CN106467580A - The spherical complex carrier in super big hole three-dimensional cubic duct and support type polyethylene catalysts and their preparation method and application - Google Patents
The spherical complex carrier in super big hole three-dimensional cubic duct and support type polyethylene catalysts and their preparation method and application Download PDFInfo
- Publication number
- CN106467580A CN106467580A CN201510504824.7A CN201510504824A CN106467580A CN 106467580 A CN106467580 A CN 106467580A CN 201510504824 A CN201510504824 A CN 201510504824A CN 106467580 A CN106467580 A CN 106467580A
- Authority
- CN
- China
- Prior art keywords
- carrier
- aperture
- pore
- bimodal
- probable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention relates to catalyst field, disclose a kind of spherical complex carrier in super big hole three-dimensional cubic duct and support type polyethylene catalysts and their preparation method and application, the average particulate diameter of this carrier of the present invention is 20-60 μm, and specific surface area is 200-600m2/ g, pore volume is 0.1-2mL/g, and pore-size distribution is bimodal distribution, and described bimodal the first most probable pore size that aperture is 3-10nm and aperture of corresponding to respectively is second most probable pore size of 30-39nm.The spherical complex carrier meso-hole structure in the described super big hole three-dimensional cubic duct that the present invention provides 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.And, the load factor of the support type polyethylene catalysts of the present invention is high.
Description
Technical field
The present invention relates to catalyst field, in particular it relates to a kind of super big hole three-dimensional cubic duct is spherical
Complex carrier, a kind of preparation method of spherical complex carrier in super big hole three-dimensional cubic duct and by the party
The spherical complex carrier in super big hole three-dimensional cubic duct that method prepares, a kind of support type polyethylene are catalyzed
Agent, a kind of preparation method of support type polyethylene catalysts and the poly- second of support type being prepared by the method
The application in catalyzed ethylene polymerization reaction of alkene catalyst, a kind of support type polyethylene catalysts.
Background technology
Meso-porous molecular sieve material has the advantages that duct is orderly, aperture is adjustable, specific surface area and pore volume are larger,
It is good catalyst and carrier material.In recent years, prepared with meso-porous molecular sieve material for template
The heterogeneous catalysts such as solid acid, heteropoly acid not only have higher ethylene polymerization catalysis activity, and
Side reaction is less, post processing is relatively simple.For example, the pore passage structure of ordered mesoporous material KIT-6 is similar to
In MCM-48, it is the orderly meso-hole structure of three-dimensional cubic, but the aperture of KIT-6 is compared with MCM-48
Greatly, and duct interconnects, this be active specy direct load provide a good template,
Loaded article dispersed and bulky grain of not forming reunion in whole duct can be made.
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 attempt different carriers, to promote carried catalyst
Development further with polyolefin industry.And 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 is mainly MCM-41 at present, with
MAO loads the MCM-41 of polyethylene catalysts again after processing to carry out catalysis activity after vinyl polymerization be 106
gPE/(mol Zr h).Carry out relatively low former of ethylene polymerization activity after Mesoporous silica MCM 41 supported catalyst
Because the mainly hole wall structure heat stability of MCM-41 and hydrothermal stability is poor, in loading process hole wall
Just there is part to cave in, have impact on load effect, so that have impact on catalysis activity.Therefore experiment seeks one
Plant the stable mesoporous material of meso-hole structure, orderly meso-hole structure after load, still can be kept to seem particularly
Necessary.
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 spherical complex carrier of high catalysis activity.
To achieve these goals, the present invention provides a kind of spherical compound load in super big hole three-dimensional cubic duct
Body, the average particulate diameter of this carrier is 20-60 μm, and specific surface area is 200-600m2/ g, pore volume
For 0.1-2mL/g, pore-size distribution is bimodal distribution, and the described bimodal aperture that corresponds to respectively is 3-10nm's
First most probable pore size and aperture are second most probable pore size of 30-39nm.
Second aspect, the present invention provides a kind of preparation of the spherical complex carrier in super big hole three-dimensional cubic duct
Method, the method comprises the following steps：
Preparation silica filter cake：Template and silicon source are carried out hybrid reaction in acidic aqueous solution, so
Afterwards the material obtaining after hybrid reaction is filtered successively and washed；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are carried out haptoreaction, so
After adjusting reaction afterwards, the pH value of resulting solution is 2-4；
Prepare carrier：Carry out after the described silica filter cake preparing and the mixing of described silica gel successively
Ball milling, spray drying and calcining,
Wherein, the method makes the average particulate diameter of the carrier preparing be 20-60 μm, specific surface
Amass as 200-600m2/ g, pore volume is 0.1-2mL/g, and pore-size distribution is bimodal distribution, and described bimodal
Corresponding to the first most probable pore size that aperture is 3-10nm and aperture respectively is second most probable of 30-39nm
Aperture；Preferably
The average particulate diameter of described carrier is 30-60 μm, and specific surface area is 250-500m2/ g, hole body
Amass as 0.5-1.8mL/g, pore-size distribution is bimodal distribution, and the described bimodal aperture that corresponds to respectively is 5-8nm
The first most probable pore size and aperture be 32-38nm the second most probable pore size.
The third aspect, the ball in the super big hole three-dimensional cubic duct that present invention offer is prepared by said method
Shape complex carrier.
Fourth aspect, the present invention provides a kind of support type polyethylene catalysts, contains super large in this catalyst
The spherical complex carrier in hole three-dimensional cubic duct and being supported in outer surface, inner hole wall and the ball of described carrier
Magnesium elements at least one in portion and/or titanium elements；The average particulate diameter of described carrier is 20-60 μm,
Specific surface area is 200-600m2/ g, pore volume is 0.1-2mL/g, and pore-size distribution is bimodal distribution, and institute
Stating bimodal the first most probable pore size that aperture is 3-10nm and aperture of corresponding to respectively is the second of 30-39nm
Most probable pore size；Preferably
The average particulate diameter of described carrier is 30-60 μm, and specific surface area is 250-500m2/ g, hole body
Amass as 0.5-1.8mL/g, pore-size distribution is bimodal distribution, and the described bimodal aperture that corresponds to respectively is 5-8nm
The first most probable pore size and aperture be 32-38nm the second most probable pore size.
5th aspect, the present invention provides a kind of preparation method of support type polyethylene catalysts, the method bag
Include：In the presence of an inert gas, by the spherical complex carrier in super big hole three-dimensional cubic duct containing magnesium unit
Impregnated in the catalyst mother solution of element and/or titanium elements, then filtered successively and be dried；Described load
The average particulate diameter of body is 20-60 μm, and specific surface area is 200-600m2/ g, pore volume is
0.1-2mL/g, pore-size distribution is bimodal distribution, and described bimodal correspond to that aperture is 3-10nm respectively the
One most probable pore size and aperture are second most probable pore size of 30-39nm；Preferably
The average particulate diameter of described carrier is 30-60 μm, and specific surface area is 250-500m2/ g, hole body
Amass as 0.5-1.8mL/g, pore-size distribution is bimodal distribution, and the described bimodal aperture that corresponds to respectively is 5-8nm
The first most probable pore size and aperture be 32-38nm the second most probable pore size；More preferably
The condition of described dipping includes：Temperature is 45-100 DEG C, and the time is 2-8h.
6th aspect, the present invention provides the support type polyethylene being prepared by the said method of the present invention to urge
Agent.
7th aspect, the present invention provides described support type polyethylene catalysts in catalyzed ethylene polymerization reaction
Application.
The spherical complex carrier meso-hole structure in the described super big hole three-dimensional cubic duct that the present invention provides is stable,
It is maintained to orderly meso-hole structure after load active component, and in load polyethylene catalysts
There is when reacting with catalyzed ethylene polymerization high catalysis activity.And, the support type polyethylene of the present invention is urged
The load factor of agent is high.
It was found by the inventors of the present invention that inclusion has the catalyst of spherical complex carrier of above-mentioned pore structure
Catalysis activity is higher, catalyzed ethylene polymerization can react and obtain higher activity.Speculate its reason, can
Can be due to：On the one hand, as a rule although the bigger serface of three-dimensional cubic duct material and high hole
Appearance can make it have higher catalysis activity, but also can make it have stronger water suction, moisture absorption energy simultaneously
Power, therefore, when three-dimensional cubic duct material is bar-shaped, will aggravate agglomeration traits, to storing, transport,
Process afterwards and application is made troubles.And the carrier in the super big hole three-dimensional cubic duct that the present invention provides is ball
Shape, can reduce the agglomeration traits of powder body, improve its mobility.On the other hand, described carrier is not only protected
Stay high-specific surface area, the feature of big pore volume of ordered mesoporous material, also add that aperture is big and narrowly distributing
Advantage, and its pore-size distribution present uniqueness bimodal distribution, the more conducively load of active component.That is,
The spherical complex carrier in the super big hole three-dimensional cubic duct that the present invention provides is dexterously by micro-sphere structure and hole
Footpath has the advantages that the ordered mesoporous material of bimodal distribution combines, thus being described super big hole three-dimensional cubic
The application of the spherical complex carrier in duct provides more preferable platform, and has expanded its application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
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 that the X-ray of the spherical complex carrier in the super big hole three-dimensional cubic duct according to the present invention is spread out
Penetrate collection of illustrative plates.
Fig. 2 is that the X-ray of the spherical complex carrier in the super big hole three-dimensional cubic duct according to the present invention is spread out
Penetrate collection of illustrative plates.
Fig. 3 is the SEM scanning electron microscope of the microscopic appearance of the support type polyethylene catalysts according to the present invention
Figure.
Fig. 4 is the particle diameter distribution of the spherical complex carrier in the super big hole three-dimensional cubic duct according to the present invention
Figure.
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.
On the one hand, the invention provides a kind of spherical complex carrier in super big hole three-dimensional cubic duct, it is special
Levy and be, the average particulate diameter of this carrier is 20-60 μm, specific surface area is 200-600m2/ g, hole
Volume is 0.1-2mL/g, and pore-size distribution is bimodal distribution, and the described bimodal aperture that corresponds to respectively is 3-10nm
The first most probable pore size and aperture be 30-39nm the second most probable pore size.
Under preferable case, in the present invention, the average particulate diameter of described carrier is 30-60 μm, compares table
Area is 250-500m2/ g, pore volume is 0.5-1.8mL/g, and pore-size distribution is bimodal distribution, and described
May be used in bimodal the first most probable pore size that aperture is 5-8nm and the aperture for 32-38nm second that correspond to respectively
Several apertures.
The spherical complex carrier in the described super big hole three-dimensional cubic duct that the present invention provides has substantially more existing
Have the spheroid pattern of the bigger Based on Dual-Aperture distribution of technology and pore volume and good flowing properties, advantageously in
The carrying out of catalytic reaction, the spherical complex carrier in this super big hole three-dimensional cubic duct is formed polyethylene catalysis
During agent, the polyethylene catalysts of acquisition have the catalysis activity apparently higher than 955 silica gel.
Second aspect, the invention provides a kind of system of the spherical complex carrier in super big hole three-dimensional cubic duct
Preparation Method is it is characterised in that the method comprises the following steps：
Preparation silica filter cake：Template and silicon source are carried out hybrid reaction in acidic aqueous solution, so
Afterwards the material obtaining after hybrid reaction is filtered successively and washed；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are carried out haptoreaction, so
After adjusting reaction afterwards, the pH value of resulting solution is 2-4；
Prepare carrier：Carry out after the described silica filter cake preparing and the mixing of described silica gel successively
Ball milling, spray drying and calcining,
Wherein, the method makes the average particulate diameter of the carrier preparing be 20-60 μm, specific surface
Amass as 200-600m2/ g, pore volume is 0.1-2mL/g, and pore-size distribution is bimodal distribution, and described bimodal
Corresponding to the first most probable pore size that aperture is 3-10nm and aperture respectively is second most probable of 30-39nm
Aperture.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct of the present invention, system
The standby carrier obtaining has substantially bigger compared with prior art Based on Dual-Aperture distribution and pore volume and mobility
The good spheroid pattern of energy, advantageously in the carrying out of catalytic reaction, by this super big hole three-dimensional cubic duct
When spherical complex carrier forms polyethylene catalysts, the polyethylene catalysts of acquisition have higher than 955 silica gel
Activity.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention, excellent
Select the method so that the average particulate diameter of the carrier obtaining is 30-60 μm, specific surface area is
250-500m2/ g, pore volume is 0.5-1.8mL/g, and pore-size distribution is bimodal distribution, and described bimodal point
Dui Ying not the second most probable hole for 32-38nm for the first most probable pore size and aperture for 5-8nm for the aperture
Footpath.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the step of described preparation silica filter cake, the condition of preferably described hybrid reaction includes：Temperature is
10-60 DEG C, the time is 10-72h, and pH value is 1-6.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the step of described preparation silica filter cake, the consumption mol ratio of preferably described template and silicon source is 1：
10-90.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the step of described preparation silica filter cake, preferably described template is triblock copolymer polyoxyethylene
- polyoxypropylene polyoxyethylene；Described acidic aqueous solution is selected from hydrochloric acid, sulphuric acid, nitric acid and hydrobromic acid
At least one aqueous solution.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the described step preparing silica gel, the consumption weight of preferably described waterglass and n-butyl alcohol is than for 1.2-10：
1.In the present invention, the consumption weight of described waterglass and n-butyl alcohol than in waterglass be containing water-soluble
The weight ratio of the form of liquid and n-butyl alcohol is that is to say, that wherein comprise the weight of water.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the described step preparing silica gel, preferably described catalytic condition includes：Temperature is 10-60 DEG C,
Time is 1-5h, and pH value is 2-4.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the described step preparing carrier, the consumption weight ratio of preferably described silica filter cake and described silica gel is
1：1-3.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the described step preparing carrier, the condition of preferably described ball milling includes：The rotating speed of abrading-ball is
300-500r/min, the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100h.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the described step preparing carrier, the condition of preferably described spray drying includes：Temperature is 100-300 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 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the described step preparing carrier, the condition of preferably described calcining includes：Temperature is 300-600 DEG C, when
Between be 10-80h.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct of the present invention, excellent
In the case of choosing, in the step of described preparation silica filter cake, add ethanol in reaction system to have
Help the dissolving of template, those skilled in the art can determine ethanol according to the conventional amount used of this area
Usage amount.
In the present invention, described template triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene
(P123) can be commercially available (for example, it is possible to be purchased from Aldrich, trade name P123,
Molecular formula is EO20PO70EO20) it is also possible to be prepared by existing various methods.Described template
The molal quantity of agent calculates according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene and obtains.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the step of described preparation silica filter cake, the material preferably just obtaining after hybrid reaction first carries out crystalline substance
Change, then filtered successively and wash.There is no particular limitation for the condition to described crystallization for the present invention,
The condition of described crystallization can be the conventional selection in this area, and for example, the condition of described crystallization can include：
Temperature is 30-150 DEG C, and the time is 10-72 hour.Under preferable case, the condition of described crystallization includes：
Temperature is 40-100 DEG C, and the time is 20-40 hour.Described crystallization is implemented by hydrothermal crystallization method.
The preparation method of the spherical complex carrier according to super big hole three-dimensional cubic duct of the present invention,
In the step of described preparation silica filter cake, preferably the silica gel obtaining is prepared into cake form, passes through
Filter and can be included with obtaining the process of filter cake：After filtration, deionized water cyclic washing (washing
Number of times can be 2-10 time), then carry out sucking filtration.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct of the present invention,
In the described 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 %.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct of the present invention,
In the described step preparing silica gel, preferably described inorganic acid solution is selected from hydrochloric acid, sulphuric acid, nitric acid and hydrogen bromine
At least one aqueous solution in acid.In the case of more preferably, the concentration of described inorganic acid solution is 1-35
Weight %.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct of the present invention,
In the described step preparing silica gel, those skilled in the art can adopt conventional use of various in the art
The pH value that reagent adjusts resulting solution after reacting is 2-4, under preferable case, in the present invention, uses
The pH value that concentrated sulphuric acid adjusts resulting solution after reacting is 2-4.
In the preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct of the present invention,
In the described step preparing silica gel, preferably also include carrying out adjusting the reaction mass that pH value is after 2-4
Washing, more preferably in the case of, by described reaction mass be washed till sodium ions content be 0.03 weight % below.
In the present invention, described ball milling can be carried out in ball mill, and in described ball mill, ball grinder is interior
Wall is preferably polytetrafluoroethyllining lining, and the diameter of the abrading-ball in ball mill can be 2-3mm；The number of abrading-ball
Amount reasonably can be selected according to the size of ball grinder, for the ball grinder for 50-150mL for the size,
1 abrading-ball generally can be used；The material of described abrading-ball can be Achatess, politef etc., preferably
For Achatess.The condition of described ball milling can include：The rotating speed of abrading-ball can be 300-500r/min, ball milling
Temperature in tank can be 15-100 DEG C, and the time of ball milling can be 0.1-100h.
The present invention is preferably calcined in Muffle furnace.
The third aspect, the invention provides the super big hole three-dimensional cubic pore being prepared by above-mentioned preparation method
The spherical complex carrier in road.
Fourth aspect, the invention provides a kind of support type polyethylene catalysts, contains super in this catalyst
The spherical complex carrier in macropore three-dimensional cubic duct and the outer surface, inner hole wall and the ball that are supported on described carrier
Magnesium elements at least one in inside and/or titanium elements；The average particulate diameter of described carrier is
20-60 μm, specific surface area is 200-600m2/ g, pore volume is 0.1-2mL/g, and pore-size distribution is bimodal
Distribution, and described bimodal correspond to that aperture is first most probable pore size of 3-10nm and aperture is respectively
Second most probable pore size of 30-39nm.
Under preferable case, in support type polyethylene catalysts of the present invention, described carrier average
Particle diameter is 30-60 μm, and specific surface area is 250-500m2/ g, pore volume is 0.5-1.8mL/g, hole
Footpath is distributed as bimodal distribution, and described bimodal correspond to respectively the first most probable pore size that aperture is 5-8nm and
Aperture is second most probable pore size of 32-38nm.
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 support type polyethylene catalysts of the present invention, with described support type polyethylene catalysts
On the basis of gross weight, the content of the spherical complex carrier in preferably described super big hole three-dimensional cubic duct is
The content sum that 50-99 weight %, described magnesium elements and titanium elements are counted with oxide is for 1-50 weight %.
5th aspect, the invention provides a kind of preparation method of support type polyethylene catalysts, the method
Including：In the presence of an inert gas, the spherical complex carrier in super big hole three-dimensional cubic duct 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 20-60 μm, and specific surface area is 200-600m2/ g, pore volume is
0.1-2mL/g, pore-size distribution is bimodal distribution, and described bimodal correspond to that aperture is 3-10nm respectively the
One most probable pore size and aperture are second most probable pore size of 30-39nm.
Under preferable case, in the preparation method of support type polyethylene catalysts of the present invention, described
The average particulate diameter of carrier is 30-60 μm, and specific surface area is 250-500m2/ g, pore volume is
0.5-1.8mL/g, pore-size distribution is bimodal distribution, and described bimodal correspond to that aperture is 5-8nm respectively the
One most probable pore size and aperture are second most probable pore size of 32-38nm.
In the preparation method of support type polyethylene catalysts of the present invention, the bar of preferably described dipping
Part includes：Temperature is 45-100 DEG C, and the time is 2-8h.
In the preparation method of support type polyethylene catalysts of the present invention, to described magnesium elements and titanium
, all as the present invention is noted earlier, this is no longer going to repeat them for the present invention for the definition of element, form and source.
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.
According to the preparation method of support type polyethylene catalysts of the present invention, preferably described being immersed in is answered
Carry out in bonding solvent, described compounded organic solvent can for can dissolve described magnesium elements and titanium elements and
Readily removed various solvents are it is preferable that described compounded organic solvent is oxolane and isopropanol.More
Plus preferably, the volume ratio of oxolane and isopropanol is 1：1-3, particularly preferably 1：1-1.5.
According to the preparation method of support type polyethylene catalysts of the present invention, particularly preferably prepare described
The step of the spherical complex carrier in super big hole three-dimensional cubic duct includes：
Preparation silica filter cake：Template and silicon source are carried out hybrid reaction in acidic aqueous solution, so
Afterwards the material obtaining after hybrid reaction is filtered successively and washed；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are carried out haptoreaction, so
After adjusting reaction afterwards, the pH value of resulting solution is 2-4；
Prepare carrier：Carry out after the described silica filter cake preparing and the mixing of described silica gel successively
Ball milling, spray drying and calcining.
In the present invention, it should be strongly noted that preparation side in described support type polyethylene catalysts
In method, prepare the related definition in the step of spherical complex carrier in super big hole three-dimensional cubic duct and restriction
All identical with the preparation method of the spherical complex carrier in the present invention aforesaid super big hole three-dimensional cubic duct, this
Invention, in order to avoid repeating, will not be described here.
6th aspect, the invention provides the support type polyethylene catalysts being prepared by said method.
The above-mentioned support type polyethylene catalysts that the present invention provides have more with respect to the product of prior art
Good acid catalytic property and good mobile performance.
7th aspect, the invention provides described support type polyethylene catalysts react in catalyzed ethylene polymerization
In application.
To described support type polyethylene catalysts, the application in catalyzed ethylene polymerization reaction does not have the present invention
Special restriction, the spherical complex carrier using super big hole three-dimensional cubic duct of the present invention is prepared into
During the catalyst ethylene polymerization arriving, it is obtained in that substantially than 955 silica gel using prior art
Higher catalytic efficiency during the catalyst ethylene polymerization preparing.
The catalyst of the spherical complex carrier containing super big hole three-dimensional cubic duct of the present invention is used
When the homopolymerization of vinyl polymerization, catalytic efficiency be substantially better than equivalent responses under the conditions of industry 955 silicon
The catalytic efficiency of glue.And, the particle diameter of described support type polyethylene catalysts is larger, and carrier has height
Orderly large aperture, the average pore size of silicon gel part is big, and pore wall strength is moderate, and catalyst decay is slower,
Polymerization process steadily continues, and catalysis activity is high.Therefore, super big hole three-dimensional cubic duct of the present invention
Spherical complex carrier be 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, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich
Company, is abbreviated as P123, and molecular formula is EO20PO70EO20, in the registration number of U.S. chemical abstract
Material for 9003-11-6, mean molecule quantity is 5800.
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 be used for illustrate super big hole three-dimensional cubic duct of the present invention spherical complex carrier,
Support type polyethylene catalysts and their preparation method.
(1) prepare carrier
6g triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123 is dissolved in 10mL dense
In hydrochloric acid and 220mL deionized water solution, at 15 DEG C, form clear solution after stirring 4h, then to this
Add 6g ethanol in clear solution and stir 1h, then this solution is placed in 30 DEG C of environment, and to it
Middle addition 12.9g tetraethyl orthosilicate, keep the temperature at 30 DEG C, pH value be 3 under conditions of stir 24h,
After transfer the solution in teflon-lined reactor, after 100 DEG C of baking oven crystallization 24h through filter,
Washing obtains silica 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 silica 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 500 DEG C in stove, obtain destination carrier.
(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 support type polyethylene catalysts of good flow performance.
Divided with XRD, scanning electron microscope, U.S. Kang Ta company Atsorb-1 type nitrogen adsorption instrument, granularity
Analyzer and x-ray fluorescence analysis characterize to this support type polyethylene catalysts.
Fig. 1 is that the X-ray of the spherical complex carrier in the super big hole three-dimensional cubic duct according to the present invention is spread out
Penetrate collection of illustrative plates (XRD spectra).
Fig. 2 is that the X-ray of the spherical complex carrier in the super big hole three-dimensional cubic duct according to the present invention is spread out
Penetrate collection of illustrative plates.As seen from the figure, the microscopic appearance of the spherical complex carrier in super big hole three-dimensional cubic duct is diameter
Mesoporous Spheres for 30-60 μm.
Fig. 3 is the SEM scanning electron microscope of the microscopic appearance of the support type polyethylene catalysts according to the present invention
Figure.As seen from the figure, the spherical complex carrier in super big hole three-dimensional cubic duct microcosmic after load active component
Pattern is still basic to keep spherical, and particle diameter is 30-60 μm.
Fig. 4 is the particle diameter distribution of the spherical complex carrier in the super big hole three-dimensional cubic duct according to the present invention
Figure, unit be μm.As seen from the figure, the mean diameter of complex carrier is 50 μm, and particle diameter divides
Cloth 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
It is diplopore by the spherical complex carrier that the data of upper table 1 can be seen that super big hole three-dimensional cubic duct
Distribution.
Drawn by xrf analysis, in the described support type polyethylene catalysts of the present embodiment, with described
The gross weight meter of support type polyethylene catalysts, the content of the magnesium elements counted with oxide is 8 weight %,
The content of the titanium elements counted with oxide is 0.7 weight %, and the content of chlorine is 1.7 weight % and remainder
It is divided into 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 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 be used for illustrate super big hole three-dimensional cubic duct of the present invention spherical complex carrier,
Support type polyethylene catalysts and their preparation method.
(1) prepare carrier
6g triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123 is dissolved in 10mL dense
In hydrochloric acid and 220mL deionized water solution, at 20 DEG C, form clear solution after stirring 6h, then to this
Add 5.6g ethanol in clear solution and stir 1h, then this solution is placed in 35 DEG C of environment, and to
Wherein add 12.9g tetraethyl orthosilicate, keep the temperature at 35 DEG C, pH value be 4 under conditions of stir
24h, after transfer the solution in teflon-lined reactor, warp after 90 DEG C of baking oven crystallization 24h
Filter, washing obtains silica 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 silica 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 destination carrier.
(2) support type polyethylene catalysts are prepared
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 support type polyethylene catalysts of good flow performance.
Table 2 is the pore structure parameter of the spherical complex carrier in super big hole three-dimensional cubic duct of the present embodiment.
Table 2
It is diplopore by the spherical complex carrier that the data of upper table 2 can be seen that super big hole three-dimensional cubic duct
Distribution.
Drawn by xrf analysis, in the described support type polyethylene catalysts of the present embodiment, with described
The gross weight meter of support type polyethylene catalysts, the content of the magnesium elements counted with oxide is 8.2 weight %,
The content of the titanium elements counted with oxide is 0.8 weight %, and the content of chlorine is 1.8 weight % and remainder
It is divided into carrier.
Embodiment 3
The present embodiment be used for illustrate super big hole three-dimensional cubic duct of the present invention spherical complex carrier,
Support type polyethylene catalysts and their preparation method.
(1) prepare carrier
6g triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123 is dissolved in 10mL dense
In hydrochloric acid and 220mL deionized water solution, at 18 DEG C, form clear solution after stirring 4.5h, then to
Add 6.5g ethanol in this clear solution and stir 1h, then this solution is placed in 40 DEG C of environment, and
Be added thereto to 12.9g tetraethyl orthosilicate, keep the temperature at 40 DEG C, pH value be 4 under conditions of stir
Mix 24h, after transfer the solution in teflon-lined reactor, after 80 DEG C of baking oven crystallization 24h
Obtain silica filter cake through filtering, washing.
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 silica 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 destination carrier.
(2) support type polyethylene catalysts are prepared
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 support type polyethylene catalysts of good flow performance.
Table 3 is the pore structure parameter of the spherical complex carrier in super big hole three-dimensional cubic duct of the present embodiment.
Table 3
It is diplopore by the spherical complex carrier that the data of upper table 3 can be seen that super big hole three-dimensional cubic duct
Distribution.
Drawn by xrf analysis, in the described support type polyethylene catalysts of the present embodiment, with described
The gross weight meter of support type polyethylene catalysts, the content of the magnesium elements counted with oxide is 8.3 weight %,
The content of the titanium elements counted with oxide is 0.8 weight %, and the content of chlorine is 1.7 weight % and remainder
It is divided into 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 2.6 weight %, the content of the titanium elements counted with oxide is 0.4 to the content of the magnesium elements counted with oxide
Weight %, the content of chlorine is 4.6 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 2.3 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 4.1 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 2.2 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 4.8 weight % and remainder is carrier.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating support type polyethylene catalysts according to the present invention in vinyl polymerization
Application in reaction.
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 70 DEG C.Obtain polyethylene particle powder, this poly- second
The heap density (BD) of alkene granule powder is 0.40g/mL, melt index MI2.16=0.70g/10min.
It is computed determining, the efficiency of catalyst is 2700g PE/gcat.h.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating support type polyethylene catalysts according to the present invention in vinyl polymerization
Application in reaction.
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=0.73g/10min.
It is computed determining, the efficiency of catalyst is 2746g PE/gcat.h.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for illustrating support type polyethylene catalysts according to the present invention in vinyl polymerization
Application in reaction.
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 90 DEG C.Obtain polyethylene particle powder,
The heap density (BD) of this polyethylene particle powder is 0.41g/mL, melt index MI2.16=
0.71g/10min.It is computed determining, the efficiency of catalyst is 2798g 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 replaces the support type polyethylene catalysts that embodiment 1 prepares.
The heap density (BD) of gained polyethylene particle powder is 0.41g/mL, melt index：MI2.16=
0.89g/10min.It is computed determining, the efficiency of catalyst is 1636g 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 replaces the support type polyethylene catalysts that embodiment 2 prepares.
The heap density (BD) of gained polyethylene particle powder is 0.40g/mL, melt index：MI2.16=
1.02g/10min.It is computed determining, the efficiency of catalyst is 1936g 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 replaces the support type polyethylene catalysts that embodiment 3 prepares.
The heap density (BD) of gained polyethylene particle powder is 0.41g/mL, melt index：MI2.16=
1.21g/10min.It is computed determining, the efficiency of catalyst is 1921g 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 replaces the support type polyethylene catalysts that embodiment 3 prepares.
The heap density (BD) of gained polyethylene particle powder is 0.42g/mL, melt index：MI2.16=
1.00g/10min.It is computed determining, the efficiency of catalyst is 1896g 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.And, the load of the present invention
The load factor of type polyethylene catalysts is high.
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 spherical complex carrier in super big hole three-dimensional cubic duct is it is characterised in that this carrier
Average particulate diameter is 20-60 μm, and specific surface area is 200-600m2/ g, pore volume is 0.1-2mL/g,
Pore-size distribution is bimodal distribution, and described bimodal corresponding respectively aperture is the first most probable hole of 3-10nm
Footpath and aperture are second most probable pore size of 30-39nm.
2. carrier according to claim 1, wherein, the average particulate diameter of described carrier is
30-60 μm, specific surface area is 250-500m2/ g, pore volume is 0.5-1.8mL/g, and pore-size distribution is double
Peak is distributed, and described bimodal corresponds to that aperture is first most probable pore size of 5-8nm and aperture is respectively
Second most probable pore size of 32-38nm.
3. a kind of preparation method of the spherical complex carrier in super big hole three-dimensional cubic duct it is characterised in that
The method comprises the following steps：
Preparation silica filter cake：Template and silicon source are carried out hybrid reaction in acidic aqueous solution, so
Afterwards the material obtaining after hybrid reaction is filtered successively and washed；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are carried out haptoreaction, so
After adjusting reaction afterwards, the pH value of resulting solution is 2-4；
Prepare carrier：Carry out after the described silica filter cake preparing and the mixing of described silica gel successively
Ball milling, spray drying and calcining,
Wherein, the method makes the average particulate diameter of the carrier preparing be 20-60 μm, specific surface
Amass as 200-600m2/ g, pore volume is 0.1-2mL/g, and pore-size distribution is bimodal distribution, and described bimodal
Corresponding to the first most probable pore size that aperture is 3-10nm and aperture respectively is second most probable of 30-39nm
Aperture；Preferably
The method makes the average particulate diameter of the carrier preparing be 30-60 μm, and specific surface area is
250-500m2/ g, pore volume is 0.5-1.8mL/g, and pore-size distribution is bimodal distribution, and described bimodal point
Dui Ying not the second most probable hole for 32-38nm for the first most probable pore size and aperture for 5-8nm for the aperture
Footpath.
4. method according to claim 3, wherein, in the step of described preparation silica filter cake
In rapid, the condition of described hybrid reaction includes：Temperature is 10-60 DEG C, and the time is 10-72h, and pH value is
1-6；Preferably
The consumption mol ratio of described template and silicon source is 1：10-90；More preferably
Described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；Described acid water
Solution is selected from least one aqueous solution in hydrochloric acid, sulphuric acid, nitric acid and hydrobromic acid.
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 1.2-10：1；Preferably
Described catalytic condition includes：Temperature is 10-60 DEG C, and the time is 1-5h, and pH value is 2-4.
6. method according to claim 3, wherein, in the described step preparing carrier, institute
State the consumption weight of silica filter cake and described silica gel than for 1：1-3.
7. the method according to claim 3 or 6, wherein, in the described step preparing carrier,
The condition of described ball milling includes：The rotating 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；Preferably
The condition of described spray drying includes：Temperature is 100-300 DEG C, and the rotating speed of rotation is
10000-15000r/min；More preferably
The condition of described calcining includes：Temperature is 300-600 DEG C, and the time is 10-80h.
8. the super big hole three-dimensional cubic pore that in claim 3-7, the method described in any one prepares
The spherical complex carrier in road.
9. a kind of support type polyethylene catalysts are it is characterised in that contain super big hole three in this catalyst
Tie up the spherical complex carrier in cube duct and be supported in outer surface, inner hole wall and the ball inside of described carrier
Magnesium elements at least one and/or titanium elements；The average particulate diameter of described carrier is 20-60 μm, compares table
Area is 200-600m2/ g, pore volume is 0.1-2mL/g, and pore-size distribution is bimodal distribution, and described double
Peak corresponds to the first most probable pore size that aperture is 3-10nm and aperture for 30-39nm second respectively and may be used
Several apertures；Preferably
The average particulate diameter of described carrier is 30-60 μm, and specific surface area is 250-500m2/ g, hole body
Amass as 0.5-1.8mL/g, pore-size distribution is bimodal distribution, and the described bimodal aperture that corresponds to respectively is 5-8nm
The first most probable pore size and aperture be 32-38nm the second most probable pore size.
10. a kind of preparation method of support type polyethylene catalysts is it is characterised in that the method includes：
In the presence of an inert gas, by the spherical complex carrier in super big hole three-dimensional cubic duct containing magnesium elements and
/ or the catalyst mother solution of titanium elements in impregnated, then filtered successively and be dried；Described carrier
Average particulate diameter is 20-60 μm, and specific surface area is 200-600m2/ g, pore volume is 0.1-2mL/g,
Pore-size distribution is bimodal distribution, and described bimodal corresponding respectively aperture is the first most probable hole of 3-10nm
Footpath and aperture are second most probable pore size of 30-39nm；Preferably
The average particulate diameter of described carrier is 30-60 μm, and specific surface area is 250-500m2/ g, hole body
Amass as 0.5-1.8mL/g, pore-size distribution is bimodal distribution, and the described bimodal aperture that corresponds to respectively is 5-8nm
The first most probable pore size and aperture be 32-38nm the second most probable pore size；More preferably
The condition of described dipping includes：Temperature is 45-100 DEG C, and the time is 2-8h.
11. methods according to claim 10, wherein, prepare described super big hole three-dimensional cubic pore
The step of the spherical complex carrier in road includes：
Preparation silica filter cake：Template and silicon source are carried out hybrid reaction in acidic aqueous solution, so
Afterwards the material obtaining after hybrid reaction is filtered successively and washed；
Prepare silica gel：In the presence of inorganic acid solution, waterglass and n-butyl alcohol are carried out haptoreaction, so
After adjusting reaction afterwards, the pH value of resulting solution is 2-4；
Prepare carrier：Carry out after the described silica filter cake preparing and the mixing of described silica gel successively
Ball milling, spray drying and calcining.
The support type polyethylene catalysts that method described in 12. claim 10 or 11 prepares.
Support type polyethylene catalysts described in 13. claim 9 or 12 react in catalyzed ethylene polymerization
In application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510504824.7A CN106467580B (en) | 2015-08-17 | 2015-08-17 | The spherical complex carrier and support type polyethylene catalysts in super big hole three-dimensional cubic duct and their preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510504824.7A CN106467580B (en) | 2015-08-17 | 2015-08-17 | The spherical complex carrier and support type polyethylene catalysts in super big hole three-dimensional cubic duct and their preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106467580A true CN106467580A (en) | 2017-03-01 |
| CN106467580B CN106467580B (en) | 2019-04-19 |
Family
ID=58213954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510504824.7A Active CN106467580B (en) | 2015-08-17 | 2015-08-17 | The spherical complex carrier and support type polyethylene catalysts in super big hole three-dimensional cubic duct and their preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106467580B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727519A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | Three-dimensional cubic mesoporous composite material and loaded catalyst and preparation method thereof |
| CN108722382A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | Spherical mesoporous composite material and loaded catalyst and preparation method thereof |
| CN108855197A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
-
2015
- 2015-08-17 CN CN201510504824.7A patent/CN106467580B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727519A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | Three-dimensional cubic mesoporous composite material and loaded catalyst and preparation method thereof |
| CN108722382A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | Spherical mesoporous composite material and loaded catalyst and preparation method thereof |
| CN108855197A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106467580B (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105330767B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN105330768B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN105175586B (en) | A kind of preparation method of mesoporous composite material and preparation method thereof and catalytic component and polyethylene | |
| CN106467579B (en) | Macropore two dimension double hole channel spherical complex carrier and composite material and their preparation method and application containing polyethylene catalysts | |
| CN106467582B (en) | The spherical complex carrier of macropore two dimension straight channels and composite material containing polyethylene catalysts with and its preparation method and application | |
| CN106467581A (en) | Three hole silica-gel carriers and support type polyethylene catalysts and its preparation method and application | |
| CN105330769B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN105440168B (en) | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application | |
| CN106554431B (en) | The method of bimodal porous silica carrier and support type polyethylene catalysts and its preparation method and application and vinyl polymerization | |
| CN107088409B (en) | A kind of three-dimensional meso-hole aluminosilicate catalyst and preparation method thereof that noble metal supports | |
| CN104248979A (en) | Spherical mesoporous silica composite carrier and catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method | |
| CN106632760A (en) | Spherical aluminum-containing mesoporous composite material and supported catalyst and preparation method and application thereof and ethylene polymerization method | |
| CN104248989A (en) | Spherical mesoporous sepiolite composite carrier, catalyst and preparation method and application thereof and preparation method of ethyl acetate | |
| CN106467580A (en) | The spherical complex carrier in super big hole three-dimensional cubic duct and support type polyethylene catalysts and their preparation method and application | |
| CN108794666A (en) | The method and polyethylene of vinyl polymerization | |
| CN108017740A (en) | Spherical porous mesoporous composite material and loaded catalyst and preparation method thereof | |
| CN107417820B (en) | Spherical diatomite mesoporous composite material, supported catalyst and preparation method thereof | |
| CN107417828A (en) | Spherical composite and support type polyethylene catalysts and their preparation method | |
| CN108003261A (en) | The method and polyethylene of a kind of vinyl polymerization | |
| CN107840912A (en) | The method and polyethylene of a kind of vinyl polymerization | |
| CN107417821A (en) | Spherical composite and support type polyethylene catalysts and their preparation method | |
| CN107417831B (en) | Method for polymerizing ethylene and polyethylene | |
| CN107417812A (en) | Spherical double meso-hole structure composites and support type polyethylene catalysts and their preparation method | |
| CN108017731A (en) | Spherical mesoporous composite material and loaded catalyst and preparation method thereof | |
| CN108623720A (en) | Spherical mesoporous composite material and loaded catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |