the pH value of the haptoreaction system of mineral acid.
In the present invention, in step (2), " offer silica gel " can directly weigh or choose silica gel
Product, or prepare silica gel.Preparing the method for silica gel can implement according to the conventional method, for example
Can include：The filter cake of silica gel is prepared according to said method, then by gained filtration cakes torrefaction.
According to the present invention, in the spherical preparation process containing aluminum mesoporous composite material, step (1)
(2) mode filtered described in can to adopt well known to a person skilled in the art various modes are carried out,
Preferably sucking filtration is separated.It is utilization air pressure reality well-known to those skilled in the art that the sucking filtration is separated
A kind of existing liquid mode detached with solid particle.Additionally, the mode of the washing can also adopt ability
Mode of washing known to field technique personnel is carried out, and can be that washing and/or alcohol are washed for example, preferably water
Wash.
According to the present invention, in step (3), component a can be according to pre- with the consumption of component b
The spherical composition containing aluminum mesoporous composite material with three-dimensional cubic duct that phase obtains is selected, example
Such as, component a and the weight ratio of component b are 1:1-3.
According to the present invention, in step (3), the present invention does not have to the concrete operation method and condition of ball milling
There is special restriction, be not destroy or not destroy carrier structure substantially and silica gel is entered in carrier duct
It is accurate.Those skilled in the art can select various suitable conditions to implement the present invention according to mentioned above principle.
Specifically, the ball milling is carried out in high alumina ceramic ball grinder, wherein, abrading-ball in high alumina ceramic ball grinder
Diameter can be 2-3mm；The quantity of abrading-ball can be carried out rationally according to the size of high alumina ceramic ball grinder
Ground is selected, and for size is the high alumina ceramic ball grinder of 50-150mL, can generally use 1 abrading-ball；
The material of the abrading-ball is high alumina ceramic ball.The condition of the high alumina ceramic ball milling includes：The rotating speed of abrading-ball
Can be 300-500r/min, the temperature in high alumina ceramic ball grinder can be 15-100 DEG C, high alumina ceramic
The time of ball milling can be 0.1-100 hours.
In the present invention, can be at 25-60 DEG C by the process of the pressed powder water slurrying obtained after ball milling
Under carry out.In pulping process, pressed powder can be 1 with the weight ratio of the consumption of water:0.5-5, it is excellent
Elect 1 as:1-2.
In the present invention, the concrete operation method and condition of the spray drying is that those skilled in the art are public
Know.Specifically, the slurry being made into by the pressed powder and water is added in nebulizer rotate at a high speed with
Realize being spray-dried.Wherein, the condition of spray drying includes that temperature can be 100-300 DEG C, rotation
Rotating speed can be 10000-15000r/min；Under preferable case, the condition of the spray drying includes：Temperature
Spend for 150-250 DEG C, the rotating speed of rotation is 11000-13000r/min；In the case of more preferably, the spraying
Dry condition includes that temperature is 200 DEG C, and the rotating speed of rotation is 12000r/min.
According to the present invention, in step (3), when component a is with three-dimensional cubic duct structure
Meso-porous molecular sieve material filter cake, component b for silica gel filter cake when, namely when step (1)
To prepare the process of the filter cake of the meso-porous molecular sieve material with three-dimensional cubic duct structure, step (2)
For the filter cake for preparing silica gel process when, the spherical preparation method containing aluminum mesoporous composite material can be with
Including：After the spray drying of step (3), removed template method in the product obtained from spray drying.
The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80 hours.
Present invention also offers the spherical mesoporous composite material containing aluminum prepared by said method.
Present invention also offers a kind of loaded catalyst, the catalyst contains carrier and is supported on the load
Magnesium component and titanium component on body, wherein, the carrier for the present invention provide it is above-mentioned spherical mesoporous containing aluminum
Composite.
According to the present invention, in the loaded catalyst, carrier and magnesium component and titanium component are contained
There is no particular limitation for amount, can suitably be determined according to the conventional loaded catalyst in this area,
For example, on the basis of the gross weight of the catalyst, the content of the carrier is 50-99 weight %, excellent
Elect 50-95 weight % as；Count in a salt form, the content sum of the magnesium component and titanium component is 1-50
Weight %, preferably 5-50 weight %.
In the present invention, it is preferred to the magnesium component and titanium component are provided respectively in the form of magnesium salt and titanium salt,
The magnesium salt and titanium salt can be conventional use of various magnesium salts in the art and titanium salt, as long as can provide
Magnesium component and titanium component.Under preferable case, in the present invention, the magnesium salt is magnesium chloride；It is described
Titanium salt is titanium tetrachloride and/or titanous chloride..
Present invention also offers a kind of preparation method of loaded catalyst, the method includes：In indifferent gas
Under atmosphere, carrier is impregnated in the catalyst mother solution containing magnesium component and/or titanium component, then carried out
Filter and be dried, wherein, the above-mentioned spherical mesoporous composite material containing aluminum that the carrier is provided for the present invention,
The catalyst mother solution is the combined organic solution containing magnesium component and/or titanium component.
In the present invention, to the magnesium component and titanium component form and source are such as institute before of the invention
State, the present invention will not be described here.
In the present invention, the inert atmosphere can not occur chemical phase by various with carrier and active component
The various gases of interaction are formed.For example, the inert atmosphere can be by nitrogen and component periodic chart zero
One or more in race's gas are providing.
According to the present invention, the condition of the dipping includes：Temperature is 45-100 DEG C, and the time is 2-8h.
In the present invention, the catalyst mother solution is compound organic molten containing magnesium component and/or titanium component
Liquid, the compounded organic solvent can be can to dissolve the magnesium component and titanium component and readily removed
Various solvents, it is preferable that the compounded organic solvent is tetrahydrofuran and isopropanol.More preferably, four
The volume ratio of hydrogen furan and isopropanol is 1:1-3, particularly preferably 1:1-1.5.
Present invention also offers the loaded catalyst prepared by said method.
Present invention also offers application of the above-mentioned loaded catalyst in ethylene polymerization.
Present invention also offers a kind of method of vinyl polymerization, the method includes：In the presence of a catalyst,
Under conditions of polyreaction, make ethylene that polyreaction to occur, wherein, the catalyst is carried for the present invention
For loaded catalyst.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich
Company, is abbreviated as P123, and molecular formula is EO20PO70EO20, it is in the registration number of U.S. chemical abstract
The material of 9003-11-6, average molecular mass Mn is 5800.
In following examples and comparative example, X-ray diffraction analysis are purchased from Bruker AXS companies of Germany
Model D8Advance X-ray diffractometer on carry out；Scanning electron microscope analysis are purchased from U.S. FEI
Carry out in the scanning electron microscope of model XL-30 of company；Pore structure parameter analysis is purchased from the U.S.
Carry out on the nitrogen adsorption desorption instrument of model Autosorb-1 of Kang Ta companies, wherein, before being tested,
Sample is deaerated 4 hours at 200 DEG C.Aluminium content result is measured by XPS Analysis instrument.
Embodiment 1
The embodiment is used to illustrate the spherical mesoporous composite material containing aluminum and supported catalyst of present invention offer
Agent and their preparation method.
(1) spherical mesoporous composite material containing aluminum is prepared
By 6g (0.001mol) triblock copolymer template P123 be dissolved in 10mL concentrated hydrochloric acid and
In 220mL deionized water solutions, 4h is stirred at 15 DEG C so that P123 to be dissolved, forms clear solution,
Add 6g (0.08mol) n-butyl alcohol in this solution again and stir 1h, then the solution is placed in into 30 DEG C
Water-bath in, and 12.9g (0.062mol) tetraethyl orthosilicate is slowly added dropwise with the speed of 1g/min, will
Temperature is maintained at 30 DEG C, and pH value is to stir 24h under conditions of 4.5, then the water under the conditions of 100 DEG C again
Heat treatment 24h, deionized water cyclic washing after finally filtering, obtains with three-dimensional cubic pore after sucking filtration
The filter cake A1 of the meso-porous molecular sieve material of road structure.
By sulfuric acid solution and n-butyl alcohol that waterglass and concentration that concentration is 15 weight % are 12 weight %,
It is 5 by waterglass, sulphuric acid and n-butyl alcohol weight ratio：1：1 mix homogeneously, then stirs anti-at 15 DEG C
Answer 1.5 hours, and be 3 by the sulphuric acid adjustment pH value that the product concentration for obtaining is 98 weight %,
Then it is 0.02 weight % reaction mass sucking filtration, distilled water wash to be washed till into sodium ions content, obtains silica gel
Filter cake B1.
The 20g filter cake A1 and 20g filter cake B1 of above-mentioned preparation are put into into together 100mL high alumina ceramic balls
(wherein, high alumina ceramic ball grinder material is high alumina ceramic, and a diameter of 3mm of abrading-ball is counted in grinding jar
Measure as 1, rotating speed is 400r/min), high alumina ceramic ball grinder is closed, in high alumina ceramic ball grinder
Temperature is high alumina ceramic ball milling 1 hour at 60 DEG C, obtains 40 grams of pressed powders.The pressed powder is molten
Solution is spray-dried in 30 grams of deionized waters at 200 DEG C, in the case where rotating speed is 12000r/min,
Then the product obtained after spray drying is calcined into 24 hours to remove template in 500 DEG C of Muffle furnace
Agent, obtain 30 grams of removed template methods target product high intensity macropore three-dimensional cubic duct it is spherical containing aluminum
Mesoporous composite material, is named as KITDKAL-1.According to the result of XPS Analysis,
The content of aluminum is 6 weight % in KITDKAL-1.
(2) loaded catalyst is prepared
Under nitrogen protection, by the MgCl of 1g2With the TiCl of 1g4It is dissolved in the compound organic molten of 500mL
(tetrahydrofuran is 1 with the volume ratio of isopropanol for agent:1.2) in, component containing Mg and Ti components are formed
Catalyst mother solution.Then add above-mentioned carrier impregnations 5h of 10g, after the completion of reaction, pass through at 80 DEG C
Filter, be dried, obtain the polyethylene powder catalyst with good flow performance, be named as
KITDKAL-BCJ-1。
With X-ray diffraction, scanning electron microscope and photoelectron spectrograph and nitrogen adsorption desorption instrument to the high intensity
The spherical mesoporous composite material containing aluminum in macropore three-dimensional cubic duct is characterized.
Fig. 1 is X-ray diffracting spectrum (XRD spectrum), and abscissa is 2 θ, and vertical coordinate is intensity.
From the result of Fig. 1 can be seen that by spray drying method obtain it is spherical containing aluminum mesoporous composite material
Diffraction maximum in XRD spectra is all remained well.
Fig. 2 is the scanning electron microscope of the microscopic appearance of spherical mesoporous composite material containing aluminum (KITDKAL-1)
Figure (SEM figures), as seen from the figure, the mesoporous composite material is spherical, and particle size distribution is at 10～80 μm.
The pore structure parameter of the spherical KITDKAL-1 of mesoporous composite material containing aluminum is as shown in table 1.
Table 1
*：First most probable pore size and the second most probable pore size are separated with comma：Before comma for first most
Can several apertures, after comma be the second most probable pore size.
The spherical mesoporous composite material containing aluminum obtained by embodiment 1 is can be seen that by the data of upper table 1 is in
Diplopore is distributed.
Elementary analysiss result shows that the content of chlorine is 3.0 weights in catalyst KITDKAL-BCJ-1
Amount %, the content of titanium is 0.9 weight %, and the content of magnesium is 2.1 weight %.
Comparative example 1
ES955 silica gel is calcined 10 hours for 400 DEG C under nitrogen protection, with eliminating hydroxide and remaining water
Point, so as to obtain the ES955 silica gel of Jing thermal activations.
Method according to the step of embodiment 1 (2) prepares loaded catalyst, except that, adopt
The ES955 silica gel of identical weight part replaces spherical containing aluminium composite material.
Elementary analysiss result shows that the content of titanium is 1.2% in ES955, and the content of chlorine is 6.8%, magnesium
Content be 1.8 weight %.
Comparative example 2
Spherical mesoporous composite material containing aluminum and loaded catalyst are prepared according to the method for embodiment 1, institute is not
With the material of ball grinder is polytetrafluoroethyl-ne during the mesoporous composite material as carrier is prepared
Alkene, Material quality of grinding balls is Achatess.
Elementary analysiss result shows that the content of chlorine is 10 weight % in catalyst obtained in comparative example 2,
The content of titanium is 3.0 weight %, and the content of magnesium is 3.1 weight %.
Comparative example 3
Spherical mesoporous composite material containing aluminum and loaded catalyst are prepared according to the method for embodiment 1, institute is not
It is same, during the mesoporous composite material as carrier is prepared, do not include dissolving pressed powder
In 30 grams of deionized waters, and it is spray-dried at 200 DEG C, in the case where rotating speed is 12000r/min, and
It is directly pressed powder to be calcined into 24 hours with removed template method in 500 DEG C of Muffle furnace.According to photoelectricity
The result of sub- energy spectrum analysiss, the content of aluminum is 5 weight % in the mesoporous composite material for obtaining.
Elementary analysiss result shows that the content of chlorine is 8.7 weight % in catalyst obtained in comparative example 3,
The content of titanium is 2.3 weight %, and the content of magnesium is 2.5 weight %.
Embodiment 2
The embodiment is used to illustrate the spherical mesoporous composite material containing aluminum and supported catalyst of present invention offer
Agent and their preparation method.
(1) spherical mesoporous composite material containing aluminum is prepared
By 6g (0.001mol) triblock copolymer template P123 be dissolved in 10mL concentrated hydrochloric acid and
In 220mL deionized water solutions, 4h is stirred at 15 DEG C so that P123 to be dissolved, forms clear solution,
Add 4.5g (0.06mol) n-butyl alcohol in this solution again and stir 1h, then the solution is placed in into 30 DEG C
Water-bath in, and 10.4g (0.05mol) tetraethyl orthosilicate is slowly added dropwise with the speed of 1g/min, by temperature
Degree is maintained at 60 DEG C, and pH value is to stir 10h under conditions of 6, then again at hydro-thermal under the conditions of 150 DEG C
Reason 10h, deionized water cyclic washing after finally filtering obtains being tied with three-dimensional cubic duct after sucking filtration
The filter cake A2 of the meso-porous molecular sieve material of structure.
By sulfuric acid solution and n-butyl alcohol that waterglass and concentration that concentration is 15 weight % are 12 weight %,
It is 6 by waterglass, sulphuric acid and n-butyl alcohol weight ratio：1：1 mix homogeneously, then stirs anti-at 60 DEG C
Answer 1 hour, and be 2 by the sulphuric acid adjustment pH value that the product concentration for obtaining is 98 weight %,
Then it is 0.02 weight % reaction mass sucking filtration, distilled water wash to be washed till into sodium ions content, obtains silica gel
Filter cake B2.
The 20g filter cake A2 and 40g filter cake B2 of above-mentioned preparation are put into into together 100mL high alumina ceramic balls
(wherein, high alumina ceramic ball grinder material is high alumina ceramic, and a diameter of 3mm of abrading-ball is counted in grinding jar
Measure as 1, rotating speed is 300r/min), high alumina ceramic ball grinder is closed, in high alumina ceramic ball grinder
Temperature is high alumina ceramic ball milling 0.5 hour at 100 DEG C, obtains 40 grams of pressed powders.By the pressed powder
In being dissolved in 30 grams of deionized waters, and it is spray-dried at 150 DEG C, in the case where rotating speed is 11000r/min,
Then the product obtained after spray drying is calcined into 72 hours to remove template in 300 DEG C of Muffle furnace
Agent, obtain 30 grams of removed template methods target product high intensity macropore three-dimensional cubic duct it is spherical containing aluminum
Mesoporous composite material, is named as KITDKAL-2.According to the result of XPS Analysis,
The content of aluminum is 9 weight % in KITDKAL-2.
(2) loaded catalyst is prepared
Under nitrogen protection, by the MgCl of 1g2With the TiCl of 1g4It is dissolved in the compound organic molten of 500mL
(tetrahydrofuran is 1 with the volume ratio of isopropanol for agent:1.2) in, component containing Mg and Ti components are formed
Catalyst mother solution.Then add above-mentioned carrier impregnations 5h of 10g, after the completion of reaction, pass through at 80 DEG C
Filter, be dried, obtain the polyethylene powder catalyst with good flow performance, be named as
KITDKAL-BCJ-2。
With X-ray diffraction, scanning electron microscope and photoelectron spectrograph and nitrogen adsorption desorption instrument to the high intensity
The spherical mesoporous composite material containing aluminum in macropore three-dimensional cubic duct is characterized.
The pore structure parameter of the spherical KITDKAL-2 of mesoporous composite material containing aluminum is as shown in table 2.
Table 2
*：First most probable pore size and the second most probable pore size are separated with comma：Before comma for first most
Can several apertures, after comma be the second most probable pore size.
The spherical mesoporous composite material containing aluminum obtained by embodiment 2 is can be seen that by the data of upper table 2 is in
Diplopore is distributed.
Elementary analysiss result shows that the content of chlorine is 9.7 weights in catalyst KITDKAL-BCJ-2
Amount %, the content of titanium is 1.5 weight %, and the content of magnesium is 2.0 weight %.
Embodiment 3
The embodiment is used to illustrate the spherical mesoporous composite material containing aluminum and supported catalyst of present invention offer
Agent and their preparation method.
(1) spherical mesoporous composite material containing aluminum is prepared
By 6g (0.001mol) triblock copolymer template P123 be dissolved in 10mL concentrated hydrochloric acid and
In 220mL deionized water solutions, 4h is stirred at 15 DEG C so that P123 to be dissolved, forms clear solution,
Add 6.75g (0.09mol) n-butyl alcohol in this solution again and stir 1h, be then placed in the solution
In 30 DEG C of water-bath, and 15.6g (0.075mol) tetraethyl orthosilicate is slowly added dropwise with the speed of 1g/min,
Keep the temperature at 10 DEG C, pH value is to stir 72h under conditions of 1, then the water under the conditions of 30 DEG C again
Heat treatment 72h, deionized water cyclic washing after finally filtering, obtains with three-dimensional cubic pore after sucking filtration
The filter cake A3 of the meso-porous molecular sieve material of road structure.
By sulfuric acid solution and n-butyl alcohol that waterglass and concentration that concentration is 15 weight % are 12 weight %,
It is 3 by waterglass, sulphuric acid and n-butyl alcohol weight ratio：1：1 mix homogeneously, then stirs anti-at 10 DEG C
Answer 5 hours, and be 4 by the sulphuric acid adjustment pH value that the product concentration for obtaining is 98 weight %,
Then it is 0.02 weight % reaction mass sucking filtration, distilled water wash to be washed till into sodium ions content, obtains silica gel
Filter cake B3.
The 20g filter cake A2 and 60g filter cake B2 of above-mentioned preparation are put into into together 100mL high alumina ceramic balls
(wherein, high alumina ceramic ball grinder material is high alumina ceramic, and a diameter of 3mm of abrading-ball is counted in grinding jar
Measure as 1, rotating speed is 500r/min), high alumina ceramic ball grinder is closed, in high alumina ceramic ball grinder
Temperature is high alumina ceramic ball milling 10 hours at 25 DEG C, obtains 40 grams of pressed powders.The pressed powder is molten
Solution is spray-dried in 30 grams of deionized waters at 300 DEG C, in the case where rotating speed is 13000r/min,
Then the product obtained after spray drying is calcined into 12 hours to remove template in 600 DEG C of Muffle furnace
Agent, obtain 30 grams of removed template methods target product high intensity macropore three-dimensional cubic duct it is spherical containing aluminum
Mesoporous composite material, is named as KITDKAL-3.According to the result of XPS Analysis,
The content of aluminum is 15 weight % in KITDKAL-3.
(2) loaded catalyst is prepared
Under nitrogen protection, by the MgCl of 1g2With the TiCl of 1g4It is dissolved in the compound organic molten of 500mL
(tetrahydrofuran is 1 with the volume ratio of isopropanol for agent:1.2) in, component containing Mg and Ti components are formed
Catalyst mother solution.Then add above-mentioned carrier impregnations 5h of 10g, after the completion of reaction, pass through at 80 DEG C
Filter, be dried, obtain the polyethylene powder catalyst with good flow performance, be named as
KITDKAL-BCJ-3。
With X-ray diffraction, scanning electron microscope and photoelectron spectrograph and nitrogen adsorption desorption instrument to the high intensity
The spherical mesoporous composite material containing aluminum in macropore three-dimensional cubic duct is characterized.
The pore structure parameter of the spherical KITDKAL-3 of mesoporous composite material containing aluminum is as shown in table 3.
Table 3
*：First most probable pore size and the second most probable pore size are separated with comma：Before comma for first most
Can several apertures, after comma be the second most probable pore size.
The spherical mesoporous composite material containing aluminum obtained by embodiment 3 is can be seen that by the data of upper table 3 is in
Diplopore is distributed.
Elementary analysiss result shows that the content of chlorine is 9.0 weights in catalyst KITDKAL-BCJ-3
Amount %, the content of titanium is 1.7 weight %, and the content of magnesium is 2.0 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating loaded catalyst of the invention in ethylene polymerization
Application.
In 2 liters of rustless steel polymerization autoclave, with respectively displacement three times of nitrogen and ethylene, 200 are subsequently adding
Milliliter hexane, by kettle temperature 80 DEG C are risen to, and add 800 milliliters of hexanes, with the addition of hexane, are added
2 milliliters of concentration is triethyl aluminum (TEA) hexane solution of 1 mol/L, is subsequently added into polyethylene and urges
Agent, is passed through ethylene and pressure is risen to into 1.0MPa and 1.0MPa is maintained, and reacts 1 hour at 70 DEG C.
Polyethylene particle powder is obtained, the heap density (BD) of the polyethylene particle powder is 0.34g/mL, is melted
Melt index M I2.16=0.69g/10min.It is computed determining, the efficiency of catalyst is 2195g PE/gcat.h.
Experimental comparison's example 1
Using with the identical method of EXPERIMENTAL EXAMPLE 1 being polymerized for ethylene is carried out, except for the difference that, employing is urged
Agent is ES955 prepared by comparative example 1.The heap density (BD) of the polyethylene particle powder is 0.4g/mL,
Melt index：MI2.16=0.87g/10min.It is computed determining, the efficiency of catalyst is 1767g PE/
gcat.h。
Experimental comparison's example 2
Ethylene polymerization, except for the difference that, employing are carried out using with the identical method of EXPERIMENTAL EXAMPLE 1
Catalyst is catalyst prepared by comparative example 2.The heap density (BD) of the polyethylene particle powder is
0.41g/mL, melt index：MI2.16=0.69g/10min.It is computed determining, the efficiency of catalyst is
1700g PE/gcat.h。
Experimental comparison's example 3
Ethylene polymerization, except for the difference that, employing are carried out using with the identical method of EXPERIMENTAL EXAMPLE 1
Catalyst is catalyst prepared by comparative example 3.The heap density (BD) of the polyethylene particle powder is
0.29g/mL, melt index：MI2.16=0.5g/10min.It is computed determining, the efficiency of catalyst is 1850g
PE/gcat.h。
EXPERIMENTAL EXAMPLE 2
Ethylene polymerization, except for the difference that, employing are carried out using with the identical method of EXPERIMENTAL EXAMPLE 1
Catalyst is catalyst KITDKAL-BCJ-2 prepared by embodiment 2.The heap of the polyethylene particle powder
Density (BD) be 0.4g/mL, melt index：MI2.16=0.8g/10min.It is computed determining, catalysis
The efficiency of agent is 2067g PE/gcat.h.
EXPERIMENTAL EXAMPLE 3
Ethylene polymerization, except for the difference that, employing are carried out using with the identical method of EXPERIMENTAL EXAMPLE 1
Catalyst is catalyst KITDKAL-BCJ-3 prepared by embodiment 3.The heap of the polyethylene particle powder
Density (BD) be 0.36g/mL, melt index：MI2.16=0.9g/10min.It is computed determining, urges
The efficiency of agent is 2065g PE/gcat.h.
Can be seen by the data of above example and comparative example and EXPERIMENTAL EXAMPLE and Experimental comparison's example
Go out, adopting the preparation method of the composite of present invention offer can obtain mean diameter for 10-80 microns,
Specific surface area is 100-180 meters squared per grams, and pore volume is 0.5-2 ml/g, and aperture is in bimodal distribution,
And the bimodal corresponding most probable pore size is respectively 4-8 nanometers and the spherical of 30-40 nanometers is combined containing aluminum
Material.Additionally, the catalytic performance of loaded catalyst that the present invention is provided is good, when being applied to second
During alkene polyreaction, with higher catalysis activity.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible compound modes.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of spherical mesoporous composite material containing aluminum, it is characterised in that described spherical composite mesoporous containing aluminum
Material contains al composition and the meso-porous molecular sieve material with three-dimensional cubic duct structure, and this spherical contains
The mean diameter of aluminum mesoporous composite material is 10-80 microns, and specific surface area is 100-180 meters squared per grams,
Pore volume is 0.5-2 ml/g, and aperture is divided in bimodal distribution, and the bimodal corresponding most probable pore size
Wei not 4-8 nanometers and 30-40 nanometers.
2. composite according to claim 1, wherein, it is described spherical containing the composite mesoporous material of aluminum
The mean diameter of material is 30-60 microns, and specific surface area is 100-170 meters squared per grams, and pore volume is 0.8-1.8
Ml/g, aperture be in bimodal distribution, and the bimodal corresponding most probable pore size be respectively 4-8 nanometers and
32-39 nanometers.
3. composite according to claim 1, wherein, relative to described in 100 weight portions
Meso-porous molecular sieve material with three-dimensional cubic duct structure, the content of the al composition is 1-20 weight
Part, preferably 5-19 weight portions.
4. a kind of spherical preparation method containing aluminum mesoporous composite material, the method is comprised the following steps：
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure is provided or is prepared and there is three-dimensional
The filter cake of the meso-porous molecular sieve material of cube pore passage structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) mixed being incorporated in high alumina ceramic tank of component a and component b is carried out into ball milling, and
By the pressed powder obtained after ball milling water slurrying, then the slurry for obtaining is spray-dried；
Wherein, it is 10-80 that component a causes the spherical mean diameter containing aluminum mesoporous composite material
Micron, specific surface area is 100-180 meters squared per grams, and pore volume is 0.5-2 ml/g, and aperture is in bimodal
Distribution, and the bimodal corresponding most probable pore size is respectively 4-8 nanometers and 30-40 nanometers.
5. preparation method according to claim 4, wherein, in step (1), preparation has
The process of the filter cake of the meso-porous molecular sieve material of three-dimensional cubic duct structure includes：In template and butanol
In the presence of, tetraethyl orthosilicate is contacted with sour agent, and the mixture obtained after contact is carried out successively
Crystallization, filtration and washing.
6. preparation method according to claim 5, wherein, template, butanol and positive silicic acid second
Ester is 1 with the sour mol ratio in sour agent:10-100:10-90:100-500.
7. the preparation method according to claim 5 or 6, wherein, it is described in step (1)
Template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；The sour agent is hydrochloric acid；Just
The condition that silester is contacted with sour agent includes：Temperature be 10-60 DEG C, the time be 10-72 hours, pH
It is worth for 1-6；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is 10-72 hours.
8. preparation method according to claim 4, wherein, in step (2), prepare silica gel
The process of filter cake include：Waterglass is contacted with mineral acid and n-butyl alcohol, and will be obtained after contact
Mixture filtered and washed.
9. preparation method according to claim 8, wherein, in step (2), the water glass
Glass is 3-6 with the weight ratio of mineral acid and n-butyl alcohol:1:1；The waterglass and mineral acid and n-butyl alcohol connect
Tactile condition includes：Temperature is 10-60 DEG C, and the time is 1-5 hours, and pH value is 2-4；It is described inorganic
Acid is one or more in sulphuric acid, nitric acid and hydrochloric acid.
10. preparation method according to claim 4, wherein, in step (3), described group
A is divided to be 1 with the weight ratio of component b:1-3.
11. preparation methoies according to claim 4 or 10, wherein, in step (3), institute
Stating carries out the condition of ball milling in high alumina ceramic tank and includes：The rotating speed of abrading-ball be 300-500r/min, high alumina
Temperature in ceramic ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hours；The spray dried
Dry condition includes：Temperature 100-300 DEG C, rotating speed is 10000-15000r/min.
12. preparation methoies according to claim 4, wherein, component a is with three-dimensional vertical
The filter cake of the meso-porous molecular sieve material of square duct structure, component b for silica gel filter cake, methods described
Also include：After the spray-drying process of step (3), remove in the product obtained from spray drying
Template；Preferably, the condition of the removed template method includes：Temperature is 300-600 DEG C, and the time is
10-80 hours.
Prepared by 13. preparation methoies by described in any one in claim 4-12 spherical mesoporous containing aluminum
Composite.
A kind of 14. loaded catalysts, the catalyst contains carrier and load magnesium group on the carrier
Divide and titanium component, it is characterised in that the carrier is described in any one in claim 1-3 and 13
Spherical mesoporous composite material containing aluminum.
15. catalyst according to claim 14, wherein, the gross weight with the catalyst is
Benchmark, the content of the carrier is 50-99 weight %, preferably 50-95 weight %；In a salt form
The content sum of meter, the magnesium component and titanium component is 1-50 weight %, preferably 5-50 weight %.
A kind of 16. preparation methoies of loaded catalyst, the method includes：Under an inert atmosphere, will carry
Body is impregnated in the catalyst mother solution containing magnesium component and/or titanium component, is then filtered and is done
It is dry, it is characterised in that the carrier is that spherical described in any one contains in claim 1-3 and 13
Aluminum mesoporous composite material, the catalyst mother solution is compound organic molten containing magnesium component and/or titanium component
Liquid.
17. preparation methoies according to claim 16, wherein, the condition of the dipping includes：
Temperature is 45-100 DEG C, and the time is 2-8h.
Loaded catalyst prepared by 18. preparation methoies by described in claim 16 or 17.
Loaded catalyst in 19. claim 14,15 and 18 described in any one is in vinyl polymerization
Application in reaction.
A kind of 20. methods of vinyl polymerization, the method includes：In the presence of a catalyst, it is anti-in polymerization
Should under conditions of, make ethylene occur polyreaction, it is characterised in that the catalyst be claim 14,
Loaded catalyst in 15 and 18 described in any one.
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