CN107840913B

CN107840913B - Spherical small-particle-size mesoporous composite material, supported catalyst and preparation method of supported catalyst

Info

Publication number: CN107840913B
Application number: CN201610833830.1A
Authority: CN
Inventors: 亢宇; 张明森; 吕新平
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2016-09-20
Filing date: 2016-09-20
Publication date: 2020-06-09
Anticipated expiration: 2036-09-20
Also published as: CN107840913A

Abstract

The invention relates to the field of mesoporous materials, and discloses a spherical small-particle-size mesoporous composite material, a supported catalyst and a preparation method thereof. The spherical small-particle-size mesoporous composite material contains a mesoporous molecular sieve material with a three-dimensional cubic cage-shaped pore channel structure, the average particle size of the spherical small-particle-size mesoporous composite material is 15-30 micrometers, the specific surface area is 200-650 square meters/g, the pore volume is 0.5-1.5 milliliters/g, and the pore size is in bimodal distribution. The mesoporous composite material with the spherical small particle size provided by the invention has a stable mesoporous structure and uniform particle size distribution, is high in strength and not easy to break as a catalyst carrier, and the supported polyethylene catalyst prepared by the mesoporous composite material has high catalytic activity when being used for catalyzing ethylene polymerization reaction, so that a polyethylene product which is low in bulk density and melt index and not easy to break can be obtained.

Description

Spherical small-particle-size mesoporous composite material, supported catalyst and preparation method of supported catalyst

Technical Field

The invention relates to the field of mesoporous materials, in particular to a spherical small-particle-size mesoporous composite material, a preparation method of the spherical small-particle-size mesoporous composite material, the spherical small-particle-size mesoporous composite material prepared by the method, a supported catalyst, a preparation method of the supported catalyst and the supported catalyst prepared by the method.

Background

Since the synthesis of a regular mesoporous material with highly ordered pore channels by the company Mobile in 1992, the application of the mesoporous material in the fields of catalysis, separation, medicine and the like has attracted much attention due to the high specific surface, the regular pore channel structure and the narrow pore size distribution. A novel mesoporous material SBA-15 is synthesized by Zhao Dongyuan et al in 1998, which has highly ordered pore diameter (6-30nm) and large pore volume (1.0 cm)³,/g), thicker pore walls (4-6nm), maintained high mechanical strength and good catalytic adsorption performance (see D.Y.ZHao, J.L.Feng, Q.S.Huo, et al Science 279(1998) 548-550). CN1341553A discloses a preparation method of a mesoporous molecular sieve carrier material, and the mesoporous material prepared by the method is used as a heterogeneous reaction catalyst carrier, so that the separation of a catalyst and a product is easy to realize.

However, the conventional ordered mesoporous material SBA-15 has a rod-like microscopic morphology, the flowability of the material is poor, and the high specific surface area and the high pore volume of the material cause the material to have strong water and moisture absorption capacity, so that the agglomeration of the ordered mesoporous material is further aggravated, and the storage, transportation, post-processing and application of the ordered mesoporous material are limited.

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. The homogeneous phase polyethylene catalyst has high activity, needs large catalyst consumption and high production cost, and the obtained polymer has no granular shape and cannot be used in a polymerization process of a slurry method or a gas phase method which is widely applied. An effective method for overcoming the above problems is to carry out a supporting treatment of the soluble polyethylene catalyst. 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 develop different supports to drive the further development of the supported catalyst and polyolefin industries.

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 still a technical problem to be solved urgently to find a mesoporous material with a stable mesoporous structure, and a supported catalyst which can still maintain an ordered mesoporous structure after an active component is supported and has high catalytic activity.

Disclosure of Invention

The invention aims to overcome the defect of unstable mesoporous structure in the prior art and provides a spherical small-particle-size mesoporous composite material and a supported catalyst containing the same. The supported catalyst containing the spherical mesoporous composite material with small particle size can obtain polyethylene products with lower bulk density and melt index and difficult breakage.

Specifically, in a first aspect, the present invention provides a spherical small-particle-size mesoporous composite material, which contains a mesoporous molecular sieve material having a three-dimensional cubic cage-shaped pore structure, and the spherical small-particle-size mesoporous composite material has an average particle size of 21-29 μm, a specific surface area of 200-650 square meters/g, a pore volume of 0.5-1.5 ml/g, and bimodal pore diameters, wherein the bimodal pore diameters correspond to the most probable pore diameters of 1-10 nm and 15-40 nm, respectively.

In a second aspect, the present invention provides a method for preparing a spherical small-particle-size mesoporous composite material, comprising the following steps:

(1) providing a mesoporous molecular sieve material with a three-dimensional cage-shaped pore channel structure or preparing a filter cake of the mesoporous molecular sieve material with the three-dimensional cage-shaped 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 first ball milling, mixing the obtained first ball milling slurry with water for pulping, performing second ball milling to obtain second ball milling slurry, performing spray drying on the second ball milling slurry, and screening by adopting a cyclone separation technology;

the average particle size of the spherical small-particle-size mesoporous composite material is 21-29 microns, the specific surface area is 200-650 square meters per gram, the pore volume is 0.5-1.5 milliliters per gram, the pore diameters are distributed in a double mode, and the most probable pore diameters corresponding to the double modes are 1-10 nanometers and 15-40 nanometers respectively.

In a third aspect, the invention provides a spherical small-particle-size mesoporous composite material prepared by the method.

In a fourth aspect, the invention provides a supported catalyst, which comprises a carrier and magnesium salt and/or titanium salt loaded on the carrier, wherein the carrier is the spherical mesoporous composite material with small particle size provided by the invention.

In a fifth aspect, the present invention provides a method for preparing a supported catalyst and a supported catalyst prepared by the method, the method comprising: contacting the support with a mother liquor containing magnesium and/or titanium salts in the presence of an inert gas; wherein, the carrier is the spherical mesoporous composite material with small particle size provided by the invention.

The invention adopts the secondary ball milling technology and the cyclone separation technology in the spray drying technology, the secondary ball milling technology enables the obtained slurry to be more exquisite, the spherical particles obtained after spray drying have stable structure, can be repeatedly used as a catalyst carrier, have high strength and are not easy to break, and the preparation of the spherical mesoporous composite material with small particle size does not need to use a binder, so that the structure of a sample can be prevented from being damaged in the process of removing the binder at high temperature. The obtained spherical small-particle-size mesoporous composite material has small particle size, uniform particle size distribution and narrow particle size distribution curve by adopting a cyclone separation technology, can avoid the agglomeration of the ordered mesoporous material in the use process, improves the fluidity of the ordered mesoporous material, and brings convenience to the storage, transportation, post-processing and application of the ordered mesoporous material.

In addition, the mesoporous structure of the spherical mesoporous composite material with small particle size provided by the invention is stable, the ordered mesoporous structure can be still maintained after the active component is loaded, and the supported catalyst prepared from the mesoporous composite material has good fluidity. When the supported catalyst is used for ethylene polymerization reaction, a polyethylene product which has low bulk density and melt index and is not easy to break can be obtained, and specifically, the bulk density of the prepared polyethylene product is less than 0.4g/mL, the melt index is less than 0.5g/10min, and the breaking rate is less than 2 weight percent.

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 spectrum) of the spherical small-diameter mesoporous composite material of example 1, with 2 θ on the abscissa and intensity on the ordinate;

FIG. 2 is a Scanning Electron Microscope (SEM) image of the micro-morphology of the spherical small-particle-size mesoporous composite material in example 1;

FIG. 3 is a graph showing the particle size distribution of the spherical small-diameter mesoporous composite material of example 1;

FIG. 4 is a diagram showing the pore size distribution of the spherical small-diameter mesoporous composite material in example 1.

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 endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a spherical small-particle-size mesoporous composite material, which contains a mesoporous molecular sieve material with a three-dimensional cubic cage-shaped pore passage structure, wherein the average particle size of the spherical small-particle-size mesoporous composite material is 21-29 micrometers, the specific surface area is 200-650 square meters per gram, the pore volume is 0.5-1.5 milliliters per gram, the pore diameter is in bimodal distribution, and the most probable pore diameters of the two peaks are 1-10 nanometers and 15-40 nanometers respectively.

According to a preferred embodiment of the invention, the average particle size of the spherical small-particle-size mesoporous composite material is 22-28 microns, the specific surface area is 250-350 square meters per gram, the pore volume is 1.0-1.5 ml/g, the pore diameters are in bimodal distribution, and the most probable pore diameters corresponding to the two modes are 5-10 nanometers and 20-35 nanometers respectively;

according to a more preferred embodiment of the present invention, the average particle size of the spherical small-particle-size mesoporous composite material is 23-27 μm, the specific surface area is 300-340 m/g, the pore volume is 1.1-1.4 ml/g, the pore diameters are distributed in two peaks, and the two peaks correspond to a maximum pore diameter of 6-9 nm and 25-35 nm, respectively.

In the invention, the average particle size of the spherical small-particle-size mesoporous composite material is measured by a laser particle size distribution instrument, the specific surface area, the pore volume and the most probable pore size are measured by a nitrogen adsorption method, and the surface morphology of the spherical small-particle-size mesoporous composite material is measured by a Scanning Electron Microscope (SEM). In the present invention, the average particle diameter is an average particle diameter.

In the invention, the spherical small-particle-size mesoporous composite material does not contain a binder such as polyvinyl alcohol or polyethylene glycol.

In the present invention, the spherical small-particle-size 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 mesoporous composite material with small particle size from silica gel as a raw material during the preparation of the spherical mesoporous composite material with small particle size. In the spherical small-particle-size mesoporous composite material, the content of the silica introduced through the silica gel may be 1 to 200 parts by weight, preferably 20 to 180 parts by weight, and more 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 cage-shaped pore structure.

The invention also provides a preparation method of the spherical small-particle-size mesoporous composite material, which comprises the following steps of:

In the present invention, the particle size of the spherical mesoporous composite material with small particle size is controlled within the above range, so that the spherical mesoporous composite material with small particle size is not easily agglomerated, and the conversion rate of the reaction raw material in the ethylene polymerization process can be improved by using the supported catalyst prepared by using the spherical mesoporous composite material as a carrier.

In the preparation process of the spherical small-particle-size mesoporous composite material, the pore size distribution of the spherical small-particle-size mesoporous composite material is controlled to be bimodal distribution mainly by controlling the composition of a mesoporous material filter cake (component a), and the microscopic morphology of the spherical small-particle-size mesoporous composite material is controlled to be spherical mainly by controlling a forming method (namely, firstly, the component a and the component b are mixed and subjected to first ball milling, the obtained first ball milling slurry is mixed with water for pulping, then, second ball milling is carried out to obtain second ball milling slurry, and the second ball milling slurry is subjected to spray drying).

According to the present invention, in the step (1), the process of preparing a filter cake of a mesoporous molecular sieve material having a three-dimensional cubic cage-like pore structure may include: and carrying out first mixing contact on a template agent, potassium sulfate, an acid agent and a silicon source, and crystallizing and filtering the obtained mixture. The order of the first mixing and contacting is not particularly limited, and the template agent, the potassium sulfate, the acid agent and the silicon source may be mixed at the same time, or any two or three of them may be mixed, and then the other components may be added and mixed uniformly. According to a preferred embodiment, the template agent, the potassium sulfate and the acid agent are mixed uniformly, and then the silicon source is added and mixed uniformly.

In the present invention, the amount of the template, potassium sulfate and silicon source may vary within a wide range, for example, the molar ratio of the template, potassium sulfate and silicon source may be 1: 100-800: 50-300, preferably 1: 150-700: 80-250, more preferably 1: 200-400: 100-200.

In the present invention, the templating agent may be various templating agents that are conventional in the art. For example, the templating agent may be a triblock copolymer Polyoxyethylene (PEO) -polyoxypropylene (PPO) -Polyoxyethylene (PEO), which may be prepared by methods known to those skilled in the art or may be obtained commercially, e.g., from Fuka under the trade name Synperonic F108, PEO₁₃₂-PPO₅₀-PEO₁₃₂Average molecular weight M_n14600. Wherein the number of moles of polyoxyethylene-polyoxypropylene-polyoxyethylene is calculated from the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.

In the present invention, the silicon source may be various silicon sources conventionally used in the art, and preferably the silicon source is at least one of tetraethoxysilane, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, and more preferably tetraethoxysilane.

In the present invention, the acid agent may be various acidic aqueous solutions conventionally used in the art, and for example, may be at least one aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid, preferably an aqueous hydrochloric acid solution.

The amount of the acid agent is not particularly limited, and may be varied within a wide range, and it is preferable that the pH value in the first mixing contact is 1 to 7.

In the present invention, the conditions of the first mixing contact are not particularly limited, and for example, the conditions of the first mixing contact include: the temperature can be 10-60 ℃, preferably 25-60 ℃; the time can be 10 to 72 hours, preferably 10 to 30 hours; the pH may be from 1 to 7, preferably from 3 to 6. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the first mixing contact is carried out under stirring conditions.

In the present invention, the crystallization conditions are not particularly limited, and for example, the crystallization conditions include: the temperature can be 30-150 ℃, preferably 90-150 ℃; the time may be 10 to 72 hours, preferably 10 to 40 hours. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.

In the present invention, in the above-described process of preparing a filter cake of a mesoporous molecular sieve material having a three-dimensional cubic cage structure, the process of obtaining the filter cake by filtration may include: after filtration, repeated washing with deionized water (washing times may be 2 to 10) and suction filtration.

In the step (1), "providing the mesoporous molecular sieve material having a three-dimensional cubic cage-shaped pore structure" may be a product obtained by directly weighing or selecting the mesoporous molecular sieve material having a three-dimensional cubic cage-shaped pore structure, or may be a product obtained by preparing the mesoporous molecular sieve material having a three-dimensional cubic cage-shaped pore structure. The preparation method of the mesoporous molecular sieve material with the three-dimensional cage-shaped pore channel structure can be implemented according to a conventional method, and for example, the preparation method can comprise the following steps: according to the method, the filter cake of the mesoporous molecular sieve material with the three-dimensional cage-shaped pore channel structure is prepared, and then the obtained filter cake is dried.

According to the present invention, in the step (2), the process for preparing the filter cake of silica gel comprises: and carrying out second mixing contact on the water glass, the polyhydric alcohol and the inorganic acid, and filtering the obtained mixture.

In the present invention, the conditions of the second mixing contact are not particularly limited and may be appropriately determined according to a conventional process for preparing silica gel. For example, the conditions of the second mixing contact include: the temperature can be 10-60 ℃, preferably 20-40 ℃; the time may be 1 to 5 hours, preferably 1 to 3 hours; the pH value is 2-4. In order to facilitate uniform mixing of the substances, the second mixing contact reaction process is preferably performed under stirring conditions.

In the present invention, the amounts of the water glass, the mineral acid and the polyol may vary within a wide range. For example, the weight ratio of water glass, mineral acid and polyol may be 1 to 8: 0.1-5: 1, preferably 3 to 6: 0.5-4: 1, more preferably 3 to 6: 1-3: 1.

in the present invention, the water glass is an aqueous solution of sodium silicate, and the concentration thereof may be 3 to 20% by weight, preferably 10 to 20% by weight. The inorganic acid may be various inorganic acids conventionally used in the art, and may be, for example, one or more of sulfuric acid, nitric acid, and hydrochloric acid. The inorganic acids can be used in pure form or in the form of their aqueous solutions, preferably in the form of 3 to 20% by weight aqueous solutions. 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, the kind of the polyol is not particularly limited, and for example, it may be glycerin and/or ethylene glycol.

According to the invention, in the step (2), "providing silica gel" may be directly weighing or selecting the silica gel product, or 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.

In the above process for preparing a filter cake of silica gel, the process for obtaining the filter cake by filtration may include: after filtration, washing is carried out until the content of sodium ions is 0.2 wt% or less, preferably 0.01 to 0.03 wt%, and then suction filtration is carried out. The washing method is a routine choice in the field, and can be water washing and/or alcohol washing, and the specific conditions are well known to those skilled in the art and are not described in detail herein.

According to the invention, in step (3), the amounts of component a and component b can vary within wide limits. For example, the component b may be used in an amount of 1 to 200 parts by weight, preferably 20 to 180 parts by weight, and more preferably 50 to 150 parts by weight, relative to 100 parts by weight of the component a.

In order to improve the strength of the spherical mesoporous composite material with small particle size and further improve the performance of the prepared polyethylene product, the invention is realized by a secondary ball milling method of slurry.

According to the present invention, in the step (3), the first ball milling and the second ball milling may be performed in a ball mill in which the inner wall of a ball milling jar is preferably an agate inner liner, and the diameter of the milling balls in the ball mill may be 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the ball milling tank, and for the ball milling tank with the size of 50-150mL, 1 grinding ball can be generally used; the material of the grinding ball can be agate, polytetrafluoroethylene and the like, and agate is preferred. The conditions of the first ball milling and the second ball milling can be the same or different, and the conditions of the first ball milling and the second ball milling respectively and independently comprise: the rotation speed of the grinding ball can be 200-; preferably, the rotation speed of the grinding balls is 300-.

According to the present invention, in the step (3), the temperature for mixing the obtained first ball-milling slurry with water for pulping may be 25 to 60 ℃, preferably 25 to 50 ℃; the weight ratio of the first ball-milling slurry to the amount of water may be 1: 0.1 to 5, preferably 1: 0.5-3.5.

According to the present invention, in the step (3), the spray drying may be performed according to a conventional manner, and may be selected from at least one of a pressure spray drying method, a centrifugal spray drying method, and a pneumatic spray drying method. According to a preferred embodiment of the present invention, the spray drying is a centrifugal spray drying method. The spray drying may be carried out in an atomizer. The conditions of the spray drying may include: the temperature is 150-; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000 r/min.

According to the invention, the step of screening the second ball-milling slurry by adopting a cyclone separation technology after spray drying comprises the following steps: and carrying out spray drying on the second ball-milling slurry, and carrying out cyclone separation on the discharged gas containing the powder particles so as to collect the powder particles. Specifically, the cyclone separation technology is adopted to separate the powder particles contained in the discharged gas, the recovered powder particles fall into the powder collecting cylinder, the waste gas is delivered to the centrifugal fan from the outlet of the separator, the butterfly valve is installed at the lower part of the cyclone separator, and when the cyclone separator works, the butterfly valve is opened, and the obtained sample has uniformly distributed particle sizes.

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 cage-shaped pore structure and the component b is a filter cake of silica gel, that is, when the step (1) is a process for preparing a filter cake of a mesoporous molecular sieve material having a three-dimensional cubic cage-shaped pore structure and the step (2) is a process for preparing a filter cake of silica gel, the preparation method of the spherical small-particle-size mesoporous composite material may further include: removing the templating agent from the powder particles collected by cyclone separation after the spray drying process of step (3). The conditions for removing the template agent comprise: the temperature can be 90-600 ℃, preferably 300-600 ℃; the time may be 10 to 80 hours, preferably 10 to 24 hours.

The invention also provides the spherical small-particle-size mesoporous composite material prepared by the method.

The invention also provides a supported catalyst, which comprises a carrier and magnesium salt and/or titanium salt loaded on the carrier, wherein the carrier is the spherical mesoporous composite material with small particle size provided by the invention.

According to the invention, the contents of the magnesium salt, titanium salt and the support may vary within wide limits. For example, the sum of the contents of the magnesium salt and the titanium salt in terms of magnesium element and titanium element, respectively, may be 1 to 10% by weight, and the content of the support may be 90 to 99% by weight, based on the total weight of the catalyst. Preferably, the sum of the contents of the magnesium salt and the titanium salt in terms of magnesium element and titanium element respectively is 1.5-9.5 wt%, and the content of the carrier is 90.5-98.5 wt%. More preferably, the sum of the contents of the magnesium salt and the titanium salt in terms of magnesium element and titanium element, respectively, is 4 to 9 wt%, and the content of the carrier is 91 to 96 wt%.

According to a preferred embodiment of the present invention, the magnesium salt and the titanium salt are used in a weight ratio of 1: 0.1 to 2, preferably 1: 0.5-2.

In the present invention, the kind of the magnesium salt and the titanium salt is not particularly limited, and may be conventionally selected in the art. For example, the magnesium salt may be one or more of magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium bromide, preferably magnesium chloride; the titanium salt may be titanium tetrachloride and/or titanium trichloride.

In the invention, the content of each element in the catalyst component can be measured by adopting an X-ray fluorescence spectrum analysis method.

In the present invention, the supported catalyst may be prepared according to various methods conventionally used in the art, as long as a magnesium salt and/or a titanium salt is supported on the carrier.

The invention also provides a preparation method of the supported catalyst, which comprises the steps of contacting a carrier with a mother solution containing magnesium salt and/or titanium salt in the presence of inert gas; wherein, the carrier is the spherical mesoporous composite material with small particle size provided by the invention.

In the present invention, the mother liquor containing magnesium salt and/or titanium salt may be an organic solvent containing magnesium salt and/or titanium salt, the organic solvent may be isopropanol and tetrahydrofuran, and the volume ratio of tetrahydrofuran to isopropanol may be 1: 1-3, preferably 1: 1-1.5.

In the preparation process of the catalyst, the magnesium salt and the titanium salt are preferably used in an excess amount relative to the spherical small-particle-size mesoporous composite material. For example, the magnesium salt, the titanium salt and the carrier may be used in amounts such that the sum of the contents of the magnesium salt and the titanium salt, respectively, in terms of magnesium element and titanium element, may be 1 to 10% by weight and the content of the carrier may be 90 to 99% by weight, based on the total weight of the catalyst, in the prepared supported catalyst. Preferably, the sum of the contents of the magnesium salt and the titanium salt in terms of magnesium element and titanium element respectively is 1.5-9.5 wt%, and the content of the carrier is 90.5-98.5 wt%. More preferably, the sum of the contents of the magnesium salt and the titanium salt in terms of magnesium element and titanium element, respectively, is 4 to 9 wt%, and the content of the carrier is 91 to 96 wt%.

Preferably, the conditions under which the support is contacted with the mother liquor containing a magnesium salt and/or a titanium salt include: the temperature is 25-100 ℃, preferably 40-60 ℃; the time is 0.1 to 5 hours, preferably 1 to 3 hours.

In the present invention, the preparation method of the supported catalyst further comprises: after the carrier is contacted with the mother liquor containing a magnesium salt and/or a titanium salt, the carrier loaded with the magnesium salt and/or the titanium salt is filtered and dried. The drying conditions are not particularly limited and may be drying means and conditions which are conventional in the art. Preferably, the preparation of the supported catalyst also comprises a washing process after filtration and before drying, and/or a milling process after drying. The washing and milling conditions can be selected by the person skilled in the art according to the practical circumstances and will not be described in detail here.

In the present invention, the inert gas is a gas which does not react with the raw materials and the product, and may be, for example, nitrogen gas or at least one of group zero element gases in the periodic table, preferably nitrogen gas, which is conventional in the art.

The invention also provides a supported catalyst prepared by the method.

The present invention will be described in detail below by way of examples.

In the following examples and comparative examples, polyoxyethylene-polyoxypropylene-polyoxyethylene was obtained from Fuka under the trade name Synperonic F108 and has the formula PEO₁₃₂-PPO₅₀-PEO₁₃₂Average molecular weight M_n＝14600。

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; 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 testing; the X-ray fluorescence analysis is carried out on an X-ray fluorescence analyzer with the model of Axios-Advanced of the Netherlands company; the particle size distribution curve was measured by a malvern laser particle sizer.

The bulk density of the polyolefin powder was determined by the method specified in GB/T1636-2008.

Polymer melt index: measured according to ASTM D1238-99.

Crushing rate of polyethylene granular powder: and (3) screening and measuring by using a 800-mesh screen, specifically, passing the polyethylene granular powder through the 800-mesh screen, wherein the crushing rate is the percentage of the weight of the polyethylene granular powder which passes through the 800-mesh screen to the weight of the polyethylene granular powder to be tested.

Example 1

This example is used to illustrate the spherical small-particle-size mesoporous composite material and supported catalyst of the present invention and their preparation methods.

(1) Preparation of spherical small-particle-size mesoporous composite material

1.46g (0.0001mol) of template F108 and 5.24g (0.03mol) of K₂SO₄Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved;

adding 4.2g (0.02mol) of ethyl orthosilicate into the solution, stirring for 15 minutes at 38 ℃, and standing for 24 hours at 38 ℃;

then transferring the mixture into a reaction kettle with an agate inner lining, crystallizing the mixture for 24 hours at the temperature of 100 ℃, then filtering the mixture, washing the mixture for 4 times by using deionized water, and then carrying out suction filtration to obtain a filter cake A1 of the mesoporous molecular sieve material with the three-dimensional cubic cage-shaped pore channel structure.

Mixing 15 wt% of water glass, 12 wt% of sulfuric acid solution and glycerol in a weight ratio of 5: 1: 1 at 30 ℃ for 1.5 hours, followed by adjustment of the pH to 3 with 98% strength by weight sulfuric acid, suction filtration of the resulting reaction mass and washing with distilled water to a sodium ion content of 0.02% by weight, to give a filter cake of silica gel B1.

And putting 10g of the prepared filter cake A1 and 10g of the prepared filter cake B1 into a 100mL ball milling tank together, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400 r/min. And sealing the ball milling tank, and carrying out first ball milling in the ball milling tank at the temperature of 25 ℃ for 5 hours. The obtained first ball-milled slurry was mixed with 40g of water at 25 ℃ for pulping, followed by second ball milling at 25 ℃ for 5 hours. And (3) spray-drying the obtained second ball-milling slurry at the temperature of 200 ℃ at the rotating speed of 12000r/min, then screening by adopting a cyclone separation technology, calcining the screened product in a muffle furnace at the temperature of 550 ℃ for 10h, and removing F108 (template agent) to obtain the spherical small-particle-size mesoporous composite material C1.

The spherical mesoporous composite material C1 with small particle size is characterized by XRD, scanning electron microscope and nitrogen adsorption instrument.

Fig. 1 is an X-ray diffraction pattern, and it can be seen from the figure that the spherical small-particle-diameter mesoporous composite material C1 has a three-dimensional cubic cage-shaped pore channel structure unique to mesoporous materials.

FIG. 2 is a SEM image of the micro-morphology of the spherical small-particle-size mesoporous composite material C1, which shows that the micro-morphology of the spherical small-particle-size mesoporous composite material C1 is microspheres with particle sizes of 21-29 μm, and the dispersion performance is good.

FIG. 3 is a graph showing the particle size distribution of the spherical small-diameter mesoporous composite material C1, wherein it can be seen that the spherical small-diameter mesoporous composite material C1 has a uniform particle size distribution.

Fig. 4 is a pore size distribution diagram of the spherical small-particle-size mesoporous composite material C1, and it can be seen from the diagram that the spherical small-particle-size mesoporous composite material C1 has a double-pore structure distribution and uniform pore channels.

The pore structure parameters of the spherical small-particle-size mesoporous composite material C1 are shown in the following 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.

(2) Preparation of the catalyst

0.1g of magnesium chloride and 0.1g of titanium tetrachloride were dissolved in 10mL of a composite solvent of tetrahydrofuran and isopropanol (the volume ratio of tetrahydrofuran to isopropanol was 1: 1.2) to form a catalyst mother liquor. 1g of the spherical small-particle-size mesoporous composite material C1 was added to the mother liquor at 45 ℃ for immersion for 1 hour, and then filtered, and washed with n-hexane for 4 times, dried at 75 ℃ and ground to obtain catalyst D1.

As a result of X-ray fluorescence analysis, in the catalyst D1 described in this example, the content of magnesium element was 4% by weight and the content of titanium element was 1.5% by weight in terms of the element.

Example 2

(1) Preparation of spherical small-particle-size mesoporous composite material

1.46g (0.0001mol) of template F108 and 6.96g (0.04mol) of K₂SO₄Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved;

adding 3.1g (0.015mol) of tetraethoxysilane into the solution, stirring for 15min at 45 ℃, and standing for 30 hours at 45 ℃;

then transferring the mixture into a reaction kettle with an agate inner lining, crystallizing the mixture for 30 hours at 120 ℃, then filtering the mixture, washing the mixture for 4 times by using deionized water, and then carrying out suction filtration to obtain a filter cake A2 of the mesoporous molecular sieve material with the three-dimensional cubic cage-shaped pore channel structure.

Mixing 20 wt% of water glass, 12 wt% of sulfuric acid solution and glycerol in a weight ratio of 3: 2: 1, and then the reaction mixture was subjected to a contact reaction at 40 ℃ for 3 hours, followed by adjusting the pH to 4 with sulfuric acid having a concentration of 98% by weight, and then the resulting reaction mass was subjected to suction filtration and washed with distilled water until the sodium ion content was 0.02% by weight, to obtain a silica gel cake B2.

And (3) putting the prepared 20g of filter cake A2 and 10g of filter cake B2 into a 100mL ball milling tank together, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 500 r/min. And sealing the ball milling tank, and carrying out first ball milling in the ball milling tank at the temperature of 35 ℃ for 20 hours. The obtained first ball-milled slurry was mixed with 15g of water at 35 ℃ for pulping, followed by second ball milling at 25 ℃ for 10 hours. And (3) spray-drying the obtained second ball-milling slurry at the rotation speed of 13000r/min at the temperature of 150 ℃, then screening by adopting a cyclone separation technology, calcining the screened product in a muffle furnace at the temperature of 600 ℃ for 15h, and removing F108 (template agent) to obtain the spherical small-particle-size mesoporous composite material C2.

The pore structure parameters of the spherical small-particle-size mesoporous composite material C2 are shown in table 2 below.

TABLE 2

(2) Preparation of the catalyst

0.1g of magnesium chloride and 0.2g of titanium tetrachloride were dissolved in 10mL of a composite solvent of tetrahydrofuran and isopropanol (the volume ratio of tetrahydrofuran to isopropanol was 1: 1.5) to form a catalyst mother liquor. 1g of the spherical small-particle-size mesoporous composite material C2 was added to the mother liquor at 60 ℃ for immersion for 1 hour, and then filtered, and washed with n-hexane for 4 times, dried at 75 ℃ and ground to obtain catalyst D2.

As a result of X-ray fluorescence analysis, in the catalyst D2 described in this example, the content of magnesium was 3.7% by weight and the content of titanium was 1.2% by weight, in terms of element.

Example 3

(1) Preparation of spherical small-particle-size mesoporous composite material

1.46g (0.0001mol) of template F108 and 3.48g (0.02mol) of K₂SO₄Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved;

adding 2.1g (0.01mol) of tetraethoxysilane into the solution, stirring at 35 ℃ for 15min, and standing at 35 ℃ for 20 hours;

then transferring the mixture into a reaction kettle with an agate inner lining, crystallizing the mixture for 20 hours at the temperature of 90 ℃, then filtering the mixture, washing the mixture for 4 times by using deionized water, and then carrying out suction filtration to obtain a filter cake A3 of the mesoporous molecular sieve material with the three-dimensional cubic cage-shaped pore channel structure.

Mixing 10 wt% of water glass, 12 wt% of sulfuric acid solution and ethylene glycol in a weight ratio of 6: 3: 1 at 45 ℃ and then adjusted to a pH of 2 with sulfuric acid having a concentration of 98% by weight, the reaction mass obtained is filtered off with suction and washed with distilled water to a sodium ion content of 0.02% by weight, giving a silica gel cake B3.

And putting 10g of the prepared filter cake A3 and 15g of the prepared filter cake B3 into a 100mL ball milling tank together, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 300 r/min. And sealing the ball milling tank, and carrying out first ball milling in the ball milling tank at the temperature of 50 ℃ for 10 hours. The resulting first ball-milled slurry was mixed with 87.5g of water at 50 ℃ for slurrying, followed by second ball milling at 40 ℃ for 5 hours. And (3) spray-drying the obtained second ball-milling slurry at 250 ℃ at the rotating speed of 11000r/min, then screening by adopting a cyclone separation technology, calcining the screened product in a muffle furnace at 400 ℃ for 24h, and removing F108 (template agent) to obtain the spherical small-particle-size mesoporous composite material C3.

The pore structure parameters of the spherical small-particle-size mesoporous composite material C3 are shown in table 3 below.

TABLE 3

(2) Preparation of the catalyst

0.2g of magnesium chloride and 0.1g of titanium tetrachloride were dissolved in 10mL of a composite solvent of tetrahydrofuran and isopropanol (the volume ratio of tetrahydrofuran to isopropanol was 1: 1) to form a catalyst mother liquor. 1g of the spherical small-particle-size mesoporous composite material C3 was added to the mother liquor at 40 ℃ for immersion for 3 hours, and then filtered, and washed with n-hexane for 4 times, dried at 75 ℃ and ground to obtain catalyst D3.

As a result of X-ray fluorescence analysis, in the catalyst D3 described in this example, the content of magnesium was 3.9% by weight and the content of titanium was 1.4% by weight in terms of element.

Example 4

This example is used to illustrate the spherical small-particle-size mesoporous composite material and supported catalyst of the present invention and their preparation methods

A spherical small-particle-size mesoporous composite material and a supported catalyst were prepared in the same manner as in example 1, except that glycerol was not added in the preparation of the filter cake of silica gel, to obtain a spherical small-particle-size mesoporous composite material C4 and a catalyst D4.

The pore structure parameters of the spherical small-particle-size mesoporous composite material C4 are shown in table 4 below.

TABLE 4

*: the first most probable aperture, the second most probable aperture and the third most probable aperture are separated by commas.

The catalyst D4 according to this example contained 3.0 wt% of magnesium and 1.5 wt% of titanium, calculated as elements, by X-ray fluorescence analysis.

Comparative example 1

Comparative example to illustrate a reference Carrier and Supported catalyst and Process for making the same

Commercially available ES955 silica Gel (GRACE) was calcined under nitrogen at 400 deg.C for 10h to remove hydroxyl groups and residual moisture, thereby obtaining heat-activated ES955 silica gel.

A catalyst was prepared by following the procedure of step (2) of example 1, except that the same parts by weight of the above-mentioned activated ES955 silica gel was used in place of the spherical small-sized mesoporous composite material C1, thereby obtaining a comparative catalyst DD 1.

Comparative example 2

Comparative example for explaining reference spherical small-particle-size mesoporous composite material, supported catalyst and preparation method of supported catalyst

The spherical small-particle-size mesoporous composite and the supported catalyst were prepared according to the method of example 1. Except that only the first ball milling was performed, and the second ball milling was not performed. Specifically, 10g of the cake A1 prepared above and 10g of the cake B1 were put together in a 100mL ball mill pot. And sealing the ball milling tank, and carrying out first ball milling in the ball milling tank at the temperature of 25 ℃ for 5 hours. The first ball-milled slurry obtained was mixed with 40g of water at 25 ℃ for slurrying, and the slurry obtained was spray-dried at 200 ℃ at 12000 r/min. The spherical mesoporous composite material DC2 with small particle size and the supported catalyst DD2 are prepared.

The pore structure parameters of the spherical small-particle-size mesoporous composite material DC2 are shown in table 5 below.

TABLE 5

According to X fluorescence analysis, in the catalyst DD2, the content of magnesium element is 2.9 wt% and the content of titanium element is 1.0 wt% calculated by element.

Comparative example 3

The spherical small-particle-size mesoporous composite and the supported catalyst were prepared according to the method of example 1. The difference is that the screening is not carried out by adopting a cyclone separation technology, specifically, the obtained second ball-milling slurry is subjected to spray drying at the temperature of 200 ℃ and the rotating speed of 12000r/min, then a product obtained after the spray drying is calcined for 10 hours at the temperature of 550 ℃ in a muffle furnace, and F108 (template) is removed, so that the spherical small-particle-size mesoporous composite material DC3 and the supported catalyst DD3 are obtained.

The pore structure parameters of the spherical small-particle-size mesoporous composite material DC3 are shown in table 6 below.

TABLE 6

According to X fluorescence analysis, in the catalyst DD3, the content of magnesium element is 2.6 wt% and the content of titanium element is 1.1 wt% calculated by element.

Comparative example 4

The spherical small-particle-size mesoporous composite and the supported catalyst were prepared according to the method of example 1. The difference is that only the first ball milling is carried out, the second ball milling is not carried out, and the cyclone separation technology is not adopted for screening. Specifically, 10g of the cake A1 prepared above and 10g of the cake B1 were put together in a 100mL ball mill pot. And sealing the ball milling tank, and carrying out first ball milling in the ball milling tank at the temperature of 25 ℃ for 5 hours. And mixing the obtained first ball-milling slurry with 40g of water at 25 ℃ for pulping, spray-drying the obtained slurry at 200 ℃ at the rotating speed of 12000r/min, calcining the spray-dried product in a muffle furnace at 550 ℃ for 10h, and removing F108 (template) to obtain the spherical small-particle-size mesoporous composite material DC4 and the supported catalyst DD 4.

The pore structure parameters of the spherical small-particle-size mesoporous composite material DC4 are shown in table 7 below.

TABLE 7

According to X fluorescence analysis, in the catalyst DD4, the content of magnesium element is 2.8 wt% and the content of titanium element is 1.3 wt% calculated by element.

Experimental example 1

This experimental example is used to illustrate the application of the supported catalyst provided by the present invention.

In a 2L stainless steel high pressure polymerization reactor, nitrogen and ethylene were each replaced three times, then 200mL of hexane was added, the reactor was warmed to 80 ℃ and 800mL of hexane was added, 2mL of a 1mol/L Triethylaluminum (TEA) solution in hexane was added with the addition of hexane, then 0.5g of catalyst component D1 was added, ethylene gas was introduced, the pressure was raised to 1.0MPa and maintained at 1.0MPa, and after 1 hour of reaction at 70 ℃, separation by suction filtration was carried out to obtain a polyethylene pellet powder. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder_2.16The pulverization rates and the catalyst efficiencies are shown in Table 8.

Experimental example 2

In a 2L stainless steel autoclave, replaced with nitrogen and ethylene three times each, then 200mL of hexane was added, the autoclave was warmed to 75 ℃ and 900mL of hexane was added, and with the addition of hexane, 2mL of a 1mol/L solution of Triethylaluminum (TEA) in hexane was added, followed by addition of 0.1g of catalyst component D2, passing ethylene gas, raising the pressure to 1MPa and maintaining it at 1MPa, and after reacting for 1.5 hours at 75 ℃ the mixture was separated by suction filtrationAnd obtaining the polyethylene granular powder. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder_2.16The pulverization rates and the catalyst efficiencies are shown in Table 8.

Experimental example 3

In a 2L stainless steel high pressure polymerization reactor, nitrogen and ethylene were each replaced three times, then 200mL of hexane was added, the reactor was warmed to 85 ℃ and 700mL of hexane was added, 2mL of a 1mol/L Triethylaluminum (TEA) solution in hexane was added with the addition of hexane, then 1g of catalyst component D3 was added, ethylene gas was introduced, the pressure was raised to 1MPa and maintained at 1MPa, and after reacting at 85 ℃ for 2 hours, separation by suction filtration, a polyethylene pellet powder was obtained. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder_2.16The pulverization rates and the catalyst efficiencies are shown in Table 8.

Experimental example 4

Polymerization of ethylene was carried out in accordance with the procedure of Experimental example 1, except that the same parts by weight of the catalyst D4 prepared in example 4 was used in place of the catalyst D1 prepared in example 1. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder_2.16The pulverization rates and the catalyst efficiencies are shown in Table 8.

Experimental comparative examples 1 to 4

This experimental comparative example serves to illustrate the use of a reference supported catalyst

Polymerization of ethylene was carried out in the same manner as in experimental example 1 except that the catalysts D1 prepared in example 1 were replaced with the comparative catalysts DD1-DD4 prepared in comparative examples 1-4, respectively, in the same parts by weight. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder_2.16The pulverization rates and the catalyst efficiencies are shown in Table 8.

TABLE 8

As can be seen from the results of comparing the above experimental examples 1 to 4 with the experimental comparative examples 1 to 4, when the spherical mesoporous composite material with small particle size and the supported catalyst provided by the present invention are used in an ethylene polymerization reaction, the catalyst has high catalytic activity, and a polyethylene product with low bulk density and melt index and being not easy to break can be obtained, specifically, the bulk density of the prepared polyethylene product is below 0.4g/mL, the melt index is below 0.5g/10min, and the crushing rate is less than 2 wt%. The polyethylene products which are not obtained by the method of the invention have the crushing rate of more than 4 weight percent.

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

1. The spherical small-particle-size mesoporous composite material is characterized by containing a mesoporous molecular sieve material with a three-dimensional cubic cage-shaped pore channel structure, wherein the average particle size of the spherical small-particle-size mesoporous composite material is 21-29 micrometers, the specific surface area is 200-650 square meters per gram, the pore volume is 0.5-1.5 milliliters per gram, the pore diameter is in bimodal distribution, and the most probable pore diameters of the two peaks are 1-10 nanometers and 15-40 nanometers respectively.

2. The spherical small-particle-size mesoporous composite material as claimed in claim 1, wherein the average particle size of the spherical small-particle-size mesoporous composite material is 22-28 μm, the specific surface area is 250-350 m/g, the pore volume is 1.0-1.5 ml/g, the pore diameters are distributed in two peaks, and the most probable pore diameters corresponding to the two peaks are 5-10 nm and 20-35 nm respectively.

3. A preparation method of a spherical mesoporous composite material with small particle size is characterized by comprising the following steps:

4. The method according to claim 3, wherein, in the step (3), the component b is used in an amount of 1 to 200 parts by weight, relative to 100 parts by weight of the component a.

5. The method according to claim 4, wherein, in the step (3), the component b is used in an amount of 20-180 parts by weight with respect to 100 parts by weight of the component a.

6. The method according to claim 5, wherein, in the step (3), the component b is used in an amount of 50 to 150 parts by weight with respect to 100 parts by weight of the component a.

7. The method of claim 3, wherein, in step (1), the process of preparing a filter cake of mesoporous molecular sieve material having a three-dimensional cubic cage pore structure comprises: and carrying out first mixing contact on a template agent, potassium sulfate, an acid agent and a silicon source, and crystallizing and filtering the obtained mixture.

8. The method of claim 7, wherein in step (1), the molar ratio of the templating agent, potassium sulfate, and silicon source is 1: 100-800: 50-300.

9. The method according to claim 7, wherein, in step (1), the templating agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene; the silicon source is at least one of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol; the acid agent is at least one aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid.

10. The process of claim 7, wherein in step (1), the conditions of the first mixing contact comprise: the temperature is 10-60 ℃, the time is 10-72 hours, and the pH value is 1-7; the crystallization conditions include: the temperature is 30-150 ℃ and the time is 10-72 hours.

11. The method according to any one of claims 3 to 10, wherein, in the step (2), the process of preparing the filter cake of silica gel comprises: and carrying out second mixing contact on the water glass, the polyhydric alcohol and the inorganic acid, and filtering the obtained mixture.

12. The method of claim 11, wherein, in step (2), the conditions of the second mixing contact comprise: the temperature is 10-60 deg.C, the time is 1-5 hr, and the pH value is 2-4.

13. The method according to claim 11, wherein in step (2), the weight ratio of the water glass, the inorganic acid and the polyol is 1-8: 0.1-5: 1.

14. the method of claim 11, wherein, in step (2), the inorganic acid is one or more of sulfuric acid, nitric acid, and hydrochloric acid; the polyalcohol is glycerol and/or ethylene glycol.

15. The method of any one of claims 3 to 10, wherein in step (3), the conditions of the first ball mill and the second ball mill are the same or different, and each of the conditions of the first ball mill and the second ball mill independently comprises: the rotation speed of the grinding ball is 200-800r/min, the temperature in the ball milling tank is 15-100 ℃, and the ball milling time is 0.1-100 hours.

16. The method of any one of claims 3-10, wherein in step (3), the first ball-milled slurry is used in an amount of 1: 0.1-5 ℃, and the temperature for mixing the first ball-milling slurry and water for pulping is 25-60 ℃.

17. The method according to any one of claims 3-10, wherein in step (3), the conditions of the spray drying comprise: the temperature is 150-600 ℃, and the rotating speed is 10000-15000 r/min.

18. The method of any of claims 3-10, wherein the step of screening the second ball-milled slurry using a cyclone technique after spray drying comprises: and carrying out spray drying on the second ball-milling slurry, and carrying out cyclone separation on the discharged gas containing the powder particles so as to collect the powder particles.

19. The process according to any one of claims 3-10, wherein component a is a filter cake of a mesoporous molecular sieve material having a three-dimensional cubic cage-like pore structure, and component b is a filter cake of silica gel; the method further comprises the following steps: after the spray drying process of step (3), the templating agent is removed from the powder particles collected by cyclone separation.

20. The method of claim 19, wherein the conditions to remove the templating agent comprise: the temperature is 90-600 ℃, and the time is 10-80 hours.

21. A spherical small-particle-size mesoporous composite prepared by the method of any one of claims 3-20.

22. A supported catalyst comprising a carrier and a magnesium salt and/or a titanium salt supported on the carrier, wherein the carrier is the spherical small-particle-diameter mesoporous composite material according to any one of claims 1 to 2 and 21.

23. The catalyst according to claim 22, wherein the carrier is contained in an amount of 90 to 99% by weight, and the sum of the contents of the magnesium salt and the titanium salt is 1 to 10% by weight, based on the total weight of the supported catalyst, in terms of the magnesium element and the titanium element, respectively.

24. A method of preparing a supported catalyst, the method comprising: contacting the support with a mother liquor containing magnesium and/or titanium salts in the presence of an inert gas; wherein the carrier is the spherical small-particle-size mesoporous composite material according to any one of claims 1 to 2 and 21.

25. The process of claim 24 wherein the magnesium salt, the titanium salt and the support are present in amounts such that the support is present in an amount of from 90 to 99 wt.%, and the sum of the amounts of the magnesium salt and the titanium salt, as magnesium and titanium, respectively, is from 1 to 10 wt.%, based on the total weight of the supported catalyst, in the resulting supported catalyst.

26. The method of claim 24 or 25, wherein the conditions of the contacting comprise: the temperature is 25-100 ℃ and the time is 0.1-5 h.

27. A supported catalyst prepared by the process of any one of claims 24-26.