CN106467580B - The spherical complex carrier and support type polyethylene catalysts in super big hole three-dimensional cubic duct and their preparation method and application - Google Patents
The spherical complex carrier and support type polyethylene catalysts in super big hole three-dimensional cubic duct and their preparation method and application Download PDFInfo
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Abstract
The present invention relates to catalyst fields, disclose the spherical complex carrier and support type polyethylene catalysts and their preparation method and application in a kind of super big hole three-dimensional cubic duct, the average grain diameter of the carrier of the invention is 20-60 μm, specific surface area 200-600m2/ g, pore volume 0.1-2mL/g, pore-size distribution are bimodal distribution, and described bimodal respectively correspond the first most probable pore size that aperture is 3-10nm and the second most probable pore size that aperture is 30-39nm.The spherical complex carrier meso-hole structure in super big hole three-dimensional cubic duct provided by the invention is stable, orderly meso-hole structure can still be maintained after load active component, and has high activity when loading polyethylene catalysts and reacting with catalyzed ethylene polymerization.Moreover, the load factor of support type polyethylene catalysts of the invention is high.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of spherical complex carrier in super big hole three-dimensional cubic duct,
A kind of preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct and the super big hole three being prepared by this method
Tie up spherical complex carrier, a kind of support type polyethylene catalysts, a kind of preparation of support type polyethylene catalysts in cube duct
Method and the support type polyethylene catalysts being prepared by this method, a kind of support type polyethylene catalysts gather in catalysis ethylene
Close the application in reaction.
Background technique
Meso-porous molecular sieve material has many advantages, such as that duct is orderly, aperture is adjustable, specific surface area and hole appearance are larger, is good
Catalyst and carrier material.In recent years, the multiphases such as the solid acid, the heteropoly acid that are prepared using meso-porous molecular sieve material as template are urged
Agent not only ethylene polymerization catalytic activity with higher, and side reaction is less, post-processing is relatively simple.For example, having
The cellular structure of sequence mesoporous material KIT-6 is similar to MCM-48, is the orderly meso-hole structure of three-dimensional cubic, but the hole of KIT-6
Diameter is big compared with MCM-48, and duct interconnects, this provides a good template for the direct load of active specy, can make
Loaded article is evenly dispersed without forming the bulky grain reunited in entire duct.
The development and application of polyethylene catalysts are the olefinic polymerization catalysis after traditional Ziegler-Natta catalyst
The another important breakthrough in agent field, this makes the research of polyethylene catalysts enter a stage grown rapidly.Due to
Catalyst amount needed for homogeneous polyethylene catalyst reaches high activity is big, high production cost, and obtained polymer is without grain
Shape can not use on widely used slurry process or gas phase polymerization technique, and overcoming the effective way of the above problem is exactly handle
Soluble poly catalyst for ethylene carries out supported processing.Currently, the related supported research report of polyethylene catalysts is very more.For
Further investigate new support/catalyst/co-catalyst system, it is necessary to attempt different carriers, with push carried catalyst and
The further development of polyolefin industry.And mesoporous material is with its big surface area (500-2000m2/ g), spacious duct and
The advantage of big and adjustable aperture size (3-50nm) is loaded by researcher for polyethylene catalysts and to be used for vinyl polymerization anti-
It answers.
The mesoporous material for the load polyethylene catalysts reported on document at present is mainly MCM-41, after being handled with MAO again
Catalytic activity is 10 after loading the MCM-41 progress vinyl polymerization of polyethylene catalysts6gPE/(mol Zr h).Mesoporous material
Carried out after MCM-41 supported catalyst hole wall structure thermal stability that the lower reason of ethylene polymerization activity is mainly MCM-41 and
Hydrothermal stability is poor, just has part collapsing in loading process hole wall, affects load effect, lives so that affecting catalysis
Property.Therefore a kind of mesoporous material that meso-hole structure is stable is sought in experiment, can still keep orderly meso-hole structure to show after load
It obtains particularly necessary.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies of existing technologies, provide a kind of meso-hole structure it is stable, in load active component
Orderly meso-hole structure can still be maintained afterwards, and there is height when loading polyethylene catalysts and reacting with catalyzed ethylene polymerization
Catalytic activity spherical complex carrier.
To achieve the goals above, the present invention provides a kind of spherical complex carrier in super big hole three-dimensional cubic duct, the load
The average grain diameter of body is 20-60 μm, specific surface area 200-600m2/ g, pore volume 0.1-2mL/g, pore-size distribution are
Bimodal distribution, and bimodal first most probable pore size that aperture is 3-10nm and aperture of respectively corresponding is the second of 30-39nm
Most probable pore size.
Second aspect, the present invention provide a kind of preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct, should
Method the following steps are included:
Preparation silica filter cake: carrying out hybrid reaction for template and silicon source in acidic aqueous solution, then will mixing
The material obtained after reaction is successively filtered and washed；
It prepares silica gel: in the presence of inorganic acid solution, waterglass and n-butanol being subjected to haptoreaction, then adjust reaction
The pH value of acquired solution is 2-4 afterwards；
It prepares carrier: successively carrying out ball milling, spray after the silica filter cake being prepared and the silica gel are mixed
Mist drying and calcination,
Wherein, this method makes the average grain diameter for the carrier being prepared be 20-60 μm, specific surface area 200-
600m2/ g, pore volume 0.1-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that respectively corresponds is 3-10nm's
The second most probable pore size that first most probable pore size and aperture are 30-39nm；It is preferred that
The average grain diameter of the carrier is 30-60 μm, specific surface area 250-500m2/ g, pore volume 0.5-
1.8mL/g, pore-size distribution are bimodal distribution, and described bimodal respectively correspond the first most probable pore size and hole that aperture is 5-8nm
Diameter is the second most probable pore size of 32-38nm.
The third aspect, the present invention provide the compound load of spherical shape in super big hole three-dimensional cubic prepared by the above method duct
Body.
Fourth aspect, the present invention provide a kind of support type polyethylene catalysts, stand in the catalyst containing super big hole three-dimensional
The spherical complex carrier of square duct and the magnesium elements being supported at least one in outer surface, inner hole wall and the ball inside of the carrier
And/or titanium elements；The average grain diameter of the carrier is 20-60 μm, specific surface area 200-600m2/ g, pore volume are
0.1-2mL/g, pore-size distribution are bimodal distribution, and it is described it is bimodal respectively correspond the first most probable pore size that aperture is 3-10nm and
Aperture is the second most probable pore size of 30-39nm；It is preferred that
The average grain diameter of the carrier is 30-60 μm, specific surface area 250-500m2/ g, pore volume 0.5-
1.8mL/g, pore-size distribution are bimodal distribution, and described bimodal respectively correspond the first most probable pore size and hole that aperture is 5-8nm
Diameter is the second most probable pore size of 32-38nm.
5th aspect, the present invention provides a kind of preparation method of support type polyethylene catalysts, this method comprises: in inertia
In the presence of gas, by the spherical complex carrier in super big hole three-dimensional cubic duct in the catalyst containing magnesium elements and/or titanium elements
It is impregnated in mother liquor, is then successively filtered and dries；The average grain diameter of the carrier is 20-60 μm, specific surface
Product is 200-600m2/ g, pore volume 0.1-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that respectively corresponds is
The second most probable pore size that the first most probable pore size of 3-10nm and aperture are 30-39nm；It is preferred that
The average grain diameter of the carrier is 30-60 μm, specific surface area 250-500m2/ g, pore volume 0.5-
1.8mL/g pore-size distribution is bimodal distribution, and described bimodal respectively corresponds the first most probable pore size and hole that aperture is 5-8nm
Diameter is the second most probable pore size of 32-38nm；More preferably
The condition of the dipping includes: that temperature is 45-100 DEG C, time 2-8h.
6th aspect, the present invention provide the support type polyethylene catalysts being prepared by the above method of the invention.
7th aspect, the present invention provide application of the support type polyethylene catalysts in catalyzed ethylene polymerization reaction.
The spherical complex carrier meso-hole structure in super big hole three-dimensional cubic duct provided by the invention is stable, lives in load
Property component after can still be maintained orderly meso-hole structure, and when loading polyethylene catalysts and being reacted with catalyzed ethylene polymerization
With high catalytic activity.Moreover, the load factor of support type polyethylene catalysts of the invention is high.
It was found by the inventors of the present invention that including the catalytic activity with the catalyst of spherical complex carrier of above-mentioned pore structure
It is higher, can catalyzed ethylene polymerization react and obtain higher activity.Speculate its reason, it may be possible to due to: on the one hand, usually come
It says, although the bigger serface and Gao Kongrong of three-dimensional cubic duct material can make it have higher catalytic activity, simultaneously
Also stronger water suction, moisture absorption ability can be made it have, therefore, when three-dimensional cubic duct material is rodlike, aggravation is reunited and is asked
Topic, to store, transport, post-processing and application are made troubles.And the carrier in super big hole three-dimensional cubic provided by the invention duct is
It is spherical, the agglomeration traits of powder can be reduced, improve its mobility.On the other hand, the carrier not only remains order mesoporous
Also add aperture greatly and the advantage of narrowly distributing the characteristics of high-specific surface area, the macropore of material hold, and its pore-size distribution is presented
Unique bimodal distribution, the more conducively load of active component.That is, the spherical shape in super big hole three-dimensional cubic provided by the invention duct is multiple
Closing carrier dexterously has the advantages that the ordered mesoporous material of bimodal distribution combines with aperture for micro-sphere structure, to be described
The application of the spherical complex carrier in super big hole three-dimensional cubic duct provides better platform, and has expanded its application field.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffracting spectrum of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct.
Fig. 2 is the X-ray diffracting spectrum of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct.
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of support type polyethylene catalysts according to the present invention.
Fig. 4 is the grain size distribution of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, the specific surface area, pore volume and most probable pore size are measured according to nitrogen adsorption methods, described average
Partial size is measured using laser fineness gage.
In the present invention, the average grain diameter is average grain diameter.
On the one hand, the present invention provides a kind of spherical complex carriers in super big hole three-dimensional cubic duct, which is characterized in that should
The average grain diameter of carrier is 20-60 μm, specific surface area 200-600m2/ g, pore volume 0.1-2mL/g, pore-size distribution
For bimodal distribution, and bimodal first most probable pore size that aperture is 3-10nm and aperture of respectively corresponding is the of 30-39nm
Two most probable pore sizes.
Under preferable case, in the present invention, the average grain diameter of the carrier is 30-60 μm, specific surface area 250-
500m2/ g, pore volume 0.5-1.8mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that respectively corresponds is 5-8nm
The first most probable pore size and aperture be 32-38nm the second most probable pore size.
The spherical complex carrier in super big hole three-dimensional cubic duct provided by the invention has obviously more compared with the prior art
The sphere pattern of big Based on Dual-Aperture distribution and pore volume and good flowing properties, is more conducive to the progress of catalysis reaction, by this
When the spherical complex carrier in super big hole three-dimensional cubic duct forms polyethylene catalysts, the polyethylene catalysts of acquisition have obvious
Higher than the catalytic activity of 955 silica gel.
Second aspect, the present invention provides a kind of preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct,
It is characterized in that, method includes the following steps:
Preparation silica filter cake: carrying out hybrid reaction for template and silicon source in acidic aqueous solution, then will mixing
The material obtained after reaction is successively filtered and washed；
It prepares silica gel: in the presence of inorganic acid solution, waterglass and n-butanol being subjected to haptoreaction, then adjust reaction
The pH value of acquired solution is 2-4 afterwards；
It prepares carrier: successively carrying out ball milling, spray after the silica filter cake being prepared and the silica gel are mixed
Mist drying and calcination,
Wherein, this method makes the average grain diameter for the carrier being prepared be 20-60 μm, specific surface area 200-
600m2/ g, pore volume 0.1-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that respectively corresponds is 3-10nm's
The second most probable pore size that first most probable pore size and aperture are 30-39nm.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, it is prepared
Carrier has a sphere pattern of obviously bigger compared with the prior art Based on Dual-Aperture distribution and pore volume and good flowing properties, more added with
It is obtained when the spherical complex carrier in the super big hole three-dimensional cubic duct is formed polyethylene catalysts conducive to the progress of catalysis reaction
The polyethylene catalysts obtained have the activity higher than 955 silica gel.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, preferably this method
So that the average grain diameter of obtained carrier is 30-60 μm, specific surface area 250-500m2/ g, pore volume 0.5-
1.8mL/g, pore-size distribution are bimodal distribution, and described bimodal respectively correspond the first most probable pore size and hole that aperture is 5-8nm
Diameter is the second most probable pore size of 32-38nm.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of silica filter cake, the condition of the preferably described hybrid reaction includes: that temperature is 10-60 DEG C, time 10-72h, pH
Value is 1-6.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of silica filter cake, the dosage molar ratio of the preferably described template and silicon source is 1:10-90.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of silica filter cake, the preferably described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；
The acidic aqueous solution is selected from least one of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid aqueous solution.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of silica gel, the dosage weight ratio of the preferably described waterglass and n-butanol is 1.2-10:1.In the present invention, the water glass
Waterglass in the dosage weight ratio of glass and n-butanol is the weight ratio of the form containing aqueous solution and n-butanol, that is to say, that
It wherein include the weight of water.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of silica gel, the preferably described catalytic condition includes: that temperature is 10-60 DEG C, time 1-5h, pH value 2-4.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of carrier, the dosage weight ratio of the preferably described silica filter cake and the silica gel is 1:1-3.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of carrier, the condition of the preferably described ball milling includes: that the revolving speed of abrading-ball is 300-500r/min, and the temperature in ball grinder is
15-100 DEG C, the time of ball milling is 0.1-100h.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of carrier, the condition of the preferably described spray drying includes: that temperature is 100-300 DEG C, and the revolving speed of rotation is 10000-
15000r/min；In more preferred situation, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is
11000-13000r/min。
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of carrier, the condition of the preferably described calcining includes: that temperature is 300-600 DEG C, time 10-80h.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, preferable case
Under, the preparation silica filter cake the step of in, ethyl alcohol is added into reaction system to facilitate the dissolution of template, this
Field technical staff can determine the usage amount of ethyl alcohol according to the conventional amount used of this field.
In the present invention, the template triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (P123) can be with
It is commercially available (for example, can be purchased from Aldrich, trade name P123, molecular formula EO20PO70EO20), it can also be with
It is prepared by existing various methods.The molal quantity of the template is according to polyoxyethylene-poly-oxypropylene polyoxyethylene
Average molecular weight calculates to obtain.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of silica filter cake, the material that will be obtained after hybrid reaction is first preferably subjected to crystallization, is then successively filtered
And washing.There is no particular limitation for condition of the present invention to the crystallization, what the condition of the crystallization can be conventional for this field
Selection, for example, it is 30-150 DEG C that the condition of the crystallization, which may include: temperature, the time is 10-72 hours.Under preferable case, institute
It is 40-100 DEG C that the condition for stating crystallization, which includes: temperature, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
The preparation method of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, in the preparation
In the step of silica filter cake, obtained silica gel is preferably prepared into cake form, the process of filter cake is obtained by filtering
It may include: after filtration, wash (washing times can be 2-10 times) repeatedly with deionized water, then filtered.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, in the preparation
In the step of silica gel, the waterglass is the aqueous solution of sodium metasilicate, and concentration can be 10-50 weight %, preferably 12-30 weight
Measure %.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, in the preparation
In the step of silica gel, the preferably described inorganic acid solution is selected from least one of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid aqueous solution.
In more preferred situation, the concentration of the inorganic acid solution is 1-35 weight %.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, in the preparation
In the step of silica gel, gained is molten after those skilled in the art can adjust reaction using conventional use of various reagents in the art
The pH value of liquid is 2-4, and under preferable case, in the present invention, the pH value that acquired solution after reaction is adjusted using the concentrated sulfuric acid is 2-4.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, in the preparation
It is that the reaction mass after 2-4 washs it is also preferable to include pH value will be adjusted, in more preferable situation, by institute in the step of silica gel
Stating reaction mass and being washed till sodium ions content is 0.03 weight % or less.
In the present invention, the ball milling can carry out in the ball mill, and the inner wall of ball grinder is preferably in the ball mill
The diameter of polytetrafluoroethyllining lining, the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can be according to the size of ball grinder
It is reasonably selected, 1 abrading-ball usually can be used in the ball grinder for being 50-150mL for size；The material of the abrading-ball
It can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling may include: that the revolving 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 0.1-100h.
The present invention preferably calcines in Muffle furnace.
The third aspect, the present invention provides the spherical shapes in super big hole three-dimensional cubic prepared by the preparation method duct
Complex carrier.
Fourth aspect, it is three-dimensional containing super big hole in the catalyst the present invention provides a kind of support type polyethylene catalysts
The spherical complex carrier in cube duct and the magnesium being supported at least one in outer surface, inner hole wall and the ball inside of carrier member
Element and/or titanium elements；The average grain diameter of the carrier is 20-60 μm, specific surface area 200-600m2/ g, pore volume are
0.1-2mL/g, pore-size distribution are bimodal distribution, and it is described it is bimodal respectively correspond the first most probable pore size that aperture is 3-10nm and
Aperture is the second most probable pore size of 30-39nm.
Under preferable case, in support type polyethylene catalysts of the present invention, the average grain diameter of the carrier
It is 30-60 μm, specific surface area 250-500m2/ g, pore volume 0.5-1.8mL/g, pore-size distribution are bimodal distribution, and described
It is bimodal to respectively correspond the first most probable pore size that aperture is 5-8nm and the second most probable pore size that aperture is 32-38nm.
In the present invention, it is preferred to the magnesium elements and titanium elements are provided in the form of magnesium salts and titanium salt respectively, the magnesium salts
It can be conventional use of various magnesium salts in the art and titanium salt with titanium salt, as long as being capable of providing magnesium elements and titanium elements.
Under preferable case, in the present invention, the magnesium salts is magnesium chloride；The titanium salt titanium tetrachloride and/or titanium trichloride.
In support type polyethylene catalysts of the present invention, the total weight with the support type polyethylene catalysts is
Benchmark, the preferably content of the spherical complex carrier in super big hole three-dimensional cubic duct be 50-99 weight %, the magnesium elements and
The sum of the content of titanium elements in terms of oxide is 1-50 weight %.
5th aspect, the present invention provides a kind of preparation methods of support type polyethylene catalysts, this method comprises: lazy
In the presence of property gas, by the spherical complex carrier in super big hole three-dimensional cubic duct in the catalysis containing magnesium elements and/or titanium elements
It is impregnated in agent mother liquor, is then successively filtered and dries；The average grain diameter of the carrier is 20-60 μm, compares table
Area is 200-600m2/ g, pore volume 0.1-2mL/g, pore-size distribution are bimodal distribution, and described bimodal respectively correspond aperture
For the second most probable pore size that the first most probable pore size of 3-10nm and aperture are 30-39nm.
Under preferable case, in the preparation method of support type polyethylene catalysts of the present invention, the carrier is put down
Equal particle diameter is 30-60 μm, specific surface area 250-500m2/ g, pore volume 0.5-1.8mL/g, pore-size distribution are bimodal
Distribution, and described bimodal respectively correspond the first most probable pore size that aperture is 5-8nm and the second most probable that aperture is 32-38nm
Aperture.
In the preparation method of support type polyethylene catalysts of the present invention, the condition of the preferably described dipping includes:
Temperature is 45-100 DEG C, time 2-8h.
In the preparation method of support type polyethylene catalysts of the present invention, the magnesium elements and titanium elements are determined
Justice, form and source are as noted earlier such as the present invention, and this is no longer going to repeat them by the present invention.
According to the present invention, the inert gas can occur for not with carrier and active component chemically interactive various
Gas.For example, the inert gas can be provided by one or more of zero group gas in nitrogen and the periodic table of elements.
The preparation method of support type polyethylene catalysts according to the present invention, it is preferably described to be immersed in double solvents
It carrying out, the compounded organic solvent can be that can dissolve the magnesium elements and titanium elements and readily removed various solvents,
Preferably, the compounded organic solvent is tetrahydrofuran and isopropanol.More preferably, the volume ratio of tetrahydrofuran and isopropanol is
1:1-3, particularly preferably 1:1-1.5.
The preparation method of support type polyethylene catalysts according to the present invention particularly preferably prepares the super big hole three
Tie up cube duct spherical complex carrier the step of include:
Preparation silica filter cake: carrying out hybrid reaction for template and silicon source in acidic aqueous solution, then will mixing
The material obtained after reaction is successively filtered and washed；
It prepares silica gel: in the presence of inorganic acid solution, waterglass and n-butanol being subjected to haptoreaction, then adjust reaction
The pH value of acquired solution is 2-4 afterwards；
It prepares carrier: successively carrying out ball milling, spray after the silica filter cake being prepared and the silica gel are mixed
Mist drying and calcination.
In the present invention, it should be strongly noted that in the preparation method of the support type polyethylene catalysts, preparation
Related definition in the step of spherical complex carrier in super big hole three-dimensional cubic duct and limit with present invention super large above-mentioned
The preparation method of the spherical complex carrier in hole three-dimensional cubic duct is identical, and the present invention is in order to avoid repeating, and details are not described herein.
6th aspect, the present invention provides support type polyethylene catalysts prepared by the above method.
There is the product of above-mentioned support type polyethylene catalysts provided by the invention compared with the existing technology better acid to urge
Change performance and good mobile performance.
7th aspect, the present invention provides the support type polyethylene catalysts answering in catalyzed ethylene polymerization reaction
With.
The present invention does not limit application of the support type polyethylene catalysts in catalyzed ethylene polymerization reaction particularly
Fixed, the catalyst ethylene being prepared using the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct is poly-
When closing reaction, the catalyst ethylene polymerization that obvious 955 silica gel than using the prior art are prepared can be obtained
When higher catalytic efficiency.
The catalyst of spherical complex carrier containing super big hole three-dimensional cubic of the present invention duct is used to ethylene to gather
When the homopolymerization of conjunction, catalytic efficiency is substantially better than the catalytic efficiency of 955 silica gel of industry under the conditions of equivalent responses.Moreover, institute
The partial size for stating support type polyethylene catalysts is larger, and carrier has the large aperture of high-sequential, and the average pore size of silicon gel part is big,
Pore wall strength is moderate, and catalyst decay is slower, and polymerization process steadily continues, and catalytic activity is high.Therefore, super large of the present invention
The spherical complex carrier in hole three-dimensional cubic duct is the Inorganic material carrier suitable for olefinic polymerization.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, writes a Chinese character in simplified form
For P123, molecular formula EO20PO70EO20, the substance for being 9003-11-6 in the registration number of U.S. chemical abstract, mean molecule
Amount is 5800.
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co., the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from U.S. Kang Ta company
It is 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 ethyl alcohol；X-ray fluorescence analysis is in Holland
It is carried out on the x-ray fluorescence analyzer of the model Axios-Advanced of company.
The heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
Melt index: it is measured according to ASTM D1238-99.
Embodiment 1
The present embodiment is used to illustrate that the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, support type to be poly-
Catalyst for ethylene and their preparation method.
(1) carrier is prepared
6g triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123 is dissolved in 10mL concentrated hydrochloric acid and 220mL
In deionized water solution, clear solution is formed after stirring 4h at 15 DEG C, then 6g ethyl alcohol is added into this clear solution and stirs
Then the solution is placed in 30 DEG C of environment by 1h, and 12.9g ethyl orthosilicate is added thereto, keeps the temperature at 30 DEG C, pH
Value be 3 under conditions of stir for 24 hours, after transfer the solution into the reaction kettle of polytetrafluoroethyllining lining, 100 DEG C of baking oven crystallization are for 24 hours
By being filtered, washed to obtain silica filter cake.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and n-butanol with weight ratio be
5:1:1 carries out mixing and the haptoreaction 1.5h at 20 DEG C, then adjusts pH value to 3, so with the sulfuric acid that concentration is 98 weight %
Obtained reaction mass is filtered afterwards, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter
Cake.
The 20g silica filter cake of above-mentioned preparation and 20g silica gel filter cake are put into togerther in 100mL ball grinder, wherein ball
The material of grinding jar is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/
min.Ball grinder is closed, temperature is ball milling 5h at 60 DEG C in ball grinder, obtains 40g solid powder；The solid powder is dissolved
In 30 grams of deionized waters, it is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；The product that will be obtained after spray drying
It is calcined for 24 hours at 500 DEG C in Muffle furnace, removed template method obtains destination carrier.
(2) composite material containing polyethylene catalysts is prepared
In N2Under protection, by the MgCl of 1g2With the TiCl of 1g4It is dissolved in the tetrahydrofuran of 500mL and the double solvents of isopropanol
In (volume ratio of tetrahydrofuran and isopropanol is 1:1.2), the catalyst mother liquor of element containing Mg and Ti element is formed.Then 75
The above-mentioned carrier impregnation 4h of 1g is added at DEG C.It after being cooled to room temperature, is then filtered, obtains solid product after removing liquid, and
It is washed repeatedly with tetrahydrofuran solid product 4 times, finally obtains having good in 75 DEG C of vacuum drying 4h by obtained solid product
The powdery support type polyethylene catalysts of good mobile performance.
It is glimmering with XRD, scanning electron microscope, U.S. Kang Ta company Atsorb-1 type nitrogen adsorption instrument, Particle Size Analyzer and X-ray
Light analysis characterizes the support type polyethylene catalysts.
Fig. 1 is the X-ray diffracting spectrum (XRD of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct
Spectrogram).
Fig. 2 is the X-ray diffracting spectrum of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct.By
Figure is it is found that the microscopic appearance of the spherical complex carrier in super big hole three-dimensional cubic duct is the Mesoporous Spheres that diameter is 30-60 μm.
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of support type polyethylene catalysts according to the present invention.It can by figure
To know, the spherical complex carrier in super big hole three-dimensional cubic duct microscopic appearance after load active component is still basic to keep spherical,
And particle diameter is 30-60 μm.
Fig. 4 is the grain size distribution of the spherical complex carrier in super big hole three-dimensional cubic according to the present invention duct, unit μ
m.As seen from the figure, the average grain diameter of complex carrier is 50 μm, and particle diameter distribution is highly uniform.
Table 1 is the pore structure parameter of the spherical complex carrier in super big hole three-dimensional cubic duct.
Table 1
The spherical complex carrier in super big hole three-dimensional cubic duct is diplopore distribution it can be seen from the data of upper table 1.
It is obtained by xrf analysis, in the embodiment of the present invention support type polyethylene catalysts, with the poly- second of the support type
The total weight of alkene catalyst, the content of the magnesium elements in terms of oxide are 8 weight %, the content of the titanium elements in terms of oxide
For 0.7 weight %, the content of chlorine is 1.7 weight % and remainder is carrier.
Comparative example 1
Commercially available ES955 silica gel (GRACE company) is calcined 10 hours for 400 DEG C under nitrogen protection, with eliminating hydroxide and
Residual water, to obtain the ES955 silica gel through thermal activation.
Catalyst is prepared according to the method for 1 step of embodiment (2), the difference is that using the ES955 silicon of identical weight part
Glue replaces carrier.To which comparative catalyst D1 be made.
Elemental analysis is the results show that in comparative catalyst D1, and relative to the total weight of catalyst D1, the content of titanium is 1.2
Weight %, it is 1.8 weight % that the content of chlorine, which is 6.8 weight %, Mg contents,.
Embodiment 2
The present embodiment is used to illustrate that the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, support type to be poly-
Catalyst for ethylene and their preparation method.
(1) carrier is prepared
6g triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123 is dissolved in 10mL concentrated hydrochloric acid and 220mL
In deionized water solution, clear solution is formed after stirring 6h at 20 DEG C, then 5.6g ethyl alcohol is added into this clear solution and stirs
Mix 1h, then the solution be placed in 35 DEG C of environment, and thereto be added 12.9g ethyl orthosilicate, keep the temperature at 35 DEG C,
PH value be 4 under conditions of stir for 24 hours, after transfer the solution into the reaction kettle of polytetrafluoroethyllining lining, 90 DEG C of baking oven crystallization are for 24 hours
By being filtered, washed to obtain silica filter cake.
By waterglass and concentration that concentration is 13 weight % be 15 weight % nitric acid solution and n-butanol with weight ratio be
4:1.2:1 carries out mixing and the haptoreaction 1.3h at 25 DEG C, then adjusts pH value extremely with the sulfuric acid that concentration is 98 weight %
3.5, then obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, is obtained
Silica gel filter cake.
The 20g silica filter cake of above-mentioned preparation and 20g silica gel filter cake are put into togerther in 100mL ball grinder, wherein ball
The material of grinding jar is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/
min.Ball grinder is closed, temperature is ball milling 5h at 60 DEG C in ball grinder, obtains 40g solid powder；The solid powder is dissolved
In 30 grams of deionized waters, it is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；The product that will be obtained after spray drying
It is calcined for 24 hours at 550 DEG C in Muffle furnace, removed template method obtains destination carrier.
(2) support type polyethylene catalysts are prepared
In N2Under protection, by the MgCl of 1g2With the TiCl of 1g4It is dissolved in the tetrahydrofuran of 500mL and the double solvents of isopropanol
In (volume ratio of tetrahydrofuran and isopropanol is 1:1.3), the catalyst mother liquor of element containing Mg and Ti element is formed.Then 85
The above-mentioned carrier impregnation 5h of 1g is added at DEG C.It after being cooled to room temperature, is then filtered, obtains solid product after removing liquid, and
It is washed repeatedly with tetrahydrofuran solid product 4 times, finally obtains having good in 75 DEG C of vacuum drying 4h by obtained solid product
The powdery support type polyethylene catalysts of good mobile performance.
Table 2 is the pore structure parameter of the spherical complex carrier in the super big hole three-dimensional cubic duct of the present embodiment.
Table 2
The spherical complex carrier in super big hole three-dimensional cubic duct is diplopore distribution it can be seen from the data of upper table 2.
It is obtained by xrf analysis, in the embodiment of the present invention support type polyethylene catalysts, with the poly- second of the support type
The total weight of alkene catalyst, the content of the magnesium elements in terms of oxide are 8.2 weight %, and the titanium elements in terms of oxide contain
Amount is 0.8 weight %, and the content of chlorine is 1.8 weight % and remainder is carrier.
Embodiment 3
The present embodiment is used to illustrate that the spherical complex carrier in super big hole three-dimensional cubic of the present invention duct, support type to be poly-
Catalyst for ethylene and their preparation method.
(1) carrier is prepared
6g triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123 is dissolved in 10mL concentrated hydrochloric acid and 220mL
In deionized water solution, clear solution is formed after stirring 4.5h at 18 DEG C, then 6.5g ethyl alcohol is added simultaneously into this clear solution
1h is stirred, then the solution is placed in 40 DEG C of environment, and 12.9g ethyl orthosilicate is added thereto, keeps the temperature at 40
DEG C, pH value be 4 under conditions of stir for 24 hours, after transfer the solution into the reaction kettle of polytetrafluoroethyllining lining, 80 DEG C of baking oven crystallization
For 24 hours afterwards through being filtered, washed to obtain silica filter cake.
By waterglass and concentration that concentration is 14 weight % be 10 weight % hydrochloric acid solution and n-butanol with weight ratio be
7:1.2:1 carries out mixing and the haptoreaction 1.2h at 30 DEG C, then adjusts pH value extremely with the sulfuric acid that concentration is 98 weight %
3.5, then obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, is obtained
Silica gel filter cake.
The 20g silica filter cake of above-mentioned preparation and 20g silica gel filter cake are put into togerther in 100mL ball grinder, wherein ball
The material of grinding jar is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/
min.Ball grinder is closed, temperature is ball milling 5h at 60 DEG C in ball grinder, obtains 40g solid powder；The solid powder is dissolved
In 30 grams of deionized waters, it is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；The product that will be obtained after spray drying
It is calcined for 24 hours at 550 DEG C in Muffle furnace, removed template method obtains destination carrier.
(2) support type polyethylene catalysts are prepared
In N2Under protection, by the MgCl of 1g2With the TiCl of 1g4It is dissolved in the tetrahydrofuran of 500mL and the double solvents of isopropanol
In (volume ratio of tetrahydrofuran and isopropanol is 1:1.4), the catalyst mother liquor of element containing Mg and Ti element is formed.Then 80
The above-mentioned carrier impregnation 5h of 1g is added at DEG C.It after being cooled to room temperature, is then filtered, obtains solid product after removing liquid, and
It is washed repeatedly with tetrahydrofuran solid product 4 times, finally obtains having good in 75 DEG C of vacuum drying 4h by obtained solid product
The powdery support type polyethylene catalysts of good mobile performance.
Table 3 is the pore structure parameter of the spherical complex carrier in the super big hole three-dimensional cubic duct of the present embodiment.
Table 3
The spherical complex carrier in super big hole three-dimensional cubic duct is diplopore distribution it can be seen from the data of upper table 3.
It is obtained by xrf analysis, in the embodiment of the present invention support type polyethylene catalysts, with the poly- second of the support type
The total weight of alkene catalyst, the content of the magnesium elements in terms of oxide are 8.3 weight %, and the titanium elements in terms of oxide contain
Amount is 0.8 weight %, and the content of chlorine is 1.7 weight % and remainder is carrier.
Comparative example 2
Catalyst is prepared according to the method for embodiment 2, the difference is that in the step of preparing the silica gel, using phase
The tert-butyl alcohol with parts by weight replaces n-butanol.To which comparative catalyst D2 be made.
Table 4 is the pore structure parameter of the carrier of this comparative example.
Table 4
Elemental analysis is the results show that magnesium in comparative catalyst D2, relative to the total weight of catalyst D2, in terms of oxide
The content of element is 2.6 weight %, and the content of the titanium elements in terms of oxide is 0.4 weight %, and the content of chlorine is 4.6 weight %
And remainder is carrier.
Comparative example 3
Catalyst is prepared according to the method for embodiment 3, the difference is that in the step of preparing the silica gel, using phase
Isobutanol with parts by weight replaces n-butanol.To which comparative catalyst D3 be made.
Table 5 is the pore structure parameter of the carrier of this comparative example.
Table 5
Elemental analysis is the results show that magnesium in comparative catalyst D3, relative to the total weight of catalyst D3, in terms of oxide
The content of element is 2.3 weight %, and the content of the titanium elements in terms of oxide is 0.5 weight %, and the content of chlorine is 4.1 weight %
And remainder is carrier.
Comparative example 4
Catalyst is prepared according to the method for embodiment 3, the difference is that in the step of preparing the silica gel, using phase
Deionized water with parts by weight replaces n-butanol.To which comparative catalyst D4 be made.
Table 6 is the pore structure parameter of the carrier of this comparative example.
Table 6
Elemental analysis is the results show that magnesium in comparative catalyst D4, relative to the total weight of catalyst D4, in terms of oxide
The content of element is 2.2 weight %, and the content of the titanium elements in terms of oxide is 0.5 weight %, and the content of chlorine is 4.8 weight %
And remainder is carrier.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used to illustrate support type polyethylene catalysts according to the present invention in ethylene polymerization
Using.
It in the stainless steel polymerization autoclave of 2L, is respectively replaced three times with nitrogen and ethylene, 200mL hexane is then added, it will
Kettle temperature rises to 80 DEG C, adds 800mL hexane, and with the addition of hexane, the concentration that 2mL is added is the triethyl aluminum of 1mol/L
(TEA) hexane solution is subsequently added into the composite material containing polyethylene catalysts that the embodiment 1 of 0.1g is prepared, is passed through
Pressure is risen to 1.0MPa and is maintained 1.0MPa by ethylene, is reacted 1 hour at 70 DEG C.Polyethylene particle powder is obtained, the poly- second
The heap density (BD) of alkene particle powder is 0.40g/mL, melt index MI2.16=0.70g/10min.It is computed determination, is catalyzed
The efficiency of agent is 2700g PE/gcat.h。
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used to illustrate support type polyethylene catalysts according to the present invention in ethylene polymerization
Using.
It in the stainless steel polymerization autoclave of 2L, is respectively replaced three times with nitrogen and ethylene, 200mL hexane is then added, it will
Kettle temperature rises to 80 DEG C, adds 800mL hexane, and with the addition of hexane, the concentration that 2.2mL is added is the triethyl aluminum of 1mol/L
(TEA) hexane solution is subsequently added into the composite material containing polyethylene catalysts that 0.1 gram of embodiment 2 is prepared, is passed through
Pressure is risen to 1.0MPa and is maintained 1.0MPa by ethylene, is reacted 1 hour at 80 DEG C.Polyethylene particle powder is obtained, the poly- second
The heap density (BD) of alkene particle powder is 0.39g/mL, melt index MI2.16=0.73g/10min.It is computed determination, is catalyzed
The efficiency of agent is 2746g PE/gcat.h。
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used to illustrate support type polyethylene catalysts according to the present invention in ethylene polymerization
Using.
It in 2 liters of stainless steel polymerization autoclave, is respectively replaced three times with nitrogen and ethylene, 200 milliliters of hexanes is then added,
Kettle temperature is risen to 85 DEG C, adds 800 milliliters of hexanes, with the addition of hexane, the concentration for being added 2.5 milliliters is 1 mol/L
Triethyl aluminum (TEA) hexane solution, be subsequently added into that 0.1 gram of embodiment 3 is prepared containing the compound of polyethylene catalysts
Material is passed through ethylene, and pressure is risen to 1.0MPa and is maintained 1.0MPa, reacts 1 hour at 90 DEG C.Obtain polyethylene particle powder
Material, the heap density (BD) of the polyethylene particle powder are 0.41g/mL, melt index MI2.16=0.71g/10min.It is computed
It determines, the efficiency of catalyst is 2798g PE/gcat.h。
Experimental comparison's example 1
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 1, unlike, using pair of identical weight part
The support type polyethylene catalysts that D1 prepared by ratio 1 replaces embodiment 1 to be prepared.The heap of gained polyethylene particle powder is close
Spending (BD) is 0.41g/mL, melt index: MI2.16=0.89g/10min.It is computed determination, the efficiency of catalyst is 1636g
PE/gcat.h。
Experimental comparison's example 2
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 2, unlike, using pair of identical weight part
The support type polyethylene catalysts that D2 prepared by ratio 2 replaces embodiment 2 to be prepared.The heap of gained polyethylene particle powder is close
Spending (BD) is 0.40g/mL, melt index: MI2.16=1.02g/10min.It is computed determination, the efficiency of catalyst is 1936g
PE/gcat.h。
Experimental comparison's example 3
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 3, unlike, using pair of identical weight part
The support type polyethylene catalysts that D3 prepared by ratio 3 replaces embodiment 3 to be prepared.The heap of gained polyethylene particle powder is close
Spending (BD) is 0.41g/mL, melt index: MI2.16=1.21g/10min.It is computed determination, the efficiency of catalyst is 1921g
PE/gcat.h。
Experimental comparison's example 4
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 3, unlike, using pair of identical weight part
The support type polyethylene catalysts that D4 prepared by ratio 4 replaces embodiment 3 to be prepared.The heap of gained polyethylene particle powder is close
Spending (BD) is 0.42g/mL, melt index: MI2.16=1.00g/10min.It is computed determination, the efficiency of catalyst is 1896g
PE/gcat.h。
It can be seen from above EXPERIMENTAL EXAMPLE 1-3 in ethylene polymerisation process, containing containing embodiment 1-3 is poly-
The composite material of catalyst for ethylene catalytic efficiency with higher.Moreover, the load of support type polyethylene catalysts of the invention
Rate is high.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (17)
1. a kind of preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct, which is characterized in that this method include with
Lower step:
Preparation silica filter cake: template and silicon source are subjected to hybrid reaction in acidic aqueous solution, then by hybrid reaction
The material obtained afterwards is successively filtered and washed；
It prepares silica gel: in the presence of inorganic acid solution, waterglass and n-butanol being subjected to haptoreaction, then adjust institute after reaction
The pH value for obtaining solution is 2-4；
It prepares carrier: successively carrying out ball milling after the silica filter cake being prepared and the silica gel are mixed, does by spraying
Dry and calcining.
2. according to the method described in claim 1, wherein, the preparation silica filter cake the step of in, the mixing is anti-
The condition answered includes: that temperature is 10-60 DEG C, time 10-72h, pH value 1-6.
3. according to the method described in claim 1, wherein, the dosage molar ratio of the template and silicon source is 1:10-90.
4. according to the method described in claim 1, wherein, the template is triblock copolymer PULLRONIC F68-
Polyoxyethylene；The acidic aqueous solution is selected from least one of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid aqueous solution.
5. according to the method described in claim 1, wherein, in described the step of preparing silica gel, the waterglass and n-butanol
Dosage weight ratio be 1.2-10:1.
6. the catalytic condition includes: that temperature is 10-60 DEG C according to the method described in claim 1, wherein, the time
For 1-5h, pH value 2-4.
7. according to the method described in claim 1, wherein, in described the step of preparing carrier, the silica filter cake and
The dosage weight ratio of the silica gel is 1:1-3.
8. method according to claim 1 or claim 7, wherein in described the step of preparing carrier, the condition packet of the ball milling
Include: the revolving speed of abrading-ball is 300-500r/min, and the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100h.
9. method according to claim 1 or claim 7, wherein the condition of the spray drying includes: that temperature is 100-300 DEG C,
The revolving speed of rotation is 10000-15000r/min.
10. method according to claim 1 or claim 7, wherein the condition of the calcining includes: that temperature is 300-600 DEG C, when
Between be 10-80h.
11. the spherical shape in the super big hole three-dimensional cubic duct that method described in any one of claim 1-10 is prepared is compound
Carrier.
12. the spherical complex carrier in super big hole three-dimensional cubic according to claim 11 duct, which is characterized in that the load
The average grain diameter of body is 30-60 μm, specific surface area 250-500m2/ g, pore volume 0.5-1.8mL/g, pore-size distribution
For bimodal distribution, and bimodal first most probable pore size that aperture is 5-8nm and aperture of respectively corresponding is the second of 32-38nm
Most probable pore size, the specific surface area are measured according to nitrogen adsorption methods.
13. a kind of support type polyethylene catalysts, which is characterized in that the ball containing super big hole three-dimensional cubic duct in the catalyst
Shape complex carrier and the magnesium elements being supported at least one in outer surface, inner hole wall and the ball inside of the carrier and/or titanium member
Element；The carrier is carrier described in claim 11 or 12.
14. the preparation method of support type polyethylene catalysts described in claim 13, which is characterized in that this method comprises:
In the presence of inert gas, by the spherical complex carrier in super big hole three-dimensional cubic duct in urging containing magnesium elements and/or titanium elements
It is impregnated in agent mother liquor, is then successively filtered and dries；The carrier is carrier described in claim 11 or 12.
15. according to the method for claim 14, wherein the condition of the dipping includes: that temperature is 45-100 DEG C, and the time is
2-8h。
16. according to the method for claim 14, wherein prepare the spherical complex carrier in super big hole three-dimensional cubic duct
The step of include:
Preparation silica filter cake: template and silicon source are subjected to hybrid reaction in acidic aqueous solution, then by hybrid reaction
The material obtained afterwards is successively filtered and washed；
It prepares silica gel: in the presence of inorganic acid solution, waterglass and n-butanol being subjected to haptoreaction, then adjust institute after reaction
The pH value for obtaining solution is 2-4；
It prepares carrier: successively carrying out ball milling after the silica filter cake being prepared and the silica gel are mixed, does by spraying
Dry and calcining.
17. application of the support type polyethylene catalysts described in claim 13 in catalyzed ethylene polymerization reaction.
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| CN104248990A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | 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 |
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| CN1246808A (en) * | 1997-02-11 | 2000-03-08 | 美孚石油公司 | Ziegler-Natta catalyst for ethylene polymerization or copolymerization |
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| CN104248981A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical composite carrier of three dimensional cube tunnel and catalyst, preparation method and application thereof, and preparation method of ethyl acetate |
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