CN106554431B - The method of bimodal porous silica carrier and support type polyethylene catalysts and its preparation method and application and vinyl polymerization - Google Patents
The method of bimodal porous silica carrier and support type polyethylene catalysts and its preparation method and application and vinyl polymerization Download PDFInfo
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Abstract
The present invention relates to catalyst field, a kind of bimodal porous silica carrier and support type polyethylene catalysts and its preparation method and application and a kind of method of vinyl polymerization are disclosed.The average particle diameter of bimodal porous silica carrier provided by the invention is 20-50 μm, specific surface area 150-600m2/ g, pore volume 0.5-1.6mL/g, aperture is in bimodal distribution, and bimodal corresponding most probable pore size is 2-4nm and 10-40nm.Bimodal porous silica carrier provided by the invention is capable of the load factor of catalyst activity component with higher, and the support type polyethylene catalysts being prepared being capable of catalytic activity with higher.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of bimodal porous silica carrier, a kind of system of bimodal porous silica carrier
Preparation Method and the bimodal porous silica carrier being prepared by this method, a kind of support type polyethylene catalysts, a kind of poly- second of support type
The preparation method of alkene catalyst and the support type polyethylene catalysts being prepared by this method and its anti-in catalyzed ethylene polymerization
Application in answering.
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.
The mesoporous material for the load polyethylene catalysts reported on document at present mainly has MCM-41, after being handled with MAO again
Catalytic activity is 10 after loading the MCM-41 progress vinyl polymerization of polyethylene catalysts6gPE/(mol Zr h).Mesoporous material
Carried out after MCM-41 supported catalyst hole wall structure thermal stability that the lower reason of ethylene polymerization activity is mainly MCM-41 and
Hydrothermal stability is poor, just has part collapsing in loading process middle hole wall, affects load effect, lives so that affecting catalysis
Property.
Therefore, the support/catalyst/co-catalyst system new for further investigation, it is necessary to different carriers is attempted, to push away
The further development of dynamic load body catalyst and polyolefin industry.
Summary of the invention
The purpose of the invention is to overcome using support type polyethylene catalysts made of existing carrier in vinyl polymerization
The lower defect of catalytic activity in reaction provides a kind of super large pore ball shaped bimodal porous silica carrier with high load rate, and should
The preparation method of silica-gel carrier, the silica-gel carrier prepared by this method, the support type polyethylene catalysts containing the silica-gel carrier,
The preparation method of the support type polyethylene catalysts, by the support type polyethylene catalysts of this method preparation and its in vinyl polymerization
Application in reaction, and a kind of method of vinyl polymerization is provided.
To achieve the goals above, the present invention provides a kind of bimodal porous silica carrier, wherein the average particle diameter of the carrier
It is 20-50 μm, specific surface area 150-600m2/ g, pore volume 0.5-1.6mL/g, aperture are in bimodal distribution, and bimodal difference
Corresponding most probable pore size is 2-4nm and 10-40nm.
The present invention also provides a kind of preparation methods of bimodal porous silica carrier, this method comprises:
(1) in inorganic acid solution, waterglass, glycerine and n-butanol are subjected to haptoreaction, and will be after haptoreaction
Gained mixture is filtered and washed, and obtains silica gel filter cake；
(2) solid powder is obtained after the silica gel filter cake obtained by (1) being carried out ball milling；
(3) solid powder obtained by (2) is configured to after slurry be successively spray-dried and calcined in aqueous solution；
Wherein, the average particle diameter of the bimodal porous silica carrier obtained using this method is 20-50 μm, and specific surface area is
150-600m2/ g, pore volume 0.5-1.6mL/g, aperture is in bimodal distribution, and bimodal corresponding most probable pore size is 2-
4nm and 10-40nm.
The present invention also provides the bimodal porous silica carriers prepared by the above method.
The present invention also provides a kind of support type polyethylene catalysts, which contains bimodal porous silica carrier and load
Magnesium elements and/or titanium elements on the bimodal porous silica carrier, wherein the bimodal porous silica carrier is provided by the invention double
Hole silica-gel carrier.
The present invention also provides a kind of preparation methods of support type polyethylene catalysts, this method comprises: in inert gas
In the presence of, carrier is impregnated in the catalyst mother liquor containing magnesium elements and/or titanium elements, be then successively filtered and
It is dry, which is characterized in that the carrier is bimodal porous silica carrier provided by the invention, and the catalyst mother liquor is to contain magnesium elements
And/or the combined organic solution of titanium elements.
The present invention also provides the support type polyethylene catalysts prepared by the above method.
The present invention also provides application of the above-mentioned support type polyethylene catalysts in catalyzed ethylene polymerization reaction.
The present invention also provides a kind of methods of vinyl polymerization, this method comprises: in above-mentioned support type polyethylene catalysts
In the presence of, under conditions of polymerization reaction, ethylene is made to carry out polymerization reaction.
The support type polyethylene catalysts that bimodal porous silica carrier provided by the present invention is prepared are in catalyzed ethylene polymerization
Catalytic activity with higher in reaction process.
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 SEM scanning electron microscope (SEM) photograph of bimodal porous silica carrier (GJ) according to the present invention；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of support type polyethylene catalysts (GJ-BCJ) according to the present invention；
Fig. 3 is that the SEM of the polyethylene product obtained in the presence of support type polyethylene catalysts (GJ-BCJ) is swept
Retouch electron microscope.
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 present invention provides a kind of bimodal porous silica carrier, wherein the average particle diameter of the carrier is 20-50 μm, specific surface
Product is 150-600m2/ g, pore volume 0.5-1.6mL/g, aperture are in bimodal distribution, and bimodal corresponding most probable pore size
For 2-4nm and 10-40nm.
Under preferable case, the average particle diameter of the carrier is 20-40 μm, specific surface area 180-600m2/ g, pore volume
For 0.8-1.6mL/g, aperture is in bimodal distribution, and bimodal corresponding most probable pore size is 2.5-4nm and 25-40nm.
In the present invention, the specific surface area, pore volume and most probable pore size are measured according to nitrogen adsorption methods, described average
Partial size is measured using laser fineness gage.
In the present invention, the average grain diameter is average grain diameter.
The present inventor has found that bimodal porous silica carrier provided by the invention has super large by a large amount of scientific research
Aperture, high-specific surface area, and aperture is in bimodal distribution, is conducive to the load of catalytic component；In addition, provided by the invention double
Hole silica-gel carrier has spherical geometric shape, which is reducing powder reuniting, improves mobility etc. with apparent excellent
Gesture.Therefore, when preparing polyethylene catalysts using the super large pore ball shaped bimodal porous silica carrier, the polyethylene catalysts of acquisition have
Higher catalytic activity.
The present invention also provides a kind of preparation methods of bimodal porous silica carrier, this method comprises:
(1) in inorganic acid solution, waterglass, glycerine and n-butanol are subjected to haptoreaction, and will be after haptoreaction
Gained mixture is filtered and washed, and obtains silica gel filter cake；
(2) solid powder is obtained after the silica gel filter cake obtained by (1) being carried out ball milling；
(3) solid powder obtained by (2) is configured to after slurry be successively spray-dried and calcined in aqueous solution；
Wherein, the average particle diameter of the bimodal porous silica carrier obtained using this method is 20-50 μm, and specific surface area is
150-600m2/ g, pore volume 0.5-1.6mL/g, aperture is in bimodal distribution, and bimodal corresponding most probable pore size is 2-
4nm and 10-40nm.
According to the present invention, in step (1), the waterglass, inorganic acid, glycerine and n-butanol dosage weight ratio be
3-6:1:1:1, wherein the waterglass is the aqueous solution of sodium metasilicate, and concentration can be 10-50 weight %, preferably 12-30
Weight %.
According to the present invention, in step (1), to the catalytic condition, there is no particular limitation, can be according to system
It is suitably determined in the common process of standby silica gel.Under preferable case, the catalytic condition includes: that Contact Temperature is 10-
60 DEG C, time of contact is 1-5 hours, pH value 2-4.In addition, in order to be more advantageous to the uniform mixing between each substance, the contact
The process of reaction preferably carries out under agitation.
According to the present invention, in step (1), the inorganic acid can be various inorganic acids commonly used in the art, example
It such as, can be at least one of sulfuric acid, nitric acid and hydrochloric acid.The inorganic acid can use in pure form, can also be with
The form of its aqueous solution uses.
According to the present invention, in step (1), to the filtering, there is no particular limitation, can use those skilled in the art
Method known to member, separates as long as reaching liquid with solid particle；The washing can use those skilled in the art
Known method, is preferably washed, and washing to sodium ions content is 0.03 weight % or less.
According to the present invention, in step (2), there is no particular limitation for condition and concrete operation method to ball milling, with not
It destroys or does not destroy carrier structure substantially and enter silica gel subject in carrier duct.Those skilled in the art can be according to above-mentioned
The various suitable methods of principle selection are implemented, such as the ball milling can carry out in the ball mill, ball grinder in the ball mill
Inner wall be preferably polytetrafluoroethyllining lining, the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can basis
The size of ball grinder is reasonably selected, and 1 abrading-ball usually can be used in the ball grinder for being 50-150ml for size；Institute
The material for stating abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling may include: abrading-ball
Revolving speed can be 300-500r/min, and the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be small for 0.1-100
When.
According to the present invention, in step (3), the spray drying can be implemented according to conventional mode, such as can be
It is carried out in atomizer.The condition of the spray drying may include: that temperature is 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: that temperature is 150-250 DEG C, the revolving speed of rotation
For 11000-13000r/min.It is highly preferred that being taken off from the product that spray drying obtains after the spray drying of step (3)
Template agent removing.The method of removed template method is usually calcination method, and the condition of the removed template method may include: that temperature is 300-
600 DEG C, the time is 10-80 hours.
The present invention also provides the bimodal porous silica carriers prepared by the above method.
The present invention also provides a kind of support type polyethylene catalysts, which contains bimodal porous silica carrier and load
Magnesium elements and/or titanium elements on the bimodal porous silica carrier, wherein the bimodal porous silica carrier is provided by the invention double
Hole silica-gel carrier.
According to the present invention, on the basis of the total weight of the catalyst, the content of the bimodal porous silica carrier is 50-99 weight
Measure %, preferably 85-99 weight %；The sum of content that the magnesium elements and titanium elements are counted in the form of salts is 1-50 weight %, excellent
It is selected as 1-15 weight %.
In the present invention, it is preferred to the magnesium elements and titanium elements are provided in the form of magnesium salts and titanium salt respectively, the magnesium salts
It can be conventional use of various magnesium salts in the art and titanium salt with titanium salt, as long as being capable of providing magnesium elements and titanium elements.
Under preferable case, in the present invention, the magnesium salts is magnesium chloride；The titanium salt is titanium tetrachloride and/or titanium trichloride.
The present invention also provides a kind of preparation methods of support type polyethylene catalysts, this method comprises: in inert gas
In the presence of, carrier is impregnated in the catalyst mother liquor containing magnesium elements and/or titanium elements, be then successively filtered and
It is dry, wherein the carrier is bimodal porous silica carrier provided by the invention, the catalyst mother liquor be containing magnesium elements and/or
The combined organic solution of titanium elements.
In the present invention, the form to the magnesium elements and titanium elements and source are as of the invention noted earlier, the present invention
Details are not described herein.
In the present invention, the inert atmosphere can be by various chemically interactive with carrier and active component generation
Various gases are formed.For example, the inert atmosphere can be by one or more of zero group gas in nitrogen and the periodic table of elements
To provide.
According to the present invention, it is 45-100 DEG C that the condition of the dipping, which includes: temperature, time 2-8h.
In the present invention, the catalyst mother liquor is the combined organic solution containing magnesium elements and/or titanium elements, described multiple
Closing organic solvent can be that can dissolve the magnesium elements and titanium elements and readily removed various solvents, it is preferable that described
Compounded organic solvent is tetrahydrofuran and isopropanol.More preferably, the volume ratio of tetrahydrofuran and isopropanol is 1:1-3, especially
Preferably 1:1-1.5.
The present invention also provides the support type polyethylene catalysts prepared by the above method.
The present invention also provides application of the above-mentioned support type polyethylene catalysts in catalyzed ethylene polymerization reaction.
The present invention does not limit application of the support type polyethylene catalysts in catalyzed ethylene polymerization reaction particularly
Fixed, the catalyst being prepared using bimodal porous silica carrier of the present invention can be obtained when catalyzed ethylene polymerization reacts
Higher catalytic efficiency.
The present invention also provides a kind of methods of vinyl polymerization, this method comprises: in above-mentioned support type polyethylene catalysts
In the presence of, under conditions of polymerization reaction, ethylene is made to carry out polymerization reaction.
It is with higher to urge when catalyst containing bimodal porous silica carrier of the present invention is used for ethylene polymerization
Change efficiency.Moreover, the partial size of the support type polyethylene catalysts is larger, carrier has the large aperture of high-sequential, silica gel portion
The average pore size divided is big, and pore wall strength is moderate, and catalyst decay is slower, and polymerization process steadily continues, and catalytic activity is high.Therefore,
Bimodal porous silica carrier of the present invention is the carrier suitable for vinyl polymerization.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, 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 carries out on the model Autosorb instrument purchased from U.S. Kang Ta company；
Average grain diameter carries out on the laser fineness gage of the model Mastersizer2000 of Malvern company；X-ray fluorescence point
Analysis carries out on the x-ray fluorescence analyzer of the model Axios-Advanced of dutch company；The heap density of polyolefine powder
It is measured using method as defined in GB/T 1636-2008；Melt index is measured according to ASTM D1238-99.
Embodiment 1
The present embodiment be used to illustrate bimodal porous silica carrier of the present invention, support type polyethylene catalysts and they
Preparation method.
(1) bimodal porous silica carrier is prepared
By waterglass that concentration is 15 weight %, sulfuric acid solution, glycerine and n-butanol that concentration is 12 weight % with weight
Amount then adjusts pH value with the sulfuric acid that concentration is 98 weight % than carrying out mixing and the haptoreaction 2h at 30 DEG C for 5:1:1:1
To 3, then obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, is obtained
Silica gel filter cake.
The above-mentioned silica gel filter cake being prepared of 10g is put into 100mL ball grinder, wherein the material of ball grinder is poly- four
Vinyl fluoride, Material quality of grinding balls are agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min.Ball grinder is closed,
Temperature is ball milling 1h at 60 DEG C in ball grinder, obtains 30g solid powder；The solid powder is dissolved in 30 grams of deionized waters,
It is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；By the product obtained after spray drying at 550 DEG C in Muffle furnace
Lower calcining for 24 hours, obtains bimodal porous silica carrier, is named as GJ-1.
(2) support type polyethylene catalysts are prepared
In N2Under protection, by the MgCl of 1g2With the TiCl of 1g4Be dissolved in 500mL compounded organic solvent (tetrahydrofuran with it is different
The volume ratio of propyl alcohol is 1:1.2) in, form the catalyst mother liquor of element containing Mg and Ti element.Then it is added on 10g at 80 DEG C
Carrier impregnation 5h is stated, after the reaction was completed, filtered, dried, the polyethylene powder catalyst with good flow performance is obtained, is ordered
Entitled GJ-BCJ-1.
The support type polyethylene is catalyzed using scanning electron microscope, U.S.'s Kang Ta company Atsorb type instrument and Particle Size Analyzer
The characterization of agent is analyzed.
Fig. 1 is the SEM scanning electron microscope (SEM) photograph of bimodal porous silica carrier (GJ) according to the present invention.As seen from the figure, bimodal porous silica carries
The microscopic appearance of body is the Mesoporous Spheres that average grain diameter is 30-60 μm.
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of support type polyethylene catalysts (GJ-BCJ) according to the present invention.As seen from the figure,
The microscopic appearance of the bimodal porous silica carrier of support type polyethylene catalysts is still basic to keep spherical, and average grain diameter is 30-60 μm.
Fig. 3 is that the SEM of the polyethylene product obtained in the presence of support type polyethylene catalysts (GJ-BCJ) is swept
Retouch electron microscope.There is figure it is found that the microcosmic shape appearance of polyethylene product is still basic to keep spherical, average grain diameter is 30-60 μm.
Table 1 is the pore structure parameter of bimodal porous silica carrier.
Table 1
*: the 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.
Spherical silica gel carrier is diplopore distribution it can be seen from the data of upper table 1.
The results show that the content of chlorine is 2.9 weight % in GJ-BCJ-1, the content of titanium is 1.6 weight %, magnesium for elemental analysis
Content be 5.1 weight %.
Comparative example 1
Commercially available ES955 silica gel (GRACE company) is calcined 10 hours for 400 DEG C under nitrogen protection, with eliminating hydroxide and
Residual water, to obtain the ES955 silica gel through thermal activation.
Catalyst is prepared according to the method for 1 step of embodiment (2), the difference is that using the ES955 silicon of identical weight part
Glue replaces bimodal porous silica carrier.To which comparative catalyst D1 be made.
Elemental analysis is the results show that the content of magnesium is 1.8 weight % in ES955, and the content of titanium is 1.2 weight %, chlorine
Content is 6.8 weight %.
Embodiment 2
The present embodiment be used to illustrate bimodal porous silica carrier of the present invention, support type polyethylene catalysts and they
Preparation method.
(1) bimodal porous silica carrier is prepared
By waterglass that concentration is 30 weight %, sulfuric acid solution, glycerine and n-butanol that concentration is 15 weight % with weight
Amount then adjusts pH value with the sulfuric acid that concentration is 98 weight % than carrying out mixing and the haptoreaction 1h at 60 DEG C for 3:1:1:1
To 2, then obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, is obtained
Silica gel filter cake.
The above-mentioned silica gel filter cake being prepared of 10g is put into 100mL ball grinder, wherein the material of ball grinder is poly- four
Vinyl fluoride, Material quality of grinding balls are agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min.Ball grinder is closed,
Temperature is ball milling 1h at 60 DEG C in ball grinder, obtains 30g solid powder；The solid powder is dissolved in 30 grams of deionized waters,
It is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；By the product obtained after spray drying at 550 DEG C in Muffle furnace
Lower calcining for 24 hours, obtains bimodal porous silica carrier, is named as GJ-2.
(2) support type polyethylene catalysts are prepared
In N2Under protection, by the MgCl of 1g2With the TiCl of 1g4Be dissolved in 500mL compounded organic solvent (tetrahydrofuran with it is different
The volume ratio of propyl alcohol is 1:1.5) in, form the catalyst mother liquor of element containing Mg and Ti element.Then it is added on 10g at 60 DEG C
Carrier impregnation 2h is stated, after the reaction was completed, filtered, dried, the polyethylene powder catalyst with good flow performance is obtained, is ordered
Entitled GJ-BCJ-2.
The support type polyethylene is catalyzed using scanning electron microscope, U.S.'s Kang Ta company Atsorb type instrument and Particle Size Analyzer
The characterization of agent is analyzed.
Table 2 is the pore structure parameter of bimodal porous silica carrier.
Table 2
Spherical silica gel carrier is diplopore distribution it can be seen from the data of upper table 2.
The results show that the content of chlorine is 2.7 weight % in GJ-BCJ-2, the content of titanium is 1.8 weight %, magnesium for elemental analysis
Content be 4.9 weight %.
Embodiment 3
The present embodiment be used to illustrate bimodal porous silica carrier of the present invention, support type polyethylene catalysts and they
Preparation method.
(1) bimodal porous silica carrier is prepared
By waterglass that concentration is 12 weight %, sulfuric acid solution, glycerine and n-butanol that concentration is 10 weight % with weight
Amount then adjusts pH value with the sulfuric acid that concentration is 98 weight % than carrying out mixing and the haptoreaction 5h at 10 DEG C for 6:1:1:1
To 4, then obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.03 weight %, is obtained
Silica gel filter cake.
The above-mentioned silica gel filter cake being prepared of 10g is put into 100mL ball grinder, wherein the material of ball grinder is poly- four
Vinyl fluoride, Material quality of grinding balls are agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min.Ball grinder is closed,
Temperature is ball milling 1h at 60 DEG C in ball grinder, obtains 30g solid powder；The solid powder is dissolved in 30 grams of deionized waters,
It is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；By the product obtained after spray drying at 550 DEG C in Muffle furnace
Lower calcining for 24 hours, obtains bimodal porous silica carrier, is named as GJ-3.
(2) support type polyethylene catalysts are prepared
In N2Under protection, by the MgCl of 1g2With the TiCl of 1g4Be dissolved in 500mL compounded organic solvent (tetrahydrofuran with it is different
The volume ratio of propyl alcohol is 1:1.1) in, form the catalyst mother liquor of element containing Mg and Ti element.Then it is added on 10g at 45 DEG C
Carrier impregnation 8h is stated, after the reaction was completed, filtered, dried, the polyethylene powder catalyst with good flow performance is obtained, is ordered
Entitled GJ-BCJ-3.
The support type polyethylene is catalyzed using scanning electron microscope, U.S.'s Kang Ta company Atsorb type instrument and Particle Size Analyzer
The characterization of agent is analyzed.
Table 3 is the pore structure parameter of bimodal porous silica carrier.
Table 3
Spherical silica gel carrier is diplopore distribution it can be seen from the data of upper table 3.
The results show that the content of chlorine is 2.8 weight % in GJ-BCJ-3, the content of titanium is 1.7 weight %, magnesium for elemental analysis
Content be 5.0 weight %.
Comparative example 2
Catalyst is prepared according to the method for embodiment 1, the difference is that in the step of preparing the carrier, using phase
Deionized water with parts by weight replaces glycerine.To which comparative catalyst D2 be made.
Table 4 is the pore structure parameter for the carrier being prepared using 2 the method for comparative example.
Table 4
The results show that the content of chlorine is 7.1 weight % in D2, the content of titanium is 1.1 weight %, the content of magnesium for elemental analysis
For 2.5 weight %.
Comparative example 3
Catalyst is prepared according to the method for embodiment 1, the difference is that in the step of preparing the carrier, using phase
Deionized water with parts by weight replaces n-butanol.To which comparative catalyst D3 be made.
Table 5 is the pore structure parameter for the carrier being prepared using 3 the method for comparative example.
Table 5
Elemental analysis is the results show that the content of chlorine is 14.3 weight % in D3, and the content of titanium is 1.1 weight %, and magnesium contains
Amount is 2.5 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used to illustrate support type polyethylene catalysts according to the present invention in ethylene polymerization
Using.
It in the stainless steel polymerization autoclave of 2L, is respectively replaced three times with nitrogen and ethylene, 200mL hexane is then added, it will
Kettle temperature rises to 80 DEG C, adds 800mL hexane, and with the addition of hexane, the concentration that 2mL is added is the triethyl aluminum of 1mol/L
(TEA) hexane solution is subsequently added into the catalyst that the embodiment 1 of 0.1g is prepared, is passed through ethylene, pressure is risen to 1.0MPa
And it is maintained 1.0MPa, it is reacted 1 hour at 70 DEG C.Polyethylene particle powder is obtained, the heap density of the polyethylene particle powder
It (BD) is 0.40g/ml, melt index MI2.16=0.70g/10min.It is computed determination, the efficiency of catalyst is 2700g PE/
gcat.h。
Experimental comparison's example 1
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 1, unlike, using pair of identical weight part
The catalyst that D1 prepared by ratio 1 replaces embodiment 1 to be prepared.The heap density (BD) of gained polyethylene particle powder is
0.41g/ml, melt index: MI2.16=0.87g/10min.It is computed determination, the efficiency of catalyst is 1767g PE/
gcat.h。
EXPERIMENTAL EXAMPLE 2
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 1, unlike, using the reality of identical weight part
Apply the catalyst that the catalyst of the preparation of example 2 replaces embodiment 1 to be prepared.The heap density (BD) of gained polyethylene particle powder is
0.41g/ml, melt index: MI2.16=0.72g/10min.It is computed determination, the efficiency of catalyst is 2650g PE/
gcat.h。
EXPERIMENTAL EXAMPLE 3
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 1, unlike, using the reality of identical weight part
Apply the catalyst that the catalyst of the preparation of example 3 replaces embodiment 1 to be prepared.The heap density (BD) of gained polyethylene particle powder is
0.39g/ml, melt index: MI2.16=0.71g/10min.It is computed determination, the efficiency of catalyst is 2730g PE/
gcat.h。
Experimental comparison's example 2
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 1, unlike, using pair of identical weight part
The catalyst that D1 prepared by ratio 2 replaces embodiment 1 to be prepared.The heap density (BD) of gained polyethylene particle powder is
0.41g/ml, melt index: MI2.16=0.98g/10min.It is computed determination, the efficiency of catalyst is 1232g PE/
gcat.h。
Experimental comparison's example 3
Polymerizeing for ethylene is carried out using with the identical method of EXPERIMENTAL EXAMPLE 1, unlike, using pair of identical weight part
The catalyst that D3 prepared by ratio 3 replaces embodiment 1 to be prepared.The heap density (BD) of gained polyethylene particle powder is
0.39g/ml, melt index: MI2.16=0.99g/10min.It is computed determination, the efficiency of catalyst is 1413g PE/
gcat.h。
It can be seen from above embodiment is compared with comparative example in ethylene polymerisation process, support type polyethylene is urged
Agent catalytic efficiency with higher, and in support type polyethylene catalysts provided by the invention metal active constituent load
Rate is high.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (15)
1. a kind of preparation method of bimodal porous silica carrier, which is characterized in that this method comprises:
(1) in inorganic acid solution, by waterglass, glycerine and n-butanol carry out haptoreaction, and by after haptoreaction gained
Mixture is filtered and washed, and obtains silica gel filter cake；
(2) solid powder is obtained after the silica gel filter cake obtained by (1) being carried out ball milling；
(3) solid powder obtained by (2) is configured to after slurry be successively spray-dried and calcined in aqueous solution；
Wherein, the average particle diameter of the bimodal porous silica carrier obtained using this method is 20-50 μm, specific surface area 150-
600m2/ g, pore volume 0.5-1.6mL/g, aperture is in bimodal distribution, and bimodal corresponding most probable pore size is 2-4nm
And 10-40nm.
2. according to the method described in claim 1, wherein, in step (1), the waterglass, inorganic acid, glycerine and positive fourth
The dosage weight ratio of alcohol is 3-6:1:1:1.
3. according to the method described in claim 1, wherein, in step (1), the catalytic condition includes: contact temperature
Degree is 10-60 DEG C, and time of contact is 1-5 hours, pH value 2-4.
4. according to the method described in claim 1, wherein, in step (1), the inorganic acid is in sulfuric acid, nitric acid and hydrochloric acid
At least one.
5. according to the method described in claim 1, wherein, in step (2), the condition of the ball milling includes: that ball radius is
2-3mm, revolving speed 300-500r/min, temperature are 15-100 DEG C, time 0.1-100h.
6. according to the method described in claim 1, wherein, in step (3), the condition of the spray drying includes: that temperature is
100-300 DEG C, revolving speed 10000-15000r/min.
7. in step (3), the temperature of the calcining is 300-600 DEG C according to the method described in claim 1, wherein, the time
For 10-80h.
8. a kind of support type polyethylene catalysts, which, which contains bimodal porous silica carrier and be supported on the bimodal porous silica, carries
Magnesium elements and/or titanium elements on body, which is characterized in that the bimodal porous silica carrier is any one of claim 1-7 institute
The bimodal porous silica carrier that the method stated is prepared.
9. catalyst according to claim 8, wherein on the basis of the total weight of the catalyst, the bimodal porous silica
The content of carrier is 50-99 weight %, and the sum of content that the magnesium elements and titanium elements are counted in a salt form is 1-50 weight %.
10. catalyst according to claim 9, wherein on the basis of the total weight of the catalyst, the bimodal porous silica
The content of carrier is 85-99 weight %, and the sum of content that the magnesium elements and titanium elements are counted in a salt form is 1-15 weight %.
11. a kind of preparation method of support type polyethylene catalysts, this method comprises: under an inert atmosphere, carrier is being contained
It is impregnated in the catalyst mother liquor of magnesium elements and/or titanium elements, is then successively filtered and dries, which is characterized in that institute
Stating carrier is the bimodal porous silica carrier that method described in any one of claim 1-7 is prepared, the catalyst mother liquor
For the combined organic solution containing magnesium elements and/or titanium elements.
12. according to the method for claim 11, wherein the condition of the dipping includes: that temperature is 45-100 DEG C, and the time is
2-8h。
13. the support type polyethylene catalysts that the method as described in claim 11 or 12 is prepared.
14. support type polyethylene catalysts described in any one of claim 8-10 and 13 are in catalyzed ethylene polymerization reaction
Application.
15. a kind of method of vinyl polymerization, this method comprises: in the presence of a catalyst, under conditions of polymerization reaction, making second
Alkene carries out polymerization reaction, which is characterized in that the catalyst is support type described in any one of claim 8-10 and 13
Polyethylene catalysts.
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| CN110496631B (en) * | 2018-05-17 | 2021-09-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
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| CN1246808A (en) * | 1997-02-11 | 2000-03-08 | 美孚石油公司 | Ziegler-Natta catalyst for ethylene polymerization or copolymerization |
| CN104248981A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical composite carrier of three dimensional cube tunnel and catalyst, preparation method and application thereof, and preparation method of ethyl acetate |
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| CN1246808A (en) * | 1997-02-11 | 2000-03-08 | 美孚石油公司 | Ziegler-Natta catalyst for ethylene polymerization or copolymerization |
| CN104248981A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical composite carrier of three dimensional cube tunnel and catalyst, preparation method and application thereof, and preparation method of ethyl acetate |
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