CN105175586B - A kind of preparation method of mesoporous composite material and preparation method thereof and catalytic component and polyethylene - Google Patents
A kind of preparation method of mesoporous composite material and preparation method thereof and catalytic component and polyethylene Download PDFInfo
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- CN105175586B CN105175586B CN201410263891.XA CN201410263891A CN105175586B CN 105175586 B CN105175586 B CN 105175586B CN 201410263891 A CN201410263891 A CN 201410263891A CN 105175586 B CN105175586 B CN 105175586B
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Abstract
The invention discloses the preparation method of a kind of mesoporous composite material and preparation method thereof and catalytic component and polyethylene.The mesoporous composite material includes molecular screen material and silica gel with hexagonal hole road structure, and the mesoporous composite material is spherical, and the pore volume of the mesoporous composite material is 0.5 1.8mL/g, and specific surface area is 200 650m2/ g, average grain diameter are 20 60 μm, and aperture is in bimodal distribution, and bimodal the first most probable pore size and the second most probable pore size, first most probable pore size of corresponding to respectively is 1 3nm, and second most probable pore size is 10 30nm.The mesoporous composite material of the present invention can still keep orderly meso-hole structure after load.After active component magnesium and titanium are supported on into the composite, when obtained catalytic component is used for vinyl polymerization, catalyst can be made to keep higher catalytic activity, and polyethylene particle powder can be obtained.
Description
Technical field
The present invention relates to a kind of mesoporous composite material, the preparation method of the mesoporous composite material, and prepared by this method
Mesoporous composite material, the invention further relates to a kind of catalytic component, and a kind of preparation method of polyethylene.
Background technology
Since the regular mesoporous material of Mobile companies synthesis duct high-sequential in 1992, because it has high ratio table
Face, regular pore passage structure and narrow pore-size distribution so that mesoporous material is applied in catalysis, separation, medicine and other fields
Very big concern is arrived.Zhao east member in 1998 et al. synthesizes a kind of new material-mesoporous material SBA-15, and the material 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 Science279 (1998) 548-
550).CN1341553A discloses a kind of preparation method of mesonic pore molecular sieve carrier material, and mesoporous material made from this method is made
For heterogeneous reaction catalyst carrier, the separation of catalyst and product is easily realized.
But conventional ordered mesoporous material SBA-15 microscopic appearances are bar-shaped, itself mobility is poor, its big ratio
Surface area and high pore volume cause to make it have stronger water suction, moisture absorption ability, and this has been further exacerbated by the group of ordered mesoporous material
It is poly-, limit the storage of ordered mesoporous material, transport, post-processing and application.
The development and application of polyethylene catalysts are the olefinic polymerization catalysis after traditional Ziegler-Natta catalyst
The another important breakthrough in agent field, this causes the research of polyethylene catalysts to enter the stage of a fast development.Due to
Homogeneous polyethylene catalyst reach needed for high activity catalyst amount is big, production cost is high, and obtained polymer is without grain
Shape, it can not be used on widely used slurry process or gas phase polymerization technique.The effective way for overcoming above mentioned problem is exactly handle
Soluble poly catalyst for ethylene carries out supported processing.
The mesoporous material for the load polyethylene catalysts reported at present on document is MCM-41, is loaded again after being handled with MAO
Catalytic activity is 10 after the MCM-41 of polyethylene catalysts carries out vinyl polymerization6gPE/(mol Zr h).Mesoporous silica MCM 41
After supported catalyst carry out ethylene polymerization activity it is relatively low the reason for be mainly MCM-41 hole wall structure heat endurance and hydro-thermal it is steady
It is qualitative poor, just there is part to cave in loading process hole wall, load effect is have impact on, so that have impact on catalytic activity.
Therefore, it is necessary to seek a kind of stable mesoporous material of new meso-hole structure, it is set still to be protected after load
Hold the meso-hole structure of sequence, so that catalyst has higher catalytic activity.
The content of the invention
It is an object of the invention to solve the low technology of the catalytic activity of support type polyethylene catalysts in the prior art to ask
Topic, there is provided a kind of mesoporous composite material, the preparation method of the mesoporous composite material, and the composite mesoporous material prepared by this method
Material, the invention further relates to a kind of catalytic component, and a kind of preparation method of polyethylene.
In order to achieve the above object, the present inventor after research by having found, by Jie with hexagonal hole road structure
Porous molecular sieve material and silica gel are mixed and made into spherical mesoporous composite material, and when the pore volume of the composite is 0.5-
1.8mL/g, specific surface area 200-650m2/ g, average grain diameter are 20-60 μm, and aperture is in bimodal distribution, and bimodal are corresponded to respectively
First most probable pore size and the second most probable pore size, first most probable pore size are 1-3nm, and second most probable pore size is
10-30nm.It is the supported catalyst component that carrier synthesizes when for ethylene polymerization using the mesoporous composite material, catalysis
Agent has the catalytic efficiency significantly improved, so as to complete the present invention.
According to the first aspect of the invention, the invention provides a kind of mesoporous composite material, wherein, the composite mesoporous material
Material includes molecular screen material and silica gel with hexagonal hole road structure, and the mesoporous composite material is described mesoporous multiple to be spherical
The pore volume of condensation material is 0.5-1.8mL/g, specific surface area 200-650m2/ g, average grain diameter are 20-60 μm, and aperture is in double
Peak is distributed, and bimodal the first most probable pore size and the second most probable pore size, first most probable pore size of corresponding to respectively is 1-
3nm, second most probable pore size are 10-30nm.
According to the second aspect of the invention, the invention provides a kind of preparation method of mesoporous composite material, this method
Comprise the following steps：
(1) filter cake of the molecular screen material with hexagonal hole road structure is provided or prepares, as component a；
(2) filter cake of silica gel is provided or prepares, as component b；
(3) component a and component b mix and after ball milling, are spray-dried spherical composite mesoporous to obtain
Material；
Wherein, the component a and component b make it that the pore volume of mesoporous composite material is 0.5-1.8mL/g, and specific surface area is
200-650m2/ g, average grain diameter are 20-60 μm, and aperture be in bimodal distribution, and bimodal the first most probable pore size corresponding respectively and the
Two most probable pore sizes, first most probable pore size are 1-3nm, and second most probable pore size is 10-30nm.
According to the third aspect of the present invention, the invention provides mesoporous composite material prepared by the above method.
According to the fourth aspect of the present invention, the invention provides a kind of catalytic component, the catalytic component includes carrying
Body and load magnesium salts and titanium salt on the carrier, wherein, the magnesium salts be magnesium chloride, the titanium salt be titanium tetrachloride with/
Or titanium trichloride；The carrier is mesoporous composite material of the invention.
According to the fifth aspect of the present invention, the invention provides a kind of preparation method of polyethylene, this method to include：
Under the conditions of solution polymerization, in the presence of a catalyst, make ethene carry out polymerisation, wherein, the catalyst contains above-mentioned
Catalytic component.
The mesoporous composite material of the present invention can still keep orderly meso-hole structure after load.By active component magnesium and
After titanium is supported on the composite, when obtained catalytic component is used for vinyl polymerization, catalyst can be made to keep higher
Catalytic activity, and polyethylene particle powder can be obtained.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the XRD spectra according to the mesoporous composite material of the present invention；
Fig. 2 a and b is schemed according to the SEM of the different amplification of the microscopic appearance of the mesoporous composite material of the present invention；
Fig. 3 is the SEM figures of the microscopic appearance of catalyst according to the invention component；
Fig. 4 is the graph of pore diameter distribution according to the mesoporous composite material of the present invention；
Fig. 5 is the grain size distribution according to the mesoporous composite material of the present invention.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
According to the first aspect of the invention, the invention provides a kind of mesoporous composite material, wherein, the composite mesoporous material
Material includes molecular screen material and silica gel with hexagonal hole road structure, and the mesoporous composite material is described mesoporous multiple to be spherical
The pore volume of condensation material is 0.5-1.8mL/g, specific surface area 200-650m2/ g, average grain diameter are 20-60 μm, and aperture is in double
Peak is distributed, and bimodal the first most probable pore size and the second most probable pore size, first most probable pore size of corresponding to respectively is 1-
3nm, second most probable pore size are 10-30nm.
Hexagonal hole road structure is had according to the mesoporous composite material of the present invention, its average grain diameter uses laser fineness gage
Measure, specific surface area, pore volume and most probable pore size measure according to nitrogen adsorption methods.
According to the mesoporous composite material of the present invention to be spherical, by by the particle size control of spherical mesoporous composite material
System is within above range, it can be ensured that the mesoporous composite material is not susceptible to reunite, and is used as made of carrier
Supported catalyst component can improve the reaction raw materials conversion ratio during ethylene polymerization.When the mesoporous composite material
Specific surface area be less than 200m2When/g and/or pore volume are less than 0.5mL/g, loaded catalyst made of carrier is used as
Catalytic activity of the component during ethylene polymerization can significantly reduce；When the specific surface area of the mesoporous composite material is more than
650m2When/g and/or pore volume are more than 1.8mL/g, supported catalyst component made of carrier is used as in vinyl polymerization
Easily reunite in course of reaction, so as to influence the conversion ratio of monomer in ethylene polymerization.Preferably, it is described composite mesoporous
The pore volume of material is 0.6-1.6mL/g, specific surface area 200-450m2/g。
The present invention is not particularly limited to the molecular screen material with hexagonal hole road structure and the content of silica gel, as long as energy
The microscopic dimensions of mesoporous composite material are made to meet above-mentioned condition.According to the present invention, have relative to described in 100 parts by weight
The meso-porous molecular sieve material of hexagonal hole road structure, the content of the silica gel can be 1-200 parts by weight.From described in further improve
The angle that mesoporous composite material is used for the catalytic activity of the catalyst of vinyl polymerization as the supported catalyst component of carrier goes out
Hair, it is preferable that relative to the meso-porous molecular sieve material described in 100 parts by weight with hexagonal hole road structure, the silica gel contains
Measure as 50-150 parts by weight.
In the present invention, the content of the molecular screen material and silica gel with hexagonal hole road structure can be according to preparing
Usage amount both during the mesoporous composite material is determined.
In the present invention, the average grain diameter of the mesoporous composite material of the invention is 20-60 μm.Preferably, given an account of
The average grain diameter of hole composite material is 30-60 μm, the reunion of the mesoporous composite material so can be further prevented, so as to enter
One step increase composite is that the catalytic component that carrier is formed is used for the catalytic activity of catalyst.
According to the second aspect of the invention, the invention provides a kind of preparation method of mesoporous composite material, this method
Comprise the following steps：
(1) filter cake of the molecular screen material with hexagonal hole road structure is provided or prepares, as component a；
(2) filter cake of silica gel is provided or prepares, as component b；
(3) component a and component b mix and after ball milling, are spray-dried spherical composite mesoporous to obtain
Material；
Wherein, the component a and component b make it that the pore volume of mesoporous composite material is 0.5-1.8mL/g, and specific surface area is
200-650m2/ g, average grain diameter are 20-60 μm, and aperture be in bimodal distribution, and bimodal the first most probable pore size corresponding respectively and the
Two most probable pore sizes, first most probable pore size are 1-3nm, and second most probable pore size is 10-30nm.
In step (1), preparing the process of the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure can include：Will
Tetraethyl orthosilicate, cetyl trimethylammonium bromide (CTAB) and ammonia carry out haptoreaction, and mixed by what is obtained after haptoreaction
Compound carries out crystallization and filtering.
Wherein, the mol ratio of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can be 1：0.1-1：0.1-5,
Preferably 1：0.2-0.5：1.5-3.5.
Ammonia adds preferably in the form of ammoniacal liquor.
According to the present invention, haptoreaction process the depositing in water of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia
In lower progress.Preferably, part water is introduced in the form of ammoniacal liquor, and part water is added in the form of deionized water.In positive silicic acid second
In the haptoreaction system of ester, cetyl trimethylammonium bromide and ammonia, the mol ratio of tetraethyl orthosilicate and water can be 1：
100-200, preferably 1：120-180.
The catalytic condition of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can include：Temperature is 25-
100 DEG C, the time is 10-72 hours.Preferably, the haptoreaction is carried out under agitation, in favor of the uniform mixing between each material.
The condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.It is described under preferable case
The condition of crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
During the filter cake in above-mentioned preparation with the meso-porous molecular sieve material of hexagonal hole road structure, obtained by filtering
Obtaining the process of filter cake can include：After filtration, (washing times can be 2-10), Ran Houjin are washed repeatedly with deionized water
Row filters.
In step (1), " providing the meso-porous molecular sieve material with hexagonal hole road structure " can directly be weighed or select
Take the product of the meso-porous molecular sieve material with hexagonal hole road structure or prepare mesoporous point with hexagonal hole road structure
Son sieve material.The preparation method of the meso-porous molecular sieve material with hexagonal hole road structure can be real according to the conventional method
Apply, for example, its preparation method can include：Meso-porous molecular sieve material with hexagonal hole road structure is prepared according to the above method
Filter cake, then by gained filtration cakes torrefaction.
In step (2), preparing the process of the filter cake of silica gel can include：By waterglass and inorganic acid using weight ratio as 3-
6：1 is contacted, and the mixture obtained after contact is filtered.
There is no particular limitation for the condition that waterglass contacts with inorganic acid, can be fitted according in the common process for preparing silica gel
Locality selection.Under preferable case, the condition that waterglass contacts with inorganic acid includes：Temperature can be 10-60 DEG C, preferably 20-
45℃；PH value can be 2-4；Time can be 1-5 hours.
In order to be more beneficial for the uniform mixing between each material, waterglass is preferably stirring with the catalytic process of inorganic acid
Under the conditions of carry out.
The waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 3-20 weight %.
The inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulfuric acid, nitric acid and hydrochloric acid
At least one of.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution.
In step (2), " offer silica gel " can directly be weighed or choose silica gel product or prepare silica gel.
Preparing the method for silica gel can implement according to the conventional method, such as can include：The filter cake of silica gel is prepared according to the above method,
Then by gained filtration cakes torrefaction.
In step (3), the dosage of the component a and component b causes relative to having hexagonal hole described in 100 parts by weight
The meso-porous molecular sieve material of road structure, the content of the silica gel can be 1-200 parts by weight, preferably 50-150 parts by weight.
In step (3), the ball milling can be carried out in ball mill, and the inwall of ball grinder is preferably poly- in the ball mill
Tetrafluoroethene liner, the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can be entered according to the size of ball grinder
Row reasonably selects, and for the ball grinder that size is 50-150mL, can generally use 1 abrading-ball；The material of the abrading-ball can
To be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling can include：The rotating speed of abrading-ball can be 300-
500r/min, the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hours.
In the step (3), the spray drying can be implemented according to the mode of routine, such as will can be obtained after ball milling
Solid powder and water, which are made into slurry and is added in atomizer, to be carried out.The condition of the spray drying can include：Temperature is 150-
600 DEG C, the rotating speed of rotation can be 10000-15000r/min；Under preferable case, the condition of the spray drying includes：Temperature
For 150-250 DEG C, the rotating speed of rotation is 11000-13000r/min.By the process of the solid powder water slurrying obtained after ball milling
Can be in 25-60 DEG C of lower progress.In pulping process, the weight ratio of the dosage of solid powder and water can be 1：0.1-5, it is excellent
Elect 1 as：0.5-3.5.
According to the present invention, the condition of the spray drying is preferably so that the average grain diameter of the mesoporous composite material is 30-
60μm.In step (3), when step (1) is the process of the filter cake of meso-porous molecular sieve material of the preparation with hexagonal hole road structure
When, the preparation method of the mesoporous composite material can also include：After the spray drying of step (3), from being spray-dried
To product in remove cetyl trimethylammonium bromide.The process of removing cetyl trimethylammonium bromide can include：Will
Obtained product is spray-dried in Muffle furnace with 90-600 DEG C of temperature calcination 10-80 hours.
According to the third aspect of the present invention, present invention also offers the mesoporous composite material prepared by the above method.
The mesoporous composite material prepared by the method for the present invention is spherical, and the meso-hole structure of the mesoporous composite material is steady
It is fixed, therefore catalytic activity of the catalytic component in vinyl polymerization as carrier can be improved.
According to the fourth aspect of the present invention, the invention provides a kind of catalytic component, the catalytic component includes carrying
Body and load magnesium salts and titanium salt on the carrier, wherein, the magnesium salts be magnesium chloride, the titanium salt be titanium tetrachloride with/
Or titanium trichloride；The carrier is above-mentioned mesoporous composite material.
In the present invention, " catalytic component " refer to the present invention catalytic component its own can be used as urged for support type
Agent, or as the component in catalyst.
In the catalytic component, the active component magnesium on the carrier and the total content of titanium are not limited particularly
It is fixed, it can be properly selected according to the conventional loaded catalyst in this area, for example, the gross weight with the catalytic component
On the basis of amount, the total content of magnesium and titanium can be 1-10 weight %, preferably 2-8 weight %.
In the present invention, the content of each element can use X-ray fluorescence spectra analytic approach to survey in the catalytic component
.
In the present invention, the catalytic component can be prepared according to various methods commonly used in the art, it is only necessary to
By magnesium salts and titanium salt load on the carrier.
According to one embodiment of the present invention, preparing the method for the catalytic component can include：By the magnesium salts
With titanium salt dissolving in organic solvent, catalyst mother liquor is formed, then at 25-100 DEG C, the mesoporous composite material is added
0.1-5 hours are impregnated into mother liquor, so as to obtain mixed material, and mixture material are spray-dried.Wherein, for making
The organic solvent of the standby catalyst mother liquor can be isopropanol and tetrahydrofuran, and the volume ratio of tetrahydrofuran and isopropanol can
Think 1：1-3, preferably 1：1-1.5.
According to the present invention, when the ratio between the dosage of magnesium salts and titanium salt when preparing the catalytic component can be vinyl polymerization
Conventional selection, usually, the magnesium salts, titanium salt dosage weight ratio can be 1：0.1-2.
According to the fifth aspect of the present invention, the invention provides a kind of preparation method of polyethylene, this method to include：
Under the conditions of solution polymerization, in the presence of a catalyst, make ethene carry out polymerisation, wherein, the catalyst contains above-mentioned
Catalytic component.
According to the present invention, in order to further improve the conversion ratio of ethene, the catalyst also contains alkyl aluminum, the alkyl
The structure of aluminium is shown in formula I：
AlRnX5 (3-n)Formulas I
In Formulas I, n R can be each C1~C5Alkyl；3-n X5Can be each one kind in halogen group, it is excellent
Elect-Cl as；N is 0,1,2 or 3.
The C1-C5Alkyl can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
One or more in base, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
The instantiation of the alkyl aluminum compound includes but is not limited to：Trimethyl aluminium, dimethylaluminum chloride, triethyl group
Aluminium, diethyl aluminum chloride, tri-n-n-propyl aluminum, diη-propyl aluminium chloride, three n-butylaluminums, three sec-butyl aluminium, tri-tert aluminium, two
N-butylmagnesium chloride aluminium and diisobutyl aluminum chloride.
Preferably, the alkyl aluminum is triethyl aluminum.
The dosage of the alkyl aluminum can also be the conventional selection in this area, usually, the alkyl aluminum and the catalysis
The mass ratio of agent amounts of components can be 1：0.1-10；Under preferable case, the alkyl aluminum and the catalytic component dosage
Mass ratio is 1：0.2-8.
According to the present invention, the condition of the solution polymerization can be the conventional condition in this area.For example, the solution
Polymerisation is carried out in the presence of an inert gas, and the solution polymerization condition includes：Temperature can be 10-100 DEG C, preferably
For 20-95 DEG C；Time can be 0.5-5 hours, preferably 1-4 hours；Pressure can be 0.1-2MPa, preferably 0.5-
1.5MPa。
The inert gas is the gas not reacted with raw material and product, such as can be the conventional nitrogen in this area
Or at least one of group 0 element gas in the periodic table of elements, preferably nitrogen.
The present invention is not particularly limited to the solvent used in the solution polymerization, for example, can be hexane.
In the present invention, methods described can also include, and after polymerization, final reactant mixture will be taken out
Filter separation, so as to which polyethylene particle powder be made.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, X-ray diffraction analysis are in the model purchased from German Bruker AXS companies
Carried out on D8Advance X-ray diffractometer；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on attached instrument, wherein, before being tested, sample is deaerated 4 hours at 200 DEG C；Type of the average grain diameter in Malvern company
Number for Mastersizer2000 laser fineness gage on carry out, sample is dissolved in ethanol；X-ray fluorescence analysis is in Holland
Carried out on the model Axios-Advanced of company x-ray fluorescence analyzer.
The heap density of polyolefine powder is measured using method as defined in GB/T1636-2008.
Melt index：Determined according to ASTM D1238-99.
Embodiment 1
The present embodiment is used for the mesoporous composite material and catalytic component and their preparation method for illustrating the present invention.
(1) mesoporous composite material is prepared
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, and
The mol ratio of ammonia and water in tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor is 1：0.37：2.8：142, and 80
Stir 24 hours at DEG C, then hydro-thermal process 24 hours at 100 DEG C again, then carry out filtering and and be washed with deionized 4
It is secondary, then filter the filter cake A1 for the meso-porous molecular sieve material for obtaining having hexagonal hole road structure.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % using weight ratio as 5：1 is mixed
Merge haptoreaction 1.5 hours at 30 DEG C, then pH value is adjusted to 3 with the sulfuric acid that concentration is 98 weight %, then to obtaining
Reaction mass filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter cake B1 of silica gel.
The 10g filter cake A1 and 10g filter cakes B1 of above-mentioned preparation is put into 100mL ball grinder together, wherein, ball grinder
Material is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 400r/min.Closing
Ball grinder, temperature is ball milling 5 hours at 25 DEG C in ball grinder, obtains solid powder；By the solid powder be dissolved in 25g go from
In sub- water, at 200 DEG C in rotating speed be 12000r/min under be spray-dried；By the product obtained after spray drying in Muffle furnace
Calcined 10 hours at 550 DEG C, remove CTAB, obtain mesoporous composite material C1.
(2) catalytic component is prepared
0.1g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in (four in 10mL tetrahydrofuran and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.2) catalyst mother liquor, is formed.At 45 DEG C, 1g mesoporous composite materials C1 is added
The thorough impregnation 1h into mother liquor, is then filtered, and carries out washing 4 times with n-hexane, in 75 DEG C of drying, and is ground, is obtained
Catalytic component D1.
Fig. 1 is mesoporous composite material C1 XRD spectrum, wherein the low-angle spectral peak occurred understands that C1 has mesoporous material
Specific two-dimentional hexagonal hole road structure.
Fig. 2 a and b are the SEM figures of the different amplification of mesoporous composite material C1 microscopic appearance.As seen from the figure, it is situated between
Hole composite material C1 microscopic appearance is the microballoon that particle diameter is 30-60 μm, and its good dispersion property.
Fig. 3 is the SEM figures of catalytic component D1 microscopic appearance.As seen from the figure, D1 microscopic appearance is kept spherical substantially,
Its particle diameter is also 30-60 μm, and particle diameter is held essentially constant.
Fig. 4 is mesoporous composite material C1 graph of pore diameter distribution, and as seen from the figure, composite has double-pore structure point
Cloth, and duct is highly uniform.
Fig. 5 is mesoporous composite material C1 grain size distribution.
Mesoporous composite material C1 and catalytic component D1 pore structure parameter are as shown in table 1.
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,
It is the second most probable pore size after comma；The most probable pore size representation of table 2 below -3 is same.
Elementary analysis result shows that the content of titanium is 1.6% in catalytic component D1, and the content of chlorine is 8.1%, Mg contents
For 3.9%.
Comparative example 1
ES955 silica gel is calcined 10 hours in 400 DEG C under nitrogen protection, with eliminating hydroxide and Residual water, lived
The ES955 silica gel of change.
Method according to the step of embodiment 1 in (2) prepares catalytic component, except that, with the work of equal mass
The ES955 silica gel of change replaces mesoporous composite material C1, so as to which catalytic component DD1 be made.
Elementary analysis result shows that the content of titanium is 1.2% in catalytic component DD1, and the content of magnesium is 3.0%, chlorine
Content is 6.8%.
Embodiment 2
The present embodiment is used for the mesoporous composite material and catalytic component and their preparation method for illustrating the present invention.
(1) composite mesoporous carrier is prepared
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, just
The mol ratio of ammonia and water in silester, cetyl trimethylammonium bromide, ammoniacal liquor is 1：0.37：2.8：142, and at 90 DEG C
Lower stirring 20 hours, then hydro-thermal process 24 hours at 100 DEG C again, then carry out filtering and and be washed with deionized 6 times,
Then the filter cake A2 for the meso-porous molecular sieve material for obtaining having hexagonal hole road structure is filtered.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % using weight ratio as 4：1 is mixed
Merge haptoreaction 1 hour at 40 DEG C, then adjust pH value to 3 with the sulfuric acid that concentration is 98 weight %, then to obtaining
Reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter cake B2 of silica gel.
The 20g filter cake A2 and 10g filter cakes B2 of above-mentioned preparation is put into 100mL ball grinder together, wherein, ball grinder
Material is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 400r/min.Closing
Ball grinder, temperature is ball milling 5 hours at 30 DEG C in ball grinder, obtains solid powder；The solid powder is dissolved in 100g
In ionized water, at 200 DEG C in rotating speed be 12000r/min under be spray-dried；By the product obtained after spray drying in Muffle furnace
In calcined 9 hours at 600 DEG C, remove CTAB, obtain mesoporous composite material C2.
(2) catalytic component is prepared
0.1g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in (four in 10mL tetrahydrofuran and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.2) catalyst mother liquor, is formed.At 45 DEG C, 1g mesoporous composite materials C2 is added
Into mother liquor, thorough impregnation 1 hour, is then filtered, and carries out washing 4 times with n-hexane, in 75 DEG C of drying, and is ground, is obtained
To catalytic component D2.
Table 2 is mesoporous composite material C2 pore structure parameter.
Table 2
Elementary analysis result shows that the content of titanium is 1.7% in catalytic component D2, and the content of magnesium is 4.0%, and chlorine contains
Measure as 8.3%.
Embodiment 3
The present embodiment is used for the mesoporous composite material and catalytic component and their preparation method for illustrating the present invention.
(1) composite mesoporous carrier is prepared
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, just
The mol ratio of ammonia and water in silester, cetyl trimethylammonium bromide, ammoniacal liquor is 1：0.42：2.5：145, and 100
Stir 10 hours at DEG C, then hydro-thermal process 24 hours at 100 DEG C again, then carry out filtering and and be washed with deionized 6
It is secondary, then filter the filter cake A3 for the meso-porous molecular sieve material for obtaining having hexagonal hole road structure.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % using weight ratio as 5：1 is mixed
Merge haptoreaction 1 hour at 45 DEG C, then adjust pH value to 3 with the sulfuric acid that concentration is 98 weight %, then to obtaining
Reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter cake B3 of silica gel.
The 5g filter cake A3 and 10g filter cakes B3 of above-mentioned preparation is put into 100mL ball grinder together, wherein, ball grinder
Material is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 400r/min.Closing
Ball grinder, temperature is ball milling 5 hours at 30 DEG C in ball grinder, obtains solid powder；By the solid powder be dissolved in 50g go from
In sub- water, at 200 DEG C in rotating speed be 11000r/min under be spray-dried；By the product obtained after spray drying in Muffle furnace
Calcined 9 hours at 600 DEG C, remove CTAB, obtain mesoporous composite material C3.
(2) catalytic component is prepared
0.1g magnesium chlorides and 0.1g titanium tetrachlorides are dissolved in (four in 10mL tetrahydrofuran and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.2) catalyst mother liquor, is formed.At 45 DEG C, 1g mesoporous composite materials C3 is added
Into mother liquor, thorough impregnation 1.5 hours, are then filtered, and carry out washing 4 times with n-hexane, in 75 DEG C of drying, and are ground,
Obtain catalytic component D3.
Table 3 is mesoporous composite material C3 pore structure parameter.
Table 3
Elementary analysis result shows that the content of titanium is 1.2% in catalytic component D3, and the content of magnesium is 3.6%, and chlorine contains
Measure as 7.8%.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for the preparation method for illustrating the polyethylene of the present invention.
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 80 DEG C, adds 800mL hexanes, and with the addition of hexane, the concentration for adding 2mL is 1mol/L triethyl aluminum
(TEA) hexane solution, 0.5g catalytic component D1 is subsequently added into, pressure is risen into 1.0MPa and is maintained 1.0MPa,
70 DEG C are reacted 1 hour.Polyethylene particle powder is obtained, the heap density (BD) of the polyethylene particle powder is 0.35g/mL, melting
Index M I2.16=0.69g/10min.It is computed determining, the efficiency of catalyst is 2623g PE/gcath.
Experimental comparison's example 1
Polymerizeing for ethene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 1, unlike, using the contrast of identical weight
DD1 prepared by example 1 replaces catalytic component D1, and so as to which polyethylene particle powder be made, the heap of gained polyethylene particle powder is close
Degree (BD) is 0.4g/mL, melt index：MI2.16=0.87g/10min.It is computed determining, the efficiency of catalyst is 1767g
PE/gcat·h。
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for the preparation method for illustrating the polyethylene of the invention according to the present invention.
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 75 DEG C, adds 900mL hexanes, and with the addition of hexane, the concentration for adding 2mL is 1mol/L triethyl aluminum
(TEA) hexane solution, 0.1g catalytic component D2 is subsequently added into, is passed through ethene, pressure is risen into 1MPa and is maintained 1MPa,
Reacted 1.5 hours at 75 DEG C.Polyethylene particle powder is obtained, the heap density (BD) of the polyethylene particle powder is 0.3g/mL, is melted
Melt index M I2.16=0.7g/10min.It is computed determining, the efficiency of catalyst is 2600gPE/gcath.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for the preparation method for illustrating the polyethylene of the invention according to the present invention.
In 2L stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 200mL hexanes, will
Kettle temperature rises to 85 DEG C, adds 700mL hexanes, and with the addition of hexane, the concentration for adding 2mL is 1mol/L triethyl aluminum
(TEA) hexane solution, 1g catalytic component D3 is subsequently added into, is passed through ethene, pressure is risen into 1MPa and is maintained 1MPa,
85 DEG C are reacted 1 hour.Polyethylene particle powder is obtained, the heap density (BD) of the polyethylene particle powder is 0.3g/mL, and melting refers to
Number MI2.16=0.6g/10min.It is computed determining, the efficiency of catalyst is 3000g PE/gcath.
It can be seen from EXPERIMENTAL EXAMPLE 1-3 more than in the preparation method of the polyethylene of the present invention, contain embodiment 1-
The catalyst of 3 catalytic component has higher catalytic efficiency, and obtained polyethylene particle powder has relatively low heap close
Degree and melt index.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of ethylene rolymerization catalyst, the ethylene rolymerization catalyst contains ethene polymerization catalyst component and alkyl aluminum, should
Ethene polymerization catalyst component includes the magnesium salts and titanium salt of carrier and load on the carrier, wherein, the magnesium salts is chlorination
Magnesium, the titanium salt are titanium tetrachloride and/or titanium trichloride, and the carrier is mesoporous composite material, it is characterised in that this is mesoporous multiple
Condensation material includes molecular screen material and silica gel with hexagonal hole road structure, and the mesoporous composite material is spherical, is given an account of
The pore volume of hole composite material is 0.5-1.8mL/g, specific surface area 200-650m2/ g, average grain diameter are 30-60 μm, aperture
In bimodal distribution, and bimodal the first most probable pore size corresponding respectively and the second most probable pore size, first most probable pore size are
1-3nm, second most probable pore size is 10-30nm, on the basis of the gross weight of the ethene polymerization catalyst component, magnesium and
The total content of titanium is 1-10 weight %, and the magnesium salts, the weight ratio of titanium salt dosage are 1：0.1-2, the alkyl aluminum and the ethene
The mass ratio of polymerization catalyst component dosage is 1：0.1-10.
2. ethylene rolymerization catalyst according to claim 1, wherein, in the carrier, relative to the institute of 100 parts by weight
The meso-porous molecular sieve material with hexagonal hole road structure is stated, the content of the silica gel is 50-150 parts by weight.
3. ethylene rolymerization catalyst according to claim 1, wherein, the preparation method of the mesoporous composite material include with
Lower step：
（1）The filter cake of the molecular screen material with hexagonal hole road structure is provided or prepares, as component a；
（2）The filter cake of silica gel is provided or prepares, as component b；
（3）Component a and component b mix and after ball milling, are spray-dried to obtain spherical mesoporous composite material；
Wherein, the component a and component b make it that the pore volume of mesoporous composite material is 0.5-1.8mL/g, specific surface area 200-
650m2/ g, average grain diameter are 30-60 μm, and aperture is in bimodal distribution, and bimodal the first most probable pore size and second corresponding respectively is most
Can several apertures, first most probable pore size is 1-3nm, and second most probable pore size is 10-30nm.
4. ethylene rolymerization catalyst according to claim 3, wherein, in step（1）In, preparing component a method includes：
By tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia using mol ratio as 1：0.1-1：0.1-5 carries out haptoreaction, described
Catalytic temperature is 25-100 DEG C.
5. ethylene rolymerization catalyst according to claim 3, wherein, in step（2）In, preparing component b method includes：
By waterglass and inorganic acid using weight ratio as 3-6：1 is contacted, and the condition of the contact includes：PH is 2-4, time 1-5
Hour；The inorganic acid is at least one of sulfuric acid, nitric acid and hydrochloric acid.
6. ethylene rolymerization catalyst according to claim 3, wherein, in step（3）In, the condition of the ball milling includes：
Temperature is 15-100 DEG C, and the time is 0.1-100 hours；The temperature of the spray drying is 150-600 DEG C.
7. ethylene rolymerization catalyst according to claim 3, wherein, the dosage of the component a and component b cause relative to
The meso-porous molecular sieve material with hexagonal hole road structure of 100 parts by weight, the content of the silica gel is 50-150 parts by weight.
8. ethylene rolymerization catalyst according to claim 1, wherein, the alkyl aluminum is triethyl aluminum.
9. a kind of preparation method of polyethylene, this method include：Under the conditions of solution polymerization, in the presence of a catalyst, make
Ethene carries out polymerisation, it is characterised in that the catalyst is that the vinyl polymerization in claim 1-8 described in any one is urged
Agent.
10. according to the method for claim 9, wherein, the solution polymerization is carried out in the presence of an inert gas, described
The condition of solution polymerization includes：Temperature is 10-100 DEG C, and the time is 0.5-5 hours, pressure 0.1-2MPa.
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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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