CN105175586A - Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method - Google Patents
Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method Download PDFInfo
- Publication number
- CN105175586A CN105175586A CN201410263891.XA CN201410263891A CN105175586A CN 105175586 A CN105175586 A CN 105175586A CN 201410263891 A CN201410263891 A CN 201410263891A CN 105175586 A CN105175586 A CN 105175586A
- Authority
- CN
- China
- Prior art keywords
- composite material
- mesoporous composite
- preparation
- meso
- pore size
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a meso-porous composite material, a preparation method thereof, a catalyst ingredient preparation method, and a polyethylene preparation method. The meso-porous composite material comprises a molecular sieve material with a hexagonal tunnel structure and silica gel, the meso-porous composite material is spherical, the pore volume of the meso-porous composite material is 0.5-1.8mL/g, the specific surface area is 200-650m<2>/g, the average particle size is 20-60[mu]m, the apertures are distributed in a double peak manner, two peaks respectively correspond to a first most probable aperture and a second most probable aperture, the first most probable aperture is 1-3nm, and the second most probable aperture is 10-30nm. The meso-porous composite material still keeps an ordered meso-structure after loading. Active components Mg and Ti are loaded on the composite material to prepare a catalyst ingredient, and the catalyst ingredient makes a catalyst keep high catalytic activity in ethylene polymerization and allows polyethylene particle powder to be obtained.
Description
Technical field
The present invention relates to a kind of mesoporous composite material, the preparation method of this mesoporous composite material, and the mesoporous composite material prepared by the method, the invention still further relates to a kind of catalyst component, and a kind of poly preparation method.
Background technology
Since the regular mesoporous material of Mobile company synthesis duct high-sequential in 1992, because it has high specific surface, regular pore passage structure and narrow pore size distribution, mesoporous material is made to obtain very large concern in the application of catalysis, separation, medicine and other fields.Within 1998, Zhao east unit waits people to synthesize a kind of type material-mesoporous material SBA-15, and this material has the aperture (6-30nm) of high-sequential, large pore volume (1.0cm
3/ g), thicker hole wall (4-6nm), the high mechanical strength kept and good catalytic adsorption performance (see D.Y.Zhao, J.L.Feng, Q.S.Huo, etalScience279 (1998) 548-550).CN1341553A discloses a kind of preparation method of mesonic pore molecular sieve carrier material, and the obtained mesoporous material of the method, as heterogeneous reaction support of the catalyst, easily realizes being separated of catalyzer and product.
But the ordered mesoporous material SBA-15 microscopic appearance of routine is bar-shaped, itself mobility is poor, its large specific surface area and high pore volume cause and make it have stronger water suction, moisture absorption ability, this exacerbates the reunion of ordered mesoporous material further, limits the storage of ordered mesoporous material, transports, post-treatment and application.
The Application and Development of polyethylene catalysts is after traditional Ziegler-Natta catalyst, the another important breakthrough in olefin polymerization catalysis field, and this makes the research of polyethylene catalysts enter into the stage of a fast development.Catalyst levels needed for homogeneous polyethylene catalyzer arrival high reactivity is large, production cost is high, and the polymkeric substance obtained is without particle shape, cannot use on widely used slurry process or gas phase polymerization technique.The effective way overcoming the problems referred to above carries out supported process soluble poly catalyst for ethylene exactly.
The mesoporous material of the load polyethylene catalysts that current document is reported is MCM-41, with catalytic activity after the MCM-41 of load polyethylene catalysts carries out vinyl polymerization again after MAO process for 10
6gPE/ (molZrh).Carry out after Mesoporous silica MCM 41 supported catalyst the lower reason of ethylene polymerization activity mainly the hole wall structure thermostability of MCM-41 and hydrothermal stability poor, part is just had to cave at loading process hole wall, have impact on load effect, to such an extent as to have impact on catalytic activity.
Therefore, be necessary to seek the stable mesoporous material of a kind of new meso-hole structure, make it after load, still can keep orderly meso-hole structure, thus make catalyzer have higher catalytic activity.
Summary of the invention
The object of the invention is to solve the technical problem that the catalytic activity of loading type polyethylene catalysts in prior art is low, a kind of mesoporous composite material is provided, the preparation method of this mesoporous composite material, and the mesoporous composite material to be prepared by the method, the invention still further relates to a kind of catalyst component, and a kind of poly preparation method.
In order to achieve the above object, the present inventor is by finding after research, the meso-porous molecular sieve material and silica gel with hexagonal hole road structure are mixed and made into spherical mesoporous composite material, and when the pore volume of this matrix material is 0.5-1.8mL/g, specific surface area is 200-650m
2/ g, median size is 20-60 μm, and aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is 1-3nm, and described second most probable pore size is 10-30nm.The supported catalyst component synthesized for carrier with this mesoporous composite material is when for ethylene polymerization, and catalyzer has the catalytic efficiency significantly improved, thus completes the present invention.
According to a first aspect of the invention, the invention provides a kind of mesoporous composite material, wherein, this mesoporous composite material comprises the molecular screen material and silica gel with hexagonal hole road structure, described mesoporous composite material is spherical, the pore volume of described mesoporous composite material is 0.5-1.8mL/g, and specific surface area is 200-650m
2/ g, median size is 20-60 μm, and aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is 1-3nm, and described second most probable pore size is 10-30nm.
According to a second aspect of the invention, the invention provides a kind of preparation method of mesoporous composite material, the method comprises the following steps:
(1) provide or prepare the filter cake of the molecular screen material with hexagonal hole road structure, as component a;
(2) provide or prepare the filter cake of silica gel, as components b;
(3) component a and components b carried out mixing and after ball milling, carry out spraying dry to obtain spherical mesoporous composite material;
Wherein, described component a and components b make the pore volume of mesoporous composite material be 0.5-1.8mL/g, and specific surface area is 200-650m
2/ g, median size is 20-60 μm, and aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is 1-3nm, and described second most probable pore size is 10-30nm.
According to a third aspect of the present invention, the invention provides mesoporous composite material prepared by aforesaid method.
According to a fourth aspect of the present invention, the invention provides a kind of catalyst component, this catalyst component comprises carrier and load magnesium salts on the carrier and titanium salt, and wherein, described magnesium salts is magnesium chloride, and described titanium salt is titanium tetrachloride and/or titanous chloride; Described carrier is mesoporous composite material of the present invention.
According to a fifth aspect of the present invention, the invention provides a kind of poly preparation method, the method comprises: under solution polymerization condition, in the presence of a catalyst, makes ethene carry out polyreaction, wherein, described catalyzer contains above-mentioned catalyst component.
Mesoporous composite material of the present invention still can keep orderly meso-hole structure after load.By active ingredient magnesium and titanium load after this matrix material, when obtained catalyst component is used for vinyl polymerization, the catalytic activity that catalyzer keeps higher can be made, and polyethylene particle powder can be obtained.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the XRD spectra according to mesoporous composite material of the present invention;
A and b of Fig. 2 is the SEM figure of the different amplification of the microscopic appearance according to mesoporous composite material of the present invention;
Fig. 3 is the SEM figure of the microscopic appearance of catalyst according to the invention component;
Fig. 4 is the graph of pore diameter distribution according to mesoporous composite material of the present invention;
Fig. 5 is the grain size distribution according to mesoporous composite material of the present invention.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to a first aspect of the invention, the invention provides a kind of mesoporous composite material, wherein, this mesoporous composite material comprises the molecular screen material and silica gel with hexagonal hole road structure, described mesoporous composite material is spherical, the pore volume of described mesoporous composite material is 0.5-1.8mL/g, and specific surface area is 200-650m
2/ g, median size is 20-60 μm, and aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is 1-3nm, and described second most probable pore size is 10-30nm.
Mesoporous composite material according to the present invention has hexagonal hole road structure, and its median size adopts laser fineness gage to record, and specific surface area, pore volume and most probable pore size record according to nitrogen adsorption methods.
Be spherical according to mesoporous composite material of the present invention, by the particle size of spherical mesoporous composite material is controlled within above-mentioned scope, can guarantee that described mesoporous composite material is not easily reunited, and the reaction raw materials transformation efficiency in ethylene polymerization process can be improved used as the supported catalyst component that carrier is made.When the specific surface area of described mesoporous composite material is less than 200m
2when/g and/or pore volume are less than 0.5mL/g, the catalytic activity of the supported catalyst component made used as carrier in ethylene polymerization process can significantly reduce; When the specific surface area of described mesoporous composite material is greater than 650m
2when/g and/or pore volume are greater than 1.8mL/g, the supported catalyst component made used as carrier is easily reunited in ethylene polymerization process, thus affects the transformation efficiency of monomer in ethylene polymerization.Preferably, the pore volume of described mesoporous composite material is 0.6-1.6mL/g, and specific surface area is 200-450m
2/ g.
The content of the present invention to the molecular screen material and silica gel with hexagonal hole road structure is not particularly limited, as long as the microscopic dimensions of mesoporous composite material can be made to meet above-mentioned condition.According to the present invention, relative to the meso-porous molecular sieve material described in 100 weight parts with hexagonal hole road structure, the content of described silica gel can be 1-200 weight part.From the angle improving further the supported catalyst component of described mesoporous composite material as carrier and be used for the catalytic activity of the catalyzer of vinyl polymerization, preferably, relative to the meso-porous molecular sieve material described in 100 weight parts with hexagonal hole road structure, the content of described silica gel is 50-150 weight part.
In the present invention, the content of the molecular screen material and silica gel described in hexagonal hole road structure can be determined according to the usage quantity when preparing described mesoporous composite material.
In the present invention, the median size of described mesoporous composite material of the present invention is 20-60 μm.Preferably, the median size of described mesoporous composite material is 30-60 μm, can prevent the reunion of described mesoporous composite material so further, thus increases the catalytic activity of catalyst component for catalyzer that matrix material is carrier formation further.
According to a second aspect of the invention, the invention provides a kind of preparation method of mesoporous composite material, the method comprises the following steps:
(1) provide or prepare the filter cake of the molecular screen material with hexagonal hole road structure, as component a;
(2) provide or prepare the filter cake of silica gel, as components b;
(3) component a and components b carried out mixing and after ball milling, carry out spraying dry to obtain spherical mesoporous composite material;
Wherein, described component a and components b make the pore volume of mesoporous composite material be 0.5-1.8mL/g, and specific surface area is 200-650m
2/ g, median size is 20-60 μm, and aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is 1-3nm, and described second most probable pore size is 10-30nm.
In step (1), the process that preparation has the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure can comprise: tetraethoxy, cetyl trimethylammonium bromide (CTAB) and ammonia are carried out contact reacts, and the mixture obtained after contact reacts is carried out crystallization and filtration.
Wherein, the mol ratio of tetraethoxy, cetyl trimethylammonium bromide and ammonia can be 1:0.1-1:0.1-5, is preferably 1:0.2-0.5:1.5-3.5.
Ammonia preferably adds with the form of ammoniacal liquor.
According to the present invention, the contact reacts process of tetraethoxy, cetyl trimethylammonium bromide and ammonia is carried out in presence of water.Preferably, part water is introduced with the form of ammoniacal liquor, and part water adds with the form of deionized water.In the contact reacts system of tetraethoxy, cetyl trimethylammonium bromide and ammonia, the mol ratio of tetraethoxy and water can be 1:100-200, is preferably 1:120-180.
The catalytic condition of tetraethoxy, cetyl trimethylammonium bromide and ammonia can comprise: temperature is 25-100 DEG C, and the time is 10-72 hour.Preferably, this contact reacts is under agitation carried out, and is beneficial to the Homogeneous phase mixing between each material.
The condition of described crystallization can comprise: temperature is 30-150 DEG C, and the time is 10-72 hour.Under preferable case, the condition of described crystallization comprises: temperature is 40-100 DEG C, and the time is 20-40 hour.Described crystallization is implemented by hydrothermal crystallization method.
Have in the process of the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure in above-mentioned preparation, can comprise with the process obtaining filter cake by filtering: after filtration, with deionized water repetitive scrubbing (washing times can be 2-10), then carry out suction filtration.
In step (1), " providing the meso-porous molecular sieve material with hexagonal hole road structure " can be the product directly taking or choose the meso-porous molecular sieve material with hexagonal hole road structure, also can be the meso-porous molecular sieve material that preparation has hexagonal hole road structure.The described preparation method with the meso-porous molecular sieve material of hexagonal hole road structure can implement according to the method for routine, such as, its preparation method can comprise: the filter cake according to aforesaid method preparation with the meso-porous molecular sieve material of hexagonal hole road structure, then by gained filtration cakes torrefaction.
In step (2), the process preparing the filter cake of silica gel can comprise: be that 3-6:1 contact with mineral acid with weight ratio by water glass, and is filtered by the mixture obtained after contact.
There is no particular limitation for the condition that water glass contacts with mineral acid, suitably can select according in the common process preparing silica gel.Under preferable case, the condition that water glass contacts with mineral acid comprises: temperature can be 10-60 DEG C, is preferably 20-45 DEG C; PH value can be 2-4; Time can be 1-5 hour.
In order to more be conducive to the Homogeneous phase mixing between each material, water glass and the catalytic process of mineral acid are preferably carried out under agitation.
Described water glass is the aqueous solution of water glass, and its concentration can be 3-20 % by weight.
Described mineral acid can be the various mineral acids that this area routine uses, and such as, can be at least one in sulfuric acid, nitric acid and hydrochloric acid.Described mineral acid can use in pure form, also can use with the form of its aqueous solution.
In step (2), " providing silica gel " can be directly take or choose silica gel product, also can be prepare silica gel.The method preparing silica gel can be implemented according to the method for routine, such as, can comprise: the filter cake preparing silica gel according to aforesaid method, then by gained filtration cakes torrefaction.
In step (3), the consumption of described component a and components b makes the meso-porous molecular sieve material relative to having hexagonal hole road structure described in 100 weight parts, and the content of described silica gel can be 1-200 weight part, is preferably 50-150 weight part.
In step (3), described ball milling can carry out in ball mill, and in described ball mill, the inwall of ball grinder is preferably polytetrafluoroethyllining lining, and the diameter of the abrading-ball in ball mill can be 2-3mm; The quantity of abrading-ball reasonably can be selected according to the size of ball grinder, is the ball grinder of 50-150mL for size, usually can use 1 abrading-ball; The material of described abrading-ball can be agate, tetrafluoroethylene etc., is preferably agate.The condition of described ball milling can comprise: the rotating speed of abrading-ball 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 0.1-100 hour.
In step (3), described spraying dry can be implemented according to the mode of routine, such as, the pressed powder obtained after ball milling and water can be made into slurry and join in spraying gun and carry out.Described spray-dired condition can comprise: temperature is 150-600 DEG C, and the rotating speed of rotation can be 10000-15000r/min; Under preferable case, described spray-dired condition comprises: temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min.The process of the pressed powder water slurrying obtained after ball milling can be carried out at 25-60 DEG C.In pulping process, the weight ratio of the consumption of pressed powder and water can be 1:0.1-5, is preferably 1:0.5-3.5.
According to the present invention, described spray-dired condition optimization makes the median size of described mesoporous composite material be 30-60 μm.In step (3), when step (1) has the process of the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure for preparation, the preparation method of described mesoporous composite material can also comprise: after the spraying dry of step (3), from the product that spraying dry obtains, remove cetyl trimethylammonium bromide.The process removing cetyl trimethylammonium bromide can comprise: the product that spraying dry is obtained in retort furnace with the temperature calcination 10-80 hour of 90-600 DEG C.
According to a third aspect of the present invention, present invention also offers the mesoporous composite material prepared by aforesaid method.
The mesoporous composite material prepared by method of the present invention is spherical, and the meso-hole structure of this mesoporous composite material is stablized, and therefore can improve the catalytic activity of catalyst component in vinyl polymerization as carrier.
According to a fourth aspect of the present invention, the invention provides a kind of catalyst component, this catalyst component comprises carrier and load magnesium salts on the carrier and titanium salt, and wherein, described magnesium salts is magnesium chloride, and described titanium salt is titanium tetrachloride and/or titanous chloride; Described carrier is above-mentioned mesoporous composite material.
In the present invention, " catalyst component " refers to that catalyst component of the present invention himself can as being loaded catalyst, or as the component in catalyzer.
In described catalyst component, to the total content of the active ingredient magnesium on described carrier and titanium, there is no particular limitation, suitably can select according to the loaded catalyst of this area routine, such as, with the gross weight of described catalyst component for benchmark, the total content of magnesium and titanium can be 1-10 % by weight, is preferably 2-8 % by weight.
In the present invention, in described catalyst component, the content of each element can adopt X-ray fluorescence spectra analytical method to record.
In the present invention, the various methods preparation that described catalyst component can use according to this area routine, only needs by magnesium salts and titanium salt load on the carrier.
According to one embodiment of the present invention, the method preparing described catalyst component can comprise: described magnesium salts and titanium salt are dissolved in organic solvent, form catalyzer mother liquor, then at 25-100 DEG C, described mesoporous composite material is joined in mother liquor and floods 0.1-5 hour, thus obtain mixture, and mixture material is carried out spraying dry.Wherein, the organic solvent for the preparation of described catalyzer mother liquor can be Virahol and tetrahydrofuran (THF), and the volume ratio of tetrahydrofuran (THF) and Virahol can be 1:1-3, is preferably 1:1-1.5.
According to the present invention, the ratio of magnesium salts when preparing described catalyst component and the consumption of titanium salt can be selected for routine during vinyl polymerization, and usually, the weight ratio of described magnesium salts, titanium salt consumption can be 1:0.1-2.
According to a fifth aspect of the present invention, the invention provides a kind of poly preparation method, the method comprises: under solution polymerization condition, in the presence of a catalyst, makes ethene carry out polyreaction, wherein, described catalyzer contains above-mentioned catalyst component.
According to the present invention, in order to improve the transformation efficiency of ethene further, described catalyzer is also containing aluminum alkyls, and the structure of described aluminum alkyls is such as formula shown in I:
AlR
nx
5 (3-n)formula I
In formula I, n R can be C separately
1~ C
5alkyl; 3-n X
5can be the one in halogen group separately, be preferably-Cl; N is 0,1,2 or 3.
Described C
1-C
5alkyl can be one or more in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
The specific examples of described alkylaluminium cpd includes but not limited to: trimethyl aluminium, dimethylaluminum chloride, triethyl aluminum, diethyl aluminum chloride, tri-n-n-propyl aluminum, diη-propyl aluminum chloride, three n-butylaluminum, three sec-butyl aluminium, tri-tert aluminium, di-n-butyl aluminum chloride and diisobutyl aluminum chloride.
Preferably, described aluminum alkyls is triethyl aluminum.
The consumption of described aluminum alkyls also can be the selection of this area routine, and usually, the mass ratio of described aluminum alkyls and described catalyst component consumption can be 1:0.1-10; Under preferable case, the mass ratio of described aluminum alkyls and described catalyst component consumption is 1:0.2-8.
According to the present invention, the condition of described solution polymerization can be the condition of this area routine.Such as, described solution polymerization carries out in the presence of an inert gas, and described solution polymerization condition comprises: temperature can be 10-100 DEG C, is preferably 20-95 DEG C; Time can be 0.5-5 hour, is preferably 1-4 hour; Pressure can be 0.1-2MPa, is preferably 0.5-1.5MPa.
Described rare gas element is the gas do not reacted with raw material and product, such as, can be at least one in the nitrogen of this area routine or the periodic table of elements in neutral element gas, be preferably nitrogen.
The present invention is not particularly limited the solvent used in described solution polymerization, such as, can be hexane.
In the present invention, described method can also comprise, and after polymerization, carries out suction filtration separation by final reaction mixture, thus obtained polyethylene particle powder.
Below will be described the present invention by embodiment.
In following examples and comparative example, X-ray diffraction analysis is that the X-ray diffractometer of D8Advance carries out in the model purchased from German BrukerAXS company; Scanning electron microscope analysis is that the scanning electronic microscope of XL-30 is carried out in the model of purchased from American FEI Co.; Pore structure parameter analysis is that the nitrogen adsorption desorption instrument of Autosorb-1 carries out in the model of purchased from American Kang Ta company, wherein, before testing, sample is degassed 4 hours at 200 DEG C; Median size is that the laser fineness gage of Mastersizer2000 carries out in the model of Malvern company, and sample is dissolved in ethanol; X-ray fluorescence analysis is that the x-ray fluorescence analyzer of Axios-Advanced carries out in the model of dutch company.
The method that the bulk density of polyolefine powder adopts GB/T1636-2008 to specify measures.
Melt index: measure according to ASTMD1238-99.
Embodiment 1
The present embodiment is for illustration of mesoporous composite material of the present invention and catalyst component and their preparation method.
(1) mesoporous composite material is prepared
Cetyl trimethylammonium bromide and tetraethoxy being joined concentration is in the ammonia soln of 25 % by weight, and the mol ratio of ammonia in tetraethoxy, cetyl trimethylammonium bromide, ammoniacal liquor and water is 1:0.37:2.8:142, and stir 24 hours at 80 DEG C, and then at 100 DEG C hydrothermal treatment consists 24 hours, then carry out filtration and also use deionized water wash 4 times, then suction filtration obtains the filter cake A1 of the meso-porous molecular sieve material with hexagonal hole road structure.
By concentration be 15 % by weight water glass and concentration be 12 % by weight sulphuric acid soln with weight ratio be 5:1 carry out mixed be incorporated in 30 DEG C at contact reacts 1.5 hours, then be the sulfuric acid adjusted to ph to 3 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B1 of silica gel.
The 10g filter cake A1 of above-mentioned preparation is put into together with 10g filter cake B1 the ball grinder of 100mL, wherein, the material of ball grinder is tetrafluoroethylene, and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 5 hours at 25 DEG C, obtains pressed powder; This pressed powder is dissolved in 25g deionized water, at 200 DEG C under rotating speed is 12000r/min spraying dry; The product obtained after spraying dry is calcined 10 hours in retort furnace at 550 DEG C, removes CTAB, obtain mesoporous composite material C1.
(2) Kaolinite Preparation of Catalyst component
0.1g magnesium chloride and 0.1g titanium tetrachloride are dissolved in (volume ratio of tetrahydrofuran (THF) and Virahol is 1:1.2) in the tetrahydrofuran (THF) of 10mL and the double solvents of Virahol, form catalyzer mother liquor.At 45 DEG C, 1g mesoporous composite material C1 is joined thorough impregnation 1h in mother liquor, then filters, and carry out washing 4 times with normal hexane, 75 DEG C of oven dry, and grind, obtain catalyst component D1.
Fig. 1 is the XRD figure spectrum of mesoporous composite material C1, and the Small angle wherein occurred spectrum peak is known, and C1 has the hexagonal hole road structure of the specific two dimension of mesoporous material.
A and b of Fig. 2 is the SEM figure of the different amplification of the microscopic appearance of mesoporous composite material C1.As seen from the figure, the microscopic appearance of mesoporous composite material C1 to be particle diameter the be microballoon of 30-60 μm, and its good dispersion property.
Fig. 3 is the SEM figure of the microscopic appearance of catalyst component D1.As seen from the figure, the microscopic appearance of D1 keeps spherical substantially, and its particle diameter is also 30-60 μm, and particle diameter remains unchanged substantially.
Fig. 4 is the graph of pore diameter distribution of mesoporous composite material C1, and as seen from the figure, matrix material has double-pore structure distribution, and duct is very even.
Fig. 5 is the grain size distribution of mesoporous composite material C1.
The pore structure parameter of mesoporous composite material C1 and catalyst component D1 is as shown in table 1.
Table 1
*: the first most probable pore size and the second most probable pore size comma separate: be the first most probable pore size before comma, are the second most probable pore size after comma; Identical with it with the most probable pore size representation of following table 2-3.
Results of elemental analyses shows, and in catalyst component D1, the content of titanium is 1.6%, and the content of chlorine is 8.1%, Mg content is 3.9%.
Comparative example 1
By ES955 silica gel under nitrogen protection in 400 DEG C of calcinings 10 hours, with eliminating hydroxide and Residual water, obtain the ES955 silica gel activated.
According to the method Kaolinite Preparation of Catalyst component in the step (2) of embodiment 1, difference is, replaces mesoporous composite material C1 with the ES955 silica gel of the activation of equal mass, thus obtained catalyst component DD1.
Results of elemental analyses shows, and in catalyst component DD1, the content of titanium is 1.2%, and the content of magnesium is 3.0%, and the content of chlorine is 6.8%.
Embodiment 2
The present embodiment is for illustration of mesoporous composite material of the present invention and catalyst component and their preparation method.
(1) composite mesoporous carrier is prepared
Cetyl trimethylammonium bromide and tetraethoxy being joined concentration is in the ammonia soln of 25 % by weight, ammonia in tetraethoxy, cetyl trimethylammonium bromide, ammoniacal liquor and the mol ratio of water are 1:0.37:2.8:142, and stir 20 hours at 90 DEG C, and then at 100 DEG C hydrothermal treatment consists 24 hours, then carry out filtration and also use deionized water wash 6 times, then suction filtration obtains the filter cake A2 of the meso-porous molecular sieve material with hexagonal hole road structure.
By concentration be 15 % by weight water glass and concentration be 12 % by weight sulphuric acid soln with weight ratio be 4:1 carry out mixed be incorporated in 40 DEG C at contact reacts 1 hour, then be the sulfuric acid adjusted to ph to 3 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B2 of silica gel.
The 20g filter cake A2 of above-mentioned preparation is put into together with 10g filter cake B2 the ball grinder of 100mL, wherein, the material of ball grinder is tetrafluoroethylene, and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 5 hours at 30 DEG C, obtains pressed powder; This pressed powder is dissolved in 100g deionized water, at 200 DEG C under rotating speed is 12000r/min spraying dry; The product obtained after spraying dry is calcined 9 hours in retort furnace at 600 DEG C, removes CTAB, obtain mesoporous composite material C2.
(2) Kaolinite Preparation of Catalyst component
0.1g magnesium chloride and 0.1g titanium tetrachloride are dissolved in (volume ratio of tetrahydrofuran (THF) and Virahol is 1:1.2) in the tetrahydrofuran (THF) of 10mL and the double solvents of Virahol, form catalyzer mother liquor.At 45 DEG C, 1g mesoporous composite material C2 to be joined in mother liquor thorough impregnation 1 hour, then filter, and carry out washing 4 times with normal hexane, 75 DEG C of oven dry, and grind, obtain catalyst component D2.
Table 2 is the pore structure parameter of mesoporous composite material C2.
Table 2
Results of elemental analyses shows, and in catalyst component D2, the content of titanium is 1.7%, and the content of magnesium is 4.0%, and the content of chlorine is 8.3%.
Embodiment 3
The present embodiment is for illustration of mesoporous composite material of the present invention and catalyst component and their preparation method.
(1) composite mesoporous carrier is prepared
Cetyl trimethylammonium bromide and tetraethoxy being joined concentration is in the ammonia soln of 25 % by weight, ammonia in tetraethoxy, cetyl trimethylammonium bromide, ammoniacal liquor and the mol ratio of water are 1:0.42:2.5:145, and stir 10 hours at 100 DEG C, and then at 100 DEG C hydrothermal treatment consists 24 hours, then carry out filtration and also use deionized water wash 6 times, then suction filtration obtains the filter cake A3 of the meso-porous molecular sieve material with hexagonal hole road structure.
By concentration be 15 % by weight water glass and concentration be 12 % by weight sulphuric acid soln with weight ratio be 5:1 carry out mixed be incorporated in 45 DEG C at contact reacts 1 hour, then be the sulfuric acid adjusted to ph to 3 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B3 of silica gel.
The 5g filter cake A3 of above-mentioned preparation is put into together with 10g filter cake B3 the ball grinder of 100mL, wherein, the material of ball grinder is tetrafluoroethylene, and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 5 hours at 30 DEG C, obtains pressed powder; This pressed powder is dissolved in 50g deionized water, at 200 DEG C under rotating speed is 11000r/min spraying dry; The product obtained after spraying dry is calcined 9 hours in retort furnace at 600 DEG C, removes CTAB, obtain mesoporous composite material C3.
(2) Kaolinite Preparation of Catalyst component
0.1g magnesium chloride and 0.1g titanium tetrachloride are dissolved in (volume ratio of tetrahydrofuran (THF) and Virahol is 1:1.2) in the tetrahydrofuran (THF) of 10mL and the double solvents of Virahol, form catalyzer mother liquor.At 45 DEG C, 1g mesoporous composite material C3 to be joined in mother liquor thorough impregnation 1.5 hours, then filter, and carry out washing 4 times with normal hexane, 75 DEG C of oven dry, and grind, obtain catalyst component D3.
Table 3 is the pore structure parameter of mesoporous composite material C3.
Table 3
Results of elemental analyses shows, and in catalyst component D3, the content of titanium is 1.2%, and the content of magnesium is 3.6%, and the content of chlorine is 7.8%.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for poly preparation method of the present invention is described.
In the stainless steel polymermaking autoclave of 2L, three times are respectively replaced with nitrogen and ethene, then 200mL hexane is added, by still temperature rise to 80 DEG C, then add 800mL hexane, along with adding of hexane, the concentration adding 2mL is the hexane solution of the triethyl aluminum (TEA) of 1mol/L, then add the catalyst component D1 of 0.5g, pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 DEG C of reactions 1 hour.Obtain polyethylene particle powder, the bulk density (BD) of this polyethylene particle powder is 0.35g/mL, melting index MI
2.16=0.69g/10min.Determine as calculated, the efficiency of catalyzer is 2623gPE/gcath.
Experimental comparison's example 1
The method identical with EXPERIMENTAL EXAMPLE 1 is adopted to carry out the polymerization of ethene, unlike, the DD1 adopting the comparative example 1 of identical weight to prepare replaces catalyst component D1, thus obtained polyethylene particle powder, the bulk density (BD) of gained polyethylene particle powder is 0.4g/mL, melting index: MI
2.16=0.87g/10min.Determine as calculated, the efficiency of catalyzer is 1767gPE/gcath.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating according to of the present invention poly preparation method.
In the stainless steel polymermaking autoclave of 2L, three times are respectively replaced with nitrogen and ethene, then add 200mL hexane, by still temperature rise to 75 DEG C, then add 900mL hexane, along with adding of hexane, the concentration adding 2mL is triethyl aluminum (TEA) hexane solution of 1mol/L, then adds the catalyst component D2 of 0.1g, passes into ethene, pressure is risen to 1MPa and is maintained 1MPa, 75 DEG C of reactions 1.5 hours.Obtain polyethylene particle powder, the bulk density (BD) of this polyethylene particle powder is 0.3g/mL, melting index MI
2.16=0.7g/10min.Determine as calculated, the efficiency of catalyzer is 2600gPE/gcath.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for illustrating according to of the present invention poly preparation method.
In the stainless steel polymermaking autoclave of 2L, three times are respectively replaced with nitrogen and ethene, then add 200mL hexane, by still temperature rise to 85 DEG C, then add 700mL hexane, along with adding of hexane, the concentration adding 2mL is triethyl aluminum (TEA) hexane solution of 1mol/L, then adds the catalyst component D3 of 1g, passes into ethene, pressure is risen to 1MPa and is maintained 1MPa, 85 DEG C of reactions 1 hour.Obtain polyethylene particle powder, the bulk density (BD) of this polyethylene particle powder is 0.3g/mL, melting index MI
2.16=0.6g/10min.Determine as calculated, the efficiency of catalyzer is 3000gPE/gcath.
As can be seen from above EXPERIMENTAL EXAMPLE 1-3, in poly preparation method of the present invention, the catalyzer of the catalyst component containing embodiment 1-3 has higher catalytic efficiency, and obtained polyethylene particle powder has lower bulk density and melting index.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a mesoporous composite material, it is characterized in that, this mesoporous composite material comprises the molecular screen material and silica gel with hexagonal hole road structure, and described mesoporous composite material is spherical, the pore volume of described mesoporous composite material is 0.5-1.8mL/g, and specific surface area is 200-650m
2/ g, median size is 20-60 μm, and aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is 1-3nm, and described second most probable pore size is 10-30nm.
2. mesoporous composite material according to claim 1, wherein, relative to the meso-porous molecular sieve material described in 100 weight parts with hexagonal hole road structure, the content of described silica gel is 50-150 weight part.
3. mesoporous composite material according to claim 1 and 2, wherein, the median size of described mesoporous composite material is 30-60 μm.
4. a preparation method for mesoporous composite material, the method comprises the following steps:
(1) provide or prepare the filter cake of the molecular screen material with hexagonal hole road structure, as component a;
(2) provide or prepare the filter cake of silica gel, as components b;
(3) component a and components b carried out mixing and after ball milling, carry out spraying dry to obtain spherical mesoporous composite material;
Wherein, described component a and components b make the pore volume of mesoporous composite material be 0.5-1.8mL/g, and specific surface area is 200-650m
2/ g, median size is 20-60 μm, and aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is 1-3nm, and described second most probable pore size is 10-30nm.
5. method according to claim 4, wherein, in step (1), the method preparing component a comprises: be that 1:0.1-1:0.1-5 carries out contact reacts with mol ratio by tetraethoxy, cetyl trimethylammonium bromide and ammonia, described catalytic temperature is 25-100 DEG C.
6. method according to claim 4, wherein, in step (2), the method preparing components b comprises: be that 3-6:1 contact with mineral acid with weight ratio by water glass, and the condition of described contact comprises: pH is 2-4, and the time is 1-5 hour; Described mineral acid is at least one in sulfuric acid, nitric acid and hydrochloric acid.
7. method according to claim 4, wherein, in step (3), the condition of described ball milling comprises: temperature is 15-100 DEG C, and the time is 0.1-100 hour; Described spray-dired temperature is 150-600 DEG C.
8. method according to claim 4, wherein, the consumption of described component a and components b makes the meso-porous molecular sieve material relative to having hexagonal hole road structure described in 100 weight parts, and the content of described silica gel is 50-150 weight part.
9. the method according to claim 4 or 7, wherein, described spray-dired condition makes the median size of described mesoporous composite material be 30-60 μm.
10. mesoporous composite material prepared by the method in claim 4-9 described in any one.
11. 1 kinds of catalyst components, this catalyst component comprises carrier and load magnesium salts on the carrier and titanium salt, and wherein, described magnesium salts is magnesium chloride, and described titanium salt is titanium tetrachloride and/or titanous chloride; Described carrier is the mesoporous composite material in claim 1-3 and 10 described in any one.
12. catalyst components according to claim 11, wherein, with the gross weight of described catalyst component for benchmark, the total content of magnesium and titanium is 1-10 % by weight.
13. 1 kinds of poly preparation methods, the method comprises: under solution polymerization condition, in the presence of a catalyst, and make ethene carry out polyreaction, it is characterized in that, described catalyzer contains the catalyst component described in claim 11 or 12.
14. methods according to claim 13, wherein, described catalyzer is also containing aluminum alkyls; Preferably, described aluminum alkyls is triethyl aluminum; The mass ratio of described aluminum alkyls and described catalyst component consumption is 1:0.1-10.
15. methods according to claim 13 or 14, wherein, described solution polymerization carries out in the presence of an inert gas, and the condition of described solution polymerization comprises: temperature is 10-100 DEG C, and the time is 0.5-5 hour, and pressure is 0.1-2MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410263891.XA CN105175586B (en) | 2014-06-13 | 2014-06-13 | A kind of preparation method of mesoporous composite material and preparation method thereof and catalytic component and polyethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410263891.XA CN105175586B (en) | 2014-06-13 | 2014-06-13 | A kind of preparation method of mesoporous composite material and preparation method thereof and catalytic component and polyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105175586A true CN105175586A (en) | 2015-12-23 |
| CN105175586B CN105175586B (en) | 2018-04-10 |
Family
ID=54898083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410263891.XA Active CN105175586B (en) | 2014-06-13 | 2014-06-13 | A kind of preparation method of mesoporous composite material and preparation method thereof and catalytic component and polyethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105175586B (en) |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417822A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical illite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107417812A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical double meso-hole structure composites and support type polyethylene catalysts and their preparation method |
| CN107417830A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of ethene polymerization method and polyethylene |
| CN107417821A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical composite and support type polyethylene catalysts and their preparation method |
| CN107417825A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107417828A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical composite and support type polyethylene catalysts and their preparation method |
| CN107417831A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107417826A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107417829A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of ethene polymerization method and polyethylene |
| CN107417824A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107417827A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107417832A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of ethene polymerization method and polyethylene |
| CN107417823A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical sepiolite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107417820A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107840912A (en) * | 2016-09-20 | 2018-03-27 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107840913A (en) * | 2016-09-20 | 2018-03-27 | 中国石油化工股份有限公司 | Spherical small particle mesoporous composite material and loaded catalyst and preparation method thereof |
| CN108017740A (en) * | 2016-11-02 | 2018-05-11 | 中国石油化工股份有限公司 | Spherical porous mesoporous composite material and loaded catalyst and preparation method thereof |
| CN108017741A (en) * | 2016-11-02 | 2018-05-11 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN108786864A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855067A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855068A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855198A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109382144A (en) * | 2017-08-07 | 2019-02-26 | 中国石油化工股份有限公司 | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108786897B (en) * | 2017-05-05 | 2019-09-27 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN110614114A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical small-hole mesoporous silica gel composite as carrier and preparation method and application thereof |
| CN111085208A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst with spherical double-mesoporous composite carrier and preparation method and application thereof |
| WO2022078492A1 (en) | 2020-10-15 | 2022-04-21 | 中国石油化工股份有限公司 | Magnesium-based solid and catalyst component having multimodal pore distribution, and preparation methods therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453144A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN103694382A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Preparation method of double-mould-pore-size-distribution silica-gel carrier |
-
2014
- 2014-06-13 CN CN201410263891.XA patent/CN105175586B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453144A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN103694382A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Preparation method of double-mould-pore-size-distribution silica-gel carrier |
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417829A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of ethene polymerization method and polyethylene |
| CN107417825A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107417822B (en) * | 2016-05-24 | 2020-05-12 | 中国石油化工股份有限公司 | Spherical illite mesoporous composite material, supported catalyst and preparation method thereof |
| CN107417821A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical composite and support type polyethylene catalysts and their preparation method |
| CN107417824A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107417828A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical composite and support type polyethylene catalysts and their preparation method |
| CN107417831A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107417827A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN107417830A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of ethene polymerization method and polyethylene |
| CN107417812A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical double meso-hole structure composites and support type polyethylene catalysts and their preparation method |
| CN107417826A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107417832A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of ethene polymerization method and polyethylene |
| CN107417823A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical sepiolite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107417820A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107417822A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical illite mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107840913A (en) * | 2016-09-20 | 2018-03-27 | 中国石油化工股份有限公司 | Spherical small particle mesoporous composite material and loaded catalyst and preparation method thereof |
| CN107840912A (en) * | 2016-09-20 | 2018-03-27 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN108017740A (en) * | 2016-11-02 | 2018-05-11 | 中国石油化工股份有限公司 | Spherical porous mesoporous composite material and loaded catalyst and preparation method thereof |
| CN108017741B (en) * | 2016-11-02 | 2020-04-07 | 中国石油化工股份有限公司 | Method for polymerizing ethylene and polyethylene |
| CN108017741A (en) * | 2016-11-02 | 2018-05-11 | 中国石油化工股份有限公司 | The method and polyethylene of a kind of vinyl polymerization |
| CN108786897B (en) * | 2017-05-05 | 2019-09-27 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108786864B (en) * | 2017-05-05 | 2019-08-20 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108786864A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855198B (en) * | 2017-05-10 | 2019-11-12 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108855068B (en) * | 2017-05-10 | 2019-08-20 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855067B (en) * | 2017-05-10 | 2019-08-20 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855198A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108855068A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855067A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN109382144A (en) * | 2017-08-07 | 2019-02-26 | 中国石油化工股份有限公司 | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN109382144B (en) * | 2017-08-07 | 2019-12-24 | 中国石油化工股份有限公司 | Composite material and preparation method thereof, catalyst and preparation method and application thereof, and method for preparing propylene by propane dehydrogenation |
| CN110614114A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical small-hole mesoporous silica gel composite as carrier and preparation method and application thereof |
| CN111085208A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst with spherical double-mesoporous composite carrier and preparation method and application thereof |
| WO2022078492A1 (en) | 2020-10-15 | 2022-04-21 | 中国石油化工股份有限公司 | Magnesium-based solid and catalyst component having multimodal pore distribution, and preparation methods therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105175586B (en) | 2018-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105175586A (en) | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method | |
| CN105330768B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN105330767A (en) | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof | |
| 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 | |
| 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 | |
| CN106554431B (en) | The method of bimodal porous silica carrier and support type polyethylene catalysts and its preparation method and application and vinyl polymerization | |
| CN104248989B (en) | The preparation method of spherical mesoporous meerschaum complex carrier and Catalysts and its preparation method and application and ethyl acetate | |
| 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 | |
| CN108017740A (en) | Spherical porous mesoporous composite material and loaded catalyst and preparation method thereof | |
| CN107417828A (en) | Spherical composite and support type polyethylene catalysts and their preparation method | |
| CN107417820B (en) | Spherical diatomite mesoporous composite material, supported catalyst and preparation method thereof | |
| CN108003261B (en) | Method for polymerizing ethylene and polyethylene | |
| CN107840912A (en) | The method and polyethylene of a kind of vinyl polymerization | |
| CN107417824B (en) | Method for polymerizing ethylene and polyethylene | |
| CN107417831B (en) | Method for polymerizing ethylene and polyethylene | |
| CN102718898A (en) | Olefin polymerization method | |
| CN107417812B (en) | Spherical double-mesoporous-structure composite material, supported polyethylene catalyst and preparation methods thereof | |
| CN107417821B (en) | Spherical composite material and supported polyethylene catalyst and preparation method thereof | |
| CN108623720A (en) | Spherical mesoporous composite material and loaded catalyst and preparation method thereof | |
| CN107417827B (en) | Method for polymerizing ethylene and polyethylene | |
| CN108017731A (en) | Spherical mesoporous composite material and loaded catalyst and preparation method thereof | |
| CN108623723A (en) | Ethene polymerization method and polyethylene | |
| CN102453143A (en) | Loaded metallocene catalyst and preparation method thereof | |
| CN107417823A (en) | Spherical sepiolite mesoporous composite material and loaded catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |