CN108929393A - Spherical double mesoporous attapulgite complex carriers and its preparation method and application - Google Patents
Spherical double mesoporous attapulgite complex carriers and its preparation method and application Download PDFInfo
- Publication number
- CN108929393A CN108929393A CN201710389562.3A CN201710389562A CN108929393A CN 108929393 A CN108929393 A CN 108929393A CN 201710389562 A CN201710389562 A CN 201710389562A CN 108929393 A CN108929393 A CN 108929393A
- Authority
- CN
- China
- Prior art keywords
- weight
- attapulgite
- mesoporous
- parts
- double mesoporous
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/025—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Polymerization Catalysts (AREA)
Abstract
The present invention relates to catalyst fields, disclose mesoporous attapulgite complex carriers of a kind of spherical shape pair and its preparation method and application.The method of the spherical double mesoporous attapulgite complex carriers of preparation includes the following steps：(1) in the presence of template, silicon source and ammonia spirit are contacted, obtain mesoporous material；(2) waterglass is contacted with inorganic acid solution, obtains silica gel；(3) mesoporous material, the silica gel are mixed with attapulgite, then mixed material is successively filtered to washing, ball milling, slurrying and spray drying, wherein, filtration washing in step (3) carries out in purpose ceramic-film filter, and content of the sodium ion in terms of sodium element is not higher than 1 weight % not higher than the content of 0.2 weight %, template in the mixed material after filtration washing.Purpose ceramic-film filter described in this method uses cross-flow filtration, and separation is efficiently simple, carries out calcining abjection template, energy conservation and environmental protection again without the later period.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of preparation of spherical double mesoporous attapulgite complex carriers
Method and the double mesoporous attapulgite complex carriers of spherical shape prepared by this method, a kind of spherical double mesoporous compound loads of attapulgite
Body is preparing the application in supported polyolefin catalyst.
Background technique
The development and application of polyethylene catalysts are the olefinic polymerization catalysis after traditional Ziegler-Natta catalyst
The another important breakthrough in agent field, this makes the research of polyethylene catalysts enter a stage grown rapidly.Due to
Catalyst amount needed for homogeneous polyethylene catalyst reaches high activity is big, high production cost, and obtained polymer is without grain
Shape can not use on widely used slurry process or gas phase polymerization technique, and overcoming the effective way of the above problem is exactly handle
Soluble poly catalyst for ethylene carries out supported processing.
However, the carrier that conventional support type polyethylene catalysts use is taken more in purification process and uses plate and frame pressure
The means that filter is filtered are to remove impurity, however plate and frame type filter-press occupied area is larger, meanwhile, and plate and frame filters pressing
Machine is discontinuous operation, and low efficiency, operation room environment is poor, generates secondary pollution, further, since the plate and frame type filter-press needs
Will use filter cloth, go deimpurity effect poor, and wash after waste liquid can not regeneration, in washing process extremely
Water source is wasted, simultaneously because discharge waste water can not be handled, and causes environmental pollution and secondary waste.Silicon is synthesized for further investigation
Glue, it is necessary to the method for attempting different vector purifications, to push the further development of carried catalyst and olefin polymetiation process.
Summary of the invention
The purpose of the invention is to overcome the existing method purification efficiency for preparing support type polyethylene catalysts carrier
It is low, effect is poor, cumbersome, water consumption is big, pollution environment, and then lead to the negative of existing support type polyethylene catalysts carrier
Load rate is low, and then causes the catalysis of the support type polyethylene catalysts prepared by existing support type polyethylene catalysts carrier living
Property it is poor the defects of, a kind of preparation method of spherical double mesoporous attapulgite complex carriers is provided and is prepared by this method spherical shape
Double mesoporous attapulgite complex carriers, a kind of mesoporous attapulgite complex carriers of spherical shape pair are preparing supported polyolefin catalyst
In application.
To achieve the goals above, the present inventor is multiple in spherical double mesoporous attapulgites by finding after research
In the preparation method for closing carrier, spherical double mesoporous attapulgite complex carriers are purified using purpose ceramic-film filter,
Purification efficiency is high, effect is good, can deviate from template without carrying out calcining, easy to operate, water consumption is small, environment is friendly, and
The high, catalytic activity by the load factor of the supported polyolefin catalyst of spherical double mesoporous attapulgite complex carrier preparations
It is good, so that anti-for olefinic polymerization using supported polyolefin catalyst made of the double mesoporous attapulgite complex carriers of the spherical shape
It can get the reaction raw materials conversion ratio significantly improved in answering, so as to complete the present invention.
One aspect of the present invention provides a kind of method for preparing spherical double mesoporous attapulgite complex carriers, this method include with
Lower step：
(1) in the presence of template, silicon source and ammonia spirit are contacted, obtain mesoporous material；
(2) waterglass is contacted with inorganic acid solution, obtains silica gel；
(3) mesoporous material, the silica gel are mixed with attapulgite, then mixed material is successively filtered and is washed
It washs, ball milling, slurrying and spray drying,
Wherein, the filtration washing in step (3) carries out in purpose ceramic-film filter, sodium in the mixed material after filtration washing
Content of the ion in terms of sodium element is not higher than 1 weight % not higher than the content of 0.2 weight %, template.
Second aspect of the present invention provides the double mesoporous compound loads of attapulgite of spherical shape of method preparation provided by the present invention
Body.
It is negative in preparation that third aspect present invention provides spherical double mesoporous attapulgite complex carriers provided by the present invention
Application in load type polyolefin catalyst.
In the method for the spherical double mesoporous attapulgite complex carriers of preparation provided by the invention, using purpose ceramic-film filter into
Row filtration washing, using cross-flow filtration, crossflow velocity with higher in filter process, it is possible to reduce pollutant is in film surface
Accumulation, membrane flux with higher, the mesoporous material and silica gel being prepared early period are directly with the state of mobile phase and concave convex rod
Stone mixing carries out washed filter, and separative efficiency is high, and separation process is simple, carries out calcining abjection template again without the later period, just
It can ensure that spherical double mesoporous attapulgite complex carriers obtained have more stable meso-hole structure and higher load factor, in turn
It ensures by the load-type alkene catalyst catalytic activity with higher of spherical double mesoporous attapulgite complex carrier preparations
And selectivity.
The slurry made present invention employs ball grinding technique and spray drying technology is finer and smoother, is being spray-dried
The spheroidal particle stable structure obtained afterwards, can recycle as catalyst carrier, and intensity height is non-breakable.Using doing by spraying
Dry technology, the partial size of obtained spherical porous mesoporous composite material is small, particle diameter distribution is uniform and grading curve is narrow, can keep away
The reunion for exempting from ordered mesoporous material in use improves its mobility, to ordered mesoporous material storage, transport, afterwards plus
Work and application are brought convenience.
The meso-hole structure of the double mesoporous attapulgite complex carriers of spherical shape made from method provided by the present invention is stablized, negative
Orderly meso-hole structure can still be maintained after carrying active component, significantly improve by the effect of its loaded catalyst being prepared
The property of rate and polyolefin products obtained, when which is used for polymerizing olefin monomers reaction, high catalytic efficiency,
And the polyolefin products for having both lower bulk density and melt index can be obtained, specifically, use the load-type alkene
Catalyst carries out in the reaction of olefinic polymerization, and for catalyst efficiency up to 2200g PE/gcat h, the accumulation of polyolefin obtained is close
Degree is 0.4g/mL hereinafter, melt index is 0.5g/10min or less.
In addition, the method preparation process of the spherical double mesoporous attapulgite complex carriers of preparation provided by the present invention is simple,
Energy saving, preparation cost is low, good economy performance.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the X-ray diffraction spectrogram of the double mesoporous attapulgite complex carriers of spherical shape of embodiment 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the double mesoporous attapulgite complex carriers of spherical shape of embodiment 1；
Fig. 3 is the pore size distribution curve of the double mesoporous attapulgite complex carriers of spherical shape of embodiment 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of methods for preparing spherical double mesoporous attapulgite complex carriers, and this method includes following step
Suddenly：
(1) in the presence of template, silicon source and ammonia spirit are contacted, obtain mesoporous material；
(2) waterglass is contacted with inorganic acid solution, obtains silica gel；
(3) mesoporous material, the silica gel are mixed with attapulgite, then mixed material is successively filtered and is washed
It washs, ball milling, slurrying and spray drying,
Wherein, the filtration washing in step (3) carries out in purpose ceramic-film filter, sodium in the mixed material after filtration washing
Content of the ion in terms of sodium element is not higher than 1 weight % not higher than the content of 0.2 weight %, template.
According to the present invention, the purpose ceramic-film filter is a set of accurate super mistake that can be widely applied to various fields
Cleaning equipment is filtered, core component is micropore ceramics membrane filter tube, it is that plurality of raw materials carry out section is waited until with kaolin, zirconium oxide
Formula is learned, a kind of mesh-structured microfiltration membranes of solid is formed through processes such as biscuiting, crushing, classification, molding, pore-creating, films, has
Excellent thermal stability and hole stability, not only intensity is high and resistant to chemical etching, is suitable for the secondary filter of various media,
Cleaning and regeneration performance is good, has both the two-fold advantage of high efficiency filter and secondary filter, can filter under 5-10m/s filtering velocity.
According to the present invention, the filtration washing in step (3) carries out in purpose ceramic-film filter, and the filtration washing is a kind of
The fluid separation process of " cross-flow filtration " form, specifically, which includes：By mesoporous material made from step (1), step
Suddenly silica gel made from (2) is directly mixed with attapulgite in liquid form, mixed raw material liquid flow at high speed in membrane tube, according to
Within the scope of certain membrane aperture, it is to drive with the pressure difference of film two sides that then permeability is different for the material molecule diameter difference of infiltration
Power, film are filter medium, under certain pressure driving effect, clarified permeation liquid (water, inorganic salts Na containing small molecule component+、
The small molecules such as template liquid) along direction normal thereto film is penetrated outward, the muddy concentrate containing macromolecular components (suspends
The macromolecular substances such as object, glue and microorganism) by the modes such as mechanical filter, absorption be blocked on film outer surface or inner surface with
The extension of filtration time, filtration resistance also increase on year-on-year basis, when pressure difference, which reaches, presets blowback pressure difference, in backwash mechanism
Motor drive and the starting of each respective valves, are run by program switch, and compressed air can be used in backwash or water is completed, and can also be used
Purified liquid or solvent are realized, fluid is finally made to achieve the purpose that separation, concentration, purifying.In the present invention, the mistake
Filter washing process carries out under 5-10m/s filtering velocity, and entire filtration washing process needs to be continuously replenished cleaning solution, the side of the washing
Formula can wash for washing and/or alcohol, such as can first be washed repeatedly with deionized water and backwash, then be carried out repeatedly with ethyl alcohol
Washing and backwash improve membrane flux, respective washing times and number of backwashes to reduce pollutant in the viscous glutinous accumulation of film surface
It can be selected according to actual experiment effect, until sodium ion is in the mixed material in membrane tube after filtration washing with sodium element
The content of meter be not higher than 0.2 weight %, preferably 0.01-0.03 weight %, template content be not higher than 1 weight %, finally
Collect the mixed material in membrane tube, with to subsequent processing, in this way, the double mesoporous attapulgite complex carriers of the spherical shape being prepared without
Subsequent calcination processing need to be carried out to deviate from template, easy to operate, energy saving.And it was carried out using purpose ceramic-film filter
When filter washing, it is not necessarily to artificial on-line operation, it is time saving and energy saving.
According to the present invention, in step (3), the object of the ball milling be by purpose ceramic-film filter filtration washing to sodium from
Content of the son in terms of sodium element be not higher than 0.2 weight %, preferably 0.01-0.03 weight %, template content be not higher than 1 weight
The mixed material in the ceramic filtering membrane tube of % is measured, the concrete operation method and condition of the ball milling are not particularly limited, with not
It destroys or does not destroy the structure of mesoporous material substantially and enter silica gel and attapulgite subject to mesoporous material duct.This field skill
Art personnel can select various suitable conditions to implement the present invention according to mentioned above principle.Specifically, the ball milling can be in ball
It is carried out in grinding machine, wherein the diameter of abrading-ball can be 2-3mm in ball mill；The quantity of abrading-ball can be according to the size of ball grinder
It is reasonably selected, 1 abrading-ball usually can be used in the ball grinder for being 50-150mL for size；The material of the abrading-ball
It can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling includes：The revolving speed of abrading-ball can be 300-
500r/min, the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hours.
According to the present invention, in step (3), the concrete operation method and condition of the spray drying are the routine of this field
Selection.Specifically, by by after the ball milling product and the slurry that is made into of water be added in atomizer high speed rotation to realize spray
Mist is dry.Wherein, the condition of the spray drying includes：Temperature can be 100-300 DEG C, and the revolving speed of rotation can be 10000-
15000r/min；Under preferable case, the condition of the spray drying includes：Temperature is 150-250 DEG C, and the revolving speed of rotation is
11000-13000r/min；Under most preferred case, the condition of the spray drying includes：Temperature is 200 DEG C, and the revolving speed of rotation is
12000r/min。
According to the present invention, in step (1), the condition that the silicon source is contacted with ammonium hydroxide is not particularly limited, for example, institute
State silicon source and ammonia spirit contact condition may include：Temperature is 25-100 DEG C, and the time is 10-72 hours；Under preferable case,
The silicon source and the condition of ammonia spirit contact may include：Temperature is 30-150 DEG C, and the time is 10-72 hours.
According to the present invention, in step (1), during preparing mesoporous material, the dosage of each substance can be wider
It is selected and is adjusted in range.For example, the dosage molar ratio of ammonia and water in the silicon source, template, ammonium hydroxide is 1：0.1-
1：0.1-5：100-200, preferably 1：0.2-0.5：1.5-3.5：120-180.
According to the present invention, in step (1), the type of the template is not particularly limited, can be normal for this field
The various templates used are advised, as long as the double mesoporous attapulgite complex carriers of the spherical shape that can make have above-mentioned pore structure i.e.
It can, it is preferable that the template can be cetyl trimethylammonium bromide (CTAB).
According to the present invention, in step (1), the type of the silicon source is not particularly limited, and can be various conventional
Silicon source, the silicon source may include in ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and silica solution extremely
Few one kind, it is preferable that the silicon source is ethyl orthosilicate.
According to the present invention, in step (2), the condition that the waterglass is contacted with inorganic acid is not particularly limited, example
Such as, the condition that the waterglass is contacted with inorganic acid generally includes：Temperature can be 10-60 DEG C, preferably 20-40 DEG C；Time
Can be 1-5 hours, preferably 1.5-3 hours, pH value 2-4.In order to be more advantageous to the uniform mixing between each substance, the water
Glass is contacted with inorganic acid preferably to carry out under agitation.
According to the present invention, the waterglass is the aqueous solution of the sodium metasilicate of this field routine, and concentration can be 10-50 weight
Measure %, preferably 12-30 weight %.
According to the present invention, the type of the inorganic acid can be the conventional selection of this field, for example, can be sulfuric acid, nitre
One of acid and hydrochloric acid are a variety of.The inorganic acid can use in pure form, can also be in the form of its aqueous solution
It uses.The dosage of the inorganic acid is preferably so that the pH value of the contact conditions reaction system of waterglass and inorganic acid is 2-4.
According to the present invention, in step (3), the dosage of the mesoporous material, silica gel and attapulgite can be according to expection
The component of the double mesoporous attapulgite complex carriers of obtained spherical shape is selected, under preferable case, with being given an account of for 100 parts by weight
On the basis of the dosage of Porous materials, the dosage of the silica gel is 1-200 parts by weight, and the dosage of the attapulgite is 1-50 weight
Part.
It is further preferred that on the basis of the dosage of the mesoporous material of 100 parts by weight, the dosage of the silica gel is
50-150 parts by weight；The dosage of the attapulgite is 20-50 parts by weight.
The present invention also provides the double mesoporous attapulgite complex carriers of the spherical shape being prepared by the method for the invention.
According to the present invention, the double mesoporous attapulgite complex carriers of the spherical shape being prepared by the method for the invention contain recessed
Convex stick stone, silica and the meso-porous molecular sieve material with the distribution of two-dimentional hexagonal hole road, and spherical double mesoporous concave convex rods
The average grain diameter of stone complex carrier is 20-50 μm, specific surface area 100-650m2/ g, pore volume 0.5-1.5mL/g, aperture
It is distributed as bimodal distribution, and the bimodal corresponding most probable pore size is respectively 2-10nm and 15-45nm.
According to the present invention, spherical double mesoporous attapulgite complex carriers have a special peacekeeping two dimension hexagonal hole road
The average grain diameter of diplopore distributed architecture, particle is measured using laser fineness gage, specific surface area, pore volume and most probable hole
Diameter is measured according to nitrogen adsorption methods.In the present invention, granularity refers to the particle size of feed particles, when feed particles are sphere
Then the diameter of granularity sphere indicates, when feed particles are cube, then the side length of granularity cube is indicated, when raw material
Then granularity is indicated with the mesh size for the sieve that can screen out the feed particles just when grain is irregular shape.
According to the present invention, spherical double mesoporous attapulgite complex carriers pass through spherical double mesoporous attapulgites are compound
The particle size of carrier controls within above range, it can be ensured that spherical double mesoporous attapulgite complex carriers are not easy to send out
It is raw to reunite, and be used as loaded catalyst made of carrier and reaction raw materials during olefin polymerization can be improved
Conversion ratio.When the specific surface areas of spherical double mesoporous attapulgite complex carriers be less than 100m2/ g and/or pore volume are less than
When 0.5mL/g, the catalytic activity for being used as loaded catalyst made of carrier can be significantly reduced；When described spherical double mesoporous
The specific surface area of attapulgite complex carrier is greater than 650m2When/g and/or pore volume are greater than 1.5mL/g, it is used as carrier system
At loaded catalyst reunion is easy to happen during olefin polymerization, to influence the catalysis in olefins reaction process
The mobility of agent efficiency and polyolefin products obtained.
Under preferable case, the average grain diameter of spherical double mesoporous attapulgite complex carriers is 35-55 μm, specific surface area
For 120-400m2/ g, pore volume 0.8-1.2mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable hole
Diameter is respectively 5-8nm and 20-30nm.
According to the present invention, the tool in spherical double mesoporous attapulgite complex carriers, relative to 100 parts by weight
There is the meso-porous molecular sieve material of two-dimentional hexagonal hole road distribution, the content of the silica is 1-200 parts by weight, the concave convex rod
The content of stone is 1-50 parts by weight.
The tool under preferable case, in spherical double mesoporous attapulgite complex carriers, relative to 100 parts by weight
There is the meso-porous molecular sieve material of two-dimentional hexagonal hole road distribution, the content of the silica is 50-150 parts by weight, the bumps
The content of stick stone is 20-50 parts by weight.
According to the present invention, the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture can be normal for this field
The meso-porous molecular sieve material used is advised, and can be prepared according to the conventional method.
The present invention also provides spherical double mesoporous attapulgite complex carriers provided by the present invention to prepare support type poly-
Application in alkene catalyst.
According to the present invention, the preparation method of the supported polyolefin catalyst can load for the preparation of this field routine
The method of type polyolefin catalyst, detailed process may include：In the presence of an inert gas, by spherical double Jie provided by the invention
Hole attapulgite complex carrier is impregnated in the catalyst mother liquor containing magnesium salts and/or titanium salt, is then successively filtered
And drying.
It according to the present invention, can be normal for this field using the method that the supported polyolefin catalyst carries out olefinic polymerization
The olefine polymerizing process of rule, detailed process may include：Under the polymerization conditions, in supported polyolefin provided by the invention
In the presence of catalyst, olefinic monomer is made to carry out polymerization reaction.
According to the present invention, there is no particular limitation for the reaction condition of the polymerization reaction, can be the alkene of this field routine
Polymerized hydrocarbon reaction condition, for example, the reaction can carry out in the presence of an inert gas, the condition of the polymerization reaction be can wrap
It includes：Temperature is 10-100 DEG C, time 0.5-5h, pressure 0.1-2MPa；Preferably, the condition of the polymerization reaction can wrap
It includes：Temperature is 20-95 DEG C, time 1-4h, pressure 0.5-1.5MPa；It is further preferred that temperature is 70-85 DEG C, the time
For 1-2h, pressure 1-1.5MPa.
Pressure of the present invention refers to gauge pressure.
In the present invention, the polymerization reaction can carry out in the presence of solvent, to used in the polymerization reaction
Solvent is not particularly limited, for example, can be hexane.
In a kind of specific embodiment, the supported polyolefin catalyst can be catalyzed for support type polyethylene
Agent, the polymerization reaction are ethylene polymerization, and the method for the vinyl polymerization includes：Under conditions of ethylene polymerization,
In the presence of catalyst and auxiliary agent, ethylene is made to carry out polymerization reaction；Preferably, the auxiliary agent is alkyl aluminum compound.
In the present invention, the structure of the alkyl aluminum compound is shown in formula I：
AlRnX5 (3-n)Formulas I
In Formulas I, R can be respectively C1-C5Alkyl；X5One of halogen group, preferably-Cl can be respectively；n
It is 0,1,2 or 3.
Preferably, the C1-C5Alkyl can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl
One of base, tert-butyl, n-pentyl, isopentyl, tertiary pentyl and neopentyl are a variety of.
In the present invention, the specific example of the alkyl aluminum compound includes but is not limited to：Trimethyl aluminium, dimethylammonium chloride
Aluminium, triethyl aluminum, diethyl aluminum chloride, tri-n-n-propyl aluminum, diη-propyl aluminium chloride, three n-butylaluminums, three sec-butyl aluminium, three uncles
Butyl aluminium, di-n-butyl aluminium chloride and diisobutyl aluminum chloride.Most preferably, the alkyl aluminum compound is triethyl aluminum.
In the present invention, the dosage of the alkyl aluminum compound may be the selection of this field routine, generally, described
The mass ratio of alkyl aluminum compound and the catalyst amount can be 1：0.1-10；Under preferable case, the alkyl aluminum chemical combination
The mass ratio of object and the catalyst amount is 1：0.2-8；More preferably 1：0.4-4.
In the present invention, the method for the vinyl polymerization can also include, after polymerization reaction, to final reaction
Mixture carries out suction filtration separation, so that polyethylene particle powder be made.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, filtration washing is in the alumina ceramic membrane filtering purchased from my long company of Nanjing
It is carried out in device；
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company of Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is in the ASAP2020-M+C purchased from the production of U.S. Micromeritics company
It is carried out on type adsorption instrument, the specific surface area and pore volume of sample, which calculate, uses BET method；The particle diameter distribution of sample swashs in Malvern
It is carried out on light particle size analyzer；Rotary Evaporators are the production of IKA company of Germany, model RV10digital；Propane dehydrogenation catalyst
Activity component load quantity is in the Wavelength Dispersive-X-Ray fluorescence spectrum for being Axios-Advanced purchased from Dutch Panaco company model
It is measured on instrument；The analysis of reaction product ingredient carries out on the gas chromatograph purchased from agilent company model 7890A；
The heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
The melt index of polyolefin is measured using method as defined in ASTM D1238-99.
Embodiment 1
(1) the spherical double mesoporous attapulgite complex carriers of preparation
At 80 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein the additional amount of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1：0.37：2.8：142, and stirred 4 hours at a temperature of 80 DEG C, had
The meso-porous molecular sieve material A1 of two-dimentional hexagonal hole road distribution.
It with weight ratio is 5 by the sulfuric acid solution that waterglass and concentration that concentration is 15 weight % are 12 weight %:1 is mixed
Merge the haptoreaction 1.5h at 30 DEG C, then adjusts pH value to 3 with the sulfuric acid that concentration is 98 weight %, obtain reaction product silicon
Glue B1.
10g mesoporous material A1,10g silica gel B1 and 10g attapulgite of above-mentioned preparation is stirred, mixed material is led to
Enter in ceramic membrane filter system with deionized water and ethyl alcohol filtration washing, is washed till sodium ion containing in terms of sodium element in mixed material
Amount is 0.02 weight %, and cetyl trimethylammonium bromide content is 0.5 weight %, then collects the mixing in ceramic filtering membrane tube
Material is put into 100ml ball grinder, wherein the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, abrading-ball it is straight
Diameter is 3mm, and quantity is 1, revolving speed 400r/min.Close ball grinder, in ball grinder temperature be 60 DEG C at ball milling 1 hour,
Obtain 30g solid powder；The solid powder is dissolved in 30 grams of deionized waters and is made into slurry, later in revolving speed at 200 DEG C
To be spray-dried under 12000r/min, obtaining 30g has the double mesoporous attapulgites of spherical shape of two-dimentional hexagonal hole road distributed architecture multiple
Close support C 1.
Spherical double mesoporous attapulgite complex carrier C1 are characterized with XRD, scanning electron microscope and nitrogen adsorption instrument.
Fig. 1 is X-ray diffracting spectrum, wherein abscissa is 2 θ, and ordinate is intensity, the small angle occurred by XRD spectra
Spectral peak is spent it is found that the XRD spectra of spherical double mesoporous attapulgite complex carrier C1 has six sides of 2D specific to mesoporous material
Cellular structure；
Fig. 2 is SEM scanning electron microscope (SEM) photograph, and as seen from the figure, the microscopic appearance of spherical double mesoporous attapulgite complex carrier C1 is
The Mesoporous Spheres that granularity is 20-50 μm, and its good dispersion property.
Fig. 3 is the size distribution curve of spherical double mesoporous attapulgite complex carrier C1, it can be seen from the figure that spherical double
Mesoporous attapulgite complex carrier C1 has uniform size distribution.
Table 1 is the pore structure parameter of spherical double mesoporous attapulgite complex carrier C1.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (mL/g) | Most probable pore size*(nm) | Partial size (μm) |
| C1 | 153 | 1 | 7,25 | 20-50 |
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.1g magnesium chloride and 0.1g titanium tetrachloride are dissolved in (four in the tetrahydrofuran of 10mL and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.2) catalyst mother liquor, is formed.By the spherical double mesoporous attapulgites of 1g at 45 DEG C
Complex carrier C1, which is added in mother liquor, impregnates 1h, then filters, and carries out washing 4 times with n-hexane, in 75 DEG C of dryings, and carries out
Grinding, obtains catalyst Cat-1.
It is obtained by x-ray fluorescence analysis, in the obtained catalyst Cat-1 of the present embodiment, based on the element, magnesium elements
Content be 4.9 weight %, the contents of titanium elements is 2.2 weight %, and the content of chlorine element is 8.8 weight %.
(3) vinyl polymerization
It in the stainless steel polymerization autoclave of 2L, is respectively replaced three times with nitrogen and ethylene, 200mL hexane is then added, it will
Kettle temperature rises to 80 DEG C, adds 800mL hexane, and with the addition of hexane, the concentration that 2mL is added is the triethyl aluminum of 1mol/L
(TEA) hexane solution is subsequently added into the catalyst Cat-1 of 0.5g, is passed through ethylene gas, pressure is risen to 1MPa and is maintained
1MPa filters separation after reacting 1 hour at 70 DEG C, obtains polyethylene particle powder.The heap density of gained polyethylene particle powder
(BD), melt index MI2.16And the efficiency of catalyst is listed in Table 4 below.
Embodiment 2
(1) the spherical double mesoporous attapulgite complex carriers of preparation
At 50 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein the additional amount of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1：0.5：1.5：180, and stir 7 hours at 50 °C, obtain having two
The meso-porous molecular sieve material A2 of Wei Liufangkongdao distribution.
It with weight ratio is 4 by the sulfuric acid solution that waterglass and concentration that concentration is 15 weight % are 12 weight %:1 is mixed
Merge the haptoreaction 2h at 40 DEG C, then adjusts pH value to 2 with the sulfuric acid that concentration is 98 weight %, obtain reaction product silica gel
B2。
20g mesoporous material A2,10g silica gel B2 and 8g attapulgite of above-mentioned preparation is stirred, mixed material is led to
Enter in ceramic membrane filter system with deionized water and ethyl alcohol filtration washing, is washed till sodium ion containing in terms of sodium element in mixed material
Amount is 0.02 weight %, and cetyl trimethylammonium bromide content is 0.3 weight %, then collects the mixing in ceramic filtering membrane tube
Material is put into 100ml ball grinder, wherein the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, abrading-ball it is straight
Diameter is 3mm, and quantity is 1, revolving speed 400r/min.Ball grinder is closed, temperature is that ball milling 0.5 is small at 80 DEG C in ball grinder
When, obtain 38g solid powder；The solid powder is dissolved in 33 grams of deionized waters and is made into slurry, is being turned at 250 DEG C later
Speed is to be spray-dried under 11000r/min, obtains the double mesoporous attapulgites of spherical shape that 35g has two-dimentional hexagonal hole road distributed architecture
Complex carrier C2.
Table 2 is the pore structure parameter of spherical double mesoporous attapulgite complex carrier C2.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (mL/g) | Most probable pore size*(nm) | Partial size (μm) |
| C2 | 162 | 1.1 | 6,22 | 25-45 |
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.1g magnesium chloride and 0.2g titanium tetrachloride are dissolved in (four in the tetrahydrofuran of 10mL and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1.5) catalyst mother liquor, is formed.By the spherical double mesoporous attapulgites of 1g at 60 DEG C
Complex carrier C2, which is added in mother liquor, impregnates 1h, then filters, and carries out washing 4 times with n-hexane, in 75 DEG C of dryings, and carries out
Grinding, obtains catalyst Cat-2.
It is obtained by x-ray fluorescence analysis, in the obtained catalyst Cat-2 of the present embodiment, based on the element, magnesium elements
Content be 6.9 weight %, the contents of titanium elements is 2.7 weight %, and the content of chlorine element is 9.1 weight %.
(3) vinyl polymerization
It in the stainless steel polymerization autoclave of 2L, is respectively replaced three times with nitrogen and ethylene, 200mL hexane is then added, it will
Kettle temperature rises to 75 DEG C, adds 900mL hexane, and with the addition of hexane, the concentration that 2mL is added is the triethyl aluminum of 1mol/L
(TEA) hexane solution is subsequently added into the catalyst Cat-2 of 0.1g, is passed through ethylene gas, pressure is risen to 1MPa and is maintained
1MPa filters separation after reacting 1.5 hours at 75 DEG C, obtains polyethylene particle powder.The heap of gained polyethylene particle powder is close
Spend (BD), melt index MI2.16And the efficiency of catalyst is listed in Table 4 below.
Embodiment 3
(1) the spherical double mesoporous attapulgite complex carriers of preparation
At 90 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein the additional amount of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1：0.2：3.5：120, and stirred 3 hours at a temperature of 90 DEG C, obtain having two
The meso-porous molecular sieve material A3 of Wei Liufangkongdao distribution.
It with weight ratio is 6 by the sulfuric acid solution that waterglass and concentration that concentration is 15 weight % are 12 weight %:1 is mixed
Merge the haptoreaction 3h at 20 DEG C, then adjusts pH value to 4 with the sulfuric acid that concentration is 98 weight %, obtain reaction product silica gel
B3。
20g mesoporous material A3,30g silica gel B3 and 12g attapulgite of above-mentioned preparation is stirred, mixed material is led to
Enter in ceramic membrane filter system with deionized water and ethyl alcohol filtration washing, is washed till sodium ion containing in terms of sodium element in mixed material
Amount is 0.02 weight %, and cetyl trimethylammonium bromide content is 0.4 weight %, then collects the mixing in ceramic filtering membrane tube
Material is put into 100ml ball grinder, wherein the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, abrading-ball it is straight
Diameter is 3mm, and quantity is 1, revolving speed 550r/min.Close ball grinder, in ball grinder temperature be 40 DEG C at ball milling 10 hours,
Obtain 55g solid powder；The solid powder is dissolved in 30 grams of deionized waters and is made into slurry, later in revolving speed at 250 DEG C
To be spray-dried under 13000r/min, obtaining 53g has the double mesoporous attapulgites of spherical shape of two-dimentional hexagonal hole road distributed architecture multiple
Close support C 3.
Table 3 is the pore structure parameter of spherical double mesoporous attapulgite complex carrier C3.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (mL/g) | Most probable pore size*(nm) | Partial size (μm) |
| C3 | 203 | 0.9 | 8,26 | 30-50 |
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
(2) catalyst is prepared
0.2g magnesium chloride and 0.1g titanium tetrachloride are dissolved in (four in the tetrahydrofuran of 10mL and the double solvents of isopropanol
The volume ratio of hydrogen furans and isopropanol is 1：1) catalyst mother liquor, is formed.The spherical double mesoporous attapulgites of 1g are answered at 40 DEG C
It closes support C 3 and is added in mother liquor and impregnate 1h, then filter, and carry out washing 4 times with n-hexane, in 75 DEG C of dryings, and ground
Mill, obtains catalyst Cat-3.
It is obtained by x-ray fluorescence analysis, in the obtained catalyst Cat-3 of the present embodiment, based on the element, magnesium elements
Content be 6.6 weight %, the contents of titanium elements is 2.3 weight %, and the content of chlorine element is 9.2 weight %.
(3) vinyl polymerization
It in the stainless steel polymerization autoclave of 2L, is respectively replaced three times with nitrogen and ethylene, 200mL hexane is then added, it will
Kettle temperature rises to 85 DEG C, adds 700mL hexane, and with the addition of hexane, the concentration that 2mL is added is the triethyl aluminum of 1mol/L
(TEA) hexane solution is subsequently added into the catalyst Cat-3 of 1g, is passed through ethylene gas, pressure is risen to 1MPa and is maintained
1MPa filters separation after reacting 2 hours at 85 DEG C, obtains polyethylene particle powder.The heap density of gained polyethylene particle powder
(BD), melt index MI2.16And the efficiency of catalyst is listed in Table 4 below.
Comparative example 1
(1) the spherical double mesoporous attapulgite complex carriers of preparation
Spherical double mesoporous attapulgite complex carriers are prepared according to the method for embodiment 1, unlike, in step (1),
It needs to obtain to be filtered with the meso-porous molecular sieve material solution of two-dimentional hexagonal hole road distribution and be washed with deionized four
It is secondary, obtain the filter cake DA1 of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distribution；In step (2), need to obtain
Silica gel is filtered, and the content being washed with deionized to sodium ion in terms of sodium element is 0.02 weight %, obtains silica gel
Filter cake DB1；The filter cake DA1 of the mesoporous material, the filter cake DB1 of silica gel and attapulgite are stirred in step (3), not
It is filtered washing through ceramic filtration membrane filter, is directly placed into ball grinder and carries out ball milling.The solid powder that ball milling is obtained according to
Obtained product will be spray-dried after secondary progress slurrying and spray drying again and calcines 15h, removing ten at 600 DEG C in Muffle furnace
Six alkyl trimethyl ammonium bromides (template) obtain spherical double mesoporous attapulgite complex carrier D1.
(2) catalyst is prepared
Catalyst is prepared according to the method for embodiment 1, unlike, using the above-mentioned spherical double mesoporous recessed of identical weight part
The convex spherical double mesoporous attapulgite complex carrier C1 of stick stone complex carrier D1 substitution, to obtain comparative catalyst Cat-D-1.
It is obtained by x-ray fluorescence analysis, in the obtained catalyst Cat-D-1 of the present embodiment, based on the element, magnesium member
The content of element is 2.2 weight %, and the content of titanium elements is 1.7 weight %, and the content of chlorine element is 12.5 weight %.
(3) vinyl polymerization
The polymerization of ethylene is carried out according to the method for embodiment 1, unlike, the comparison catalysis of identical weight part is respectively adopted
Agent Cat-D-1 replaces the catalyst Cat-1 being prepared by embodiment 1.The heap density (BD) of gained polyethylene particle powder melts
Melt index M I2.16And the efficiency of catalyst is listed in Table 4 below.
Comparative example 2
(1) silica-gel carrier is prepared
Silica gel is prepared according to the method in embodiment 1, and silica gel obtained is filtered using plate and frame type filter-press, so
The silica gel that plate and frame type filter-press is obtained by filtration afterwards is calcined 10 hours for 400 DEG C under nitrogen protection, with eliminating hydroxide and remaining water
Point, to obtain the silica-gel carrier D2 of the plate and frame type filter-press preparation through thermal activation.During the preparation process, one ton of silicon is obtained
Glue carrier needs 11 tons of water consumption.
(2) catalyst is prepared
Catalyst is prepared according to the method for embodiment 1, unlike, it is replaced using the above-mentioned silica-gel carrier D2 of identical weight part
Generation spherical double mesoporous attapulgite complex carrier C1, to obtain comparative catalyst Cat-D-2.
It is obtained by x-ray fluorescence analysis, in the obtained catalyst Cat-D-2 of the present embodiment, based on the element, magnesium member
The content of element is 1.1 weight %, and the content of titanium elements is 1.6 weight %, and the content of chlorine element is 18.63 weight %.
(3) vinyl polymerization
The polymerization of ethylene is carried out according to the method for embodiment 1, unlike, the comparison catalysis of identical weight part is respectively adopted
Agent Cat-D-2 replaces the catalyst Cat-1 being prepared by embodiment 1.The heap density (BD) of gained polyethylene particle powder melts
Melt index M I2.16And the efficiency of catalyst is listed in Table 4 below.
Table 4
The result compared from above embodiments 1-3 and comparative example 1-2 can be seen that the ball prepared using method of the invention
When the double mesoporous attapulgite complex carriers of shape and loaded catalyst are used for olefin polymerization, catalyst catalysis with higher
Efficiency, and heap density and the lower polyolefin products of melt index can be obtained, specifically, prepared using method of the invention
The double mesoporous attapulgite complex carriers of spherical shape and loaded catalyst when being used for ethylene polymerization, catalytic efficiency is reachable
2200g PE/gcat h, the heap density of the polyethylene product of preparation is up to 0.4g/mL hereinafter, melt index is 0.5g/10min
Below.And it is lower not adopt the catalyst efficiency being obtained by the present invention, and when being used for catalyzed ethylene polymerization, obtains
The bulk density of the polyethylene product arrived is higher, and mobility is poor.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method for preparing spherical double mesoporous attapulgite complex carriers, which is characterized in that this approach includes the following steps：
(1) in the presence of template, silicon source and ammonia spirit are contacted, obtain mesoporous material；
(2) waterglass is contacted with inorganic acid solution, obtains silica gel；
(3) mesoporous material, the silica gel are mixed with attapulgite, then mixed material is successively filtered washing,
Ball milling, slurrying and spray drying,
Wherein, the filtration washing in step (3) carries out in purpose ceramic-film filter, sodium ion in the mixed material after filtration washing
Content in terms of sodium element is not higher than 1 weight % not higher than the content of 0.2 weight %, template.
2. according to the method described in claim 1, wherein, in step (1), the condition of the contact includes：Temperature is 25-
100 DEG C, time 1-10h；
Preferably, the dosage molar ratio of the silicon source, template, the ammonia in ammonium hydroxide and water is 1：0.1-1：0.1-5：100-200；
It is highly preferred that the template is cetyl trimethylammonium bromide；The silicon source includes ethyl orthosilicate, positive silicic acid first
At least one of ester, positive silicic acid propyl ester, sodium metasilicate and silica solution；
It is further preferred that the silicon source is ethyl orthosilicate.
3. according to the method described in claim 1, wherein, in step (2), the condition of the contact includes：Temperature is 10-60
DEG C, time 1-5h, pH value 2-4；
Preferably, the inorganic acid solution is at least one of sulfuric acid, nitric acid and hydrochloric acid aqueous solution.
4. according to the method described in claim 1, wherein, in step (3), with the use of the mesoporous material of 100 parts by weight
On the basis of amount, the dosage of the silica gel is 1-200 parts by weight, and the dosage of the attapulgite is 1-50 parts by weight.
5. according to the method described in claim 1, wherein, in step (3), with the use of the mesoporous material of 100 parts by weight
On the basis of amount, the dosage of the silica gel is 50-150 parts by weight, and the dosage of the attapulgite is 20-50 parts by weight.
6. the double mesoporous attapulgite complex carriers of the spherical shape of the preparation of the method as described in any one of claim 1-5.
7. spherical double mesoporous attapulgite complex carriers according to claim 6, wherein the double mesoporous attapulgites of the spherical shape
Complex carrier contains attapulgite, silica and the meso-porous molecular sieve material with the distribution of two-dimentional hexagonal hole road, and the ball
The average grain diameter of the double mesoporous attapulgite complex carriers of shape is 20-50 μm, specific surface area 100-650m2/ g, pore volume are
0.5-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 2-10nm and 15-
45nm。
8. spherical double mesoporous attapulgite complex carriers according to claim 7, wherein the institute relative to 100 parts by weight
The meso-porous molecular sieve material with two-dimentional hexagonal hole road distribution is stated, the content of the silica is 1-200 parts by weight, described recessed
The content of convex stick stone is 1-50 parts by weight.
9. spherical double mesoporous attapulgite complex carriers according to claim 7, wherein the institute relative to 100 parts by weight
The meso-porous molecular sieve material with two-dimentional hexagonal hole road distribution is stated, the content of the silica is 50-150 parts by weight, described
The content of attapulgite is 20-50 parts by weight.
10. prepared by the double mesoporous attapulgite complex carriers of spherical shape described in any one of claim 6 and claim 7-9
Application in supported polyolefin catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710389562.3A CN108929393B (en) | 2017-05-27 | 2017-05-27 | Spherical double-mesoporous attapulgite composite carrier and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710389562.3A CN108929393B (en) | 2017-05-27 | 2017-05-27 | Spherical double-mesoporous attapulgite composite carrier and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108929393A true CN108929393A (en) | 2018-12-04 |
| CN108929393B CN108929393B (en) | 2020-10-23 |
Family
ID=64451381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710389562.3A Active CN108929393B (en) | 2017-05-27 | 2017-05-27 | Spherical double-mesoporous attapulgite composite carrier and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108929393B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114873603A (en) * | 2022-05-23 | 2022-08-09 | 淮阴工学院 | Photoinduced self-assembly synthesis method of one-dimensional mesoporous and microporous composite molecular sieve material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752113A (en) * | 2004-09-20 | 2006-03-29 | 中国石油天然气集团公司 | Polyolefin nano-structured calalyst carrier and its preparation method |
| US7691773B2 (en) * | 2004-03-23 | 2010-04-06 | Samsung Sdi Co., Ltd. | Supported catalyst and method for preparing the same |
| CN105524193A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method therefor |
-
2017
- 2017-05-27 CN CN201710389562.3A patent/CN108929393B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7691773B2 (en) * | 2004-03-23 | 2010-04-06 | Samsung Sdi Co., Ltd. | Supported catalyst and method for preparing the same |
| CN1752113A (en) * | 2004-09-20 | 2006-03-29 | 中国石油天然气集团公司 | Polyolefin nano-structured calalyst carrier and its preparation method |
| CN105524193A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method therefor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114873603A (en) * | 2022-05-23 | 2022-08-09 | 淮阴工学院 | Photoinduced self-assembly synthesis method of one-dimensional mesoporous and microporous composite molecular sieve material |
| CN114873603B (en) * | 2022-05-23 | 2023-09-29 | 淮阴工学院 | Photo-induced self-assembly synthesis method of one-dimensional mesoporous composite molecular sieve material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108929393B (en) | 2020-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| 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 | |
| CN105330767B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| 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 | |
| CN106467579B (en) | Macropore two dimension double hole channel spherical complex carrier and composite material and their preparation method and application containing polyethylene catalysts | |
| CN105330769B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts 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 | |
| CN106467581B (en) | Three hole silica-gel carriers and support type polyethylene catalysts and its preparation method and application | |
| CN108794666A (en) | The method and polyethylene of vinyl polymerization | |
| CN106467580B (en) | The spherical complex carrier and support type polyethylene catalysts in super big hole three-dimensional cubic duct and their preparation method and application | |
| CN108929393A (en) | Spherical double mesoporous attapulgite complex carriers and its preparation method and application | |
| CN106430234A (en) | Synthesis method for ZSM-11 molecular sieve with nano multi-stage pores | |
| CN108794667A (en) | Silica-gel carrier and loaded catalyst and preparation method thereof | |
| CN108929394A (en) | Polyolefin catalyst and polyolefin and their preparation method | |
| CN108948234A (en) | Spherical double mesoporous montmorillonite complex carriers and its preparation method and application | |
| CN108948239A (en) | Polyolefin catalyst and polyolefin and their preparation method | |
| CN108727523A (en) | The method and polyethylene of vinyl polymerization | |
| CN110734511B (en) | Polyolefin catalyst with spherical double-mesoporous composite material as carrier, polyolefin and preparation methods of polyolefin catalyst and polyolefin | |
| CN107417828A (en) | Spherical composite and support type polyethylene catalysts and their preparation method | |
| CN108794668A (en) | Silica-gel carrier and loaded catalyst and preparation method thereof | |
| CN110496637B (en) | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation | |
| CN107417820A (en) | Spherical diatomite mesoporous composite material and loaded catalyst and preparation method thereof | |
| CN108727518B (en) | Process for the polymerization of ethylene and polyethylene | |
| CN108727522A (en) | The method and polyethylene of vinyl polymerization | |
| CN108794665A (en) | The method and polyethylene of vinyl polymerization |
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 |