CN106467582A - Macropore two dimension the spherical complex carrier of straight channels and the composite containing polyethylene catalysts with and its preparation method and application - Google Patents
Macropore two dimension the spherical complex carrier of straight channels and the composite containing polyethylene catalysts with and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to catalyst field, disclose a kind of macropore two dimension spherical complex carrier of straight channels and the composite containing polyethylene catalysts with and its preparation method and application, the average particulate diameter of the carrier of the present invention is 10-80 μm, and specific surface area is 200-600m2/ g, pore volume is 0.1-2.5mL/g, and pore-size distribution is bimodal distribution, and bimodal the first most probable pore size that aperture is 1.2-4.5nm and aperture of corresponding to respectively is second most probable pore size of 32-60nm.The carrier meso-hole structure of the present invention is stable, be maintained to orderly meso-hole structure after load active component, and has high activity loading when polyethylene catalysts are reacted with catalyzed ethylene polymerization.
Description
Technical field
The present invention relates to catalyst field, in particular it relates to a kind of macropore two dimension straight channels is spherical multiple
Close carrier, a kind of macropore two dimension straight channels the preparation method of spherical complex carrier and by party's legal system
The standby spherical complex carrier of macropore two dimension straight channels obtaining, a kind of being combined containing polyethylene catalysts
Material, a kind of preparation method of the composite containing polyethylene catalysts and prepared by the method
The composite containing polyethylene catalysts, a kind of composite containing polyethylene catalysts catalysis
Application in ethylene polymerization.
Background technology
Mobile company synthesizes the regular mesoporous material of duct high-sequential within 1992, has high ratio
Surface area, regular pore passage structure and narrow pore-size distribution so that mesoporous material catalysis, separate,
The application of medicine and other fields has obtained very big concern (Beck J S, Vartuli J C, Roth W J, et al.J.
Am.Chem.Soc.,1992,114(27):10834-10843)；Zhao in 1998 east unit et al. synthesizes one
Plant new material-mesoporous material SBA-15, this material has the mesoporous material aperture of high-sequential
(6-30nm), the big (1.0cm of pore volume3/ g), thicker hole wall (4-6nm), high machinery can be kept
Intensity and good catalytic adsorption performance (D.Y.Zhao, J.L.Feng, Q.S.Huo, et al Science
279(1998)548-550；Zhao Dongyuan, Yu Chengzhong, Yu Yonghao)；CN1341553A, a kind of mesoporous point
The preparation method of son sieve carrier material, it discloses mesoporous material as heterogeneous reaction catalyst carrier, holds
Easily realize catalyst to separate with product.
However, the ordered mesoporous material SBA-15 microscopic appearance of routine is bar-shaped, and microscopic appearance is ball
The material of shape compares that 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, this will be further exacerbated by the reunion of ordered mesoporous material, to ordered mesoporous material
Storage, transport, afterwards process and application make troubles.And the geometric shape of microsphere is in the group reducing powder body
Poly-, improving the aspects such as its mobility has obvious advantage, therefore makes ordered mesoporous material spherical permissible
Microsphere is combined with the advantage of ordered mesoporous material, the high-ratio surface of ordered mesoporous material can be retained
Long-pending, big pore volume, aperture be big and the feature of narrowly distributing, can reduce the reunion of ordered mesoporous material again, increase
Its mobility.Application for ordered mesoporous material is provided more preferable platform by this, and expands order mesoporous material
The application of material.
The development and application of polyethylene catalysts are after traditional Ziegler-Natta catalyst, and alkene gathers
Close catalyst field another important breakthrough, this make the research of polyethylene catalysts entered into one fast
Hail the stage of exhibition.The catalyst amount being reached due to homogeneous polyethylene catalyst needed for high activity is big, raw
Produce high cost, and the polymer obtaining no particle shape is it is impossible to gather in widely used slurry process or vapor phase method
Close and use in technique, the effective way overcoming the problems referred to above is exactly that soluble poly catalyst for ethylene is born
Loadization is processed.At present, very many about polyethylene catalysts supported research report.New for further investigation
Support/catalyst/co-catalyst system it is necessary to the different carriers of research, to promote carried catalyst
Development further with polyolefin industry.Mesoporous material is with its big surface area (500-2000m2/g)、
The advantage of spacious duct and big and adjustable aperture size (3-50nm) is used for polyethylene by researcher
Catalyst loads and is used for ethylene polymerization.
On document, the mesoporous material of the load polyethylene catalysts of report mainly has MCM-41 at present, with
MAO process after load again polyethylene catalysts MCM-41 carry out vinyl polymerization after catalysis activity be
106gPE/(mol Zr h).Carry out ethylene polymerization activity relatively low after Mesoporous silica MCM 41 supported catalyst
The reason be mainly the hole wall structure heat stability of MCM-41 and hydrothermal stability is poor, in loading process
Middle hole wall just has part to cave in, and have impact on load effect, so that have impact on catalysis activity.Therefore test
Seek a kind of stable mesoporous material of meso-hole structure, after load, still can keep orderly meso-hole structure.
Content of the invention
The purpose of the present invention is the defect overcoming prior art, provides a kind of meso-hole structure stable, in load
It is maintained to orderly meso-hole structure after active component, and in load polyethylene catalysts to be catalyzed
There is during ethylene polymerization the carrier of high catalytic activity.
To achieve these goals, on the one hand, the present invention provides a kind of the spherical of macropore two dimension straight channels
Complex carrier, the average particulate diameter of this carrier is 10-80 μm, and specific surface area is 200-600m2/ g,
Pore volume is 0.1-2.5mL/g, and pore-size distribution is bimodal distribution, and the bimodal aperture that corresponds to respectively is
First most probable pore size of 1.2-4.5nm and aperture are second most probable pore size of 32-60nm.
Second aspect, the present invention provides a kind of preparation side of the spherical complex carrier of macropore two dimension straight channels
Method, the method comprises the following steps：
Prepare mesoporous material：In the presence of alkaline solution, template and silicon source are carried out hybrid reaction, and
The mixture obtaining after hybrid reaction is filtered；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are reacted, is then adjusted
After section reaction, the pH value of resulting solution is 2-4；
Prepare carrier：Ground after the described mesoporous material preparing and the mixing of described silica gel successively
Mill, spray drying and calcining；
Wherein, the method makes the average particulate diameter of the carrier obtaining be 10-80 μm, and specific surface area is
200-600m2/ g, pore volume is 0.1-2.5mL/g, and pore-size distribution is bimodal distribution, and bimodal right respectively
The first most probable pore size that aperture is 1.2-4.5nm and aperture is answered to be second most probable pore size of 32-60nm；
Preferably
The average particulate diameter of described carrier is 20-60 μm, and specific surface area is 300-500m2/ g, hole body
Amass as 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that corresponds to respectively is 1.5-4.2nm's
First most probable pore size and aperture are second most probable pore size of 32-55nm；More preferably
Bimodal the first most probable pore size that aperture is 2-4nm and aperture of corresponding to respectively is the second of 35-55nm
Most probable pore size.
The third aspect, the present invention provides the spherical of the macropore two dimension straight channels being prepared by said method
Complex carrier.
Fourth aspect, the present invention provides a kind of composite containing polyethylene catalysts, this composite
In the spherical complex carrier containing macropore two dimension straight channels and be supported on outer surface, the endoporus of described carrier
Magnesium elements at least one in wall and ball inside and/or titanium elements；The average particulate diameter of described carrier is
10-80 μm, specific surface area is 200-600m2/ g, pore volume is 0.1-2.5mL/g, and pore-size distribution is double
Peak is distributed, and bimodal corresponds to that aperture is first most probable pore size of 1.2-4.5nm and aperture is respectively
Second most probable pore size of 32-60nm；Preferably
The average particulate diameter of described carrier is 20-60 μm, and specific surface area is 300-500m2/ g, hole body
Amass as 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that corresponds to respectively is 1.5-4.2nm's
First most probable pore size and aperture are second most probable pore size of 32-55nm；More preferably
Bimodal the first most probable pore size that aperture is 2-4nm and aperture of corresponding to respectively is the second of 35-55nm
Most probable pore size.
5th aspect, the present invention provides a kind of preparation method of the composite containing polyethylene catalysts,
The method includes：In the presence of an inert gas, the spherical complex carrier of macropore two dimension straight channels is being contained
Have in magnesium elements and/or the catalyst mother solution of titanium elements and impregnated, then filtered successively and be dried；
The average particulate diameter of described carrier is 10-80 μm, and specific surface area is 200-600m2/ g, pore volume is
0.1-2.5mL/g, pore-size distribution is bimodal distribution, and bimodal correspond to that aperture is 1.2-4.5nm respectively the
One most probable pore size and aperture are second most probable pore size of 32-60nm；Preferably
The average particulate diameter of described carrier is 20-60 μm, and specific surface area is 300-500m2/ g, hole body
Amass as 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that corresponds to respectively is 1.5-4.2nm's
First most probable pore size and aperture are second most probable pore size of 32-55nm；More preferably
Bimodal the first most probable pore size that aperture is 2-4nm and aperture of corresponding to respectively is the second of 35-55nm
Most probable pore size.
6th aspect, the present invention provides being combined containing polyethylene catalysts being prepared by said method
Material.
7th aspect, the present invention provides the described composite containing polyethylene catalysts to gather in catalyzed ethylene
Close the application in reaction.
The spherical complex carrier meso-hole structure of the above-mentioned macropore two dimension straight channels that the present invention provides is stable,
Be maintained to orderly meso-hole structure after load active component, and load polyethylene catalysts with
During catalyzed ethylene polymerization reaction, there is high activity.
The spherical complex carrier mean diameter of the macropore two dimension straight channels that the present invention provides is 10-80 μm,
Spheroid good flowing properties, pore structure is regular, is conducive to catalytic reaction to carry out；Carrier loaded using this
, as catalyst, during ethylene polymerization, catalysis activity is high for polyethylene catalysts active component.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.?
In accompanying drawing：
Fig. 1 is the macropore two dimension straight channels spherical complex carrier that embodiments of the invention 1 prepare
XRD spectra.
Fig. 2 is the macropore two dimension straight channels spherical complex carrier that embodiments of the invention 1 prepare
Scanning electron microscope (SEM) photograph (SEM).
Fig. 3 is sweeping of the composite containing polyethylene catalysts that embodiments of the invention 1 prepare
Retouch electron microscope (SEM).
Fig. 4 is the macropore two dimension straight channels spherical complex carrier that embodiments of the invention 1 prepare
Grain size distribution.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, described specific surface area, pore volume and most probable pore size record according to nitrogen adsorption methods,
Described mean diameter is recorded using laser fineness gage.
In the present invention, described mean diameter is average particulate diameter.
In a first aspect, the present invention provides a kind of spherical complex carrier of macropore two dimension straight channels, this carrier
Average particulate diameter be 10-80 μm, specific surface area be 200-600m2/ g, pore volume is 0.1-2.5mL/g,
Pore-size distribution is bimodal distribution, and bimodal corresponding respectively aperture is first most probable pore size of 1.2-4.5nm
With the second most probable pore size for 32-60nm for the aperture.
Under preferable case, according to the spherical complex carrier of macropore of the present invention two dimension straight channels, institute
The average particulate diameter stating carrier is 20-60 μm, and specific surface area is 300-500m2/ g, pore volume is
0.5-2mL/g, pore-size distribution is bimodal distribution, and bimodal corresponding respectively aperture is the first of 1.5-4.2nm
Most probable pore size and aperture are second most probable pore size of 32-55nm.
In the case of more preferably, according to the spherical compound load of macropore of the present invention two dimension straight channels
Body, pore-size distribution is bimodal distribution, and bimodal corresponding respectively aperture is first most probable pore size of 2-4nm
With the second most probable pore size for 35-55nm for the aperture.
The spherical complex carrier of the described macropore two dimension straight channels that the present invention provides has substantially more existing
The bigger Based on Dual-Aperture distribution of technology and the spheroid pattern of pore volume and good flowing properties, advantageously in urging
Change the carrying out of reaction, the spherical complex carrier of this macropore two dimension straight channels is formed polyethylene catalysts
When, the polyethylene catalysts of acquisition have the catalysis activity apparently higher than 955 silica gel.
Second aspect, the present invention provides a kind of preparation side of the spherical complex carrier of macropore two dimension straight channels
Method, the method comprises the following steps：
Prepare mesoporous material：In the presence of alkaline solution, template and silicon source are carried out hybrid reaction, and
The mixture obtaining after hybrid reaction is filtered；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are reacted, is then adjusted
After section reaction, the pH value of resulting solution is 2-4；
Prepare carrier：Ground after the described mesoporous material preparing and the mixing of described silica gel successively
Mill, spray drying and calcining；
Wherein, the method makes the average particulate diameter of the carrier obtaining be 10-80 μm, and specific surface area is
200-600m2/ g, pore volume is 0.1-2.5mL/g, and pore-size distribution is bimodal distribution, and bimodal right respectively
The first most probable pore size that aperture is 1.2-4.5nm and aperture is answered to be second most probable pore size of 32-60nm.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, preparation
The carrier obtaining has substantially bigger compared with prior art Based on Dual-Aperture distribution and pore volume and mobile performance
Good spheroid pattern is advantageously in the carrying out of catalytic reaction, spherical by this macropore two dimension straight channels
When complex carrier forms polyethylene catalysts, the polyethylene catalysts of acquisition have apparently higher than 955 silica gel
Catalysis activity.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, preferably
The method makes the average particulate diameter of the carrier obtaining be 20-60 μm, and specific surface area is
300-500m2/ g, pore volume is 0.5-2mL/g, and pore-size distribution is bimodal distribution, and bimodal corresponds to respectively
Second most probable pore size for 32-55nm for first most probable pore size and aperture for 1.5-4.2nm for the aperture.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, more
Preferably the method makes the pore-size distribution of the carrier obtaining is bimodal distribution, and the bimodal aperture that corresponds to respectively is
First most probable pore size of 2-4nm and aperture are second most probable pore size of 35-55nm.
The preparation method of the spherical complex carrier according to macropore of the present invention two dimension straight channels, in institute
State in the step preparing mesoporous material, preferably described template is 0.1-1.2 with the consumption mol ratio of silicon source：
1.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, preferably
In the case of, in the described step preparing mesoporous material, described alkaline solution passes through to add in reaction system
Enter alkaline reagent and formed.Exemplarily alkalescence is formed using ammonia spirit in embodiments of the invention molten
Liquid.More preferably described template：Ammonia：The consumption mol ratio of silicon source is 0.1-1.2：0.8-10：1.
The described ammonia of the present invention can be 10-25 weight % for concentration.
The preparation method of the spherical complex carrier according to macropore of the present invention two dimension straight channels, in institute
State in the step preparing mesoporous material, the condition of preferably described hybrid reaction includes：Reaction temperature is
25-100 DEG C, the response time is 2-8h, and pH value is 7.5-11, and more preferably pH value is 8-10.
The preparation method of the spherical complex carrier according to macropore of the present invention two dimension straight channels, in institute
State in the step preparing mesoporous material, preferably described silicon source is selected from tetraethyl orthosilicate, methyl silicate, just
At least one in silicic acid propyl ester, sodium metasilicate and Ludox, described template is cetyl trimethyl
Ammonium bromide.
The preparation method of the spherical complex carrier according to macropore of the present invention two dimension straight channels, in institute
State in the step preparing mesoporous material, preferably the mesoporous material obtaining is prepared into cake form, by mistake
Filter can be included with obtaining the process of filter cake：After filtration, deionized water cyclic washing (washing time
Number can be 2-10 time), then carry out sucking filtration.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, in institute
State in the step preparing silica gel, described waterglass is the aqueous solution of sodium silicate, and its concentration can be 10-50
Weight %, preferably 12-30 weight %.
The preparation method of the spherical complex carrier according to macropore of the present invention two dimension straight channels, in institute
State in the step preparing silica gel, the consumption weight of preferably described waterglass and n-butyl alcohol is than for 2-10：1.
In the present invention, the consumption weight of described waterglass and n-butyl alcohol than in waterglass be containing aqueous solution
The weight ratio of form and n-butyl alcohol.
The preparation method of the spherical complex carrier according to macropore of the present invention two dimension straight channels, in institute
State in the step preparing silica gel, the condition that preferably described waterglass and n-butyl alcohol are reacted includes：Reaction
Temperature is 5-50 DEG C, and the response time is 0.5-8h.
The preparation method of the spherical complex carrier according to macropore of the present invention two dimension straight channels, in institute
State in the step preparing silica gel, preferably described inorganic acid solution is selected from hydrochloric acid, sulphuric acid, nitric acid and hydrobromic acid
In at least one aqueous solution.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, in institute
State in the step preparing silica gel, those skilled in the art can adopt conventional use of various examination in the art
The pH value that agent adjusts resulting solution after reacting is 2-4, under preferable case, in the present invention, using dense
The pH value that sulphuric acid adjusts resulting solution after reacting is 2-4.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, in institute
State in the step preparing silica gel, preferably also include being washed adjusting the reaction mass that pH value is after 2-4
Wash, more preferably in the case of, by described reaction mass be washed till sodium ions content be 0.03 weight % below.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, in institute
State in the step preparing carrier, the condition of preferably described grinding includes：Temperature is 15-100 DEG C, and the time is
0.1-100h.
In the present invention, described grinding can be realized by way of using ball milling, specifically, described
Ball milling can be carried out in ball mill, and in described ball mill, the inwall of ball grinder is preferably in politef
Lining, the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can be big according to ball grinder
Little reasonably selected, for the ball grinder for 50-150mL for the size, generally can be using 1 mill
Ball；The material of described abrading-ball can be Achatess, politef etc., preferably Achatess.Described ball milling
Condition can include：The rotating speed of abrading-ball can be 300-500r/min, and the temperature in ball grinder can be
15-100 DEG C, the time of ball milling can be 0.1-100h.
The preparation method of the spherical complex carrier according to macropore of the present invention two dimension straight channels, in institute
State in the step preparing carrier, the condition of preferably described spray drying includes：Temperature is 150-600 DEG C,
The rotating speed of rotation is 10000-15000r/min；In the case of more preferably, the condition bag of described spray drying
Include：Temperature is 170-450 DEG C, and the rotating speed of rotation is 11000-13000r/min.
In the preparation method of the spherical complex carrier of macropore of the present invention two dimension straight channels, in institute
State in the step preparing carrier, the condition of preferably described calcining includes：Temperature is 90-600 DEG C, and the time is
10-80h.
According to the preparation method of macropore of the present invention two dimension straight channels spherical complex carrier, described
Prepare in the step of carrier, the consumption weight of preferably described mesoporous material and described silica gel is than for 1：0.8-2.
The present invention is preferably calcined in Muffle furnace.
The third aspect, the present invention provides the spherical of the macropore two dimension straight channels being prepared by said method
Complex carrier.
The spherical complex carrier mean diameter of macropore that the present invention prepares two dimension straight channels is
10-80 μm, spheroid good flowing properties, pore structure is regular, is conducive to catalytic reaction to carry out；Using
This composite carrier load polyethylene catalysts active component as catalyst, during ethylene polymerization
Catalysis activity is high.
Fourth aspect, the present invention provides a kind of composite containing polyethylene catalysts, this composite
In the spherical complex carrier containing macropore two dimension straight channels and be supported on outer surface, the endoporus of described carrier
Magnesium elements at least one in wall and ball inside and/or titanium elements；The average particulate diameter of described carrier is
10-80 μm, specific surface area is 200-600m2/ g, pore volume is 0.1-2.5mL/g, and pore-size distribution is double
Peak is distributed, and bimodal corresponds to that aperture is first most probable pore size of 1.2-4.5nm and aperture is respectively
Second most probable pore size of 32-60nm.
According to the composite containing polyethylene catalysts of the present invention, preferably described carrier average
Particle diameter is 20-60 μm, and specific surface area is 300-500m2/ g, pore volume is 0.5-2mL/g, aperture
It is distributed as bimodal distribution, and bimodal corresponding respectively aperture is the first most probable pore size and the hole of 1.5-4.2nm
Footpath is second most probable pore size of 32-55nm.
In the case of more preferably, according to the composite containing polyethylene catalysts of the present invention, preferably
The pore-size distribution of described carrier is bimodal distribution, and may be used in the bimodal aperture for 2-4nm first that corresponds to respectively
Several apertures and aperture are second most probable pore size of 35-55nm.
In the present invention, it is preferred to described magnesium elements and titanium elements are provided respectively in the form of magnesium salt and titanium salt,
Described magnesium salt and titanium salt can be conventional use of various magnesium salt and titanium salt in the art, as long as can provide
Magnesium elements and titanium elements.Under preferable case, in the present invention, described magnesium salt is magnesium chloride；Described
Titanium salt titanium tetrachloride and/or titanous chloride..
In the composite containing polyethylene catalysts of the present invention, urged containing polyethylene with described
On the basis of the gross weight of the composite of agent, the spherical compound load of preferably described macropore two dimension straight channels
The content of body is 50-99 weight %, and the described magnesium elements and titanium elements content sum in terms of oxide is
1-50 weight %.
5th aspect, the present invention provides a kind of preparation method of the composite containing polyethylene catalysts,
The method includes：In the presence of an inert gas, the spherical complex carrier of macropore two dimension straight channels is being contained
Have in magnesium elements and/or the catalyst mother solution of titanium elements and impregnated, then filtered successively and be dried；
The average particulate diameter of described carrier is 10-80 μm, and specific surface area is 200-600m2/ g, pore volume is
0.1-2.5mL/g, pore-size distribution is bimodal distribution, and bimodal correspond to that aperture is 1.2-4.5nm respectively the
One most probable pore size and aperture are second most probable pore size of 32-60nm.
In the preparation method containing the composite of polyethylene catalysts of the present invention, preferably described
The average particulate diameter of carrier is 20-60 μm, and specific surface area is 300-500m2/ g, pore volume is
0.5-2mL/g, pore-size distribution is bimodal distribution, and bimodal corresponding respectively aperture is the first of 1.5-4.2nm
Most probable pore size and aperture are second most probable pore size of 32-55nm.
In the preparation method containing the composite of polyethylene catalysts of the present invention, more preferably institute
The pore-size distribution stating carrier is bimodal distribution, and bimodal corresponding respectively aperture is first most probable of 2-4nm
Aperture and aperture are second most probable pore size of 35-55nm.
In the preparation method containing the composite of polyethylene catalysts of the present invention, to described magnesium
, all as the present invention is noted earlier, here of the present invention is not another for the definition of element and titanium elements, form and source
One repeats.
According to the present invention, can be for there is not chemical phase interaction with carrier and active component in described noble gases
Various gases.For example, described noble gases can be by zero group gas in nitrogen and the periodic table of elements
One or more providing.
In the preparation method containing the composite of polyethylene catalysts of the present invention, preferably described
The condition of dipping includes：Temperature is 50-120 DEG C, and the time is 2-8h.
According to the preparation method of the composite containing polyethylene catalysts of the present invention, preferably described
It is immersed in double solventss and carries out, described compounded organic solvent can be for dissolving described magnesium elements and titanium
Element and readily removed various solvents are it is preferable that described compounded organic solvent is oxolane and different
Propanol.More preferably, the volume ratio of oxolane and isopropanol is 1：1-3, particularly preferably 1：1-1.5.
In the preparation method containing the composite of polyethylene catalysts of the present invention, preferably prepare
The step of described carrier includes：
Prepare mesoporous material：In the presence of alkaline solution, template and silicon source are carried out hybrid reaction, and
The mixture obtaining after hybrid reaction is filtered；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are reacted, is then adjusted
After section reaction, the pH value of resulting solution is 2-4；
Prepare carrier：Ground after the described mesoporous material preparing and the mixing of described silica gel successively
Mill, spray drying and calcining.
In the present invention, it should be strongly noted that in the described composite containing polyethylene catalysts
Preparation method in, prepare the correlation in the step of spherical complex carrier of described macropore two dimension straight channels
Definition and the preparation side limiting the spherical complex carrier of aforesaid macropore two dimension straight channels all with the present invention
Method is identical, and the present invention, in order to avoid repeating, will not be described here.
6th aspect, the present invention provides being combined containing polyethylene catalysts being prepared by said method
Material.
The above-mentioned composite containing polyethylene catalysts that the present invention provides is with respect to the product of prior art
Product have more preferable acid catalytic property and good mobile performance.
7th aspect, the present invention provides the described composite containing polyethylene catalysts to gather in catalyzed ethylene
Close the application in reaction.
The present invention is to the described composite containing polyethylene catalysts in catalyzed ethylene polymerization reaction
There is no particular limitation for application, using the spherical complex carrier of macropore of the present invention two dimension straight channels
During the catalyst ethylene polymerization preparing, it is obtained in that substantially than using prior art
Higher catalytic efficiency during the catalyst ethylene polymerization that 955 silica gel prepare.
The catalyst of the spherical complex carrier containing macropore of the present invention two dimension straight channels is used for
During the homopolymerization of vinyl polymerization, catalytic efficiency be substantially better than equivalent responses under the conditions of industry 955 silica gel
Catalytic efficiency.And, the particle diameter of the described composite containing polyethylene catalysts is larger, and carrier has
There is the large aperture of high-sequential, the average pore size of silicon gel part is big, and pore wall strength is moderate, catalyst decay
Relatively slow, polymerization process steadily continues, and catalysis activity is high.Therefore, macropore two dimension of the present invention is straight-through
The spherical complex carrier in duct is the Inorganic material carrier being suitable for olefinic polymerization.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples, cetyl trimethylammonium bromide is from commercially available.
In following examples and comparative example, X-ray diffraction analysis are purchased from German Bruker AXS company
The X-ray diffractometer of model D8Advance on carry out；Scanning electron microscope analysis are purchased from U.S. FEI
Carry out in the scanning electron microscope of model XL-30 of company；Pore structure parameter is analyzed purchased from the U.S.
Carry out on the nitrogen adsorption desorption instrument of model Autosorb-1 of Kang Ta company, wherein, before being tested,
Sample is deaerated 4 hours at 200 DEG C；Mean diameter is in model Mastersizer2000 of Malvern company
Laser fineness gage on carry out, sample is dissolved in ethanol；X-ray fluorescence analysis are in dutch company
Carry out on the x-ray fluorescence analyzer of model Axios-Advanced.
The heap density of polyolefine powder is measured using the method that GB/T 1636-2008 specifies.
Melt index：Measured according to ASTM D1238-99.
Embodiment 1
The present embodiment is used for the spherical complex carrier of macropore two dimension straight channels of the present invention is described, contains
There are composite and their preparation method of polyethylene catalysts.
(1) prepare carrier
0.1mol tetraethyl orthosilicate and 0.037mol cetyl trimethylammonium bromide are added to 25 weights
In the ammonia spirit of amount %, it is to carry out hybrid reaction 4h under conditions of 9 in 80 DEG C and pH value, then will
The mixture obtaining after hybrid reaction is filtered and is washed, and finally gained reactant material is carried out sucking filtration shape
Become filter cake.
By concentration be 15 weight % waterglass and sulfuric acid solution that concentration is 12 weight % and n-butyl alcohol with
Weight is than for 5：1：1 carry out mixed be incorporated in haptoreaction 1.5h at 20 DEG C, then use concentration to be 98 weights
The sulphuric acid adjustment pH value of amount %, to 3, then carries out sucking filtration to the reaction mass obtaining, and uses distilled water
Washing to sodium ions content is 0.02 weight %, obtains silica gel filter cake.
The 20g mesoporous material filter cake of above-mentioned preparation is put into 100mL ball milling together with 20g silica gel filter cake
In tank, wherein, the material of ball grinder be politef, Material quality of grinding balls be Achatess, abrading-ball a diameter of
3mm, quantity is 1, and rotating speed is 400r/min.Closing ball grinder, in ball grinder, temperature is 60 DEG C
Lower ball milling 5h, obtains 40g pressed powder；This pressed powder is dissolved in 30 grams of deionized waters,
It is spray-dried under rotating speed is for 12000r/min at 200 DEG C；The product obtaining after being spray-dried is in Muffle
Calcine 24h, removed template method at 550 DEG C in stove, obtain 30 grams of carriers.
(2) prepare the composite containing polyethylene catalysts
In N2Under protection, by the MgCl of 1g2TiCl with 1g4Be dissolved in 500mL oxolane and
(oxolane is 1 with the volume ratio of isopropanol to the double solventss of isopropanol：1.2), in, formed and contain Mg
The catalyst mother solution of element and Ti element.Then add above-mentioned carrier impregnation 4h of 1g at 75 DEG C.Cold
But to room temperature, then filtered, after removing liquid, obtained solid product, and with oxolane repeatedly
The solid product obtaining finally is vacuum dried 4h at 75 DEG C, is had by washing solid product 4 times
The powdery of good flow performance contains the composite of polyethylene catalysts.
Divided with XRD, scanning electron microscope, U.S. Kang Ta company Atsorb-1 type nitrogen adsorption instrument, granularity
The composite that analyzer and x-ray fluorescence analysis contain polyethylene catalysts to this characterizes.
Fig. 1 is the X-ray diffraction of the spherical complex carrier of the macropore two dimension straight channels according to the present invention
Collection of illustrative plates (XRD spectra).The low-angle spectral peak being occurred from XRD spectra, the XRD spectra of carrier
There is the hexagonal hole road structure of 2D specific to mesoporous material.
Fig. 2 is the microscopic appearance of the spherical complex carrier of the macropore two dimension straight channels according to the present invention
SEM scanning electron microscope (SEM) photograph.As seen from the figure, the microcosmic shape of the spherical complex carrier of macropore two dimension straight channels
The mean diameter of looks is 30-60 μm, and good dispersion.
Fig. 3 is the SEM according to the microscopic appearance containing the composite of polyethylene catalysts for the present invention
Scanning electron microscope (SEM) photograph.As seen from the figure, the microscopic appearance of the composite containing polyethylene catalysts is with respect to negative
The pattern of spherical complex carrier of macropore two dimension straight channels before load and mean diameter are held essentially constant.
Fig. 4 is the grain size distribution of the macropore two dimension straight channels spherical complex carrier according to the present invention, single
Position for μm.As seen from the figure, the mean diameter of carrier is 47 μm, and particle diameter distribution is highly uniform.
Table 1 is the pore structure parameter of macropore two dimension straight channels spherical complex carrier.
Table 1
Can be seen that macropore two dimension straight channels spherical complex carrier by the data of upper table 1 to be distributed for diplopore.
Drawn by xrf analysis, the described composite containing polyethylene catalysts of the present embodiment
In, with the gross weight meter of the described composite containing polyethylene catalysts, the magnesium elements in terms of oxide
Content be 2.8 weight %, the content of the titanium elements counted with oxide is 0.8 weight %, and the content of chlorine is
7.8 weight % and remainder are 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, thus obtaining the ES955 silica gel through thermal activation.
Method according to embodiment 1 step (2) prepares catalyst, except that, using identical heavy
The ES955 silica gel of amount part replaces complex carrier.Thus comparative catalyst D1 is obtained.
Elementary analysiss result shows, in comparative catalyst D1, with respect to the gross weight of catalyst D1,
The content of titanium is 1.2 weight %, and the content of chlorine is 6.8 weight %, and Mg content is 1.8 weight %.
Embodiment 2
The present embodiment is used for macropore two dimension straight channels spherical complex carrier of the present invention is described, contains
The composite of polyethylene catalysts and their preparation method.
(1) prepare carrier
0.1mol tetraethyl orthosilicate and 0.032mol cetyl trimethylammonium bromide are added to 22 weights
In the ammonia spirit of amount %, it is to carry out hybrid reaction under conditions of 9.5 in 75 DEG C and pH value, then will
The mixture obtaining after hybrid reaction is filtered and is washed, and finally gained reactant material is carried out sucking filtration shape
Become filter cake.
By concentration be 13 weight % waterglass and salpeter solution that concentration is 15 weight % and n-butyl alcohol with
Weight is than for 4：1.2：1 carry out mixed be incorporated in haptoreaction 1.3h at 25 DEG C, then use concentration to be 98
The sulphuric acid adjustment pH value of weight %, to 3.5, then carries out sucking filtration to the reaction mass obtaining, and with distilling
Water washing is 0.02 weight % to sodium ions content, obtains silica gel filter cake.
The 20g mesoporous material filter cake of above-mentioned preparation is put into 100mL ball milling together with 20g silica gel filter cake
In tank, wherein, the material of ball grinder be politef, Material quality of grinding balls be Achatess, abrading-ball a diameter of
3mm, quantity is 1, and rotating speed is 400r/min.Closing ball grinder, in ball grinder, temperature is 60 DEG C
Lower ball milling 5h, obtains 40g pressed powder；This pressed powder is dissolved in 30 grams of deionized waters,
It is spray-dried under rotating speed is for 12000r/min at 200 DEG C；The product obtaining after being spray-dried is in Muffle
Calcine 24h, removed template method at 550 DEG C in stove, obtain 30 grams of carriers.
(2) prepare the composite containing polyethylene catalysts
In N2Under protection, by the MgCl of 1g2TiCl with 1g4Be dissolved in 500mL oxolane and
(oxolane is 1 with the volume ratio of isopropanol to the double solventss of isopropanol：1.3), in, formed and contain Mg
The catalyst mother solution of element and Ti element.Then add above-mentioned carrier impregnation 5h of 1g at 85 DEG C.Cold
But to room temperature, then filtered, after removing liquid, obtained solid product, and with oxolane repeatedly
The solid product obtaining finally is vacuum dried 4h at 75 DEG C, is had by washing solid product 4 times
The powdery of good flow performance contains the composite of polyethylene catalysts.
Table 2 is the pore structure parameter of the macropore two dimension straight channels spherical complex carrier of the present embodiment.
Table 2
Can be seen that macropore two dimension straight channels spherical complex carrier by the data of upper table 2 to be distributed for diplopore.
Drawn by xrf analysis, the described composite containing polyethylene catalysts of the present embodiment
In, with the gross weight meter of the described composite containing polyethylene catalysts, the magnesium elements in terms of oxide
Content be 2.9 weight %, the content of the titanium elements counted with oxide is 0.8 weight %, and the content of chlorine is
8.2 weight % and remainder are carrier.
Embodiment 3
The present embodiment is used for macropore two dimension straight channels spherical complex carrier of the present invention is described, contains
The composite of polyethylene catalysts and their preparation method.
(1) prepare carrier
0.1mol tetraethyl orthosilicate and 0.032mol cetyl trimethylammonium bromide are added to 15 weights
In the ammonia spirit of amount %, it is to carry out hybrid reaction under conditions of 10 in 70 DEG C and pH value, then will
The mixture obtaining after hybrid reaction is filtered and is washed, and finally gained reactant material is carried out sucking filtration shape
Become filter cake.
By concentration be 14 weight % waterglass and hydrochloric acid solution that concentration is 10 weight % and n-butyl alcohol with
Weight is than for 7：1.2：1 carry out mixed be incorporated in haptoreaction 1.2h at 30 DEG C, then use concentration to be 98
The sulphuric acid adjustment pH value of weight %, to 3.5, then carries out sucking filtration to the reaction mass obtaining, and with distilling
Water washing is 0.02 weight % to sodium ions content, obtains silica gel filter cake.
The 20g mesoporous material filter cake of above-mentioned preparation is put into 100mL ball milling together with 20g silica gel filter cake
In tank, wherein, the material of ball grinder be politef, Material quality of grinding balls be Achatess, abrading-ball a diameter of
3mm, quantity is 1, and rotating speed is 400r/min.Closing ball grinder, in ball grinder, temperature is 60 DEG C
Lower ball milling 5h, obtains 40g pressed powder；This pressed powder is dissolved in 30 grams of deionized waters,
It is spray-dried under rotating speed is for 12000r/min at 200 DEG C；The product obtaining after being spray-dried is in Muffle
Calcine 24h, removed template method at 550 DEG C in stove, obtain 30 grams of carriers.
(2) prepare the composite containing polyethylene catalysts
In N2Under protection, by the MgCl of 1g2TiCl with 1g4Be dissolved in 500mL oxolane and
(oxolane is 1 with the volume ratio of isopropanol to the double solventss of isopropanol：1.4), in, formed and contain Mg
The catalyst mother solution of element and Ti element.Then add above-mentioned carrier impregnation 5h of 1g at 80 DEG C.Cold
But to room temperature, then filtered, after removing liquid, obtained solid product, and with oxolane repeatedly
The solid product obtaining finally is vacuum dried 4h at 75 DEG C, is had by washing solid product 4 times
The powdery of good flow performance contains the composite of polyethylene catalysts.
Table 3 is the pore structure parameter of the macropore two dimension straight channels spherical complex carrier of the present embodiment.
Table 3
Can be seen that macropore two dimension straight channels spherical complex carrier by the data of upper table 3 to be distributed for diplopore.
Drawn by xrf analysis, the described composite containing polyethylene catalysts of the present embodiment
In, with the gross weight meter of the described composite containing polyethylene catalysts, the magnesium elements in terms of oxide
Content be 3.0 weight %, the content of the titanium elements counted with oxide is 0.9 weight %, and the content of chlorine is
8.3 weight % and remainder are carrier.
Comparative example 2
Method according to embodiment 2 prepares catalyst, except that, in the step preparing described silica gel
In, the tert-butyl alcohol using identical weight part replaces n-butyl alcohol.Thus comparative catalyst D2 is obtained.
Table 4 is the pore structure parameter of the carrier of this comparative example.
Table 4
Elementary analysiss result shows, in comparative catalyst D2, with respect to the gross weight of catalyst D2,
For 2.8 weight %, the content of the titanium elements counted with oxide is 0.5 to the content of the magnesium elements counted with oxide
Weight %, the content of chlorine is 8.6 weight % and remainder is carrier.
Comparative example 3
Method according to embodiment 3 prepares catalyst, except that, in the step preparing described silica gel
In, the isobutanol using identical weight part replaces n-butyl alcohol.Thus comparative catalyst D3 is obtained.
Table 5 is the pore structure parameter of the carrier of this comparative example.
Table 5
Elementary analysiss result shows, in comparative catalyst D3, with respect to the gross weight of catalyst D3,
For 2.5 weight %, the content of the titanium elements counted with oxide is 0.9 to the content of the magnesium elements counted with oxide
Weight %, the content of chlorine is 9.8 weight % and remainder is carrier.
Comparative example 4
Method according to embodiment 3 prepares catalyst, except that, in the step preparing described silica gel
In, the deionized water using identical weight part replaces n-butyl alcohol.Thus comparative catalyst D4 is obtained.
Table 6 is the pore structure parameter of the carrier of this comparative example.
Table 6
Elementary analysiss result shows, in comparative catalyst D4, with respect to the gross weight of catalyst D4,
For 2.5 weight %, the content of the titanium elements counted with oxide is 1.1 to the content of the magnesium elements counted with oxide
Weight %, the content of chlorine is 8.8 weight % and remainder is carrier.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating to be existed according to the composite containing polyethylene catalysts for the present invention
Application in ethylene polymerization.
In the rustless steel polymerization autoclave of 2L, replaced three times with nitrogen and ethylene are each, be subsequently adding
200mL hexane, kettle temperature is risen to 80 DEG C, adds 800mL hexane, with the addition of hexane, plus
The concentration entering 2mL is triethyl aluminum (TEA) hexane solution of 1mol/L, is subsequently added into the reality of 0.1g
Apply the composite containing polyethylene catalysts that example 1 prepares, be passed through ethylene, pressure is risen to 1.0
MPa is simultaneously maintained 1.0MPa, reacts 1 hour at 90 DEG C.Obtain polyethylene particle powder, this poly- second
The heap density (BD) of alkene granule powder is 0.4g/mL, melt index MI2.16=0.80g/10min.
It is computed determining, the efficiency of catalyst is 2800g PE/gcat.h.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating to be existed according to the composite containing polyethylene catalysts for the present invention
Application in ethylene polymerization.
In the rustless steel polymerization autoclave of 2L, replaced three times with nitrogen and ethylene are each, be subsequently adding
200mL hexane, kettle temperature is risen to 80 DEG C, adds 800mL hexane, with the addition of hexane, plus
The concentration entering 2.2mL is triethyl aluminum (TEA) hexane solution of 1mol/L, is subsequently added into 0.1 gram
The composite containing polyethylene catalysts that embodiment 2 prepares, is passed through ethylene, pressure is risen to
1.0MPa is simultaneously maintained 1.0MPa, reacts 1 hour at 80 DEG C.Obtain polyethylene particle powder, should
The heap density (BD) of polyethylene particle powder is 0.39g/mL, melt index MI2.16=0.81g/10min.
It is computed determining, the efficiency of catalyst is 2816g PE/gcat.h.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for illustrating to be existed according to the composite containing polyethylene catalysts for the present invention
Application in ethylene polymerization.
In 2 liters of rustless steel polymerization autoclave, replaced three times with nitrogen and ethylene are each, be subsequently adding 200
Milliliter hexane, kettle temperature is risen to 85 DEG C, adds 800 milliliters of hexanes, with the addition of hexane, adds
2.5 milliliters of concentration is triethyl aluminum (TEA) hexane solution of 1 mol/L, is subsequently added into 0.1 gram
The composite containing polyethylene catalysts for preparing of embodiment 3, be passed through ethylene, by pressure liter
To 1.0MPa and be maintained 1.0MPa, react 1 hour at 70 DEG C.Obtain polyethylene particle powder,
The heap density (BD) of this polyethylene particle powder is 0.38g/mL, melt index MI2.16=
0.82g/10min.It is computed determining, the efficiency of catalyst is 2956g PE/gcat.h.
Experimental comparison's example 1
Carry out being polymerized of ethylene using with EXPERIMENTAL EXAMPLE 1 identical method, except for the difference that, using identical
The D1 of comparative example 1 preparation of weight portion replace that embodiment 1 prepares containing polyethylene catalysts
Composite.The heap density (BD) of gained polyethylene particle powder is 0.41g/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
Carry out being polymerized of ethylene using with EXPERIMENTAL EXAMPLE 2 identical method, except for the difference that, using identical
The D2 of comparative example 2 preparation of weight portion replace that embodiment 2 prepares containing polyethylene catalysts
Composite.The heap density (BD) of gained polyethylene particle powder is 0.40g/mL, melt index：
MI2.16=0.89g/10min.It is computed determining, the efficiency of catalyst is 2001g PE/gcat.h.
Experimental comparison's example 3
Carry out being polymerized of ethylene using with EXPERIMENTAL EXAMPLE 3 identical method, except for the difference that, using identical
The D3 of comparative example 3 preparation of weight portion replace that embodiment 3 prepares containing polyethylene catalysts
Composite.The heap density (BD) of gained polyethylene particle powder is 0.41g/mL, melt index：
MI2.16=0.92g/10min.It is computed determining, the efficiency of catalyst is 1968g PE/gcat.h.
Experimental comparison's example 4
Carry out being polymerized of ethylene using with EXPERIMENTAL EXAMPLE 3 identical method, except for the difference that, using identical
The D4 of comparative example 4 preparation of weight portion replace that embodiment 3 prepares containing polyethylene catalysts
Composite.The heap density (BD) of gained polyethylene particle powder is 0.42g/mL, melt index：
MI2.16=0.90g/10min.It is computed determining, the efficiency of catalyst is 2101g PE/gcat.h.
Can be seen that in ethylene polymerisation process by above EXPERIMENTAL EXAMPLE 1-3, containing embodiment 1-3
The composite containing polyethylene catalysts there is higher catalytic efficiency.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Apply the detail in mode, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention no longer separately illustrates to various possible compound modes.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it equally should be considered as content disclosed in this invention.
Claims (13)
1. a kind of macropore two dimension straight channels spherical complex carrier it is characterised in that this carrier flat
All particle diameter is 10-80 μm, and specific surface area is 200-600m2/ g, pore volume is 0.1-2.5mL/g,
Pore-size distribution is bimodal distribution, and bimodal corresponding respectively aperture is first most probable pore size of 1.2-4.5nm
With the second most probable pore size for 32-60nm for the aperture.
2. carrier according to claim 1, wherein, the average particulate diameter of described carrier is
20-60 μm, specific surface area is 300-500m2/ g, pore volume is 0.5-2mL/g, and pore-size distribution is bimodal
Distribution, and bimodal the first most probable pore size that aperture is 1.5-4.2nm and aperture of corresponding to respectively is 32-55nm
The second most probable pore size；Preferably
Bimodal the first most probable pore size that aperture is 2-4nm and aperture of corresponding to respectively is the second of 35-55nm
Most probable pore size.
3. a kind of spherical complex carrier of macropore two dimension straight channels preparation method it is characterised in that
The method comprises the following steps：
Prepare mesoporous material：In the presence of alkaline solution, template and silicon source are carried out hybrid reaction, and
The mixture obtaining after hybrid reaction is filtered；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are reacted, is then adjusted
After section reaction, the pH value of resulting solution is 2-4；
Prepare carrier：Ground after the described mesoporous material preparing and the mixing of described silica gel successively
Mill, spray drying and calcining；
Wherein, the method makes the average particulate diameter of the carrier obtaining be 10-80 μm, and specific surface area is
200-600m2/ g, pore volume is 0.1-2.5mL/g, and pore-size distribution is bimodal distribution, and bimodal right respectively
The first most probable pore size that aperture is 1.2-4.5nm and aperture is answered to be second most probable pore size of 32-60nm；
Preferably
The average particulate diameter of described carrier is 20-60 μm, and specific surface area is 300-500m2/ g, hole body
Amass as 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that corresponds to respectively is 1.5-4.2nm's
First most probable pore size and aperture are second most probable pore size of 32-55nm；More preferably
Bimodal the first most probable pore size that aperture is 2-4nm and aperture of corresponding to respectively is the second of 35-55nm
Most probable pore size.
4. method according to claim 3, wherein, in the described step preparing mesoporous material,
Described template is 0.1-1.2 with the consumption mol ratio of silicon source：1；Preferably
The condition of described hybrid reaction includes：Reaction temperature is 25-100 DEG C, and the response time is 2-8h, pH
It is worth for 7.5-11；More preferably
It is molten that described silicon source is selected from tetraethyl orthosilicate, methyl silicate, positive silicic acid propyl ester, sodium metasilicate and silicon
At least one in glue, described template is cetyl trimethylammonium bromide.
5. method according to claim 3, wherein, in the described step preparing silica gel, institute
State the consumption weight of waterglass and n-butyl alcohol than for 2-10：1；Preferably
The condition that described waterglass and n-butyl alcohol are reacted includes：Reaction temperature is 5-50 DEG C, during reaction
Between be 0.5-8h；More preferably
Described inorganic acid solution is selected from least one aqueous solution in hydrochloric acid, sulphuric acid, nitric acid and hydrobromic acid.
6. method according to claim 3, wherein, in the described step preparing carrier, institute
The condition stating grinding includes：Temperature is 15-100 DEG C, and the time is 0.1-100h；Preferably
The condition of described spray drying includes：Temperature is 150-600 DEG C, and the rotating speed of rotation is
10000-15000r/min；More preferably
The condition of described calcining includes：Temperature is 90-600 DEG C, and the time is 10-80h.
7. the macropore two dimension straight channels that in claim 3-6, the method described in any one prepares
Spherical complex carrier.
8. a kind of composite containing polyethylene catalysts is it is characterised in that contain in this composite
Have macropore two dimension straight channels spherical complex carrier and be supported on the outer surface of described carrier, inner hole wall and
Magnesium elements at least one in ball inside and/or titanium elements；The average particulate diameter of described carrier is
10-80 μm, specific surface area is 200-600m2/ g, pore volume is 0.1-2.5mL/g, and pore-size distribution is double
Peak is distributed, and bimodal corresponds to that aperture is first most probable pore size of 1.2-4.5nm and aperture is respectively
Second most probable pore size of 32-60nm；Preferably
The average particulate diameter of described carrier is 20-60 μm, and specific surface area is 300-500m2/ g, hole body
Amass as 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that corresponds to respectively is 1.5-4.2nm's
First most probable pore size and aperture are second most probable pore size of 32-55nm；More preferably
Bimodal the first most probable pore size that aperture is 2-4nm and aperture of corresponding to respectively is the second of 35-55nm
Most probable pore size.
9. a kind of preparation method of the composite containing polyethylene catalysts is it is characterised in that the party
Method includes：In the presence of an inert gas, the spherical complex carrier of macropore two dimension straight channels is being contained magnesium
Impregnated in the catalyst mother solution of element and/or titanium elements, then filtered successively and be dried；Described
The average particulate diameter of carrier is 10-80 μm, and specific surface area is 200-600m2/ g, pore volume is
0.1-2.5mL/g, pore-size distribution is bimodal distribution, and bimodal correspond to that aperture is 1.2-4.5nm respectively the
One most probable pore size and aperture are second most probable pore size of 32-60nm；Preferably
The average particulate diameter of described carrier is 20-60 μm, and specific surface area is 300-500m2/ g, hole body
Amass as 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal aperture that corresponds to respectively is 1.5-4.2nm's
First most probable pore size and aperture are second most probable pore size of 32-55nm；More preferably
Bimodal the first most probable pore size that aperture is 2-4nm and aperture of corresponding to respectively is the second of 35-55nm
Most probable pore size.
10. method according to claim 9, wherein, the condition of described dipping includes：Temperature is
50-120 DEG C, the time is 2-8h.
11. methods according to claim 9, wherein, the step preparing described carrier includes：
Prepare mesoporous material：In the presence of alkaline solution, template and silicon source are carried out hybrid reaction, and
The mixture obtaining after hybrid reaction is filtered；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are reacted, is then adjusted
After section reaction, the pH value of resulting solution is 2-4；
Prepare carrier：Ground after the described mesoporous material preparing and the mixing of described silica gel successively
Mill, spray drying and calcining.
12. what the method described in any one in claim 9-11 prepared is catalyzed containing polyethylene
The composite of agent.
The composite containing polyethylene catalysts described in 13. claim 8 or claim 12 exists
Application in catalyzed ethylene polymerization reaction.
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