CN106632760B - Spherical aluminum-containing mesoporous composite material, supported catalyst, preparation method and application of supported catalyst, and ethylene polymerization method - Google Patents
Spherical aluminum-containing mesoporous composite material, supported catalyst, preparation method and application of supported catalyst, and ethylene polymerization method Download PDFInfo
- Publication number
- CN106632760B CN106632760B CN201510740436.9A CN201510740436A CN106632760B CN 106632760 B CN106632760 B CN 106632760B CN 201510740436 A CN201510740436 A CN 201510740436A CN 106632760 B CN106632760 B CN 106632760B
- Authority
- CN
- China
- Prior art keywords
- component
- composite material
- catalyst
- spherical aluminum
- mesoporous composite
- 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.)
- Active
Links
Images
Abstract
The invention relates to a spherical aluminum-containing mesoporous composite material, a preparation method of the spherical aluminum-containing mesoporous composite material, the spherical aluminum-containing mesoporous composite material prepared by the method, a supported catalyst containing the spherical aluminum-containing mesoporous composite material, a preparation method of the supported catalyst, the supported catalyst prepared by the method, application of the supported catalyst in ethylene polymerization reaction, and a method for ethylene polymerization by using the supported catalyst, wherein the spherical aluminum-containing mesoporous composite material contains an aluminum component and a mesoporous molecular sieve material with a three-dimensional cubic pore structure. The supported catalyst prepared by using the spherical aluminum-containing mesoporous composite material as a carrier has higher catalytic activity in the ethylene polymerization reaction process.
Description
Technical Field
The invention relates to a spherical aluminum-containing mesoporous composite material, a preparation method of the spherical aluminum-containing mesoporous composite material, the spherical aluminum-containing mesoporous composite material prepared by the method, a supported catalyst containing the spherical aluminum-containing mesoporous composite material, a preparation method of the supported catalyst, the supported catalyst prepared by the method, application of the supported catalyst in ethylene polymerization reaction, and a method for ethylene polymerization by using the supported catalyst.
Background
The development and application of polyethylene catalysts is a major breakthrough in the field of olefin polymerization catalysts after traditional Ziegler-Natta catalysts, which makes the research of polyethylene catalysts enter a rapidly developing stage. Because the homogeneous polyethylene catalyst needs a large amount of catalyst to reach high activity, the production cost is high, and the obtained polymer has no granular shape and cannot be used in the polymerization process of a slurry method or a gas phase method which is widely applied, the soluble polyethylene catalyst is effectively carried. At present, a great number of researches on the loading of polyethylene catalysts are reported. In order to develop new support/catalyst/cocatalyst systems in depth, it is necessary to try different supports to drive the further development of the supported catalyst and polyolefin industries. Mesoporous materials are used for polyethylene catalyst loading and ethylene polymerization by researchers with the advantages of large surface area (500-2000m2/g), open pore channels and large and adjustable pore size (3-50 nm).
The mesoporous material of the supported polyethylene catalyst reported in the previous literature is MCM-41, and the catalytic activity of the MCM-41 which is treated by MAO and then supported by the polyethylene catalyst after ethylene polymerization is 106gPE/(mol Zr h). The reason that the mesoporous material MCM-41 is low in ethylene polymerization activity after loading a catalyst is mainly that the thermal stability and the hydrothermal stability of a pore wall structure of the MCM-41 are low, partial collapse of the pore wall is caused in the loading process, the loading effect is influenced, and the catalytic activity is influenced. Therefore, it is necessary to find a mesoporous material with a stable mesoporous structure, which can maintain an ordered mesoporous structure after loading.
The invention utilizes high-aluminum ceramic ball milling and spray drying to synthesize a high-strength aluminum-containing macroporous double-hole mesoporous composite material, carries out polyethylene catalyst loading to obtain the composite material of the polyethylene catalyst, and uses the composite material in a reaction process of ethylene polymerization reaction to obtain a polyethylene product.
Disclosure of Invention
The invention aims to overcome the defect that a supported catalyst prepared by adopting the existing carrier has lower catalytic activity in ethylene polymerization reaction, and provides a spherical aluminum-containing mesoporous composite material suitable for being used as the carrier, a preparation method of the spherical aluminum-containing mesoporous composite material, the spherical aluminum-containing mesoporous composite material prepared by the method, a supported catalyst containing the spherical aluminum-containing mesoporous composite material, a preparation method of the supported catalyst, the supported catalyst prepared by the method, application of the supported catalyst in ethylene polymerization reaction and a method for ethylene polymerization reaction by using the supported catalyst.
In order to achieve the above object, the present invention provides a spherical aluminum-containing mesoporous composite material, wherein the spherical aluminum-containing mesoporous composite material contains an aluminum component and a mesoporous molecular sieve material having a three-dimensional cubic pore structure, and the spherical aluminum-containing mesoporous composite material has an average particle size of 10-80 μm, a specific surface area of 100-180 square meters/g, a pore volume of 0.5-2 ml/g, a bimodal distribution of pore diameters, and the most probable pore diameters corresponding to the bimodal distribution are respectively 4-8 nm and 30-40 nm.
The invention also provides a preparation method of the spherical aluminum-containing mesoporous composite material, which comprises the following steps:
(1) providing a mesoporous molecular sieve material with a three-dimensional cubic pore channel structure or preparing a filter cake of the mesoporous molecular sieve material with the three-dimensional cubic pore channel structure as a component a;
(2) providing silica gel or preparing a filter cake of silica gel as component b;
(3) mixing the component a and the component b, performing ball milling in a high-alumina ceramic pot, pulping solid powder obtained after ball milling by using water, and then performing spray drying on the obtained slurry;
wherein the component a enables the average particle diameter of the spherical aluminum-containing mesoporous composite material to be 10-80 microns, the specific surface area to be 100-180 square meters per gram, the pore volume to be 0.5-2 milliliters per gram, the pore diameter to be in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are respectively 4-8 nanometers and 30-40 nanometers.
The invention also provides the spherical aluminum-containing mesoporous composite material prepared by the method.
The invention also provides a supported catalyst which comprises a carrier, a magnesium component and a titanium component which are loaded on the carrier, wherein the carrier is the spherical aluminum-containing mesoporous composite material provided by the invention.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps: in an inert atmosphere, a carrier is soaked in a catalyst mother liquor containing a magnesium component and/or a titanium component, and then filtration and drying are carried out, wherein the carrier is the spherical aluminum-containing mesoporous composite material provided by the invention, and the catalyst mother liquor is a composite organic solution containing the magnesium component and/or the titanium component.
The invention also provides a supported catalyst prepared by the method.
The invention also provides the application of the supported catalyst in ethylene polymerization reaction.
The present invention also provides a process for the polymerization of ethylene, the process comprising: in the presence of a catalyst, carrying out polymerization reaction on ethylene under the condition of polymerization reaction, wherein the catalyst is the supported catalyst provided by the invention.
The inventors of the present invention have conducted extensive studies to find that a catalyst containing the spherical aluminum-containing mesoporous composite material has a high catalytic activity, and can catalyze a polymerization reaction of ethylene to obtain a high activity. The reason may be due to: on the one hand, generally speaking, although the mesoporous molecular sieve material with a three-dimensional cubic pore structure has a large specific surface area and a high pore volume, which enables the mesoporous molecular sieve material to have high catalytic activity, the mesoporous molecular sieve material also has strong water and moisture absorption capability, and therefore, when the mesoporous molecular sieve material with a three-dimensional cubic pore structure is rod-shaped, the agglomeration problem is aggravated, and inconvenience is brought to storage, transportation, post-processing and application. The spherical aluminum-containing mesoporous composite material provided by the invention is spherical, has high sphere strength, and can reduce the agglomeration problem and the crushing problem of powder and improve the flowability of the powder; in addition, the strength of the spheres is increased due to the introduction of aluminum in the ball milling process, so that the crushing of the spheres in the catalyst loading process is reduced; finally, the carrier not only retains the characteristics of high specific surface area and large pore volume of the ordered mesoporous material, but also increases the advantages of large pore diameter and narrow distribution, and the pore diameter distribution of the carrier presents unique bimodal distribution, thereby being more beneficial to the loading of active components. Therefore, the spherical aluminum-containing mesoporous composite material skillfully combines the advantages of a microsphere structure and an ordered mesoporous material with bimodal distribution of pore diameters, thereby providing a better platform for the application of the spherical aluminum-containing mesoporous composite material and expanding the application field of the spherical aluminum-containing mesoporous composite material.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray diffraction pattern (XRD pattern) of the spherical aluminum-containing mesoporous composite material according to the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the micro-morphology of the spherical aluminum-containing mesoporous composite material according to the invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a spherical aluminum-containing mesoporous composite material, wherein the spherical aluminum-containing mesoporous composite material contains an aluminum component and a mesoporous molecular sieve material with a three-dimensional cubic pore channel structure, the average particle size of the spherical aluminum-containing mesoporous composite material is 10-80 microns, the specific surface area is 100-180 square meters per gram, the pore volume is 0.5-2 ml/g, the pore diameter is bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are respectively 4-8 nanometers and 30-40 nanometers.
Preferably, the average particle size of the spherical aluminum-containing mesoporous composite material is 30-60 microns, the specific surface area is 100-170 square meters/gram, the pore volume is 0.8-1.8 ml/gram, the pore diameters are in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are respectively 4-8 nanometers and 32-39 nanometers. In this case, not only a satisfactory catalytic effect can be obtained, but also the cost can be reduced.
According to the invention, the spherical aluminum-containing mesoporous composite material has a three-dimensional cubic pore channel structure, the average particle size of particles is measured by adopting a laser particle size distribution instrument, and the specific surface area, the pore volume and the most probable pore diameter are measured by adopting a nitrogen adsorption method.
In the present invention, the average particle diameter is an average particle diameter.
According to the invention, the particle size of the spherical aluminum-containing mesoporous composite material is controlled within the range, so that the spherical aluminum-containing mesoporous composite material is not easy to agglomerate, and the spherical aluminum-containing mesoporous composite material has high catalytic activity when being used as a supported catalyst prepared from a carrier. When the specific surface area of the spherical aluminum-containing mesoporous composite material is less than 100 square meters per gram and/or the pore volume is less than 0.5 ml/gram, the catalytic activity of a supported catalyst prepared by using the spherical aluminum-containing mesoporous composite material as a carrier is remarkably reduced; when the specific surface area of the spherical aluminum-containing mesoporous composite material is more than 180 square meters per gram and/or the pore volume is more than 2 milliliters per gram, a supported catalyst prepared by using the spherical aluminum-containing mesoporous composite material as a carrier is easy to agglomerate in the ethylene polymerization reaction process, so that the conversion rate of reaction raw materials in the ethylene polymerization reaction process is influenced.
According to the present invention, the content of the aluminum component may be 1 to 20 parts by weight, preferably 5 to 19 parts by weight, with respect to 100 parts by weight of the mesoporous molecular sieve material having a three-dimensional cubic channel structure.
In the present invention, the spherical aluminum-containing mesoporous composite material may further contain silica introduced through silica gel. The term "silica introduced through silica gel" refers to a silica component which is introduced into the finally prepared spherical aluminum-containing mesoporous composite material from silica gel as a preparation raw material during the preparation of the spherical aluminum-containing mesoporous composite material. In the spherical aluminum-containing mesoporous composite material, the content of the silica introduced through the silica gel may be 1 to 200 parts by weight, preferably 50 to 150 parts by weight, with respect to 100 parts by weight of the mesoporous molecular sieve material having a three-dimensional cubic pore structure.
In the present invention, the mesoporous molecular sieve material having a three-dimensional cubic pore structure may be various mesoporous molecular sieve materials conventionally used in the art, and may be prepared according to a conventional method.
The invention also provides a preparation method of the spherical aluminum-containing mesoporous composite material, which comprises the following steps:
(1) providing a mesoporous molecular sieve material with a three-dimensional cubic pore channel structure or preparing a filter cake of the mesoporous molecular sieve material with the three-dimensional cubic pore channel structure as a component a;
(2) providing silica gel or preparing a filter cake of silica gel as component b;
(3) mixing the component a and the component b, performing ball milling in a high-alumina ceramic pot, pulping solid powder obtained after ball milling by using water, and then performing spray drying on the obtained slurry;
the component a enables the average particle size of the spherical aluminum-containing mesoporous composite material to be 10-100 micrometers, the specific surface area to be 80-200 square meters per gram, the pore volume to be 0.5-2 milliliters per gram, the pore diameters to be in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are 2-10 nanometers and 30-40 nanometers respectively.
According to the present invention, in the step (1), the process for preparing a filter cake of a mesoporous molecular sieve material having a three-dimensional cubic channel structure comprises: in the presence of a template agent and butanol, ethyl orthosilicate and an acid agent are contacted, and the mixture obtained after the contact is crystallized, filtered and washed sequentially.
According to the invention, in the step (1), the molar ratio of the template agent, the butanol and the ethyl orthosilicate to the acid in the acid agent is 1:10-100:10-90:100-500, preferably 1:30-80:40-80:300-500, and most preferably 1:78:60: 323.
In the present invention, the templating agent is not particularly limited and may be various templating agents conventionally used in the art, and preferably, the templating agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, which is commercially available (e.g., commercially available from Aldric)h company, trade name P123, molecular formula EO20PO70EO20) It can also be prepared by various conventional methods. When the template is polyoxyethylene-polyoxypropylene-polyoxyethylene, the number of moles of the template is calculated from the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.
In the present invention, the acid agent may be any of various substances or mixtures (e.g., solutions) conventionally used for adjusting pH. Preferably, the acid agent is hydrochloric acid. Hydrochloric acid as an acid agent is preferably used in the form of an aqueous solution. The pH of the aqueous hydrochloric acid solution may be 1-6.
The butanol is preferably n-butanol.
In the present invention, the conditions under which the tetraethoxysilane is contacted with the acid agent may include: the temperature is 10-60 deg.C, the time is 10-72 hr, and the pH value is 1-6. In order to facilitate uniform mixing of the substances, the contact of the tetraethoxysilane with the acid agent is preferably carried out under stirring. The dosage of the acid agent is preferably that the pH value of a contact reaction system of the tetraethoxysilane and the acid agent is 1-6.
Further, the contact mode between the template agent, butanol, ethyl orthosilicate and the acidic aqueous solution is not particularly limited, for example, the four substances may be simultaneously mixed and contacted, or several substances may be mixed and contacted first, and then the rest substances may be added to the obtained mixture to be continuously mixed and contacted. Preferably, the contacting mode is that the template agent, butanol and acidic aqueous solution are mixed uniformly, the obtained mixture is placed in a water bath at the temperature of 30-45 ℃, then the temperature is kept unchanged, ethyl orthosilicate is slowly dripped into the mixture, and the mixture is stirred and reacts for 20-40 hours. The dropping rate of the tetraethoxysilane can be 0.1-1g/min based on 1g of the template agent.
In the present invention, the crystallization conditions may include: the temperature is 30-150 ℃ and the time is 10-72 hours. Preferably, the crystallization conditions include: the temperature is 40-100 ℃ and the time is 20-40 hours. The crystallization is carried out by a hydrothermal crystallization method.
In the present invention, in the above-mentioned process of preparing a filter cake of a mesoporous molecular sieve material having a three-dimensional cubic channel structure, the process of obtaining the filter cake by filtration may include: after filtration, washing with deionized water was repeated (the number of washing may be 2 to 10 times), followed by suction filtration.
In the present invention, in the step (1), "providing the mesoporous molecular sieve material having a three-dimensional cubic pore structure" may be a product obtained by directly weighing or selecting the mesoporous molecular sieve material having a three-dimensional cubic pore structure, or may be a product obtained by preparing the mesoporous molecular sieve material having a three-dimensional cubic pore structure. The preparation method of the mesoporous molecular sieve material with the three-dimensional cubic pore channel structure can be implemented according to a conventional method, and for example, the preparation method can comprise the following steps: preparing a filter cake of the mesoporous molecular sieve material with the three-dimensional cubic pore channel structure according to the method, drying the obtained filter cake, and removing the template agent in the dried product. The conditions for removing the template agent may include: the temperature is 300 ℃ and 600 ℃, and the time is 10-80 hours.
According to the present invention, in the step (2), the process of preparing the filter cake of silica gel may include: the water glass is contacted with inorganic acid and n-butanol, and the mixture obtained after the contact is filtered and washed.
According to the present invention, in step (2), the conditions of the contacting may be selected conventionally in the art, for example, the conditions of the contacting of the water glass with the inorganic acid and n-butanol may include: the temperature is 10-60 deg.C, the time is 1-5 hr, and the pH value is 2-4. In order to facilitate uniform mixing of the materials, the contact reaction of the water glass and the inorganic acid is preferably carried out under stirring.
Preferably, the weight ratio of the water glass to the inorganic acid and n-butanol may be 3-6:1: 1.
In the present invention, the water glass is an aqueous solution of sodium silicate, and the concentration thereof may be 10 to 50% by weight, preferably 12 to 30% by weight. The inorganic acid may be various inorganic acids conventionally used in the art, and for example, may be at least one of sulfuric acid, nitric acid, and hydrochloric acid. The inorganic acid may be used in a pure form or in the form of an aqueous solution thereof. The inorganic acid is preferably used in such an amount that the pH of the contact reaction system of the water glass and the inorganic acid is 2 to 4.
In the present invention, in the step (2), "providing silica gel" may be directly weighing or selecting the silica gel product, or may be preparing silica gel. The method for preparing silica gel may be carried out according to conventional methods, and may include, for example: a filter cake of silica gel was prepared according to the above method and the resulting filter cake was then dried.
According to the present invention, in the preparation process of the spherical aluminum-containing mesoporous composite material, the filtration in steps (1) and (2) can be performed in various manners known to those skilled in the art, and preferably, suction filtration separation is performed. The suction filtration separation is a well known way to achieve separation of liquid from solid particles using air pressure to those skilled in the art. The washing may be carried out by a washing method known to those skilled in the art, and may be, for example, water washing and/or alcohol washing, preferably water washing.
According to the invention, in the step (3), the amount of the component a and the component b can be selected according to the composition of the spherical aluminum-containing mesoporous composite material with three-dimensional cubic pore canals, for example, the weight ratio of the component a to the component b is 1: 1-3.
According to the invention, in the step (3), the specific operation method and conditions of the ball milling are not particularly limited, so as to ensure that the structure of the carrier is not damaged or basically not damaged and the silica gel enters the pore channels of the carrier. One skilled in the art can select various suitable conditions to implement the present invention based on the above principles. Specifically, the ball milling is carried out in a high-alumina ceramic ball milling tank, wherein the diameter of the grinding balls in the high-alumina ceramic ball milling tank can be 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the high-alumina ceramic ball-milling tank, and 1 grinding ball can be generally used for the high-alumina ceramic ball-milling tank with the size of 50-150 mL; the grinding balls are made of high-alumina ceramic balls. The high-alumina ceramic ball milling conditions comprise: the rotation speed of the grinding ball can be 300-.
In the present invention, the process of slurrying the solid powder obtained after ball milling with water may be performed at 25 to 60 ℃. The weight ratio of solid powder to water used in the pulping process may be 1:0.5-5, preferably 1: 1-2.
In the present invention, the specific operation method and conditions of the spray drying are well known to those skilled in the art. Specifically, a slurry prepared from the solid powder and water is added into an atomizer and rotated at a high speed to realize spray drying. Wherein, the spray drying conditions comprise that the temperature can be 100-300 ℃, and the rotating speed can be 10000-15000 r/min; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000 r/min; more preferably, the spray drying conditions include a temperature of 200 ℃ and a rotational speed of 12000 r/min.
According to the present invention, in the step (3), when the component a is a filter cake of a mesoporous molecular sieve material having a three-dimensional cubic pore structure and the component b is a filter cake of silica gel, that is, when the step (1) is a process of preparing a filter cake of a mesoporous molecular sieve material having a three-dimensional cubic pore structure and the step (2) is a process of preparing a filter cake of silica gel, the preparation method of the spherical aluminum-containing mesoporous composite material may further include: after the spray drying of step (3), the template agent is removed from the spray-dried product. The conditions for removing the template agent may include: the temperature is 300 ℃ and 600 ℃, and the time is 10-80 hours.
The invention also provides the spherical aluminum-containing mesoporous composite material prepared by the method.
The invention also provides a supported catalyst which comprises a carrier, a magnesium component and a titanium component which are loaded on the carrier, wherein the carrier is the spherical aluminum-containing mesoporous composite material provided by the invention.
In the supported catalyst according to the present invention, the content of the carrier and the magnesium component and the titanium component is not particularly limited and may be suitably determined according to the supported catalyst which is conventional in the art, for example, the content of the carrier is 50 to 99% by weight, preferably 50 to 95% by weight, based on the total weight of the catalyst; the sum of the contents of the magnesium component and the titanium component is 1 to 50% by weight, preferably 5 to 50% by weight, in the form of a salt.
In the present invention, it is preferable that the magnesium component and the titanium component are provided in the form of a magnesium salt and a titanium salt, respectively, which may be various magnesium salts and titanium salts conventionally used in the art, as long as the magnesium component and the titanium component can be provided. Preferably, in the present invention, the magnesium salt is magnesium chloride; the titanium salt is titanium tetrachloride and/or titanium trichloride.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps: in an inert atmosphere, a carrier is soaked in a catalyst mother liquor containing a magnesium component and/or a titanium component, and then filtration and drying are carried out, wherein the carrier is the spherical aluminum-containing mesoporous composite material provided by the invention, and the catalyst mother liquor is a composite organic solution containing the magnesium component and/or the titanium component.
In the present invention, the forms and sources of the magnesium component and the titanium component are as described above, and the present invention will not be described herein.
In the present invention, the inert atmosphere may be formed of various gases that do not chemically interact with the carrier and the active component. For example, the inert atmosphere may be provided by nitrogen and one or more of the group zero gases of the periodic table of components.
According to the invention, the impregnation conditions include: the temperature is 45-100 ℃ and the time is 2-8 h.
In the present invention, the catalyst mother liquor is a complex organic solution containing a magnesium component and/or a titanium component, and the complex organic solvent may be various solvents capable of dissolving the magnesium component and the titanium component and being easily removed, and preferably, the complex organic solvent is tetrahydrofuran and isopropanol. More preferably, the volume ratio of tetrahydrofuran to isopropanol is 1:1 to 3, particularly preferably 1:1 to 1.5.
The invention also provides a supported catalyst prepared by the method.
The invention also provides the application of the supported catalyst in ethylene polymerization reaction.
The present invention also provides a process for the polymerization of ethylene, the process comprising: in the presence of a catalyst, carrying out polymerization reaction on ethylene under the condition of polymerization reaction, wherein the catalyst is the supported catalyst provided by the invention.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, polyoxyethylene-polyoxypropylene-polyoxyethylene, available from Aldrich, abbreviated as P123, and having the formula EO20PO70EO20The substance having a registration number of 9003-11-6 in the American chemical Abstract had an average molecular weight Mn of 5800.
In the following examples and comparative examples, X-ray diffraction analysis was carried out on an X-ray diffractometer, model D8Advance, available from Bruker AXS, Germany; scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; the pore structure parameter analysis was performed on a nitrogen desorption apparatus model Autosorb-1 available from corna, usa, wherein the sample was degassed at 200 ℃ for 4 hours before the test was performed. The aluminum content results were measured by a photoelectron analyzer.
Example 1
This example is provided to illustrate the spherical aluminum-containing mesoporous composite material and supported catalyst and the preparation methods thereof according to the present invention.
(1) Preparation of spherical aluminum-containing mesoporous composite material
Dissolving 6g (0.001mol) of triblock copolymer template agent P123 in 10mL of concentrated hydrochloric acid and 220mL of deionized water solution, stirring for 4h at 15 ℃ to dissolve the P123 to form a transparent solution, adding 6g (0.08mol) of n-butanol into the solution, stirring for 1h, then placing the solution in a water bath at 30 ℃, slowly dropwise adding 12.9g (0.062mol) of ethyl orthosilicate at the speed of 1g/min, stirring for 24h under the conditions that the temperature is kept at 30 ℃ and the pH value is 4.5, then performing hydrothermal treatment for 24h at 100 ℃, finally repeatedly washing with deionized water after filtration, and performing suction filtration to obtain a filter cake A1 of the mesoporous molecular sieve material with the three-dimensional cubic pore structure.
Mixing 15 wt% of water glass, 12 wt% of sulfuric acid solution and n-butyl alcohol according to the weight ratio of water glass, sulfuric acid and n-butyl alcohol of 5: 1:1, stirring and reacting for 1.5 hours at 15 ℃, adjusting the pH value of the obtained reaction product to 3 by using sulfuric acid with the concentration of 98 weight percent, and then carrying out suction filtration and washing with distilled water until the content of sodium ions is 0.02 weight percent to obtain a silica gel filter cake B1.
And (2) putting 20g of the prepared filter cake A1 and 20g of the prepared filter cake B1 into a 100mL high-alumina ceramic ball milling tank (wherein the high-alumina ceramic ball milling tank is made of high-alumina ceramic, the diameter of the grinding balls is 3mm, the number of the grinding balls is 1, and the rotating speed is 400r/min), sealing the high-alumina ceramic ball milling tank, and carrying out high-alumina ceramic ball milling for 1 hour at the temperature of 60 ℃ in the high-alumina ceramic ball milling tank to obtain 40g of solid powder. The solid powder is dissolved in 30 g of deionized water, and is spray-dried at the temperature of 200 ℃ and the rotating speed of 12000r/min, and then a product obtained after spray-drying is calcined in a muffle furnace at the temperature of 500 ℃ for 24 hours to remove a template agent, so that a target product of 30 g of the template agent removed spherical aluminum-containing mesoporous composite material with a high-strength macroporous three-dimensional cubic pore canal is obtained, and the material is named as KITDKAL-1. According to the results of photoelectron spectroscopy, the content of aluminum in KITDKAL-1 was 6% by weight.
