CN105440168B - The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application - Google Patents
The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application Download PDFInfo
- Publication number
- CN105440168B CN105440168B CN201410514325.1A CN201410514325A CN105440168B CN 105440168 B CN105440168 B CN 105440168B CN 201410514325 A CN201410514325 A CN 201410514325A CN 105440168 B CN105440168 B CN 105440168B
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- spherical
- weight
- carrier
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of spherical composite mesoporous carrier of montmorillonite and preparation method thereof and support type polyethylene catalysts and preparation method thereof and application of the catalyst in catalytic reaction.The spherical composite mesoporous carrier of montmorillonite contains montmorillonite and dioxide/silica gel, and the average grain diameter of the composite mesoporous carrier of spherical montmorillonite is 30 60 microns, specific surface area is 200 650 meters squared per grams, pore volume is 0.5 1.5 mls/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 9 12 nanometers and 15 30 nanometers.In addition, the catalytic performance of support type polyethylene catalysts provided by the invention is preferable, when this catalyst of application is to be catalyzed the polymerisation of ethene, there is higher catalytic activity.
Description
Technical field
The present invention relates to a kind of composite mesoporous carrier of spherical montmorillonite, a kind of preparation of the spherical composite mesoporous carrier of montmorillonite
Method, the composite mesoporous carrier of spherical montmorillonite being prepared by this this method, a kind of support type polyethylene catalysts, one kind are negative
The preparation method of load type polyethylene catalysts, the application of the support type polyethylene catalysts in catalytic reaction.
Background technology
Mobile companies in 1992 synthesize the regular mesoporous material of duct high-sequential, have high ratio surface, regular
Pore passage structure and narrow pore-size distribution so that mesoporous material catalysis, separation, medicine and other fields application obtained it is very big
Concern (Beck J S, Vartuli J C, Roth W J, et al.J.Am.Chem.Soc., 1992,114 (27):10834-
10843), Zhao east member in 1998 et al. synthesizes a kind of new material-mesoporous material SBA-15, and the material has high-sequential
Mesoporous material aperture (6-30nm), the big (1.0cm of pore volume3/ g), thicker hole wall (4-6nm) keep high mechanical properties and
Good catalytic adsorption performance, see D.Y.Zhao, J.L.Feng, Q.S.Huo, (1998) 548- of et al Science 279
550；Zhao Dongyuan, Yu Chengzhong, a kind of remaining forever bold and unconstrained preparation methods of mesonic pore molecular sieve carrier material of, CN1341553A.The mesoporous material
Material is used as heterogeneous reaction catalyst carrier, easily realizes the separation of catalyst and product.
But conventional ordered mesoporous material SBA-15 microscopic appearances are bar-shaped, compared with microscopic appearance is spherical material
Mobility itself is poor, and its big specific surface area and high pore volume cause to make it have stronger water suction, moisture absorption ability, and this will enter one
The reunion of step aggravation ordered mesoporous material, storage to ordered mesoporous material, transport, post-processing and application are made troubles.It is and micro-
The geometric shape of ball is reducing the reunion of powder, and improving its mobility etc. has an obvious advantage, therefore by order mesoporous material
Material be made it is spherical microballoon can be combined with the advantages of ordered mesoporous material, the Gao Bibiao of ordered mesoporous material can be retained
Area, big pore volume, aperture be big and the characteristics of narrowly distributing, can reduce the reunion of ordered mesoporous material again, increase its mobility.This will
More preferable platform is provided for the application of ordered mesoporous material, and expands the application field of ordered mesoporous material.
Montmorillonite is that earth's surface is distributed one of most commonly used clay mineral, and it has the particle diameter of nano-micrometer level, Large ratio surface
The physical and chemical performance such as interchangeability of product, interlayer ion, thus can by physico-chemical process in the Intercalation reaction of montmorillonite or
The lewis' acid that some carry specific functional groups in surface graft, so as to realize the modification and performance regulation and control to its surface.By
It can increase effective hole of montmorillonite and surface scission of link in acidification, mutually be fitted so as to inlay and be detained external particle diameter
Suitable material (such as pollutant) or progress adsorption.
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
The catalyst amount that homogeneous polyethylene catalyst is reached needed for high activity is big, and 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.
At present, the supported research report of relevant polyethylene catalysts is very more.For further investigate new support/catalyst/
Co-catalyst system, it is necessary to different carriers is attempted, to promote the further development of carried catalyst and polyolefin industry.
The content of the invention
The purpose of the present invention is overcome using loaded catalyst made of existing meso-porous molecular sieve material for urging
Change the defects of catalyst activity is low in course of reaction, and it is de- to provide a kind of composite mesoporous carrier of spherical montmorillonite, a kind of spherical illiteracy
The preparation method of the composite mesoporous carrier of stone, the composite mesoporous carrier of spherical montmorillonite, a kind of support type being prepared by this method
Polyethylene catalysts, a kind of preparation method of support type polyethylene catalysts, the support type polyethylene catalysts are in catalytic reaction
In application.
In order to achieve the above object, the present inventor after research by having found, in the mesoporous material with double-pore structure
Montmorillonite is introduced in material, montmorillonite is entered inside outer surface, inner hole wall and the ball of mesoporous material, and this is composite mesoporous
Material be made is not susceptible to reunite it is spherical, can so retain the high-specific surface area of mesoporous material, big pore volume, large aperture and
There is double-pore structure, the reunion of mesoporous material can be reduced again, increase its mobility so that using the mesoporous composite material
Manufactured loaded catalyst can obtain the reaction raw materials conversion ratio significantly improved when for catalytic reaction, so as to complete
The present invention.
The invention provides a kind of spherical composite mesoporous carrier of montmorillonite, wherein, the spherical composite mesoporous carrier of montmorillonite
Containing montmorillonite and dioxide/silica gel, and the average grain diameter of the composite mesoporous carrier of spherical montmorillonite is 30-60 microns, compares table
Area is 200-650 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and pore-size distribution is bimodal distribution, and described bimodal right
The most probable pore size answered is respectively 9-12 nanometers and 15-30 nanometers.
In addition, the invention provides a kind of preparation method of the spherical composite mesoporous carrier of montmorillonite, this method includes following
Step：
(1) template, N,N-dimethylformamide and hydrochloric acid are stirred at a temperature of 25-60 DEG C to dissolving；
(2) step (1) resulting solution and tetraethyl orthosilicate are stirred into 1-2 hours at a temperature of 25-60 DEG C, obtains mesoporous material
The filter cake of material；
(3) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(4) filter cake of the mesoporous material, the silica gel filter cake are well mixed to simultaneously ball milling, and by after ball milling with montmorillonite
Obtained solid powder after water slurrying with being spray-dried, then the template in the product that will be obtained after spray drying takes off
Remove.
Present invention also offers a kind of composite mesoporous carrier of spherical montmorillonite being prepared by the above method.
Present invention also offers a kind of support type polyethylene catalysts, wherein, the catalyst takes off including above-mentioned spherical illiteracy
The composite mesoporous carrier of stone and the component containing Mg, Ti and Cl being supported on the composite mesoporous carrier of spherical montmorillonite.
Present invention also offers a kind of preparation method of support type polyethylene catalysts, wherein, this method includes having
The composite mesoporous carrier impregnation of spherical montmorillonite of double-pore structure is in by MgCl2And TiCl4Be dissolved in compounded organic solvent and containing for being formed
Have in the catalyst mother liquor of Mg and Ti components.
Present invention also offers application of the above-mentioned support type polyethylene catalysts in catalytic reaction.
It was found by the inventors of the present invention that including the above-mentioned composite mesoporous load of spherical montmorillonite with certain physical property
The catalyst activity of body and the polyethylene being supported on the composite mesoporous carrier of spherical montmorillonite is higher, and this is probably
Because：On the one hand, carrier provided by the invention is spherical that can reduce the reunion of powder, improve its mobility；On the other hand,
Carrier provided by the invention not only retain ordered mesoporous material high-specific surface area, big pore volume, aperture be big and double-pore structure
Feature, and unique bimodal distribution is presented in its pore-size distribution, is more beneficial for the load of active component, so as to be urged with higher
Change activity.
In addition, cheap montmorillonite is incorporated into composite, being produced into for carrier can be largely reduced
This.That is, the composite mesoporous carrier of spherical montmorillonite provided by the invention is dexterously by micro-sphere structure, the mesoporous material with double-pore structure
The advantages of material and montmorillonite, is combined, so as to provide more preferable platform for the application of the spherical composite mesoporous carrier of montmorillonite,
And its application field is expanded.
In addition, catalyst provided by the invention also have do not corrode instrument, side reaction is few and aftertreatment technology is simply excellent
Point.
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 X-ray diffracting spectrum (XRD spectrum), wherein, a is the composite mesoporous load of spherical montmorillonite according to the present invention
The XRD spectra of body (C1)；B is mesoporous according to the spherical montmorillonite for loading polyethylene obtained by spray drying process of the invention
The XRD spectra of complex carrier (Cat-1), abscissa are 2 θ, and ordinate is intensity；
Fig. 2 is the scanning electron microscope (SEM) photograph according to the microscopic appearance of the composite mesoporous carrier of spherical montmorillonite (C1) of the present invention
(SEM)；
Fig. 3 is the composite mesoporous load of spherical montmorillonite according to the load polyethylene obtained by spray drying process of the present invention
The scanning electron microscope (SEM) photograph (SEM) of the microscopic appearance of body (Cat-1).
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of spherical composite mesoporous carrier of montmorillonite, wherein, the spherical composite mesoporous carrier of montmorillonite
Containing montmorillonite and dioxide/silica gel, and the average grain diameter of the composite mesoporous carrier of spherical montmorillonite is 30-60 microns, compares table
Area is 200-650 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and pore-size distribution is bimodal distribution, and described bimodal right
The most probable pore size answered is respectively 9-12 nanometers and 15-30 nanometers.Under preferable case, the spherical composite mesoporous carrier of montmorillonite
Average grain diameter be 25-35 microns, specific surface area is 250-580 meters squared per grams, and pore volume is 0.9-1.2 mls/g, aperture
Bimodal distribution is distributed as, and the bimodal corresponding most probable pore size is respectively 9-10 nanometers and 26-28 nanometers.
The composite mesoporous carrier of spherical montmorillonite according to the present invention has double-pore structure, and the average grain diameter of its particle is adopted
Measured with laser fineness gage, specific surface area, pore volume and most probable pore size measure according to nitrogen adsorption methods.
The composite mesoporous carrier of spherical montmorillonite according to the present invention, by by the composite mesoporous carrier of spherical montmorillonite
Particle size is controlled within above range, it can be ensured that and the spherical composite mesoporous carrier of montmorillonite is not susceptible to reunite, and
And it is used as loaded catalyst made of carrier and can improves the catalytic activity of catalyst.When the spherical montmorillonite is mesoporous
The specific surface area of composite is less than 200 meters squared per grams and/or pore volume is less than 0.5 ml/g, and and/or bimodal correspondence
Most probable pore size when being less than 9 nanometers, the catalytic activity for being used as support type polyethylene catalysts made of carrier can be notable
Reduce；When the specific surface area of the spherical composite mesoporous carrier of montmorillonite is more than 650 meters squared per grams and/or pore volume more than 1.5
Ml/g, and and/or it is bimodal corresponding to most probable pore size be more than 30 nanometers when, be used as support type made of carrier and gather
Catalyst for ethylene is easily reunited in catalytic reaction process, so as to influence the conversion of the reaction raw materials in catalytic reaction process
Rate.
In the spherical composite mesoporous carrier of montmorillonite, relative to the dioxide/silica gel of 100 parts by weight, the illiteracy
The content of de- stone can be 10-90 parts by weight, preferably 20-60 parts by weight.
In the present invention, the composite mesoporous carrier of spherical montmorillonite can also contain the titanium dioxide introduced by waterglass
Silicon." silica being introduced into by waterglass " refers in the preparation process of the spherical composite mesoporous carrier of montmorillonite, by
The silica component that waterglass is brought into as preparing raw material in the spherical montmorillonite complex carrier finally prepared.Described spherical
In the composite mesoporous carrier of montmorillonite, relative to the mesopore molecular sieve material described in 100 parts by weight with three-dimensional cubic duct structure
Material, the content of the silica introduced by waterglass can be 1-200 parts by weight, preferably 50-150 parts by weight.
In the present invention, the dioxide/silica gel can be meso-porous molecular sieve material commonly used in the art, Er Qieke
To be prepared according to the conventional method.As a rule, its main component is silica, and the dioxide/silica gel is averaged
Particle diameter is 30-60 microns, and specific surface area is 200-400 meters squared per grams, and pore volume is 1-2 mls/g.
Present invention also offers a kind of preparation method of the spherical composite mesoporous carrier of montmorillonite, this method includes following step
Suddenly：
(1) template, N,N-dimethylformamide and hydrochloric acid are stirred at a temperature of 25-60 DEG C to dissolving；
(2) step (1) resulting solution and tetraethyl orthosilicate are stirred into 1-2 hours at a temperature of 25-60 DEG C, obtains mesoporous material
The filter cake of material；
(3) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(4) filter cake of the mesoporous material, the silica gel filter cake are well mixed to simultaneously ball milling, and by after ball milling with montmorillonite
Obtained solid powder after water slurrying with being spray-dried, then the template in the product that will be obtained after spray drying takes off
Remove.
In the preparation process of the above-mentioned spherical composite mesoporous carrier of montmorillonite, mainly by controlling Jie with double-pore structure
It is bimodal point that the composition of Porous materials filter cake and silica gel filter cake, which controls the pore-size distribution of the spherical composite mesoporous carrier of montmorillonite,
Cloth, and make the spherical composite mesoporous carrier of montmorillonite that there is double-pore structure, and by controlling forming method (that is, first will be mesoporous
Material filter cake, silica gel filter cake are well mixed with montmorillonite and ball milling, then that obtained solid powder is dry with being sprayed after water slurrying
It is dry) microscopic appearance of the spherical composite mesoporous carrier of montmorillonite is controlled to be spherical.
According to the present invention, the template can be polyethylene glycol oxide-PPOX-polyethylene glycol oxide.
According to the present invention, the hydrochloric acid can be the conventional selection of this area, and under preferable case, the hydrochloric acid is with the aqueous solution
Form use, for example, can be the solution of water and hydrogen chloride.The pH value of aqueous hydrochloric acid solution can be 1-6.
According to the present invention, according to the molar ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide：N, N- dimethyl formyl
Amine：Water：HCl=1：300-700：10000-20000：100-500, preferably 1：550-650：10000-13000：150-480,
Particularly preferably 1：595：11628：329.Wherein, the molal quantity of polyethylene glycol oxide-PPOX-polyethylene glycol oxide is according to poly-
The mean molecule quantity of ethylene oxide-PPOX-polyethylene glycol oxide calculates to obtain.
According to the present invention, to the species of the template, there is no particular limitation, as long as the spherical illiteracy that can make to obtain takes off
The composite mesoporous carrier of stone has above-mentioned pore structure, for example, the template can be commonly used in the art various three
Block copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide template.Wherein, the template can be obtained by commercially available
To (for example, Aldrich, trade name P123, molecular formula EO can be purchased from20PO70EO20), can also be by existing
Various methods are prepared.
According to the present invention, the mol ratio of the dosage of the template and tetraethyl orthosilicate can be with 1：10-90, preferably 1：
50-75。
The condition of the invention contacted to the tetraethyl orthosilicate with step (1) resulting solution is no particularly to be limited, example
Such as, the condition of contact generally includes：Temperature can be 25-60 DEG C, and the time can be 1-2 hours.In order to be more beneficial for each material
Between uniform mixing, the tetraethyl orthosilicate contacts with step (1) resulting solution and preferably carries out under agitation.The stirring
It is not particularly limited, can is the conventional selection of this area.
According to the present invention, the way of contact to the template, DMF and hydrochloric acid does not limit particularly
It is fixed, such as above-mentioned three kinds of materials can be mixed contact simultaneously, two of which material can also mix first to contact, then by residue
The material mixture that adds to obtain in continue mixing contact.Under preferable case, the way of contact is first by the template
DMF stirring is added after being stirred with the hydrochloric acid, obtained mixture is then placed at water-bath
In, keeping temperature is constant, then tetraethyl orthosilicate is slowly added dropwise into gained mixture, and continues stirring reaction.
The condition that the present invention contacts to waterglass with inorganic acid is not particularly limited, can be according to the routine for preparing silica gel
Technique suitably determines.Under preferable case, the condition that waterglass contacts with inorganic acid generally includes：Temperature can be 10-60 DEG C,
Preferably 20-40 DEG C；Time can be 1-5 hours, preferably 1.5-3 hours；PH value is 2-4.In order to be more beneficial for each material
Between uniform mixing, the waterglass contacts with inorganic acid preferably to be carried out under agitation.
As well known to those skilled in the art, the waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 weights
Measure %, preferably 12-30 weight %.
The species of the inorganic acid can be the conventional selection of this area, for example, can be in sulfuric acid, nitric acid and hydrochloric acid
It is one or more.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution.It is described inorganic
The dosage of acid is preferably so that the pH value of the haptoreaction system of waterglass and inorganic acid is 2-4.
According to the present invention, in the filter cake of the mesoporous material with double-pore structure and the preparation process of the silica gel filter cake
In, the mode of the filtering can be carried out using well known to a person skilled in the art various modes, preferably filter separation.It is described
It is a kind of mode well-known to those skilled in the art for realizing that liquid separates with solid particle using air pressure to filter separation.
During the filter cake and silica gel filter cake in above-mentioned preparation with the mesoporous material of double-pore structure, obtained by filtering
Obtaining the process of filter cake can include：After filtration, wash that (washing times can be 2-10 repeatedly with deionized water (distilled water)
It is secondary), then filtered.
According to the present invention, in step (4), the mesoporous material filter cake with double-pore structure, silica gel filter cake and the montmorillonite
Dosage can be selected according to the component of the expected obtained composite mesoporous carrier of spherical montmorillonite, for example, with 100 parts by weight
The mesoporous material with double-pore structure filter cake dosage on the basis of, the dosage of the silica gel filter cake is 1-200 weight
Part, preferably 50-150 parts by weight；The dosage of the montmorillonite can be 1-50 parts by weight, preferably 20-50 parts by weight.
According to the present invention, in step (3), there is no particular limitation for concrete operation method and condition to the ball milling,
It is defined by the structure for not destroying or not destroying substantially meso-porous molecular sieve material.Those skilled in the art can select according to mentioned above principle
Various suitable conditions are selected to implement the present invention.Specifically, the ball milling is carried out in ball mill, ball grinder in the ball mill
Inwall be preferably polytetrafluoroethyllining lining, wherein, the diameter of abrading-ball can be 2-3mm in ball mill；The quantity of abrading-ball can be with
Reasonably selected according to the size of ball grinder, for the ball grinder that size is 50-150mL, can generally use 1 mill
Ball；The material of the abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling includes：Abrading-ball
Rotating speed can be 300-500r/min, and the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be that 0.1-100 is small
When.
In step (4), the solid powder obtained after ball milling can be carried out with the process of water slurrying at 25-60 DEG C.
In pulping process, the weight ratio of the dosage of solid powder and water can be 1：0.1-2, preferably 1：0.3-1.
According to the present invention, the concrete operation method and condition of the spray drying are known to the skilled person, such as
It can be carried out in atomizer.Specifically, the slurry being made into by the solid powder and water is added in atomizer and revolved at a high speed
Turn to realize spray drying.Wherein, it can be 100-300 DEG C that the condition of spray drying, which includes temperature, and the rotating speed of rotation can be
10000-15000r/min；Under preferable case, it is 150-250 DEG C that the condition of the spray drying, which includes temperature, the rotating speed of rotation
For 11000-13000r/min.
According to the present invention, the method for removed template method is usually calcination method.The condition of the removed template method can be this
The conventional selection in field, for example, the condition of the removed template method includes：Temperature can be 300-600 DEG C, preferably 350-
550 DEG C, most preferably 500 DEG C；Time can be 10-80 hours, preferably 20-30 hours, most preferably 24 hours.
Present invention also offers the composite mesoporous carrier of spherical montmorillonite being prepared by the above method.
Present invention also offers a kind of support type polyethylene catalysts, wherein, the catalyst includes above-mentioned spherical montmorillonite
Composite mesoporous carrier and the component containing Mg, Ti and Cl being supported on the composite mesoporous carrier of spherical montmorillonite.
According to the present invention, in the support type polyethylene catalysts, the composite mesoporous carrier of the spherical montmorillonite and contain
The content for having Mg, Ti and Cl component can be the conventional selection of this area, for example, with the support type polyethylene catalysts
On the basis of gross weight, the content of the carrier can be 50-99 weight %, the total content of the component containing Mg, Ti and Cl
Can be 1-50 weight %, under preferable case, on the basis of the gross weight of the support type polyethylene catalysts, the carrier
Content is 50-95 weight %, and the total content of the component containing Mg, Ti and Cl is 5-50 weight %.
According to the present invention, the average grain diameters of the support type polyethylene catalysts is 30-59 microns, specific surface area 250-
300 meters squared per grams, pore volume are 1.1-1.4 mls/g, and pore-size distribution is bimodal distribution, and it is described it is bimodal corresponding to most probable
Aperture is respectively 9.5-9.7 nanometers and 24-25 nanometers.
Present invention also offers a kind of preparation method of support type polyethylene catalysts, wherein, this method is included by described in
The composite mesoporous carrier impregnation of spherical montmorillonite in by MgCl2And TiCl4What is be dissolved in compounded organic solvent and formed contains Mg and Ti
In the catalyst mother liquor of component.
It is above-mentioned prepare support type polyethylene catalysts during, with total dosage of the support type polyethylene catalysts
On the basis of, the dosage of the carrier can be 50-99 weight %, preferably 50-95 weight %；The MgCl2And TiCl4Use
The total amount of amount can be 1-50 weight %, preferably 5-50 weight %.In addition, the MgCl2And TiCl4Weight ratio can be
1：0.1-1.5.
According to the present invention, the scope of the compounded organic solvent is very wide in range, can be the conventional selection of this area, in this hair
In bright, the compounded organic solvent can be the mixed solution of tetrahydrofuran and isopropanol.
According to the present invention, the condition of the dipping is not particularly limited, and can be the conventional selection of this area, in the present invention
In, the condition of the dipping includes：Temperature can be 10-60 DEG C, and the time can be 10-72 hours.
Also include in the preparation method of above-mentioned support type polyethylene catalysts after the completion of carrying out impregnation, it is filtered, wash
Wash, dry, finally give the powdery polyethylene catalyst with good flow performance.Wherein, it is filtered, washed and dried and does not have
There is specific restriction, can be the conventional selection of this area.
Present invention also offers application of the above-mentioned support type polyethylene catalysts in catalytic reaction.
The present invention will be described in detail by way of examples below.
In following examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, is abbreviated as P123, point
Minor is EO20PO70EO20, the material for being 9003-11-6 in the registration number of U.S. chemical abstract, average molecular mass Mn 5800.
In following examples and comparative example, X-ray diffraction analysis are in the model D8 purchased from German Bruker AXS companies
Carried out on Advance X-ray diffractometer；Scanning electricity of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on sub- microscope；Pore structure parameter analyzes the nitrogen adsorption desorption in the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on instrument, wherein, before being tested, sample is deaerated 4 hours at 200 DEG C；The analysis of reaction product liquid phase ingredient is being purchased
Carried out from Agilent companies of Britain 7890A/5973N gas chromatograph-mass spectrometers.
Embodiment 1
The embodiment is used to illustrate the composite mesoporous carrier of spherical montmorillonite provided by the invention and the catalysis of support type polyethylene
Agent and preparation method thereof.
(1) preparation of the composite mesoporous carrier of spherical montmorillonite
By 2.0 grams of P123 (U.S. chemical abstract registration number be 9003-11-6 material, its average molecular mass Mn=
5800) it is added to 15 grams of DMFs (DMF) in 11.2 gram 37% of hydrochloric acid and the solution of 64ml water, at 40 DEG C
Stir to P123 and be completely dissolved；4.45 grams of tetraethyl orthosilicates are added in above-mentioned solution again and stirred 1 hour at 40 DEG C, were passed through
The filter cake of mesoporous material with double-pore structure is obtained after filter, washing, drying；
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % by waterglass and sulfuric acid weight
Than for 5：After 1 is well mixed, reaction 2 hours is stirred at 30 DEG C, and be 98 weights by obtained reaction product concentration
The sulfuric acid adjustment pH for measuring % is 3, and it is 0.02 weight then to filter reaction mass, sodium ions content is washed till with distillation water washing
% is measured, obtains silica gel filter cake.
The 10 grams of meso-porous molecular sieve material filter cakes, 10 grams of silica gel filter cakes and 5 grams of montmorillonites of above-mentioned preparation are put into together
(wherein, ball grinder material is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, a diameter of 3mm of abrading-ball, quantity in 100mL ball grinders
For 1, rotating speed 400r/min), ball grinder is closed, temperature is ball milling 1 hour at 60 DEG C in ball grinder, obtains 25 grams of solids
Powder；The solid powder is dissolved in 25 grams of deionized waters, is spray-dried at 200 DEG C, in the case where rotating speed is 12000r/min；
Then the product obtained after spray drying is calcined 24 hours in 500 DEG C of Muffle furnace, removed template method, obtains 20 grams of removings
The target product of template has the composite mesoporous carrier of spherical montmorillonite of double-pore structure, is named as C1.
(2) preparation of support type polyethylene catalysts
Under inert gas shielding, by MgCl2And TiCl4It is dissolved in the compounded organic solvent of tetrahydrofuran and isopropanol, shape
Into in the catalyst mother liquor containing Mg and Ti components；Wherein, on the basis of the gross weight of the support type polyethylene catalysts, institute
The dosage for stating the composite mesoporous support C 1 of spherical montmorillonite is 95 weight %, the MgCl2And TiCl4The total amount of dosage be 5 weights
Measure %, and MgCl2And TiCl4Weight ratio be 1：0.1；
Then at a temperature of 75 DEG C, the composite mesoporous support C 1 of the spherical montmorillonite with double-pore structure of above-mentioned preparation is added
Impregnated, after the completion of reaction, wash 4 times after then being filtered repeatedly with deionized water, obtain having after then filtering good
The composite mesoporous carrier of spherical montmorillonite (i.e. support type polyethylene catalysts) of the powdered loaded polyethylene of good mobile performance, life
Entitled Cat-1.
With XRD, ESEM and nitrogen adsorption desorption instrument come to the composite mesoporous carrier of the spherical montmorillonite and the poly- second of support type
Alkene catalyst is characterized.
Fig. 1 is X-ray diffracting spectrum (XRD), wherein, a is that the XRD of the composite mesoporous carrier of spherical montmorillonite (C1) is composed
Figure, b are the XRD spectra of the composite mesoporous carrier of spherical montmorillonite (Cat-1) of load polyethylene, and abscissa is 2 θ, and ordinate is
Intensity.It was found from the low-angle spectral peak that XRD spectra occurs from Fig. 1, XRD spectra a and the b tool of the spherical composite mesoporous carrier of montmorillonite
There is the hexagonal hole road structure of 2D specific to mesoporous material.
Fig. 2 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the composite mesoporous carrier of spherical montmorillonite (C1), as shown in Figure 2, spherical
The microscopic appearance of the composite mesoporous carrier of montmorillonite (C1) is the Mesoporous Spheres that particle diameter is 30-60 μm.
Fig. 3 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the composite mesoporous carrier of spherical montmorillonite (Cat-1) of load polyethylene.
The base from the figure 3, it may be seen that microscopic appearance that the composite mesoporous carrier of spherical montmorillonite (Cat-1) of polyethylene is loaded by infusion process remains unchanged
This holding is spherical, and particle diameter is 30-60 μm.
Table 1 is spherical montmorillonite composite mesoporous carrier of the composite mesoporous carrier of spherical montmorillonite (C1) with loading polyethylene
(Cat-1) pore structure parameter.
Table 1
The composite mesoporous carrier of spherical montmorillonite is can be seen that after polyethylene is loaded from the data of table 1, specific surface area and hole
Volume has reduced, and this explanation polyethylene during load-reaction is entered in the composite mesoporous carrier of spherical montmorillonite
Portion.
In addition, the content that magnesium in the sample for loading polyethylene catalysts is drawn by xrf analysis is 3.4 weight %, titanium
Content be 1.4 weight %, the content of chlorine is 16.7 weight %.
Embodiment 2
The embodiment is used to illustrate the composite mesoporous carrier of spherical montmorillonite provided by the invention and the catalysis of support type polyethylene
Agent and preparation method thereof.
(1) preparation of the composite mesoporous carrier of spherical montmorillonite
By 2.0 grams of P123 (U.S. chemical abstract registration number be 9003-11-6 material, its average molecular mass Mn=
5800) it is added to 15 grams of DMFs (DMF) in 11.2 gram 37% of hydrochloric acid and the solution of 64ml water, at 40 DEG C
Stir to P123 and be completely dissolved；4.45 grams of tetraethyl orthosilicates are added in above-mentioned solution again and stirred 1 hour at 40 DEG C, were passed through
The filter cake of mesoporous material with double-pore structure is obtained after filter, washing, drying；
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % by waterglass and sulfuric acid weight
Than for 4：After 1 is well mixed, reaction 1.5 hours is stirred at 40 DEG C, and be 98 weights by obtained reaction product concentration
The sulfuric acid adjustment pH for measuring % is 2, and it is 0.02 weight then to filter reaction mass, sodium ions content is washed till with distillation water washing
% is measured, obtains silica gel filter cake.
The 20 grams of mesoporous material filter cakes, 30 grams of silica gel filter cakes and 10 grams of montmorillonites of above-mentioned preparation are put into 100mL balls together
In grinding jar (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 is 300r/min), ball grinder is closed, temperature is ball milling 0.5 hour at 80 DEG C in ball grinder, obtains 54 grams of solid powder
End；The solid powder is dissolved in 27 grams of deionized waters, is spray-dried at 250 DEG C in the case where rotating speed is 11000r/min；So
The product obtained after spray drying is calcined 15 hours in 550 DEG C of Muffle furnace afterwards, removed template method, obtain 50 grams of removing moulds
The target product of plate agent has the composite mesoporous carrier of spherical montmorillonite of double-pore structure, is named as C2.
(2) preparation of support type polyethylene catalysts
Under inert gas shielding, by MgCl2And TiCl4It is dissolved in the compounded organic solvent of tetrahydrofuran and isopropanol, shape
Into in the catalyst mother liquor containing Mg and Ti components；Wherein, on the basis of the gross weight of the support type polyethylene catalysts, institute
The dosage for stating the composite mesoporous support C 1 of spherical montmorillonite is 50 weight %, the MgCl2And TiCl4The total amount of dosage be 50 weights
Measure %, and MgCl2And TiCl4Weight ratio be 1：1.5；
Then at a temperature of 75 DEG C, the composite mesoporous support C 2 of the spherical montmorillonite with double-pore structure of above-mentioned preparation is added
Impregnated, after the completion of reaction, wash 4 times after then being filtered repeatedly with deionized water, obtain having after then filtering good
The composite mesoporous carrier of spherical montmorillonite (i.e. support type polyethylene catalysts) of the powdered loaded polyethylene of good mobile performance, life
Entitled Cat-2.
Table 2 is spherical mesoporous montmorillonite complex carrier of the spherical mesoporous montmorillonite complex carrier (C2) with loading polyethylene
(Cat-2) pore structure parameter.
Table 2
Spherical mesoporous montmorillonite complex carrier is can be seen that after polyethylene is loaded from the data of table 2, pore volume and Bi Biao
Area has reduced, it is possible thereby to illustrate, it is compound to have entered spherical mesoporous montmorillonite for polyethylene during load-reaction
The inside of carrier.
Embodiment 3
The embodiment is used to illustrate the composite mesoporous carrier of spherical montmorillonite provided by the invention and the catalysis of support type polyethylene
Agent and preparation method thereof.
(1) preparation of the composite mesoporous carrier of spherical montmorillonite
By 2.0 grams of P123 (U.S. chemical abstract registration number be 9003-11-6 material, its average molecular mass Mn=
5800) it is added to 15 grams of DMFs (DMF) in 11.2 gram 37% of hydrochloric acid and the solution of 64ml water, at 40 DEG C
Stir to P123 and be completely dissolved；4.45 grams of tetraethyl orthosilicates are added in above-mentioned solution again and stirred 1 hour at 40 DEG C, were passed through
The filter cake of mesoporous material with double-pore structure is obtained after filter, washing, drying；
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % by waterglass and sulfuric acid weight
Than for 4：After 1 is well mixed, reaction 3 hours is stirred at 20 DEG C, then adjusts pH with the sulfuric acid that concentration is 98 weight %
For 4, then obtained reaction mass is filtered, and it is 0.02 weight % to be washed till sodium ions content with distillation water washing, obtains silicon
Glue filter cake.
The 20 grams of mesoporous material filter cakes, 10 grams of silica gel filter cakes and 1 gram of montmorillonite of above-mentioned preparation are put into 100mL ball millings 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, is turned in tank
Speed is 500r/min), ball grinder is closed, temperature is ball milling 10 hours at 40 DEG C in ball grinder, obtains 38 grams of solid powders；Will
The solid powder is dissolved in 11.4 grams of deionized waters, is spray-dried at 150 DEG C in the case where rotating speed is 13000r/min；Then will
The product obtained after spray drying is calcined 70 hours in 450 DEG C of Muffle furnace, removed template method, obtains 35 grams of removed template methods
Target product there is the composite mesoporous carrier of spherical montmorillonite of double-pore structure, be named as C3.
(2) preparation of support type polyethylene catalysts
Under inert gas shielding, by MgCl2And TiCl4It is dissolved in the compounded organic solvent of tetrahydrofuran and isopropanol, shape
Into in the catalyst mother liquor containing Mg and Ti components；Wherein, on the basis of the gross weight of the support type polyethylene catalysts, institute
The dosage for stating the composite mesoporous support C 1 of spherical montmorillonite is 99 weight %, the MgCl2And TiCl4The total amount of dosage be 1 weight
Measure %, and MgCl2And TiCl4Weight ratio be 1：1；
Then at a temperature of 75 DEG C, the composite mesoporous support C 2 of the spherical montmorillonite with double-pore structure of above-mentioned preparation is added
Impregnated, after the completion of reaction, wash 4 times after then being filtered repeatedly with deionized water, obtain having after then filtering good
The composite mesoporous carrier of spherical montmorillonite (i.e. support type polyethylene catalysts) of the powdered loaded polyethylene of good mobile performance, life
Entitled Cat-2.
Table 3 is spherical mesoporous montmorillonite complex carrier of the spherical mesoporous montmorillonite complex carrier (C3) with loading polyethylene
(Cat-3) pore structure parameter.
Table 3
Spherical mesoporous montmorillonite complex carrier is can be seen that after polyethylene is loaded from the data of table 3, pore volume and Bi Biao
Area has reduced, it is possible thereby to illustrate, it is compound to have entered spherical mesoporous montmorillonite for polyethylene during load-reaction
The inside of carrier.
Embodiment 4
The embodiment is used to illustrate spherical mesoporous montmorillonite complex carrier and support type polyethylene catalysis provided by the invention
Agent and preparation method thereof.
Spherical mesoporous montmorillonite complex carrier and support type polyethylene catalysts are prepared according to the method for embodiment 1, institute is not
With, not over the method for dipping during support type polyethylene catalysts are prepared, but the step for passing through spray drying
Suddenly polyethylene is supported on spherical mesoporous montmorillonite complex carrier, so as to which support type polyethylene catalysts Cat-4 be made.
Comparative example 1
This comparative example is used to illustrate the composite mesoporous carrier of spherical montmorillonite and catalyst of reference and preparation method thereof.
Method according to embodiment 1 carries out the system of the composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts
It is standby, unlike, during the composite mesoporous carrier of spherical montmorillonite is prepared, replaced using the ES955 silica gel of identical weight part
For mesoporous material filter cake, ES955 silica gel is calcined 10 hours at 400 DEG C under nitrogen protection, with eliminating hydroxide and Residual water,
So as to obtain the ES955 silica gel through thermal activation；
As a result the composite mesoporous carrier of spherical montmorillonite (DC1) is obtained with loading the composite mesoporous load of spherical montmorillonite of polyethylene
Body (DCat-1).
Comparative example 2
The comparative example is used to illustrate the composite mesoporous carrier of spherical montmorillonite and catalyst of reference and preparation method thereof.
Method according to embodiment 1 carries out the system of the composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts
It is standby, unlike, in the preparation process of the composite mesoporous carrier of spherical montmorillonite, montmorillonite is added without, obtains the spherical of reference
The composite mesoporous carrier of montmorillonite (DC2) and support type polyethylene catalysts (DCat-2).
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for the catalytic activity for illustrating support type polyethylene catalysts provided by the invention.
In 2 liters of stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 200 milliliters of hexanes,
Kettle temperature is risen to 80 DEG C, adds 800 milliliters of hexanes, with the addition of hexane, the concentration for adding 2 milliliters is the three of 1 mol/L
Aluminium ethide (TEA) hexane solution, is subsequently added into polyethylene catalysts Cat-1, is passed through ethene and pressure is risen into 1.0MPa and maintained
For 1.0MPa, reacted 1 hour at 70 DEG C.Polyethylene particle powder is obtained, the heap density (BD) of the polyethylene particle powder is
0.37g/ml, melt index MI2.16=0.81g/10min.It is computed determining, the efficiency of catalyst is 4925gPE/gcat.h.
EXPERIMENTAL EXAMPLE 2-4
This EXPERIMENTAL EXAMPLE is used for the catalytic activity for illustrating support type polyethylene catalysts provided by the invention.
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, except that, prepared respectively with embodiment 2-4
Support type polyethylene catalysts Cat-2, Cat-3 and Cat-4 replace the loaded catalyst Cat-1.As a result, it is computed really
Fixed, the efficiency of catalyst is respectively 3500g PE/gcat.h, 5000gPE/gcat.h and 2500g PE/gcat.h.
Experimental comparison's example 1
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, except that, the ES955 prepared using comparative example 1
Instead of the loaded catalyst Cat-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
The polymerization of ethene is carried out according to the method for EXPERIMENTAL EXAMPLE 1, except that, the DCat- prepared using comparative example 2
2 replace the loaded catalyst Cat-1.It is computed determining, the efficiency of catalyst is 1600g PE/gcat.h.
It is straight that the preparation method that be can be seen that by above-mentioned data using carrier provided by the invention can obtain average grain
Footpath is 30-60 microns, and specific surface area is 200-650 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and pore-size distribution is double
Peak is distributed, and it is described it is bimodal corresponding to most probable pore size be respectively 9-12 nanometers and 15-30 nanometers spherical montmorillonite it is mesoporous multiple
Close carrier.In addition, the catalytic performance of support type polyethylene catalysts provided by the invention is preferable, urged when this catalyst of application
When changing the polymerisation of ethene, there is higher catalytic activity.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of composite mesoporous carrier of spherical montmorillonite, it is characterised in that it is de- that the spherical composite mesoporous carrier of montmorillonite contains illiteracy
Stone and dioxide/silica gel, and the average grain diameter of the composite mesoporous carrier of spherical montmorillonite is 30-60 microns, specific surface area is
200-650 meters squared per grams, pore volume are 0.5-1.5 mls/g, and pore-size distribution is bimodal distribution, and it is described it is bimodal corresponding to most
Can several apertures be respectively 9-12 nanometers and 15-30 nanometers；
The preparation method of the described composite mesoporous carrier of spherical montmorillonite, this method comprise the following steps：
(1) template, N,N-dimethylformamide and hydrochloric acid are stirred at a temperature of 25-60 DEG C to dissolving；
(2) step (1) resulting solution and tetraethyl orthosilicate are stirred into 1-2 hours at a temperature of 25-60 DEG C, obtains mesoporous material
Filter cake；
(3) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(4) filter cake of the mesoporous material, the silica gel filter cake are well mixed to simultaneously ball milling, and being obtained after ball milling with montmorillonite
Solid powder with being spray-dried after water slurrying, then the template removal in the product that will be obtained after spray drying.
2. carrier according to claim 1, wherein, relative to the dioxide/silica gel of 100 parts by weight, the montmorillonite
Content be 10-90 parts by weight.
3. carrier according to claim 2, wherein, relative to the dioxide/silica gel of 100 parts by weight, the montmorillonite
Content be 20-60 parts by weight.
4. a kind of preparation method of the composite mesoporous carrier of spherical montmorillonite in claim 1-3 described in any one, this method
Comprise the following steps：
(1) template, N,N-dimethylformamide and hydrochloric acid are stirred at a temperature of 25-60 DEG C to dissolving；
(2) step (1) resulting solution and tetraethyl orthosilicate are stirred into 1-2 hours at a temperature of 25-60 DEG C, obtains mesoporous material
Filter cake；
(3) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(4) filter cake of the mesoporous material, the silica gel filter cake are well mixed to simultaneously ball milling, and being obtained after ball milling with montmorillonite
Solid powder with being spray-dried after water slurrying, then the template removal in the product that will be obtained after spray drying.
5. preparation method according to claim 4, wherein, the template is triblock copolymer polyoxyethylene-polyoxy
Proplyene-polyoxyethylene.
6. preparation method according to claim 4, wherein, in step (1), according to the molar ratio, polyethylene glycol oxide-polyoxy
Change propylene-polyethylene glycol oxide：N,N-dimethylformamide：Water：Hydrogen chloride=1：300-700：10000-20000：100-500.
7. preparation method according to claim 4, wherein, in step (2), the use of the template and tetraethyl orthosilicate
The mol ratio of amount is 1：10-90.
8. preparation method according to claim 7, wherein, in step (2), the use of the template and tetraethyl orthosilicate
The mol ratio of amount is 1：50-75.
9. preparation method according to claim 4, wherein, in step (3), condition bag that waterglass contacts with inorganic acid
Include：Temperature is 10-60 DEG C, and the time is 1-5 hours, pH value 2-4；The inorganic acid is one kind in sulfuric acid, nitric acid and hydrochloric acid
It is or a variety of.
10. preparation method according to claim 4, wherein, in step (4), with the mesoporous material of 100 parts by weight
Filter cake dosage on the basis of, the dosage of the silica gel filter cake is 1-200 parts by weight；The dosage of the montmorillonite is 1-50 weight
Part.
11. preparation method according to claim 10, wherein, in step (4), with the mesoporous material of 100 parts by weight
On the basis of the dosage of the filter cake of material, the dosage of the silica gel filter cake is 50-150 parts by weight；The dosage of the montmorillonite is 20-50
Parts by weight.
12. preparation method according to claim 4, wherein, in step (4), the condition of the ball milling includes：Abrading-ball
Rotating speed is 300-500r/min, and the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hours；The spraying
Dry condition includes：Temperature is 100-300 DEG C, rotating speed 10000-15000r/min；The condition of removed template method includes：Temperature
Spend for 300-600 DEG C, the time is 10-80 hours.
13. the composite mesoporous carrier of spherical montmorillonite being prepared as the method described in any one in claim 4-12.
14. a kind of support type polyethylene catalysts, it is characterised in that the catalyst includes appointing in claim 1,2,3 or 13
Meaning one described in the composite mesoporous carrier of spherical montmorillonite and be supported on containing on the composite mesoporous carrier of spherical montmorillonite
Mg, Ti and Cl component.
15. support type polyethylene catalysts according to claim 14, wherein, with the support type polyethylene catalysts
On the basis of gross weight, the content of the spherical composite mesoporous carrier of montmorillonite is 50-99 weight %, described to contain Mg, Ti and Cl
The total content of component be 1-50 weight %.
16. a kind of preparation method of support type polyethylene catalysts, it is characterised in that this method is by claim 1,2,3 or 13
The composite mesoporous carrier impregnation of spherical montmorillonite described in middle any one is in by MgCl2And TiCl4Be dissolved in compounded organic solvent and shape
Into the catalyst mother liquor containing Mg and Ti components in.
17. according to the method for claim 16, wherein, the compounded organic solvent is the mixing of tetrahydrofuran and isopropanol
Solution.
18. the method according to claim 11, wherein, on the basis of the gross weight of the support type polyethylene catalysts,
The dosage of the composite mesoporous carrier of spherical montmorillonite is 50-99 weight %, the MgCl2And TiCl4The total amount of dosage be 1-
50 weight %；And the MgCl2And TiCl4Dosage weight ratio be 1：0.1-1.5.
19. according to the method for claim 16, wherein, the condition of the dipping includes：Temperature is 10-60 DEG C, and the time is
10-72 hours.
20. application of the support type polyethylene catalysts in catalytic reaction described in claims 14 or 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514325.1A CN105440168B (en) | 2014-09-29 | 2014-09-29 | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514325.1A CN105440168B (en) | 2014-09-29 | 2014-09-29 | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105440168A CN105440168A (en) | 2016-03-30 |
| CN105440168B true CN105440168B (en) | 2018-03-02 |
Family
ID=55550846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410514325.1A Active CN105440168B (en) | 2014-09-29 | 2014-09-29 | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105440168B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786897B (en) * | 2017-05-05 | 2019-09-27 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108786864B (en) * | 2017-05-05 | 2019-08-20 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855198B (en) * | 2017-05-10 | 2019-11-12 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108855068B (en) * | 2017-05-10 | 2019-08-20 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855067B (en) * | 2017-05-10 | 2019-08-20 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108948239B (en) * | 2017-05-27 | 2020-10-20 | 中国石油化工股份有限公司 | Polyolefin catalyst and polyolefin and preparation method thereof |
| CN108948234B (en) * | 2017-05-27 | 2020-10-23 | 中国石油化工股份有限公司 | Spherical double-mesoporous montmorillonite composite carrier and preparation method and application thereof |
| CN110496634B (en) * | 2018-05-17 | 2021-09-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN111100223B (en) * | 2018-10-26 | 2022-10-21 | 中国石油化工股份有限公司 | Polyolefin catalyst prepared by spray drying method, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315839A (en) * | 1979-02-26 | 1982-02-16 | Rhone-Poulenc Industries | Spheroidal alumina particulates having bifold porosity and process for their preparation |
| CN101239322A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing montmorillonite/molecular sieve composite material |
| CN101530812A (en) * | 2009-04-15 | 2009-09-16 | 中国科学院大连化学物理研究所 | ITQ-13 molecular sieve catalyst and method for preparing same |
| CN102049285A (en) * | 2010-11-10 | 2011-05-11 | 上海师范大学 | Multistage pore-structure molecular sieve catalyst and preparation method thereof |
-
2014
- 2014-09-29 CN CN201410514325.1A patent/CN105440168B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315839A (en) * | 1979-02-26 | 1982-02-16 | Rhone-Poulenc Industries | Spheroidal alumina particulates having bifold porosity and process for their preparation |
| CN101239322A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing montmorillonite/molecular sieve composite material |
| CN101530812A (en) * | 2009-04-15 | 2009-09-16 | 中国科学院大连化学物理研究所 | ITQ-13 molecular sieve catalyst and method for preparing same |
| CN102049285A (en) * | 2010-11-10 | 2011-05-11 | 上海师范大学 | Multistage pore-structure molecular sieve catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105440168A (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105440168B (en) | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application | |
| CN105175586B (en) | A kind of preparation method of mesoporous composite material and preparation method thereof and catalytic component and polyethylene | |
| CN105330767B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN104248991B (en) | The preparation method of the composite mesoporous carrier of spherical montmorillonite and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN104248985A (en) | Spherical montmorillonite mesoporous composite carrier, supported catalyst and preparation method and application thereof, and ethyl acetate preparation method | |
| CN106467579B (en) | Macropore two dimension double hole channel spherical complex carrier and composite material and their preparation method and application containing polyethylene catalysts | |
| CN106467582B (en) | The spherical complex carrier of macropore two dimension straight channels and composite material containing polyethylene catalysts with and its preparation method and application | |
| CN104248990A (en) | Spherical attapulgite mesoporous composite carrier, supported catalyst, preparation methods of spherical attapulgite mesoporous composite carrier and supported catalyst, use of supported catalyst and preparation method of ethyl acetate | |
| CN105330769B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN104248986A (en) | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate | |
| CN106467581B (en) | Three hole silica-gel carriers and support type polyethylene catalysts and its preparation method and application | |
| CN106554431A (en) | The method of bimodal porous silica carrier and support type polyethylene catalysts and its preparation method and application and vinyl polymerization | |
| CN106632760A (en) | Spherical aluminum-containing mesoporous composite material and supported catalyst and preparation method and application thereof and ethylene polymerization method | |
| CN105524193B (en) | A kind of carried metallocene catalyst and preparation method thereof | |
| CN106467580B (en) | The spherical complex carrier and support type polyethylene catalysts in super big hole three-dimensional cubic duct and their preparation method and application | |
| CN107840913B (en) | Spherical small-particle-size mesoporous composite material, supported catalyst and preparation method of supported catalyst | |
| CN107417820B (en) | Spherical diatomite mesoporous composite material, supported catalyst and preparation method thereof | |
| CN104248971B (en) | A kind of carried phospho-tungstic acid catalyst and its preparation method and application and the preparation method of cyclohexanone glycerol ketal | |
| CN108003261B (en) | Method for polymerizing ethylene and polyethylene | |
| CN107840912B (en) | Method for polymerizing ethylene and polyethylene | |
| CN107417828A (en) | Spherical composite and support type polyethylene catalysts and their preparation method | |
| CN104248974B (en) | The preparation method of a kind of carried phospho-tungstic acid Catalysts and its preparation method and application and cyclohexanone glycerol ketal | |
| CN107417823B (en) | Spherical sepiolite mesoporous composite material, supported catalyst and preparation method thereof | |
| CN107417831B (en) | Method for polymerizing ethylene and polyethylene | |
| CN107417821B (en) | Spherical composite material and supported polyethylene catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |