CN105440168A - Spherical montmorillonite mesoporous composite carrier, loaded polyethylene catalyst, preparation methods of spherical montmorillonite mesoporous composite carrier and loaded polyethylene catalyst and use of loaded polyethylene catalyst - Google Patents
Spherical montmorillonite mesoporous composite carrier, loaded polyethylene catalyst, preparation methods of spherical montmorillonite mesoporous composite carrier and loaded polyethylene catalyst and use of loaded polyethylene catalyst Download PDFInfo
- Publication number
- CN105440168A CN105440168A CN201410514325.1A CN201410514325A CN105440168A CN 105440168 A CN105440168 A CN 105440168A CN 201410514325 A CN201410514325 A CN 201410514325A CN 105440168 A CN105440168 A CN 105440168A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- carrier
- spherical
- weight
- spherical montmorillonite
- 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
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a spherical montmorillonite mesoporous composite carrier, a loaded polyethylene catalyst, preparation methods of the spherical montmorillonite mesoporous composite carrier and the loaded polyethylene catalyst and a use of the loaded polyethylene catalyst. The spherical montmorillonite mesoporous composite carrier contains montmorillonite and silica gel. The spherical montmorillonite mesoporous composite carrier has the average particle size of 30-60 micrometers, a specific surface area of 200-650m<2>/g and a pore volume of 0.5-1.5ml/g. The aperture size distribution is bimodal distribution. The most probable aperture sizes corresponding to two peaks are respectively in a range of 9-12nm and in a range of 15-30nm. The loaded polyethylene catalyst has good catalysis performances. In ethene polymerization, the loaded polyethylene catalyst has high catalytic activity.
Description
Technical field
The present invention relates to the composite mesoporous carrier of a kind of spherical montmorillonite, the preparation method of the composite mesoporous carrier of a kind of spherical montmorillonite, the composite mesoporous carrier of spherical montmorillonite prepared by this method, a kind of loading type polyethylene catalysts, a kind of preparation method of loading type polyethylene catalysts, this loading type polyethylene catalysts application in catalyzed reaction.
Background technology
Within 1992, Mobile company synthesizes the regular mesoporous material of duct high-sequential, there is high specific surface, regular pore passage structure and narrow pore size distribution, mesoporous material is made to obtain very large concern (BeckJS in the application of catalysis, separation, medicine and other fields, VartuliJC, RothWJ, etal.J.Am.Chem.Soc., 1992,114 (27): 10834-10843), within 1998, Zhao east unit waits people to synthesize a kind of type material-mesoporous material SBA-15, and this material has mesoporous material aperture (6-30nm), the large (1.0cm of pore volume of high-sequential
3/ g), the high mechanical strength that keeps of thicker hole wall (4-6nm) and good catalytic adsorption performance, see D.Y.Zhao, J.L.Feng, Q.S.Huo, etalScience279 (1998) 548-550; Zhao Dongyuan, Yu Chengzhong, Yu Yonghao. a kind of preparation method of mesonic pore molecular sieve carrier material, CN1341553A.This mesoporous material, 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, compared with being spherical material with microscopic appearance, mobility own is poor, its large specific surface area and high pore volume cause and make it have stronger water suction, moisture absorption ability, this will aggravate the reunion of ordered mesoporous material further, to the storage of ordered mesoporous material, transport, post-treatment and application make troubles.And the geometric shape of microballoon is in the reunion reducing powder, improve the aspects such as its mobility and have obvious advantage, therefore ordered mesoporous material is made spherical can the advantages of microballoon and ordered mesoporous material, large and the feature of narrowly distributing in the high-specific surface area of ordered mesoporous material, large pore volume, aperture can be retained, the reunion of ordered mesoporous material can be reduced again, increase its mobility.Application for ordered mesoporous material is provided better platform by this, and expands the Application Areas of ordered mesoporous material.
Montmorillonite is earth's surface distribution one of clay mineral the most widely, it has the physical and chemical performance such as interchangeability of the particle diameter of nano-micrometer level, bigger serface, interlayer ion, therefore can by physico-chemical process at the Intercalation reaction of montmorillonite or at some lewis' acids with specific functional groups of surface graft, thus the modification realized its surface and performance regulation and control.Because acidification can make effective hole of montmorillonite and surperficial scission of link increase, thus can inlay and be detained the suitable material of external particle diameter (as pollutent etc.) or carry out surface adsorption.
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.The catalyst levels arrived needed for high reactivity due to homogeneous polyethylene catalyzer 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.
At present, relevant polyethylene catalysts supported research report is very many.For furtheing investigate new support/catalyst/co-catalyst system, be necessary to attempt different carrier, to promote further developing of carried catalyst and polyolefin industry.
Summary of the invention
The object of the invention is to overcome the defect that the loaded catalyst that adopts existing meso-porous molecular sieve material to make catalyst activity in for catalytic reaction process is low, and preparation method, this loading type polyethylene catalysts application in catalyzed reaction of the preparation method of the composite mesoporous carrier of a kind of spherical montmorillonite, the composite mesoporous carrier of a kind of spherical montmorillonite, the composite mesoporous carrier of spherical montmorillonite prepared by the method, a kind of loading type polyethylene catalysts, a kind of loading type polyethylene catalysts are provided.
In order to achieve the above object, the present inventor is by finding after research, montmorillonite is introduced in the mesoporous material with double-pore structure, montmorillonite is made to enter the outside surface of mesoporous material, inner hole wall and ball inside, and this mesoporous composite material is made the spherical of reunion not easily occurs, the high-specific surface area of mesoporous material can be retained like this, large pore volume, wide aperture and there is the features such as double-pore structure, the reunion of mesoporous material can be reduced again, increase its mobility, the loaded catalyst making to adopt this mesoporous composite material to make is for obtaining the reaction raw materials transformation efficiency significantly improved during catalyzed reaction, thus complete the present invention.
The invention provides the composite mesoporous carrier of a kind of spherical montmorillonite, wherein, the composite mesoporous carrier of this spherical montmorillonite contains montmorillonite and dioxide/silica gel, and the median size of the composite mesoporous carrier of described spherical montmorillonite is 30-60 micron, specific surface area is 200-650 meters squared per gram, pore volume is 0.5-1.5 ml/g, and pore size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 9-12 nanometer and 15-30 nanometer.
In addition, the invention provides the preparation method of the composite mesoporous carrier of a kind of spherical montmorillonite, the method comprises the following steps:
(1) template, DMF and hydrochloric acid are stirred to dissolving at 25-60 DEG C of temperature;
(2) step (1) gained solution and tetraethoxy are stirred 1-2 hour at 25-60 DEG C of temperature, obtain the filter cake of mesoporous material;
(3) water glass is contacted with mineral acid, and the product obtained after contact is filtered, obtain silica gel filter cake;
(4) filter cake of described mesoporous material, described silica gel filter cake to be mixed with montmorillonite and ball milling, and carry out spraying dry by after the pressed powder water slurrying obtained after ball milling, then by the described template removal in the product that obtains after spraying dry.
Present invention also offers a kind of composite mesoporous carrier of spherical montmorillonite prepared by aforesaid method.
Present invention also offers a kind of loading type polyethylene catalysts, wherein, this catalyzer comprises the above-mentioned composite mesoporous carrier of spherical montmorillonite and the component containing Mg, Ti and Cl of load on the composite mesoporous carrier of described spherical montmorillonite.
Present invention also offers a kind of preparation method of loading type polyethylene catalysts, wherein, the method comprises the composite mesoporous carrier impregnation of spherical montmorillonite with double-pore structure in by MgCl
2and TiCl
4be dissolved in compounded organic solvent and formed containing Mg and Ti component catalyzer mother liquor in.
Present invention also offers the application of above-mentioned loading type polyethylene catalysts in catalyzed reaction.
The present inventor finds, comprise the above-mentioned composite mesoporous carrier of spherical montmorillonite with certain physical properties and the poly catalyst activity of load on the composite mesoporous carrier of described spherical montmorillonite higher, this may be because: on the one hand, carrier provided by the invention is spherical, the reunion of powder can be reduced, improve its mobility; On the other hand, carrier provided by the invention not only retains the feature of the large and double-pore structure in the high-specific surface area of ordered mesoporous material, large pore volume, aperture, and its pore size distribution presents unique bimodal distribution, is more conducive to the load of active ingredient, thus has higher catalytic activity.
In addition, the montmorillonite of cheapness is incorporated in matrix material, the production cost of carrier can be reduced to a great extent.Namely, micro-sphere structure, the advantage of mesoporous material and montmorillonite with double-pore structure combine by spherical montmorillonite provided by the invention composite mesoporous carrier dexterously, thus provide better platform for the application of the composite mesoporous carrier of described spherical montmorillonite, and expand its Application Areas.
In addition, catalyzer provided by the invention also has and does not corrode the few and simple advantage of aftertreatment technology of instrument, side reaction.
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 X-ray diffracting spectrum (XRD figure spectrum), and wherein, a is the XRD spectra according to the composite mesoporous carrier of spherical montmorillonite of the present invention (C1); B is the XRD spectra according to the load composite mesoporous carrier of poly spherical montmorillonite (Cat-1) obtained by spray-drying process of the present invention, and X-coordinate is 2 θ, and ordinate zou is intensity;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) according to the microscopic appearance of the composite mesoporous carrier of spherical montmorillonite of the present invention (C1);
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the microscopic appearance according to the load composite mesoporous carrier of poly spherical montmorillonite (Cat-1) obtained by spray-drying process 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.
The invention provides the composite mesoporous carrier of a kind of spherical montmorillonite, wherein, the composite mesoporous carrier of described spherical montmorillonite contains montmorillonite and dioxide/silica gel, and the median size of the composite mesoporous carrier of described spherical montmorillonite is 30-60 micron, specific surface area is 200-650 meters squared per gram, pore volume is 0.5-1.5 ml/g, and pore size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 9-12 nanometer and 15-30 nanometer.Under preferable case, the median size of the composite mesoporous carrier of described spherical montmorillonite is 25-35 micron, specific surface area is 250-580 meters squared per gram, pore volume is 0.9-1.2 ml/g, pore size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 9-10 nanometer and 26-28 nanometer.
The composite mesoporous carrier of spherical montmorillonite according to the present invention has double-pore structure, and the median size of its particle adopts laser fineness gage to record, and specific surface area, pore volume and most probable pore size record according to nitrogen adsorption methods.
The composite mesoporous carrier of spherical montmorillonite according to the present invention, by the particle size of composite mesoporous for spherical montmorillonite carrier is controlled within above-mentioned scope, can guarantee that the composite mesoporous carrier of described spherical montmorillonite is not easily reunited, and the catalytic activity of catalyzer can be improved used as the loaded catalyst that carrier is made.When the specific surface area of described spherical montmorillonite mesoporous composite material is less than 200 meters squared per gram and/or pore volume is less than 0.5 ml/g, and and/or the most probable pore size of bimodal correspondence is less than 9 nanometer time, the catalytic activity of the loading type polyethylene catalysts made used as carrier can significantly reduce; When the specific surface area of the composite mesoporous carrier of described spherical montmorillonite is greater than 650 meters squared per gram and/or pore volume is greater than 1.5 mls/g, and and/or the most probable pore size of bimodal correspondence is greater than 30 nanometer time, the loading type polyethylene catalysts made used as carrier is easily reunited in catalytic reaction process, thus affects the reaction raw materials transformation efficiency in catalytic reaction process.
In the composite mesoporous carrier of described spherical montmorillonite, relative to the described dioxide/silica gel of 100 weight parts, the content of described montmorillonite can be 10-90 weight part, is preferably 20-60 weight part.
In the present invention, the composite mesoporous carrier of described spherical montmorillonite can also containing the silicon-dioxide introduced by water glass." silicon-dioxide introduced by water glass " refers in the preparation process of the composite mesoporous carrier of described spherical montmorillonite, to be brought into the silica component in the spherical montmorillonite complex carrier of final preparation by water glass as raw materials.In the composite mesoporous carrier of described spherical montmorillonite, relative to the meso-porous molecular sieve material described in 100 weight parts with three-dimensional cubic duct structure, the content of the described silicon-dioxide introduced by water glass can be 1-200 weight part, is preferably 50-150 weight part.
In the present invention, described dioxide/silica gel can be the meso-porous molecular sieve material that this area routine uses, and can prepare according to the method for routine.As a rule, its main component is silicon-dioxide, and the median size of described dioxide/silica gel is 30-60 micron, and specific surface area is 200-400 meters squared per gram, and pore volume is 1-2 ml/g.
Present invention also offers the preparation method of the composite mesoporous carrier of a kind of spherical montmorillonite, the method comprises the following steps:
(1) template, DMF and hydrochloric acid are stirred to dissolving at 25-60 DEG C of temperature;
(2) step (1) gained solution and tetraethoxy are stirred 1-2 hour at 25-60 DEG C of temperature, obtain the filter cake of mesoporous material;
(3) water glass is contacted with mineral acid, and the product obtained after contact is filtered, obtain silica gel filter cake;
(4) filter cake of described mesoporous material, described silica gel filter cake to be mixed with montmorillonite and ball milling, and carry out spraying dry by after the pressed powder water slurrying obtained after ball milling, then by the described template removal in the product that obtains after spraying dry.
In the preparation process of the composite mesoporous carrier of above-mentioned spherical montmorillonite, the pore size distribution of the composite mesoporous carrier of described spherical montmorillonite is controlled be bimodal distribution mainly through controlling that there is the mesoporous material filter cake of double-pore structure and the composition of silica gel filter cake, and make the composite mesoporous carrier of this spherical montmorillonite have double-pore structure, and by controlling forming method (namely, first by mesoporous material filter cake, silica gel filter cake mixes with montmorillonite and ball milling, then by spraying dry after the pressed powder water slurrying obtained) microscopic appearance of the composite mesoporous carrier of described spherical montmorillonite is controlled as spherical.
According to the present invention, described template can be polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
According to the present invention, described hydrochloric acid can be that the routine of this area is selected, and under preferable case, described hydrochloric acid uses in form of an aqueous solutions, such as, can be the solution of water and hydrogenchloride.The pH value of aqueous hydrochloric acid can be 1-6.
According to the present invention, ratio, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: N, dinethylformamide: water: HCl=1:300-700:10000-20000:100-500, be preferably 1:550-650:10000-13000:150-480, be particularly preferably 1:595:11628:329.Wherein, the mole number of polyoxyethylene-polyoxytrimethylene-polyoxyethylene calculates according to the molecular-weight average of polyoxyethylene-polyoxytrimethylene-polyoxyethylene and obtains.
According to the present invention, to the kind of described template, there is no particular limitation, as long as the composite mesoporous carrier of spherical montmorillonite obtained can be made to have above described holes structure, such as, described template can be various triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene template that this area routine uses.Wherein, this template can be commercially available (such as, can available from Aldrich Co, commodity are called P123, and molecular formula is EO
20pO
70eO
20), also can be prepared by existing various method.
According to the present invention, the mol ratio of the consumption of described template and tetraethoxy can 1:10-90, preferably 1:50-75.
The present invention does not limit especially to the condition that described tetraethoxy contacts with step (1) gained solution, and such as, the condition of contact generally includes: temperature can be 25-60 DEG C, and the time can be 1-2 hour.In order to more be conducive to the Homogeneous phase mixing between each material, described tetraethoxy contacts with step (1) gained solution and preferably carries out under agitation.Described stirring is not particularly limited, and can be that the routine of this area is selected.
According to the present invention, to described template, N, there is no particular limitation in the way of contact of dinethylformamide and hydrochloric acid, such as above-mentioned three kinds of materials can be mixed contact simultaneously, also wherein two kinds of materials first can be mixed contact, more remaining material be added in the mixture that obtains and continue mixing contact.Under preferable case, the described way of contact adds N again after first described template and described hydrochloric acid being uniformly mixed, dinethylformamide stirs, then the mixture obtained is placed in a water bath, keep temperature-resistant, again tetraethoxy is slowly dropped in gained mixture, and continue stirring reaction.
The present invention is not particularly limited the condition that water glass contacts with mineral acid, suitably can determine according to the common process preparing silica gel.Under preferable case, the condition that water glass contacts with mineral acid generally includes: temperature can be 10-60 DEG C, is preferably 20-40 DEG C; Time can be 1-5 hour, is preferably 1.5-3 hour; PH value is 2-4.In order to more be conducive to the Homogeneous phase mixing between each material, described water glass contacts with mineral acid and preferably carries out under agitation.
As well known to those skilled in the art, described water glass is the aqueous solution of water glass, and its concentration can be 10-50 % by weight, is preferably 12-30 % by weight.
The kind of described mineral acid can be that the routine of this area is selected, and such as, can be one or more 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.The consumption of described mineral acid preferably makes the pH value of the contact reacts system of water glass and mineral acid be 2-4.
According to the present invention, have in the filter cake of the mesoporous material of double-pore structure and the preparation process of described silica gel filter cake described, the mode of described filtration can adopt and well known to a person skilled in the art that various mode is carried out, and is preferably suction filtration and is separated.It is a kind of mode utilizing air pressure to realize liquid to be separated with solid particulate well-known to those skilled in the art that described suction filtration is separated.
Have in the filter cake of the mesoporous material of double-pore structure and the process of silica gel filter cake in above-mentioned preparation, can comprise with the process obtaining filter cake by filtering: after filtration, with deionized water (distilled water) repetitive scrubbing (washing times can be 2-10 time), then carry out suction filtration.
According to the present invention, in step (4), the consumption of described mesoporous material filter cake, silica gel filter cake and the montmorillonite with double-pore structure can according to expecting that the component of the composite mesoporous carrier of spherical montmorillonite obtained is selected, such as, there is the consumption of the filter cake of the mesoporous material of double-pore structure for benchmark described in 100 weight parts, the consumption of described silica gel filter cake is 1-200 weight part, is preferably 50-150 weight part; The consumption of described montmorillonite can be 1-50 weight part, is preferably 20-50 weight part.
According to the present invention, in step (3), to the concrete operation method of described ball milling and condition, there is no particular limitation, is as the criterion with the structure not destroying or substantially do not destroy meso-porous molecular sieve material.Those skilled in the art can select various suitable condition to implement the present invention according to mentioned above principle.Particularly, described ball milling carries out in ball mill, and in described ball mill, the inwall of ball grinder is preferably polytetrafluoroethyllining lining, and wherein, in ball mill, the diameter of abrading-ball 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 comprises: 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 (4), 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 1:0.1-2, is preferably 1:0.3-1.
According to the present invention, described spray-dired concrete operation method and condition are known to the skilled person, such as, can carry out in spraying gun.Particularly, the slurry be made into by described pressed powder and water to be joined in spraying gun high speed rotating to realize spraying dry.Wherein, it can be 100-300 DEG C that spray-dired condition comprises temperature, and the rotating speed of rotation can be 10000-15000r/min; Under preferable case, it is 150-250 DEG C that described spray-dired condition comprises temperature, and the rotating speed of rotation is 11000-13000r/min.
According to the present invention, the method for removed template method is generally calcination method.The condition of described removed template method can be the selection of this area routine, and such as, the condition of described removed template method comprises: temperature can be 300-600 DEG C, is preferably 350-550 DEG C, most preferably is 500 DEG C; Time can be 10-80 hour, is preferably 20-30 hour, most preferably is 24 hours.
Present invention also offers the composite mesoporous carrier of spherical montmorillonite prepared by aforesaid method.
Present invention also offers a kind of loading type polyethylene catalysts, wherein, this catalyzer comprises the composite mesoporous carrier of above-mentioned spherical montmorillonite and the component containing Mg, Ti and Cl of load on the composite mesoporous carrier of described spherical montmorillonite.
According to the present invention, in described loading type polyethylene catalysts, the composite mesoporous carrier of described spherical montmorillonite and containing Mg, the content of the component of Ti and Cl can be the routine selection of this area, such as, with the gross weight of described loading type polyethylene catalysts for benchmark, the content of described carrier can be 50-99 % by weight, described containing Mg, the total content of the component of Ti and Cl can be 1-50 % by weight, under preferable case, with the gross weight of described loading type polyethylene catalysts for benchmark, the content of described carrier is 50-95 % by weight, described containing Mg, the total content of the component of Ti and Cl is 5-50 % by weight.
According to the present invention, the median size of described loading type polyethylene catalysts is 30-59 micron, specific surface area is 250-300 meters squared per gram, pore volume is 1.1-1.4 ml/g, pore size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 9.5-9.7 nanometer and 24-25 nanometer.
Present invention also offers a kind of preparation method of loading type polyethylene catalysts, wherein, the method comprises the described composite mesoporous carrier impregnation of spherical montmorillonite in by MgCl
2and TiCl
4be dissolved in compounded organic solvent and formed containing Mg and Ti component catalyzer mother liquor in.
Prepare in the process of loading type polyethylene catalysts above-mentioned, with total consumption of described loading type polyethylene catalysts for benchmark, the consumption of described carrier can be 50-99 % by weight, is preferably 50-95 % by weight; Described MgCl
2and TiCl
4the total amount of consumption can be 1-50 % by weight, be preferably 5-50 % by weight.In addition, described MgCl
2and TiCl
4weight ratio can be 1:0.1-1.5.
According to the present invention, the scope of described compounded organic solvent is very wide in range, and can be that the routine of this area is selected, in the present invention, described compounded organic solvent can be the mixing solutions of tetrahydrofuran (THF) and Virahol.
According to the present invention, the condition of described dipping is not particularly limited, and can be that the routine of this area is selected, in the present invention, the condition of described dipping comprises: temperature can be 10-60 DEG C, and the time can be 10-72 hour.
Also comprise in the preparation method of above-mentioned loading type polyethylene catalysts and carry out after impregnation completes, after filtration, washing, dry, finally obtain the powdery polyethylene catalyzer with good flow performance.Wherein, filtration, washing and drying are all not particularly limited, and can be that the routine of this area is selected.
Present invention also offers the application of above-mentioned loading type polyethylene catalysts in catalyzed reaction.
Below will be described the present invention by embodiment.
In following examples, polyoxyethylene-poly-oxypropylene polyoxyethylene available from Aldrich Co, is abbreviated as P123, and molecular formula is EO
20pO
70eO
20, be the material of 9003-11-6 in the registration number of U.S. chemical abstract, average molecular mass Mn is 5800.
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; The analysis of reaction product liquid composition is being carried out purchased from Britain Agilent company 7890A/5973N gas chromatograph-mass spectrometer.
Embodiment 1
This embodiment is for illustration of the composite mesoporous carrier of spherical montmorillonite provided by the invention and loading type polyethylene catalysts and preparation method thereof.
(1) preparation of the composite mesoporous carrier of spherical montmorillonite
(be the material of 9003-11-6 in the registration number of U.S. chemical abstract by 2.0 grams of P123, its average molecular mass Mn=5800) and 15 grams of N, dinethylformamide (DMF) joins in the solution of the hydrochloric acid of 11.2 gram 37% and 64ml water, is stirred to P123 dissolves completely at 40 DEG C; Again 4.45 grams of tetraethoxys are joined in above-mentioned solution and stir 1 hour at 40 DEG C, after filtration, washing, drying, obtain the filter cake of the mesoporous material with double-pore structure;
By concentration be 15 % by weight water glass and concentration be 12 % by weight sulphuric acid soln be after 5:1 mixes by water glass and sulfuric acid weight ratio, stirring reaction is carried out 2 hours at 30 DEG C, and by the reaction product concentration obtained be 98 % by weight sulfuric acid adjustment pH be 3, then by reaction mass suction filtration, to be washed till sodium ions content with distilled water wash be 0.02 % by weight, obtains silica gel filter cake.
10 of above-mentioned preparation grams of meso-porous molecular sieve material filter cakes, 10 grams of silica gel filter cakes are put into 100mL ball grinder (wherein together with 5 grams of montmorillonites, ball grinder material is tetrafluoroethylene, Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, quantity is 1, and rotating speed is 400r/min), closure ball grinding jar, in ball grinder, temperature is ball milling 1 hour at 60 DEG C, obtains 25 grams of pressed powders; This pressed powder is dissolved in 25 grams of deionized waters, spraying dry at 200 DEG C, under rotating speed is 12000r/min; Then calcined 24 hours in the retort furnace of 500 DEG C by the product obtained after spraying dry, removed template method, the target product obtaining 20 grams of removed template methods has the composite mesoporous carrier of spherical montmorillonite of double-pore structure, called after C1.
(2) preparation of loading type polyethylene catalysts
Under protection of inert gas, by MgCl
2and TiCl
4be dissolved in the compounded organic solvent of tetrahydrofuran (THF) and Virahol, formed in the catalyzer mother liquor containing Mg and Ti component; Wherein, with the gross weight of described loading type polyethylene catalysts for benchmark, the consumption of the composite mesoporous support C 1 of described spherical montmorillonite is 95 % by weight, described MgCl
2and TiCl
4the total amount of consumption be 5 % by weight, and MgCl
2and TiCl
4weight ratio be 1:0.1;
Then at 75 DEG C of temperature, the composite mesoporous support C 1 of the spherical montmorillonite with double-pore structure adding above-mentioned preparation is flooded, after having reacted, then carry out filtering rear deionized water repetitive scrubbing 4 times, then the composite mesoporous carrier of the poly spherical montmorillonite of powdered loaded (i.e. loading type polyethylene catalysts) with good flow performance is obtained after suction filtration, called after Cat-1.
With XRD, scanning electron microscope and nitrogen adsorption desorption instrument, the composite mesoporous carrier of this spherical montmorillonite and loading type polyethylene catalysts are characterized.
Fig. 1 is X-ray diffracting spectrum (XRD figure), wherein, the XRD spectra that the XRD spectra that a is the composite mesoporous carrier of spherical montmorillonite (C1), b are the load composite mesoporous carrier of poly spherical montmorillonite (Cat-1), X-coordinate is 2 θ, and ordinate zou is intensity.The Small angle spectrum peak that XRD spectra occurs from Fig. 1 is known, and the XRD spectra a of the composite mesoporous carrier of spherical montmorillonite and b has the hexagonal hole road structure of 2D specific to mesoporous material.
Fig. 2 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the composite mesoporous carrier of spherical montmorillonite (C1), as shown in Figure 2, and the microscopic appearance of the composite mesoporous carrier of spherical montmorillonite (C1) to be particle diameter the be Mesoporous Spheres of 30-60 μm.
Fig. 3 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the load composite mesoporous carrier of poly spherical montmorillonite (Cat-1).As shown in Figure 3, keep spherical by the microscopic appearance of the pickling process load composite mesoporous carrier of poly spherical montmorillonite (Cat-1) is still basic, particle diameter is 30-60 μm.
Table 1 is the pore structure parameter of the composite mesoporous carrier of spherical montmorillonite (C1) and the load composite mesoporous carrier of poly spherical montmorillonite (Cat-1).
Table 1
As can be seen from the data of table 1, the composite mesoporous carrier of spherical montmorillonite is after load polyethylene, and specific surface area and pore volume reduce all to some extent, and this illustrates that polyethylene enters into the inside of the composite mesoporous carrier of spherical montmorillonite in load-reaction process.
In addition, shown that the content of magnesium in the sample of load polyethylene catalysts is 3.4 % by weight by xrf analysis, the content of titanium is 1.4 % by weight, and the content of chlorine is 16.7 % by weight.
Embodiment 2
This embodiment is for illustration of the composite mesoporous carrier of spherical montmorillonite provided by the invention and loading type polyethylene catalysts and preparation method thereof.
(1) preparation of the composite mesoporous carrier of spherical montmorillonite
(be the material of 9003-11-6 in the registration number of U.S. chemical abstract by 2.0 grams of P123, its average molecular mass Mn=5800) and 15 grams of N, dinethylformamide (DMF) joins in the solution of the hydrochloric acid of 11.2 gram 37% and 64ml water, is stirred to P123 dissolves completely at 40 DEG C; Again 4.45 grams of tetraethoxys are joined in above-mentioned solution and stir 1 hour at 40 DEG C, after filtration, washing, drying, obtain the filter cake of the mesoporous material with double-pore structure;
By concentration be 15 % by weight water glass and concentration be 12 % by weight sulphuric acid soln be after 4:1 mixes by water glass and sulfuric acid weight ratio, stirring reaction is carried out 1.5 hours at 40 DEG C, and by the reaction product concentration obtained be 98 % by weight sulfuric acid adjustment pH be 2, then by reaction mass suction filtration, to be washed till sodium ions content with distilled water wash be 0.02 % by weight, obtains silica gel filter cake.
20 of above-mentioned preparation grams of mesoporous material filter cakes, 30 grams of silica gel filter cakes are put into 100mL ball grinder (wherein together with 10 grams of montmorillonites, ball grinder material is tetrafluoroethylene, Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, quantity is 1, and rotating speed is 300r/min), closure ball grinding jar, in ball grinder, temperature is ball milling 0.5 hour at 80 DEG C, obtains 54 grams of pressed powders; This pressed powder is dissolved in 27 grams of deionized waters, at 250 DEG C under rotating speed is 11000r/min spraying dry; Then calcined 15 hours in the retort furnace of 550 DEG C by the product obtained after spraying dry, removed template method, the target product obtaining 50 grams of removed template methods has the composite mesoporous carrier of spherical montmorillonite of double-pore structure, called after C2.
(2) preparation of loading type polyethylene catalysts
Under protection of inert gas, by MgCl
2and TiCl
4be dissolved in the compounded organic solvent of tetrahydrofuran (THF) and Virahol, formed in the catalyzer mother liquor containing Mg and Ti component; Wherein, with the gross weight of described loading type polyethylene catalysts for benchmark, the consumption of the composite mesoporous support C 1 of described spherical montmorillonite is 50 % by weight, described MgCl
2and TiCl
4the total amount of consumption be 50 % by weight, and MgCl
2and TiCl
4weight ratio be 1:1.5;
Then at 75 DEG C of temperature, the composite mesoporous support C 2 of the spherical montmorillonite with double-pore structure adding above-mentioned preparation is flooded, after having reacted, then carry out filtering rear deionized water repetitive scrubbing 4 times, then the composite mesoporous carrier of the poly spherical montmorillonite of powdered loaded (i.e. loading type polyethylene catalysts) with good flow performance is obtained after suction filtration, called after Cat-2.
Table 2 is the pore structure parameter of spherical mesoporous montmorillonite complex carrier (C2) and the poly spherical mesoporous montmorillonite complex carrier (Cat-2) of load.
Table 2
As can be seen from the data of table 2, spherical mesoporous montmorillonite complex carrier is after load polyethylene, and pore volume and specific surface area reduce all to some extent, it can be said that bright, and in load-reaction process, polyethylene has entered into the inside of spherical mesoporous montmorillonite complex carrier.
Embodiment 3
This embodiment is for illustration of the composite mesoporous carrier of spherical montmorillonite provided by the invention and loading type polyethylene catalysts and preparation method thereof.
(1) preparation of the composite mesoporous carrier of spherical montmorillonite
(be the material of 9003-11-6 in the registration number of U.S. chemical abstract by 2.0 grams of P123, its average molecular mass Mn=5800) and 15 grams of N, dinethylformamide (DMF) joins in the solution of the hydrochloric acid of 11.2 gram 37% and 64ml water, is stirred to P123 dissolves completely at 40 DEG C; Again 4.45 grams of tetraethoxys are joined in above-mentioned solution and stir 1 hour at 40 DEG C, after filtration, washing, drying, obtain the filter cake of the mesoporous material with double-pore structure;
By concentration be 15 % by weight water glass and concentration be 12 % by weight sulphuric acid soln be after 4:1 mixes by water glass and sulfuric acid weight ratio, stirring reaction is carried out 3 hours at 20 DEG C, then adjusting pH with the sulfuric acid that concentration is 98 % by weight is 4, then the reaction mass suction filtration will obtained, and to be washed till sodium ions content with distilled water wash be 0.02 % by weight, obtain silica gel filter cake.
20 of above-mentioned preparation grams of mesoporous material filter cakes, 10 grams of silica gel filter cakes are put into 100mL ball grinder (wherein together with 1 gram of montmorillonite, ball grinder material is tetrafluoroethylene, Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, quantity is 1, and rotating speed is 500r/min), closure ball grinding jar, in ball grinder, temperature is ball milling 10 hours at 40 DEG C, obtains 38 grams of pressed powders; This pressed powder is dissolved in 11.4 grams of deionized waters, at 150 DEG C under rotating speed is 13000r/min spraying dry; Then calcined 70 hours in the retort furnace of 450 DEG C by the product obtained after spraying dry, removed template method, the target product obtaining 35 grams of removed template methods has the composite mesoporous carrier of spherical montmorillonite of double-pore structure, called after C3.
(2) preparation of loading type polyethylene catalysts
Under protection of inert gas, by MgCl
2and TiCl
4be dissolved in the compounded organic solvent of tetrahydrofuran (THF) and Virahol, formed in the catalyzer mother liquor containing Mg and Ti component; Wherein, with the gross weight of described loading type polyethylene catalysts for benchmark, the consumption of the composite mesoporous support C 1 of described spherical montmorillonite is 99 % by weight, described MgCl
2and TiCl
4the total amount of consumption be 1 % by weight, and MgCl
2and TiCl
4weight ratio be 1:1;
Then at 75 DEG C of temperature, the composite mesoporous support C 2 of the spherical montmorillonite with double-pore structure adding above-mentioned preparation is flooded, after having reacted, then carry out filtering rear deionized water repetitive scrubbing 4 times, then the composite mesoporous carrier of the poly spherical montmorillonite of powdered loaded (i.e. loading type polyethylene catalysts) with good flow performance is obtained after suction filtration, called after Cat-2.
Table 3 is the pore structure parameter of spherical mesoporous montmorillonite complex carrier (C3) and the poly spherical mesoporous montmorillonite complex carrier (Cat-3) of load.
Table 3
As can be seen from the data of table 3, spherical mesoporous montmorillonite complex carrier is after load polyethylene, and pore volume and specific surface area reduce all to some extent, it can be said that bright, and in load-reaction process, polyethylene has entered into the inside of spherical mesoporous montmorillonite complex carrier.
Embodiment 4
This embodiment is for illustration of spherical mesoporous montmorillonite complex carrier provided by the invention and loading type polyethylene catalysts and preparation method thereof.
Spherical mesoporous montmorillonite complex carrier and loading type polyethylene catalysts is prepared according to the method for embodiment 1, difference, not by the method for dipping in the process preparing loading type polyethylene catalysts, but by spray-dired step by polyethylene load on spherical mesoporous montmorillonite complex carrier, thus obtained loading type polyethylene catalysts Cat-4.
Comparative example 1
This comparative example is for illustration of the composite mesoporous carrier of spherical montmorillonite of reference and Catalysts and its preparation method.
The preparation of the composite mesoporous carrier of spherical montmorillonite and loading type polyethylene catalysts is carried out according to the method for embodiment 1, unlike, in the process of the composite mesoporous carrier of the spherical montmorillonite of preparation, the ES955 silica gel of identical weight part is adopted to substitute mesoporous material filter cake, by ES955 silica gel under nitrogen protection 400 DEG C of calcinings 10 hours, with eliminating hydroxide and Residual water, thus obtain the ES955 silica gel through thermal activation;
Result obtains the composite mesoporous carrier of spherical montmorillonite (DC1) and the load composite mesoporous carrier of poly spherical montmorillonite (DCat-1).
Comparative example 2
This comparative example is for illustration of the composite mesoporous carrier of spherical montmorillonite of reference and Catalysts and its preparation method.
The preparation of the composite mesoporous carrier of spherical montmorillonite and loading type polyethylene catalysts is carried out according to the method for embodiment 1, unlike, in the preparation process of the composite mesoporous carrier of spherical montmorillonite, do not add montmorillonite, obtain the composite mesoporous carrier of spherical montmorillonite (DC2) and the loading type polyethylene catalysts (DCat-2) of reference.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity of loading type polyethylene catalysts provided by the invention.
In the stainless steel polymermaking autoclave of 2 liters, three times are respectively replaced with nitrogen and ethene, then 200 milliliters of hexanes are added, by still temperature rise to 80 DEG C, then add 800 milliliters of hexanes, along with adding of hexane, the concentration adding 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol/L, then add polyethylene catalysts Cat-1, pass into ethene and 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 0.37g/ml, melting index MI2.16=0.81g/10min.Determine as calculated, the efficiency of catalyzer is 4925gPE/gcat.h.
EXPERIMENTAL EXAMPLE 2-4
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity of loading type polyethylene catalysts provided by the invention.
Carry out the polymerization of ethene according to the method for EXPERIMENTAL EXAMPLE 1, difference is, replaces described loaded catalyst Cat-1 respectively with loading type polyethylene catalysts Cat-2, Cat-3 and Cat-4 prepared by embodiment 2-4.As a result, determine as calculated, the efficiency of catalyzer is respectively 3500gPE/gcat.h, 5000gPE/gcat.h and 2500gPE/gcat.h.
Experimental comparison's example 1
Carry out the polymerization of ethene according to the method for EXPERIMENTAL EXAMPLE 1, difference is, the ES955 adopting comparative example 1 to prepare replaces described loaded catalyst Cat-1.The bulk density (BD) of this polyethylene particle powder is 0.4g/ml, melting index: MI
2.16=0.87g/10min.Determine as calculated, the efficiency of catalyzer is 1767gPE/gcat.h.
Experimental comparison's example 2
Carry out the polymerization of ethene according to the method for EXPERIMENTAL EXAMPLE 1, difference is, the DCat-2 adopting comparative example 2 to prepare replaces described loaded catalyst Cat-1.Determine as calculated, the efficiency of catalyzer is 1600gPE/gcat.h.
Can be found out by above-mentioned data, adopting the preparation method of carrier provided by the invention can obtain average particulate diameter is 30-60 micron, specific surface area is 200-650 meters squared per gram, pore volume is 0.5-1.5 ml/g, pore size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively the composite mesoporous carrier of spherical montmorillonite of 9-12 nanometer and 15-30 nanometer.In addition, the catalytic performance of loading type polyethylene catalysts provided by the invention is better, when applying this catalyzer and carrying out the polyreaction of catalyzed ethylene, has higher catalytic activity.
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 the 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 (17)
1. the composite mesoporous carrier of spherical montmorillonite, it is characterized in that, the composite mesoporous carrier of this spherical montmorillonite contains montmorillonite and dioxide/silica gel, and the median size of the composite mesoporous carrier of described spherical montmorillonite is 30-60 micron, specific surface area is 200-650 meters squared per gram, pore volume is 0.5-1.5 ml/g, and pore size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 9-12 nanometer and 15-30 nanometer.
2. carrier according to claim 1, wherein, relative to the described dioxide/silica gel of 100 weight parts, the content of described montmorillonite is 10-90 weight part, is preferably 20-60 weight part.
3. a preparation method for the composite mesoporous carrier of spherical montmorillonite described in claim 1 or 2, the method comprises the following steps:
(1) template, DMF and hydrochloric acid are stirred to dissolving at 25-60 DEG C of temperature;
(2) step (1) gained solution and tetraethoxy are stirred 1-2 hour at 25-60 DEG C of temperature, obtain the filter cake of mesoporous material;
(3) water glass is contacted with mineral acid, and the product obtained after contact is filtered, obtain silica gel filter cake;
(4) filter cake of described mesoporous material, described silica gel filter cake to be mixed with montmorillonite and ball milling, and carry out spraying dry by after the pressed powder water slurrying obtained after ball milling, then by the described template removal in the product that obtains after spraying dry.
4. preparation method according to claim 3, wherein, described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.
5. preparation method according to claim 3, wherein, in step (1), ratio, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: DMF: water: hydrogenchloride=1:300-700:10000-20000:100-500.
6. preparation method according to claim 3, wherein, in step (2), the mol ratio of the consumption of described template and tetraethoxy is 1:10-90, is preferably 1:50-75.
7. preparation method according to claim 3, wherein, in step (3), the condition that water glass contacts with mineral acid comprises: temperature is 10-60 DEG C, and the time is 1-5 hour, and pH value is 2-4; Described mineral acid is one or more in sulfuric acid, nitric acid and hydrochloric acid.
8. preparation method according to claim 3, wherein, in step (4), with the consumption of the filter cake of the described mesoporous material of 100 weight parts for benchmark, the consumption of described silica gel filter cake is 1-200 weight part, is preferably 50-150 weight part; The consumption of described montmorillonite is 1-50 weight part, is preferably 20-50 weight part.
9. preparation method according to claim 3, wherein, in step (4), the condition of described ball milling comprises: the rotating speed of abrading-ball is 300-500r/min, and the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hour; Described spray-dired condition comprises: temperature is 100-300 DEG C, and rotating speed is 10000-15000r/min; The condition of removed template method comprises: temperature is 300-600 DEG C, and the time is 10-80 hour.
10. the composite mesoporous carrier of spherical montmorillonite prepared by the method in claim 3-9 described in any one.
11. 1 kinds of loading type polyethylene catalysts, it is characterized in that, described catalyzer comprises the composite mesoporous carrier of spherical montmorillonite in claim 1,2 or 10 described in any one and the component containing Mg, Ti and Cl of load on the composite mesoporous carrier of described spherical montmorillonite.
12. loading type polyethylene catalysts according to claim 11, wherein, with the gross weight of described loading type polyethylene catalysts for benchmark, the content of described carrier is 50-99 % by weight, and the total content of the described component containing Mg, Ti and Cl is 1-50 % by weight.
The preparation method of 13. 1 kinds of loading type polyethylene catalysts, is characterized in that, the method by the composite mesoporous carrier impregnation of spherical montmorillonite in claim 1,2 or 10 described in any one in by MgCl
2and TiCl
4be dissolved in compounded organic solvent and formed containing Mg and Ti component catalyzer mother liquor in.
14. methods according to claim 13, wherein, described compounded organic solvent is the mixing solutions of tetrahydrofuran (THF) and Virahol.
15. methods according to claim 13, wherein, with the gross weight of described loading type polyethylene catalysts for benchmark, the consumption of described carrier is 50-99 % by weight, described MgCl
2and TiCl
4the total amount of consumption be 1-50 % by weight; And described MgCl
2and TiCl
4the weight ratio of consumption be 1:0.1-1.5.
16. methods according to claim 13, wherein, the condition of described dipping comprises: temperature is 10-60 DEG C, and the time is 10-72 hour.
The application of loading type polyethylene catalysts in catalyzed reaction described in 17. claims 11 or 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514325.1A CN105440168B (en) | 2014-09-29 | 2014-09-29 | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514325.1A CN105440168B (en) | 2014-09-29 | 2014-09-29 | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105440168A true CN105440168A (en) | 2016-03-30 |
| CN105440168B CN105440168B (en) | 2018-03-02 |
Family
ID=55550846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410514325.1A Active CN105440168B (en) | 2014-09-29 | 2014-09-29 | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105440168B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN108948234A (en) * | 2017-05-27 | 2018-12-07 | 中国石油化工股份有限公司 | Spherical double mesoporous montmorillonite complex carriers and its preparation method and application |
| CN108948239A (en) * | 2017-05-27 | 2018-12-07 | 中国石油化工股份有限公司 | Polyolefin catalyst and polyolefin and their preparation method |
| 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 |
| CN110496634A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN111100223A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyolefin catalyst prepared by spray drying method, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315839A (en) * | 1979-02-26 | 1982-02-16 | Rhone-Poulenc Industries | Spheroidal alumina particulates having bifold porosity and process for their preparation |
| CN101239322A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing montmorillonite/molecular sieve composite material |
| CN101530812A (en) * | 2009-04-15 | 2009-09-16 | 中国科学院大连化学物理研究所 | ITQ-13 molecular sieve catalyst and method for preparing same |
| CN102049285A (en) * | 2010-11-10 | 2011-05-11 | 上海师范大学 | Multistage pore-structure molecular sieve catalyst and preparation method thereof |
-
2014
- 2014-09-29 CN CN201410514325.1A patent/CN105440168B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315839A (en) * | 1979-02-26 | 1982-02-16 | Rhone-Poulenc Industries | Spheroidal alumina particulates having bifold porosity and process for their preparation |
| CN101239322A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing montmorillonite/molecular sieve composite material |
| CN101530812A (en) * | 2009-04-15 | 2009-09-16 | 中国科学院大连化学物理研究所 | ITQ-13 molecular sieve catalyst and method for preparing same |
| CN102049285A (en) * | 2010-11-10 | 2011-05-11 | 上海师范大学 | Multistage pore-structure molecular sieve catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 朱洪法: "《催化剂载体制备及应用技术》", 31 May 2002, 石油工业出版社 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| CN108948234A (en) * | 2017-05-27 | 2018-12-07 | 中国石油化工股份有限公司 | Spherical double mesoporous montmorillonite complex carriers and its preparation method and application |
| CN108948239A (en) * | 2017-05-27 | 2018-12-07 | 中国石油化工股份有限公司 | Polyolefin catalyst and polyolefin and their preparation method |
| CN110496634A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN111100223A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyolefin catalyst prepared by spray drying method, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105440168B (en) | 2018-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105440168A (en) | Spherical montmorillonite mesoporous composite carrier, loaded polyethylene catalyst, preparation methods of spherical montmorillonite mesoporous composite carrier and loaded polyethylene catalyst and use of loaded polyethylene catalyst | |
| CN105330767B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN104248988B (en) | The preparation method of spherical mesoporous sepiolite complex carrier and Catalysts and its preparation method and application and ethyl acetate | |
| CN104248991B (en) | The preparation method of the composite mesoporous carrier of spherical montmorillonite and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN104248990B (en) | The preparation method of the composite mesoporous carrier of spherical attapulgite and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN105175586A (en) | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method | |
| CN104248985A (en) | Spherical montmorillonite mesoporous composite carrier, supported catalyst and preparation method and application thereof, and ethyl acetate preparation method | |
| CN106467582B (en) | The spherical complex carrier of macropore two dimension straight channels and composite material containing polyethylene catalysts with and its preparation method and application | |
| CN106467579B (en) | Macropore two dimension double hole channel spherical complex carrier and composite material and their preparation method and application containing polyethylene catalysts | |
| CN104248979A (en) | Spherical mesoporous silica composite carrier and catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method | |
| 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 | |
| CN104248986A (en) | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate | |
| CN104248981A (en) | Spherical composite carrier of three dimensional cube tunnel and catalyst, preparation method and application thereof, and preparation method of ethyl acetate | |
| CN105330769A (en) | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof | |
| CN106632760B (en) | Spherical aluminum-containing mesoporous composite material, supported catalyst, preparation method and application of supported catalyst, and ethylene polymerization method | |
| 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 | |
| CN107840913B (en) | Spherical small-particle-size mesoporous composite material, supported catalyst and preparation method of supported catalyst | |
| CN107417828B (en) | Spherical composite material and supported polyethylene catalyst and preparation method thereof | |
| CN104248971B (en) | A kind of carried phospho-tungstic acid catalyst and its preparation method and application and the preparation method of cyclohexanone glycerol ketal | |
| CN107417820B (en) | Spherical diatomite mesoporous composite material, supported catalyst and preparation method thereof | |
| CN107840912B (en) | Method for polymerizing ethylene and polyethylene | |
| CN104248974B (en) | The preparation method of a kind of carried phospho-tungstic acid Catalysts and its preparation method and application and cyclohexanone glycerol ketal | |
| 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 |
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 |