(2) Preparation of Supported catalysts
Under the protection of nitrogen, 1g of MgCl2And 1g of TiCl4Dissolving the mixed solution in 500mL of composite organic solvent (the volume ratio of tetrahydrofuran to isopropanol is 1:1.2) to form catalyst mother liquor containing Mg component and Ti component. Then 10g of the carrier is added at 80 ℃ for soaking for 5h, and after the reaction is finished, the powder polyethylene catalyst with good flow property is obtained by filtering and drying, and is named as KITDKAL-BCJ-1.
The spherical aluminum-containing mesoporous composite material of the high-strength macroporous three-dimensional cubic pore canal is characterized by X-ray diffraction, a scanning electron microscope, a photoelectron spectrometer and a nitrogen adsorption and desorption instrument.
FIG. 1 is an X-ray diffraction pattern (XRD pattern) with the abscissa at 2 θ and the ordinate at intensity. From the results of fig. 1, it can be seen that the diffraction peaks in the XRD spectrum of the spherical aluminum-containing mesoporous composite material obtained by the spray drying method are well preserved.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the microstructure of a spherical aluminum-containing mesoporous composite material (KITDKAL-1), and it can be seen from the SEM image that the mesoporous composite material is spherical and has a particle size distribution of 10-80 μm.
The pore structure parameters of the spherical aluminum-containing mesoporous composite material KITDKAL-1 are shown in Table 1.
TABLE 1
*: the first most probable aperture and the second most probable aperture are separated by a comma: the comma is preceded by a first most probable aperture and the comma is followed by a second most probable aperture.
As can be seen from the data in table 1 above, the spherical aluminum-containing mesoporous composite material obtained in example 1 has a bimodal distribution.
The elemental analysis result showed that the content of chlorine was 3.0% by weight, the content of titanium was 0.9% by weight, and the content of magnesium was 2.1% by weight in the catalyst KITDKAL-BCJ-1.
Comparative example 1
The ES955 silica gel is calcined at 400 c for 10 hours under nitrogen to remove hydroxyl groups and residual moisture to provide a heat activated ES955 silica gel.
A supported catalyst was prepared by following the procedure of step (2) of example 1, except that the same parts by weight of ES955 silica gel was used instead of the spherical aluminum-containing composite material.
Elemental analysis showed 1.2% titanium, 6.8% chlorine and 1.8% magnesium in ES 955.
Comparative example 2
A spherical aluminum-containing mesoporous composite material and a supported catalyst were prepared according to the method of example 1, except that the material of the ball mill pot was Teflon and the material of the milling balls was agate in the preparation of the mesoporous composite material used as the carrier.
The elemental analysis results showed that the catalyst prepared in comparative example 2 had a chlorine content of 10 wt%, a titanium content of 3.0 wt% and a magnesium content of 3.1 wt%.
Comparative example 3
Spherical aluminum-containing mesoporous composites and supported catalysts were prepared according to the method of example 1, except that, in the preparation of the mesoporous composite used as the support, the solid powder was directly calcined in a muffle furnace at 500 ℃ for 24 hours to remove the template agent, instead of being dissolved in 30 g of deionized water and spray-dried at 200 ℃ at 12000 r/min. According to the result of photoelectron spectroscopy analysis, the content of aluminum in the obtained mesoporous composite material was 5% by weight.
The elemental analysis results showed that the catalyst prepared in comparative example 3 had a chlorine content of 8.7 wt%, a titanium content of 2.3 wt% and a magnesium content of 2.5 wt%.
Example 2
This example is provided to illustrate the spherical aluminum-containing mesoporous composite material and supported catalyst and the preparation methods thereof according to the present invention.
(1) Preparation of spherical aluminum-containing mesoporous composite material
Dissolving 6g (0.001mol) of triblock copolymer template agent P123 in 10mL of concentrated hydrochloric acid and 220mL of deionized water solution, stirring for 4h at 15 ℃ to dissolve the P123 to form a transparent solution, adding 4.5g (0.06mol) of n-butyl alcohol into the solution, stirring for 1h, then placing the solution in a water bath at 30 ℃, slowly dropwise adding 10.4g (0.05mol) of tetraethoxysilane at the speed of 1g/min, stirring for 10h under the conditions that the temperature is kept at 60 ℃ and the pH value is 6, then performing hydrothermal treatment for 10h at 150 ℃, finally repeatedly washing with deionized water after filtration, and obtaining a filter cake A2 of the mesoporous molecular sieve material with the three-dimensional cubic pore structure after suction filtration.
Mixing 15 wt% of water glass, 12 wt% of sulfuric acid solution and n-butyl alcohol according to the weight ratio of the water glass to the sulfuric acid to the n-butyl alcohol of 6:1:1, stirring and reacting for 1 hour at 60 ℃, adjusting the pH value of the obtained reaction product to 2 by using sulfuric acid with the concentration of 98 weight percent, and then carrying out suction filtration and washing with distilled water until the content of sodium ions is 0.02 weight percent to obtain a silica gel filter cake B2.
And (2) putting 20g of the prepared filter cake A2 and 40g of the prepared filter cake B2 into a 100mL high-alumina ceramic ball milling tank (wherein the high-alumina ceramic ball milling tank is made of high-alumina ceramic, the diameter of the grinding balls is 3mm, the number of the grinding balls is 1, and the rotating speed is 300r/min), sealing the high-alumina ceramic ball milling tank, and carrying out high-alumina ceramic ball milling for 0.5 hour at the temperature of 100 ℃ in the high-alumina ceramic ball milling tank to obtain 40g of solid powder. The solid powder is dissolved in 30 g of deionized water, and is spray-dried at the temperature of 150 ℃ and the rotating speed of 11000r/min, and then a product obtained after spray-drying is calcined in a muffle furnace at the temperature of 300 ℃ for 72 hours to remove a template agent, so that a target product of 30 g of the template agent removed spherical aluminum-containing mesoporous composite material with a high-strength macroporous three-dimensional cubic pore canal is obtained, and the material is named as KITDKAL-2. According to the result of photoelectron spectroscopy, the aluminum content in KITDKAL-2 was 9% by weight.
(2) Preparation of Supported catalysts
Under the protection of nitrogen, 1g of MgCl2And 1g of TiCl4Dissolving the mixed solution in 500mL of composite organic solvent (the volume ratio of tetrahydrofuran to isopropanol is 1:1.2) to form catalyst mother liquor containing Mg component and Ti component. Then 10g of the carrier is added at 80 ℃ for soaking for 5h, and after the reaction is finished, the powder polyethylene catalyst with good flow property is obtained by filtering and drying, and is named as KITDKAL-BCJ-2.
The spherical aluminum-containing mesoporous composite material of the high-strength macroporous three-dimensional cubic pore canal is characterized by X-ray diffraction, a scanning electron microscope, a photoelectron spectrometer and a nitrogen adsorption and desorption instrument.
The pore structure parameters of the spherical aluminum-containing mesoporous composite material KITDKAL-2 are shown in Table 2.
TABLE 2
*: the first most probable aperture and the second most probable aperture are separated by a comma: comma preceded by the first most
Several apertures, followed by a comma followed by the second most probable aperture.
As can be seen from the data in table 2 above, the spherical aluminum-containing mesoporous composite material obtained in example 2 has a bimodal distribution.
The elemental analysis result showed that the content of chlorine was 9.7% by weight, the content of titanium was 1.5% by weight, and the content of magnesium was 2.0% by weight in the catalyst KITDKAL-BCJ-2.
Example 3
This example is provided to illustrate the spherical aluminum-containing mesoporous composite material and supported catalyst and the preparation methods thereof according to the present invention.
(1) Preparation of spherical aluminum-containing mesoporous composite material
Dissolving 6g (0.001mol) of triblock copolymer template agent P123 in 10mL of concentrated hydrochloric acid and 220mL of deionized water solution, stirring for 4h at 15 ℃ to dissolve the P123 to form a transparent solution, adding 6.75g (0.09mol) of n-butyl alcohol into the solution, stirring for 1h, placing the solution in a water bath at 30 ℃, slowly dropwise adding 15.6g (0.075mol) of ethyl orthosilicate at the rate of 1g/min, stirring for 72h under the condition that the temperature is kept at 10 ℃ and the pH value is 1, then performing hydrothermal treatment for 72h at 30 ℃, repeatedly washing with deionized water after filtration, and performing suction filtration to obtain a filter cake A3 of the mesoporous molecular sieve material with the three-dimensional cubic pore structure.
Mixing 15 wt% of water glass, 12 wt% of sulfuric acid solution and n-butyl alcohol according to the weight ratio of water glass, sulfuric acid and n-butyl alcohol of 3: 1:1, stirring and reacting for 5 hours at 10 ℃, adjusting the pH value of the obtained reaction product to 4 by using sulfuric acid with the concentration of 98 weight percent, and then carrying out suction filtration and washing with distilled water until the content of sodium ions is 0.02 weight percent to obtain a silica gel filter cake B3.
And (2) putting 20g of the prepared filter cake A2 and 60g of the prepared filter cake B2 into a 100mL high-alumina ceramic ball milling tank (wherein the high-alumina ceramic ball milling tank is made of high-alumina ceramic, the diameter of the grinding balls is 3mm, the number of the grinding balls is 1, and the rotating speed is 500r/min), sealing the high-alumina ceramic ball milling tank, and carrying out high-alumina ceramic ball milling for 10 hours at the temperature of 25 ℃ in the high-alumina ceramic ball milling tank to obtain 40g of solid powder. The solid powder is dissolved in 30 g of deionized water, and is spray-dried at the temperature of 300 ℃ and the rotating speed of 13000r/min, then a product obtained after spray-drying is calcined in a muffle furnace at the temperature of 600 ℃ for 12 hours to remove the template agent, and the target product of 30 g of the template agent removed spherical aluminum-containing mesoporous composite material with the high-strength macroporous three-dimensional cubic pore canal is obtained, and is named as KITDKAL-3. According to the results of photoelectron spectroscopy, the aluminum content of KITDKAL-3 was 15% by weight.
(2) Preparation of Supported catalysts
Under the protection of nitrogen, 1g of MgCl2And 1g of TiCl4Dissolving the mixed solution in 500mL of composite organic solvent (the volume ratio of tetrahydrofuran to isopropanol is 1:1.2) to form catalyst mother liquor containing Mg component and Ti component. Then 10g of the carrier is added at 80 ℃ for soaking for 5h, and after the reaction is finished, the powder polyethylene catalyst with good flow property is obtained by filtering and drying, and is named as KITDKAL-BCJ-3.
The spherical aluminum-containing mesoporous composite material of the high-strength macroporous three-dimensional cubic pore canal is characterized by X-ray diffraction, a scanning electron microscope, a photoelectron spectrometer and a nitrogen adsorption and desorption instrument.
The pore structure parameters of the spherical aluminum-containing mesoporous composite material KITDKAL-3 are shown in Table 3.
TABLE 3
*: the first most probable aperture and the second most probable aperture are separated by a comma: the comma is preceded by a first most probable aperture and the comma is followed by a second most probable aperture.
As can be seen from the data in table 3 above, the spherical aluminum-containing mesoporous composite material obtained in example 3 has a bimodal distribution.
The elemental analysis result showed that the content of chlorine, the content of titanium and the content of magnesium were 9.0 wt%, 1.7 wt% and 2.0 wt% in the catalyst KITDKAL-BCJ-3.
Experimental example 1
This experimental example serves to illustrate the use of the supported catalyst according to the invention in the polymerization of ethylene.
In a 2-liter stainless steel high-pressure polymerization vessel, nitrogen and ethylene were each replaced three times, then 200 ml of hexane was added, the vessel was warmed to 80 ℃ and 800 ml of hexane was added, and with the addition of hexane, 2 ml of a1 mol/l Triethylaluminum (TEA) hexane solution was added, followed by addition of a polyethylene catalyst, and the pressure was raised to 1.0MPa and maintained at 1.0MPa by passing ethylene, and reacted at 70 ℃ for 1 hour. Obtaining a polyethylene granular powder having a Bulk Density (BD) of 0.34g/mL and a melt index MI2.160.69g/10 min. The efficiency of the catalyst was determined by calculation to be 2195g PE/gcat.h.
Experimental comparative example 1
Polymerization of ethylene was carried out in the same manner as in experimental example 1, except that the catalyst used was ES955 prepared in comparative example 1. The polyethylene granular powder has a Bulk Density (BD) of 0.4g/mL, a melt index: MI2.160.87g/10 min. The efficiency of the catalyst was found by calculation to be 1767g PE/gcat.
Experimental comparative example 2
Ethylene polymerization was carried out in the same manner as in experimental example 1, except that the catalyst used was the catalyst prepared in comparative example 2. The polyethylene granular powder had a Bulk Density (BD) of 0.41g/mL, a melt index: MI2.160.69g/10 min. The efficiency of the catalyst was determined by calculation to be 1700g PE/gcat.h.
Experimental comparative example 3
Ethylene polymerization was carried out in the same manner as in experimental example 1, except that the catalyst used was the catalyst prepared in comparative example 3. The polyethylene granular powder had a Bulk Density (BD) of 0.29g/mL, a melt index: MI2.160.5g/10 min. The efficiency of the catalyst was determined by calculation to be 1850g PE/gcat.h.
Experimental example 2
Ethylene polymerization was carried out in the same manner as in Experimental example 1, except that the catalyst used was KITDKAL-BCJ-2 prepared in example 2. The polyethylene granular powder has a Bulk Density (BD) of 0.4g/mL, a melt index: MI2.160.8g/10 min. The efficiency of the catalyst was determined by calculation to be 2067g PE/gcat.h.
Experimental example 3
Ethylene polymerization was carried out in the same manner as in Experimental example 1, except that the catalyst used was KITDKAL-BCJ-3 prepared in example 3. The polyethylene granular powder had a Bulk Density (BD) of 0.36g/mL, a melt index: MI2.160.9g/10 min. The efficiency of the catalyst was determined by calculation to be 2065g PE/gcat.h.
As can be seen from the data of the above examples and comparative examples and the data of the experimental examples and experimental comparative examples, the preparation method of the composite material provided by the invention can obtain the spherical aluminum-containing composite material with the average particle size of 10-80 microns, the specific surface area of 100-180 square meters/g, the pore volume of 0.5-2 ml/g, the pore diameter in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are 4-8 nanometers and 30-40 nanometers respectively. In addition, the supported catalyst provided by the invention has good catalytic performance, and has higher catalytic activity when being applied to ethylene polymerization reaction.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (19)
1. A method for preparing a spherical aluminum-containing mesoporous composite material comprises the following steps:
(1) providing a mesoporous molecular sieve material with a three-dimensional cubic pore channel structure or preparing a filter cake of the mesoporous molecular sieve material with the three-dimensional cubic pore channel structure as a component a;
(2) providing silica gel or preparing a filter cake of silica gel as component b;
(3) mixing the component a and the component b, performing ball milling in a high-alumina ceramic pot, pulping solid powder obtained after ball milling by using water, and then performing spray drying on the obtained slurry;
wherein the component a enables the average particle diameter of the spherical aluminum-containing mesoporous composite material to be 10-80 microns, the specific surface area to be 100-180 square meters per gram, the pore volume to be 0.5-2 milliliters per gram, the pore diameter to be in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are respectively 4-8 nanometers and 30-40 nanometers.
2. The preparation method according to claim 1, wherein the component a is such that the average particle diameter of the spherical aluminum-containing mesoporous composite material is 30-60 μm, the specific surface area is 100-170 m/g, the pore volume is 0.8-1.8 ml/g, the pore diameter is bimodal, and the most probable pore diameters corresponding to the bimodal are 4-8 nm and 32-39 nm, respectively.
3. The preparation method according to claim 1 or 2, wherein, in the step (1), the process of preparing the filter cake of the mesoporous molecular sieve material having a three-dimensional cubic channel structure comprises: in the presence of a template agent and butanol, ethyl orthosilicate and an acid agent are contacted, and the mixture obtained after the contact is crystallized, filtered and washed sequentially.
4. The method according to claim 3, wherein the molar ratio of the template agent, butanol and ethyl orthosilicate to the acid in the acid agent is 1:10-100:10-90: 100-.
5. The preparation method according to claim 3, wherein, in step (1), the template is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene; the acid agent is hydrochloric acid; the condition of contacting the tetraethoxysilane with the acid agent comprises the following steps: the temperature is 10-60 ℃, the time is 10-72 hours, and the pH value is 1-6; the crystallization conditions include: the temperature is 30-150 ℃ and the time is 10-72 hours.
6. The production method according to claim 1 or 2, wherein, in the step (2), the process of producing the filter cake of silica gel comprises: the water glass is contacted with inorganic acid and n-butanol, and the mixture obtained after the contact is filtered and washed.
7. The preparation method according to claim 6, wherein in the step (2), the weight ratio of the water glass to the inorganic acid and n-butanol is 3-6:1: 1; the contact conditions of the water glass with the inorganic acid and the n-butyl alcohol comprise that: the temperature is 10-60 ℃, the time is 1-5 hours, and the pH value is 2-4; the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid.
8. The production method according to claim 1 or 2, wherein in step (3), the weight ratio of the component a to the component b is 1: 1-3.
9. The production method according to claim 1 or 2, wherein, in the step (3), the conditions for ball-milling in the high alumina ceramic pot include: the rotation speed of the grinding ball is 300-; the conditions of the spray drying include: the temperature is 100-300 ℃, and the rotating speed is 10000-15000 r/min.
10. The production method according to claim 1 or 2, wherein the component a is a cake of a mesoporous molecular sieve material having a three-dimensional cubic channel structure, and the component b is a cake of silica gel, the method further comprising: after the spray-drying process of step (3), the template is removed from the spray-dried product.
11. The method of claim 10, wherein the conditions for removing the template agent comprise: the temperature is 300 ℃ and 600 ℃, and the time is 10-80 hours.
12. The spherical aluminum-containing mesoporous composite material prepared by the method of any one of claims 1 to 11.
13. A supported catalyst comprising a carrier and a magnesium component and a titanium component supported on the carrier, characterized in that the carrier is the spherical aluminum-containing mesoporous composite material according to claim 12.
14. The catalyst of claim 13, wherein the support is present in an amount of 50 to 99 wt%, based on the total weight of the catalyst; the sum of the contents of the magnesium component and the titanium component is 1 to 50% by weight in the form of a salt.
15. The catalyst of claim 13, wherein the support is present in an amount of 50 to 95 wt%, based on the total weight of the catalyst; the sum of the contents of the magnesium component and the titanium component is 5 to 50% by weight in the form of a salt.
16. A process for the preparation of a supported catalyst as claimed in any one of claims 13 to 15, which process comprises: the method is characterized in that a carrier is impregnated in a catalyst mother liquor containing a magnesium component and/or a titanium component under an inert atmosphere, and then is filtered and dried, wherein the carrier is the spherical aluminum-containing mesoporous composite material as claimed in any one of claims 1-2, and the catalyst mother liquor is a composite organic solution containing the magnesium component and/or the titanium component.
17. The production method according to claim 16, wherein the impregnation conditions include: the temperature is 45-100 ℃ and the time is 2-8 h.
18. Use of a supported catalyst according to any one of claims 13 to 15 in the polymerisation of ethylene.
19. A process for the polymerization of ethylene, the process comprising: polymerizing ethylene under polymerization conditions in the presence of a catalyst, wherein the catalyst is a supported catalyst according to any one of claims 13 to 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510740436.9A CN106632760B (en) | 2015-11-04 | 2015-11-04 | Spherical aluminum-containing mesoporous composite material, supported catalyst, preparation method and application of supported catalyst, and ethylene polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510740436.9A CN106632760B (en) | 2015-11-04 | 2015-11-04 | Spherical aluminum-containing mesoporous composite material, supported catalyst, preparation method and application of supported catalyst, and ethylene polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632760A CN106632760A (en) | 2017-05-10 |
| CN106632760B true CN106632760B (en) | 2020-04-07 |
Family
ID=58851141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510740436.9A Active CN106632760B (en) | 2015-11-04 | 2015-11-04 | Spherical aluminum-containing mesoporous composite material, supported catalyst, preparation method and application of supported catalyst, and ethylene polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632760B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109746028B (en) * | 2017-11-03 | 2022-03-15 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst, preparation method thereof and method for preparing propylene by propane dehydrogenation |
| CN109746033B (en) * | 2017-11-03 | 2021-11-19 | 中国石油化工股份有限公司 | Method for preparing propane dehydrogenation catalyst, propane dehydrogenation catalyst and method for preparing propylene by propane dehydrogenation |
| CN110614112A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being spherical aluminum-containing mesoporous molecular sieve silica gel composite material, and preparation method and application thereof |
| CN110732341A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical aluminum-containing double mesoporous molecular sieve silica gel composite as carrier and preparation method and application thereof |
| CN111100223B (en) * | 2018-10-26 | 2022-10-21 | 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 (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941712A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Preparation method of mesopore molecular sieve containing beta zeolite secondary structural unit |
| CN103028433A (en) * | 2011-09-29 | 2013-04-10 | 湖南石油化学株式会社 | ZSM-5 catalyst having micro-pore and meso pore, preparing method thereof and method of using the catalyst to conduct catalytic cracking on hydrocarbon to produce light olefins |
| CN104248991A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite carrier, supported catalyst, preparation methods of spherical montmorillonite mesoporous composite carrier and supported catalyst, use of supported catalyst and preparation method of ethyl acetate |
| CN104248985A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite carrier, supported catalyst and preparation method and application thereof, and ethyl acetate preparation method |
| CN104248990A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical attapulgite mesoporous composite carrier, supported catalyst, preparation methods of spherical attapulgite mesoporous composite carrier and supported catalyst, use of supported catalyst and preparation method of ethyl acetate |
| CN106622377A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Spherical aluminum-containing mesoporous composite, supported catalyst, and preparation method of spherical aluminum-containing mesoporous composite, preparation method of supported catalyst, application of supported catalyst, and preparation method of ethyl acetate |
| CN106622378A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Spherical aluminium-containing mesoporous composite material, supported catalyst, preparation method and applications of spherical aluminium-containing mesoporous composite material and supported catalyst, and method used for preparing cyclohexanone glyceryl |
-
2015
- 2015-11-04 CN CN201510740436.9A patent/CN106632760B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941712A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Preparation method of mesopore molecular sieve containing beta zeolite secondary structural unit |
| CN103028433A (en) * | 2011-09-29 | 2013-04-10 | 湖南石油化学株式会社 | ZSM-5 catalyst having micro-pore and meso pore, preparing method thereof and method of using the catalyst to conduct catalytic cracking on hydrocarbon to produce light olefins |
| CN104248991A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite carrier, supported catalyst, preparation methods of spherical montmorillonite mesoporous composite carrier and supported catalyst, use of supported catalyst and preparation method of ethyl acetate |
| CN104248985A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite carrier, supported catalyst and preparation method and application thereof, and ethyl acetate preparation method |
| CN104248990A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical attapulgite mesoporous composite carrier, supported catalyst, preparation methods of spherical attapulgite mesoporous composite carrier and supported catalyst, use of supported catalyst and preparation method of ethyl acetate |
| CN106622377A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Spherical aluminum-containing mesoporous composite, supported catalyst, and preparation method of spherical aluminum-containing mesoporous composite, preparation method of supported catalyst, application of supported catalyst, and preparation method of ethyl acetate |
| CN106622378A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Spherical aluminium-containing mesoporous composite material, supported catalyst, preparation method and applications of spherical aluminium-containing mesoporous composite material and supported catalyst, and method used for preparing cyclohexanone glyceryl |
Non-Patent Citations (1)
| Title |
|---|
| Aluminum Impregnation into Mesoporous Silica Molecular Sieves for Catalytic Application to Friedel-Crafts Alkylation;Shinae Jun等;《Journal of Catalysis》;2000;第237-243页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632760A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106632760B (en) | Spherical aluminum-containing mesoporous composite material, supported catalyst, preparation method and application of supported catalyst, and ethylene polymerization method | |
| CN105330768B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN105330767B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| CN106467579B (en) | Macropore two dimension double hole channel spherical complex carrier and composite material and their preparation method and application containing polyethylene catalysts | |
| CN105330769B (en) | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application | |
| 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 | |
| CN105440168B (en) | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application | |
| CN106467581B (en) | Three hole silica-gel carriers and support type polyethylene catalysts and its preparation method and application | |
| CN106554431B (en) | The method of bimodal porous silica carrier and support type polyethylene catalysts and its preparation method and application and vinyl polymerization | |
| CN108017740B (en) | Spherical porous mesoporous composite material, supported catalyst and preparation method thereof | |
| 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 | |
| CN107417820B (en) | Spherical diatomite mesoporous composite material, supported catalyst and preparation method thereof | |
| CN111100223B (en) | Polyolefin catalyst prepared by spray drying method, and preparation method and application thereof | |
| CN107417828B (en) | Spherical composite material and supported polyethylene catalyst and preparation method thereof | |
| CN108794666A (en) | The method and polyethylene of vinyl polymerization | |
| CN107840912B (en) | Method for polymerizing ethylene and polyethylene | |
| CN107417824B (en) | Method for polymerizing ethylene and polyethylene | |
| CN107417821B (en) | Spherical composite material and supported polyethylene catalyst and preparation method thereof | |
| CN110734511B (en) | Polyolefin catalyst with spherical double-mesoporous composite material as carrier, polyolefin and preparation methods of polyolefin catalyst and polyolefin | |
| CN107417812B (en) | Spherical double-mesoporous-structure composite material, supported polyethylene catalyst and preparation methods thereof | |
| CN107417831B (en) | Method for polymerizing ethylene and polyethylene | |
| CN108727523B (en) | Process for the polymerization of ethylene and polyethylene | |
| CN108727518B (en) | Process for the polymerization of ethylene and polyethylene | |
| CN108623720B (en) | Spherical mesoporous composite material, supported catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |