CN105435851B - The preparation method of mesoporous composite material and catalyst and its preparation method and application and the dioxolanes of 2,2 dimethyl, 4 methyl 1,3 - Google Patents
The preparation method of mesoporous composite material and catalyst and its preparation method and application and the dioxolanes of 2,2 dimethyl, 4 methyl 1,3 Download PDFInfo
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Abstract
The present invention relates to a kind of spherical zeolite mesoporous composite material, the preparation method of the spherical zeolite mesoporous composite material, the spherical zeolite mesoporous composite material prepared by this method, loaded catalyst containing the spherical zeolite mesoporous composite material, the preparation method of the loaded catalyst, the loaded catalyst prepared by this method, application of the loaded catalyst in ketal reaction, and use the preparation 2 of the loaded catalyst, the methyl 1 of 2 dimethyl 4, the method of 3 dioxolanes, wherein, the spherical zeolite mesoporous composite material contains zeolite, meso-porous molecular sieve material with three-dimensional cubic duct structure and the meso-porous molecular sieve material with hexagonal hole road structure.The loaded catalyst being made using the spherical zeolite mesoporous composite material of the present invention as carrier can significantly improve the conversion ratio of reaction raw materials during ketal reaction.
Description
Technical field
The present invention relates to a kind of spherical zeolite mesoporous composite material, the preparation method of the spherical zeolite mesoporous composite material,
The spherical zeolite mesoporous composite material prepared by this method, the loaded catalyst containing the spherical zeolite mesoporous composite material,
A kind of method for preparing loaded catalyst, the loaded catalyst prepared by this method, the loaded catalyst are anti-in ketal
Application in answering, and use the preparation 2 of the loaded catalyst, 2- dimethyl -4- methyl isophthalic acids, the method for 3- dioxolanes.
Background technology
The ring of 2,2- dimethyl -4- methyl-1,3-dioxies penta is important organic synthesis intermediate.Generally, 2,2-
The ring of dimethyl -4- methyl-1,3-dioxies penta is mainly made by oxidation cyclopropane and acetone by ketal reaction.Traditional oxidation ring
The catalyst of the ketal reaction of propane and acetone is inorganic liquid (such as sulfuric acid, hydrochloric acid, phosphoric acid), but because of its corrosiveness
Greatly, the side reaction of initiation is more, product separation is complicated after reaction and the defect such as liquid waste processing difficulty and cause it using by one
Fixed limitation.Attention degree increase with the whole world to Catalytic processes greenization, solid acid catalysis technique substitution liquid acid catalysis
Technique is imperative.In recent years research showed, some solid acids, Lewis hydrochlorates, molecular sieve and ionic liquid etc. to synthesis 2,
The ring of 2- dimethyl -4- methyl-1,3-dioxies penta has good catalytic action.
Natural zeolite is the porous aluminosilicate mineral material of aqueous rack-like structure, is the general name of zeolite race mineral.Zeolite
Chemical composition is main by SiO2、Al2O3、H2O and alkali, the part of alkaline-earth metal ions four composition, this four fraction have very big change
Change, so as to constitute a variety of zeolite group minerals.Having found 40 kinds of natural zeolite mineral, with analcime, chabasie, clinoptilolite,
Heulandite, erionite, ferrierite, laumontite, modenite, phillipsite are relatively conventional.Current China finds the side's of having boiling
More than the 10 kinds of natural zeolite mineral products such as stone, clinoptilolite, modenite, ferrierite, phillipsite, epidesmine.A large amount of profits
, mainly clinoptilolite, modenite, next has analcime, epidesmine.The specific physical property of zeolite depends on boiling
The lattice structure of stone, zeolite is by SiO2And Al2O3Tetrahedron element is staggered to spatial network.Due to the opening of crystal structure
Property, zeolite contains the uneven duct of many sizes and cavity.Caused by aluminium displacement silicon electricity price imbalance in tetrahedron
The need for compensating positive charge, in these ducts and cavity often occupied by alkali metal or alkaline-earth metal ions and zeolite hydrone.
The structures shape of zeolite it possess unique physical and chemical performance such as ion exchangeable and adsorptive selectivity.In addition, zeolite also has
Good heat endurance, acid resistance, can dehydration property, catalytic cracking, radiation resistance and the low bulk density of chemical reaction, porous
Etc. characteristic.
In existing loaded catalyst, carrier is used as using conventional meso-porous molecular sieve material.Mesopore molecular sieve material
Material has the advantages that duct is orderly, aperture is adjustable, specific surface area and pore volume are larger so that made using these meso-porous molecular sieve materials
The loaded catalyst being made for carrier shows lot of advantages in the preparation technology in organic catalytic reaction, for example, catalysis
Activity is high, side reaction is few, post processing is simple etc., however, big specific surface area and high pore volume cause these mesopore molecular sieve materials
Material has stronger water suction, moisture absorption ability, so that these loaded catalysts can be caused to reunite in catalytic reaction process,
And then reduce the conversion ratio that cyclopropane is aoxidized in the ring preparation technology of 2,2- dimethyl -4- methyl-1,3-dioxies penta.
The content of the invention
The invention aims to overcome the loaded catalyst being made of existing meso-porous molecular sieve material in contracting
There is provided a kind of composite mesoporous material of the spherical zeolite for being suitable as carrier for the relatively low defect of reaction raw materials conversion ratio during reactive ketone
Material, and the spherical zeolite mesoporous composite material preparation method, the spherical zeolite mesoporous composite material prepared by this method contains
There is the loaded catalyst of the spherical zeolite mesoporous composite material, the preparation method of the loaded catalyst is prepared by this method
Loaded catalyst, application of the loaded catalyst in ketal reaction, and using the loaded catalyst preparation 2,
The method of the ring of 2- dimethyl -4- methyl-1,3-dioxies penta.
In order to achieve the above object, the present inventor after research by having found, with three-dimensional cubic duct structure
Meso-porous molecular sieve material and meso-porous molecular sieve material with hexagonal hole road structure in introduce zeolite, zeolite is entered mesoporous point
In the duct of son sieve material, and the mesoporous composite material is made to be not susceptible to reunite spherical, can so retained mesoporous
The high-specific surface area of molecular screen material, big pore volume, large aperture and with three-dimensional cubic duct structure and hexagonal hole road structure etc.
Feature, can reduce the reunion of meso-porous molecular sieve material again, increase its mobility so that using bearing that the mesoporous composite material is made
Supported catalyst can obtain the reaction raw materials conversion ratio significantly improved when for ketal reaction, so as to complete the present invention.
Therefore, the invention provides a kind of spherical zeolite mesoporous composite material, wherein, the spherical zeolite mesoporous composite material
Meso-porous molecular sieve material containing zeolite, with three-dimensional cubic duct structure and the mesopore molecular sieve material with hexagonal hole road structure
Material, and the spherical zeolite mesoporous composite material average grain diameter be 20-50 micron, specific surface area for 150-600 square metres/
Gram, pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal the first most probable pore size and second corresponding respectively is most
Can several apertures, first most probable pore size is less than second most probable pore size, and first most probable pore size receives for 2-5
Rice, second most probable pore size is 5-25 nanometers.
Present invention also offers a kind of method for preparing spherical zeolite mesoporous composite material, this method comprises the following steps：
(1) providing the meso-porous molecular sieve material with three-dimensional cubic duct structure or preparing has three-dimensional cubic duct knot
The filter cake of the meso-porous molecular sieve material of structure, is used as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or prepared mesoporous with hexagonal hole road structure
The filter cake of molecular screen material, is used as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(4) the component a1, the component a2, the component b and zeolite are mixed and ball milling, and will be obtained after ball milling
Obtained slurry, is then spray-dried by the solid powder arrived water slurrying；
Wherein, the component a1 and the component a2 make it that the average grain diameter of the spherical zeolite mesoporous composite material is
20-50 microns, specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and
Bimodal to correspond to the first most probable pore size, the second most probable pore size respectively, first most probable pore size most may be used less than described second
Several apertures, and first most probable pore size is 2-5 nanometers, second most probable pore size is 5-25 nanometers.The present invention is also carried
The spherical zeolite mesoporous composite material prepared by the above method is supplied.
Present invention also offers a kind of loaded catalyst, the catalyst contains the benzene of carrier and load on the carrier
Sulfonic acid, wherein, the carrier is the spherical zeolite mesoporous composite material according to the present invention.
Present invention also offers a kind of method for preparing loaded catalyst, this method includes：By carrier, benzene sulfonic acid and water
It is well mixed, and obtained mixture is spray-dried, wherein, the carrier is the spherical zeolite according to the present invention
Mesoporous composite material.
Present invention also offers the loaded catalyst prepared by the above method.
Present invention also offers application of the above-mentioned loaded catalyst in ketal reaction.
Present invention also offers one kind 2,2- dimethyl -4- methyl isophthalic acids, the preparation method of 3- dioxolanes, this method bag
Include：In the presence of a catalyst, under conditions of ketal reaction, oxidation cyclopropane and acetone are contacted, to obtain 2,2- diformazans
Base -4- methyl isophthalic acids, 3- dioxolanes, wherein, the catalyst is the above-mentioned loaded catalyst according to the present invention.
Spherical zeolite mesoporous composite material according to the present invention, is combined with the mesoporous of three-dimensional cubic duct structure
Molecular screen material, the meso-porous molecular sieve material with hexagonal hole road structure, zeolite and ball type carrier so that this is spherical
Zeolite mesoporous composite material is suitable as the carrier of loaded catalyst, and be particularly suitable as using in ketal reaction is negative
The carrier of supported catalyst.
In the loaded catalyst of the present invention, there is mesoporous point as the spherical zeolite mesoporous composite material of carrier
The characteristics of loose structure of son sieve material, but also it is loaded with benzene sulfonic acid so that the loaded catalyst is both urged with support type
The advantage of agent such as catalytic activity is high, side reaction is few, post processing is simple etc., has the catalytic performance of acid again so that the support type
Catalyst will not only cause equipment corrosion when during for ketal reaction, but also can significantly improve reaction raw materials
Conversion ratio.
In addition, when preparing the loaded catalyst by the method for spray drying, the loaded catalyst can be with
Reused, and still can obtain during recycling higher reaction raw materials conversion ratio.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is that the X-ray of spherical zeolite mesoporous composite material according to the present invention and the loaded catalyst is spread out
Penetrate spectrogram；
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of spherical zeolite mesoporous composite material according to the present invention；
Fig. 3 is the pore size distribution curve of spherical zeolite mesoporous composite material according to the present invention.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of spherical zeolite mesoporous composite material, wherein, the spherical zeolite mesoporous composite material contains
There are zeolite, the meso-porous molecular sieve material with three-dimensional cubic duct structure and the mesopore molecular sieve material with hexagonal hole road structure
Material, and the spherical zeolite mesoporous composite material average grain diameter be 20-50 micron, specific surface area for 150-600 square metres/
Gram, pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal the first most probable pore size and second corresponding respectively is most
Can several apertures, first most probable pore size is less than second most probable pore size, and first most probable pore size receives for 2-5
Rice, second most probable pore size is 5-25 nanometers.
Spherical zeolite mesoporous composite material according to the present invention has three-dimensional cubic duct structure and hexagonal hole simultaneously
Road structure, the average grain diameter of its particle is measured using laser fineness gage, specific surface area, pore volume and most probable pore size according to
Nitrogen adsorption methods are measured.
Spherical zeolite mesoporous composite material according to the present invention, by by the particle of spherical zeolite mesoporous composite material
Size Control is within above range, it can be ensured that the spherical zeolite mesoporous composite material be not susceptible to reunite, and by its
The reaction raw materials conversion ratio during ketal reaction can be improved as the loaded catalyst that carrier is made.When the spherical boiling
When the specific surface area of stone mesoporous composite material is less than 150 meters squared per grams and/or pore volume less than 0.5 ml/g, it is used as
The catalytic activity for the loaded catalyst that carrier is made can be significantly reduced；When the ratio surface of the spherical zeolite mesoporous composite material
When product is more than 1.5 mls/g more than 600 meters squared per grams and/or pore volume, the loaded catalyst that carrier is made is used as
Easily reunite during ketal reaction, so that the reaction raw materials conversion ratio during influenceing ketal reaction.
In the preferred case, the average grain diameter of the spherical zeolite mesoporous composite material is 20-40 microns, and specific surface area is
210-600 meters squared per grams, pore volume is 0.8-1.5 mls/g, and first most probable pore size is 2-4 nanometers, described the
Two most probable pore sizes are 8-20 nanometers.
In the spherical zeolite mesoporous composite material, relative to described in 100 parts by weight there is three-dimensional cubic duct to tie
The total amount of the meso-porous molecular sieve material of structure and the meso-porous molecular sieve material with hexagonal hole road structure, the content of the zeolite
Can be 1-50 parts by weight, preferably 20-50 parts by weight；The meso-porous molecular sieve material with three-dimensional cubic duct structure with
The weight ratio of the meso-porous molecular sieve material with hexagonal hole road structure can be 1：0.1-10, preferably 1：0.5-2.
In the present invention, the spherical zeolite mesoporous composite material can also contain the silica introduced by silica gel.
" silica being introduced into by silica gel " refers in the preparation process of the spherical zeolite mesoporous composite material, by silica gel conduct
The silica component that preparing raw material is brought into the spherical zeolite mesoporous composite material finally prepared.It is mesoporous in the spherical zeolite
In composite, relative to the meso-porous molecular sieve material and the tool described in 100 parts by weight with three-dimensional cubic duct structure
There is the total amount of the meso-porous molecular sieve material of hexagonal hole road structure, the content of the silica introduced by silica gel can be 1-
200 parts by weight, preferably 50-150 parts by weight.
In the present invention, the meso-porous molecular sieve material with three-dimensional cubic duct structure and described there is hexagonal hole road
The meso-porous molecular sieve material of structure can be each meso-porous molecular sieve material commonly used in the art, and each can basis
Conventional method is prepared.
Present invention also offers a kind of method for preparing spherical zeolite mesoporous composite material, this method comprises the following steps：
(1) providing the meso-porous molecular sieve material with three-dimensional cubic duct structure or preparing has three-dimensional cubic duct knot
The filter cake of the meso-porous molecular sieve material of structure, is used as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or prepared mesoporous with hexagonal hole road structure
The filter cake of molecular screen material, is used as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(4) the component a1, the component a2, the component b and zeolite are mixed and ball milling, and will be obtained after ball milling
Obtained slurry, is then spray-dried by the solid powder arrived water slurrying；
Wherein, the component a1 and the component a2 make it that the average grain diameter of the spherical zeolite mesoporous composite material is
20-50 microns, specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and
Bimodal to correspond to the first most probable pore size and the second most probable pore size respectively, first most probable pore size most may be used less than described second
Several apertures, and first most probable pore size is 2-5 nanometers, second most probable pore size is 8-25 nanometers.
In the preferred case, the component a1 and the component a2 cause being averaged for the spherical zeolite mesoporous composite material
Particle diameter is 20-40 microns, and specific surface area is 210-600 meters squared per grams, and pore volume is 0.8-1.5 mls/g, and described first
Most probable pore size is 2-4 nanometers, and second most probable pore size is 8-20 nanometers.
In step (1), the process for preparing the filter cake of the meso-porous molecular sieve material with three-dimensional cubic duct structure can be with
Including：In the presence of template and butanol, tetraethyl orthosilicate is contacted with sour agent, and the mixture that will be obtained after contact
Carry out crystallization and filtering.
The mol ratio of the consumption of the template, butanol and tetraethyl orthosilicate can be 1：10-100：10-90, be preferably
1：60-90：50-75.
The template can be various templates commonly used in the art.Most preferably, the template is three embedding
Section copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, the template can be commercially available (for example, can be purchased from
Aldrich, trade name P123, molecular formula is EO20PO70EO20), it can also be prepared into by existing various methods
Arrive.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template according to polyoxyethylene-
The mean molecule quantity of polyoxypropylene polyoxyethylene is calculated and obtained.
The sour agent can be used for the material or mixture (such as solution) for adjusting pH value for various routines.Preferably,
The sour agent is hydrochloric acid.Preferably used in form of an aqueous solutions as the hydrochloric acid of sour agent.The pH value of aqueous hydrochloric acid solution can be 1-
6。
The butanol is preferably n-butanol.
The condition that tetraethyl orthosilicate is contacted with sour agent can include：Temperature is 10-60 DEG C, and the time is 10-72 hours, pH value
For 1-7.In order to be more beneficial for the uniform mixing between each material, the tetraethyl orthosilicate is contacted preferably under agitation with sour agent
Carry out.The consumption of the sour agent is preferably so that the pH value of tetraethyl orthosilicate and the haptoreaction system of sour agent is 1-7.
The condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.It is described under preferable case
The condition of crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
During the filter cake of meso-porous molecular sieve material in above-mentioned preparation with three-dimensional cubic duct, obtained by filtering
Obtaining the process of filter cake can include：After filtration, with deionized water cyclic washing (washing times can be 2-10), Ran Houjin
Row suction filtration.
In step (1), " providing the meso-porous molecular sieve material with three-dimensional cubic duct structure " can directly be weighed
Or choose the product of the meso-porous molecular sieve material with three-dimensional cubic duct structure or prepare with three-dimensional cubic duct
The meso-porous molecular sieve material of structure.The preparation method of the meso-porous molecular sieve material with three-dimensional cubic duct structure can root
Implement according to conventional method, for example, its preparation method can include：Being prepared according to the above method has three-dimensional cubic duct structure
Meso-porous molecular sieve material filter cake, then by gained filtration cakes torrefaction, and the template removal in the product that will be obtained after drying.
The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80 hours.
The process of the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure is prepared in step (2) to be included：Will
Tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia haptoreaction, and the mixture obtained after haptoreaction is subjected to crystalline substance
Change and filter.
The mol ratio of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can be 1：0.1-1：0.1-5, be preferably
1：0.2-0.5：1.5-3.5.
Ammonia is added preferably in the form of ammoniacal liquor.
The haptoreaction process of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia is carried out in presence of water.It is excellent
Selection of land, part water is introduced in the form of ammoniacal liquor, and part water is added in the form of deionized water.In tetraethyl orthosilicate, cetyl
In the haptoreaction system of trimethylammonium bromide and ammonia, the mol ratio of tetraethyl orthosilicate and water can be 1:100-200, be preferably
1:120-180。
The catalytic condition of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can include：Temperature is 25-
100 DEG C, the time is 10-72 hours.Preferably, the haptoreaction is carried out under agitation, in favor of the uniform mixing between each material.
The condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.It is described under preferable case
The condition of crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
During the filter cake of meso-porous molecular sieve material in above-mentioned preparation with hexagonal hole road structure, obtained by filtering
Obtaining the process of filter cake can include：After filtration, with deionized water cyclic washing (washing times can be 2-10), Ran Houjin
Row suction filtration.
In step (2), " providing the meso-porous molecular sieve material with hexagonal hole road structure " can directly be weighed or select
The product or preparation that take the meso-porous molecular sieve material with hexagonal hole road structure have mesoporous point of hexagonal hole road structure
Son sieve material.The preparation method of the meso-porous molecular sieve material with hexagonal hole road structure can be real according to the conventional method
Apply, for example, its preparation method can include：Meso-porous molecular sieve material with hexagonal hole road structure is prepared according to the above method
Filter cake, then by gained filtration cakes torrefaction.
In step (3), preparing the process of the filter cake of silica gel can include：Waterglass is contacted with inorganic acid, and
The mixture obtained after contact is filtered.
There is no particular limitation for the condition that waterglass is contacted with inorganic acid, can be fitted according in the common process for preparing silica gel
Locality is determined.Under preferable case, the condition that waterglass is contacted with inorganic acid can include：Temperature is 10-60 DEG C, preferably 20-
40℃；Time is 1-5 hours, preferably 1.5-3 hours；PH value is 2-4.
In order to be more beneficial for the uniform mixing between each material, waterglass is with the catalytic process of inorganic acid preferably in stirring
Under the conditions of carry out.
The waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 weight %, preferably 12-30 weight %.
The inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulfuric acid, nitric acid and hydrochloric acid
At least one of.The inorganic acid can be used in pure form, can also be used in the form of its aqueous solution.The nothing
The consumption of machine acid is preferably so that the pH value of the haptoreaction system of waterglass and inorganic acid is 2-4.
In step (3), " offer silica gel " can directly be weighed or choose silica gel product or prepare silica gel.
Preparing the method for silica gel can implement according to the conventional method, for example, can include：The filter cake of silica gel is prepared according to the above method,
Then by gained filtration cakes torrefaction.
It is above-mentioned prepare the filter cake of silica gel during, can be included with the process for obtaining filter cake by filtering：In filtering
Afterwards, it is 0.01-0.03 weight % with the content of distilled water cyclic washing to sodium ion, then carries out suction filtration.
In step (4), relative to the component a1 and the component a2 of 100 parts by weight total consumption, the component b
Consumption can be 1-200 parts by weight, preferably 50-150 parts by weight；The consumption of the zeolite can be 1-50 parts by weight, excellent
Elect 20-50 parts by weight as；The weight ratio of the component a1 and the component a2 consumption can be 1：0.1-10, preferably 1：
0.5-2。
In step (4), the ball milling can be carried out in ball mill, and the inwall of ball grinder is preferably in the ball mill
The diameter of abrading-ball in polytetrafluoroethyllining lining, ball mill can be 2-3mm；The quantity of abrading-ball can be according to the size of ball grinder
Reasonably selected, for the ball grinder that size is 50-150ml, can generally use 1 abrading-ball；The material of the abrading-ball
Can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling can include：The rotating speed of abrading-ball can be
Temperature in 300-500r/min, ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hours.
In step (4), the process of the solid powder water slurrying obtained after ball milling can be entered at 25-60 DEG C
OK.In pulping process, the weight ratio of the consumption of solid powder and water can be 1：0.1-2, preferably 1：0.3-0.9.
In step (4), the spray drying can be implemented according to conventional mode, for example, can enter in atomizer
OK.The condition of the spray drying can include：Temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/
min；Under preferable case, the condition of the spray drying includes：Temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-
13000r/min。
In step (4), when the filter cake that the component a1 is the meso-porous molecular sieve material with three-dimensional cubic duct structure,
The component a2 be the meso-porous molecular sieve material with hexagonal hole road structure filter cake, and the component b be silica gel filter cake when,
Namely when step (1) is prepares the process of the filter cake of the meso-porous molecular sieve material with three-dimensional cubic duct structure, step (1) is
The process of the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure is prepared, step (3) is the mistake for the filter cake for preparing silica gel
Cheng Shi, the preparation method of the spherical zeolite mesoporous composite material can also include：After the spray drying of step (4), from
It is spray-dried removed template method in obtained product.The condition of the removed template method can include：Temperature is 300-600 DEG C,
Time is 10-80 hours.
Present invention also offers the spherical zeolite mesoporous composite material prepared by the above method.
Present invention also offers a kind of loaded catalyst, the catalyst contains the benzene of carrier and load on the carrier
Sulfonic acid, wherein, the above-mentioned spherical zeolite mesoporous composite material that the carrier provides for the present invention.
In the loaded catalyst, there is no particular limitation for the content of the carrier and benzene sulfonic acid, can be according to this
The conventional loaded catalyst in field suitably determined, for example, on the basis of the gross weight of the loaded catalyst, benzene
The content of sulfonic acid can be 1-50 weight %, preferably 5-50 weight %；The content of the carrier is 50-99 weight %, preferably
For 50-95 weight %.
In the present invention, the loaded catalyst can be prepared according to various methods commonly used in the art, only be needed
By benzene sulfonic acid load on the carrier.
In a preferred embodiment, in order that the loaded catalyst prepared may be repeated utilization, and
Still higher reaction raw materials conversion ratio can be obtained during recycling, preparing the method for loaded catalyst includes：Will
Carrier, benzene sulfonic acid and water are well mixed, and obtained mixture is spray-dried, wherein, the carrier carries for the present invention
The above-mentioned spherical zeolite mesoporous composite material supplied.
It is above-mentioned prepare loaded catalyst during, on the basis of total consumption of the carrier and benzene sulfonic acid, benzene sulphur
The consumption of acid can be 1-50 weight %, preferably 5-50 weight %；The consumption of the carrier can be 50-99 weight %, excellent
Elect 50-95 weight % as.
The spray drying can be implemented according to conventional mode, for example, can be carried out in atomizer.The spraying is dry
Dry condition can include：Temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min；Under preferable case,
The condition of the spray drying includes：Temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min.
Present invention also offers the loaded catalyst prepared by above-mentioned spray drying process.
Present invention also offers application of the above-mentioned loaded catalyst in ketal reaction.
In addition, present invention also offers one kind 2,2- dimethyl -4- methyl isophthalic acids, the preparation method of 3- dioxolanes, the party
Method includes：In the presence of a catalyst, under conditions of ketal reaction, oxidation cyclopropane and acetone are contacted, to obtain 2,2-
Dimethyl -4- methyl isophthalic acids, 3- dioxolanes, wherein, the above-mentioned loaded catalyst that the catalyst provides for the present invention.
In 2, the 2- dimethyl -4- methyl isophthalic acids, the preparation method of 3- dioxolanes, the use of oxidation cyclopropane and acetone
There is no particular limitation for amount, and 2,2- dimethyl -4- methyl isophthalic acids are obtained as long as can react, 3- dioxolanes, but in order to carry
Under the utilization rate of high raw material, preferable case, the mol ratio of oxidation cyclopropane and acetone is 1：0.5-10.
In 2, the 2- dimethyl -4- methyl isophthalic acids, the preparation method of 3- dioxolanes, the consumption of the catalyst does not have yet
There is special restriction, can be carried out suitably according to conventional 2,2- dimethyl -4- methyl isophthalic acids, the preparation technology of 3- dioxolanes
It is determined that.Under preferable case, relative to the oxidation cyclopropane of 100 parts by weight, the consumption of the catalyst is 1-15 parts by weight, more excellent
Elect 2-14 parts by weight as.
In 2, the 2- dimethyl -4- methyl isophthalic acids, the preparation method of 3- dioxolanes, in order to be more beneficial for ketal reaction
Progress, the reaction carries out preferably in high pressure polytetrafluoroethyllining lining reactor, and the reaction temperature can be 25-100
DEG C, preferably 60-100 DEG C.Reaction time can be 0.5-20 hours, preferably 2-15 hours.
The preparation method of the ring of 2,2- dimethyl -4- methyl-1,3-dioxies penta is additionally may included in ketal reaction and terminated
Afterwards, final reactant mixture is centrifuged, and by the solid product being centrifugally separating to obtain at 25-200 DEG C vacuum
Dry 1-24 hours, be dried in vacuo 6-10 hours preferably at 50-150 DEG C, to reclaim catalyst.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, writes a Chinese character in simplified form
For P123, molecular formula is EO20PO70EO20, the material for being 9003-11-6 in the registration number of U.S. chemical abstract, mean molecule
Measure as 5800.
In following examples and comparative example, X-ray diffraction analysis are in the model purchased from German Bruker AXS companies
Carried out on D8Advance X-ray diffractometer；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on electron microscope；Pore structure parameter analysis inhales de- in the nitrogen of the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on attached instrument, wherein, before being tested, sample is deaerated 4 hours at 200 DEG C；The analysis of reaction product liquid phase ingredient exists
Carried out purchased from Agilent companies of Britain 7890A/5973N gas chromatograph-mass spectrometers.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio and 2,2- dimethyl -4- methyl isophthalic acids of cyclopropane are aoxidized,
The selectivity of 3- dioxolanes is calculated according to below equation and obtained.
Aoxidize conversion ratio (%)=(content that cyclopropane is aoxidized in consumption-reaction product of oxidation cyclopropane) of cyclopropane
÷ aoxidizes consumption × 100% of cyclopropane
The selectivity (%) of the ring of 2,2- dimethyl -4- methyl-1,3-dioxies penta=2,2- dimethyl -4- methyl isophthalic acids, 3- bis-
Theoretical yield × 100% of the ring of actual production ÷ 2,2- dimethyl -4- methyl-1,3-dioxies penta of butyl oxide link
Embodiment 1
The present embodiment be used for illustrate the present invention spherical zeolite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical zeolite mesoporous composite material is prepared
6g (0.001mol) triblock copolymer surfactant P123 is dissolved in the hydrochloric acid that 10ml, pH value are 4 water-soluble
In liquid and 220ml deionized water solutions, stirring 4h to P123 dissolvings form clear solution, then add into the clear solution
6g (0.08mol) n-butanols simultaneously stir 1h, in the water-bath for being subsequently placed in 40 DEG C, and 12.9g (0.062mol) tetraethyl orthosilicate is slow
Slowly be added drop-wise in the solution, keep the temperature at about 40 DEG C, pH value be 4.5 under conditions of stir 24h, then again at 100 DEG C
Hydro-thermal process 24h, then carry out filtering and and be washed with deionized 4 times, then suction filtration is obtained with three-dimensional cubic duct
The filter cake X1 of meso-porous molecular sieve material.
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is ammonia and water in 1.0g, tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor
Mol ratio is 1：0.37：2.8：142, and stir at 80 DEG C 24h, then the hydro-thermal process 24h at 100 DEG C again, is then carried out
Filtering and and be washed with deionized 4 times, then suction filtration obtains the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure
Y1。
The sulfuric acid solution that the waterglass and concentration for being 15 weight % by concentration are 12 weight % is using weight ratio as 5:1 is mixed
Merge haptoreaction 2 hours at 30 DEG C, then adjust pH value to 3 with concentration for 98 weight % sulfuric acid, then to obtaining
Reaction mass carries out suction filtration, and is washed with distilled water to sodium ions content for 0.02 weight %, obtains the filter cake B1 of silica gel.
5g filter cake X1,5g filter cake Y1,10g filter cake B1 and 5g zeolites of above-mentioned preparation are put into 100ml ball grinders together,
Wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, and rotating speed is
400r/min.Ball grinder is closed, temperature is ball milling 1 hour at 60 DEG C in ball grinder, obtains 25g solid powders；By the solid
Powder is dissolved in 22.5 grams of deionized waters, is spray-dried at 200 DEG C in the case where rotating speed is 12000r/min；After being spray-dried
Obtained product is calcined 24 hours in Muffle furnace at 500 DEG C, and removed template method obtains 24 grams of composite mesoporous materials of spherical zeolite
Expect C1.
(2) loaded catalyst is prepared
At 25 DEG C, the 30g spherical zeolite mesoporous composite materials C1 prepared in above-mentioned steps (1) is put together with benzene sulfonic acid
Enter in deionized water, stirring to dissolving, and the weight ratio of spherical zeolite mesoporous composite material C1 and benzene sulfonic acid is 50:50, go from
The mol ratio of sub- water and benzene sulfonic acid is 25:1, it is spray-dried at 200 DEG C in the case where rotating speed is 12000r/min, obtains support type and urge
Agent Cat-1.
The support type benzene sulfonic acid catalyst is entered with XRD, ESEM and U.S.'s Kang Ta companies Atsorb-1 types instrument
Row is characterized.
Fig. 1 is X-ray diffracting spectrum, is spherical zeolite mesoporous composite material C1 XRD spectra.Occur in XRD spectra
Low-angle spectral peak understand that spherical zeolite mesoporous composite material C1 has orderly three-dimensional cubic duct structure and hexagonal hole road knot
Structure.
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of spherical zeolite mesoporous composite material C1 microscopic appearance.As seen from the figure, spherical boiling
Stone mesoporous composite material C1 microscopic appearance is the Mesoporous Spheres that particle diameter is 50 μm.
Fig. 3 is spherical zeolite mesoporous composite material C1 pore size distribution curve.As seen from the figure, the pore size distribution curve of material
For bimodal distribution.
Spherical zeolite mesoporous composite material C1 and loaded catalyst Cat-1 pore structure parameter are as shown in table 1 below.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C1 | 224 | 1.3 | 3,20 | 50 |
| Catalyst Cat-1 | 196 | 0.9 | 2.0,11 | 50 |
By spherical zeolite mesoporous composite material it can be seen from the data of upper table 1 load benzene sulfonic acid after, specific surface area and
Pore volume has reduced, and this explanation benzene sulfonic acid during load-reaction is entered in spherical zeolite mesoporous composite material
Portion.
Comparative example 1
Spherical zeolite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different, in system
Zeolite is added without during the standby mesoporous composite material for making carrier, so that mesoporous composite material D1 and support type be made respectively
Catalyst Cat-D-1.
Comparative example 2
Spherical zeolite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different, in system
During standby loaded catalyst, (Jilin University's high-tech is purchased from the bar-shaped mesoporous silicon oxide SBA-15 of identical weight
Limited company) the filter cake X1 and filter cake Y1 is replaced, so that obtained mesoporous composite material D2 and support type are urged respectively
Agent Cat-D-2.
Embodiment 2
The present embodiment be used for illustrate the present invention spherical zeolite mesoporous composite material and loaded catalyst and they
Preparation method.
Spherical zeolite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different, in system
The step of not being spray-dried during standby loaded catalyst, and be only supported on benzene sulfonic acid by the method for dipping spherical
On zeolite mesoporous composite material, so that loaded catalyst Cat-2 is made.
Embodiment 3
The present embodiment be used for illustrate the present invention spherical zeolite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical zeolite mesoporous composite material is prepared
6g (0.001mol) triblock copolymer surfactant P123 is dissolved in the hydrochloric acid that 10ml, pH value are 5 water-soluble
In liquid and 220ml deionized water solutions, stirring 4h to P123 dissolvings form clear solution, then add into the clear solution
4.5g (0.06mol) n-butanols simultaneously stir 1h, in the water-bath for being subsequently placed in 40 DEG C, and 10.4g (0.05mol) tetraethyl orthosilicate is slow
Slowly be added drop-wise in the solution, keep the temperature at about 60 DEG C, pH value be to stir 48h under conditions of 5.5, the then water at 80 DEG C again
Be heat-treated 20h, then carry out filtering and and be washed with deionized 4 times, then suction filtration obtains Jie with three-dimensional cubic duct
The filter cake X3 of porous molecular sieve material.
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is ammonia and water in 1.0g, tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor
Mol ratio is 1：0.2：3.5：120, and stir at 60 DEG C 48h, then the hydro-thermal process 20h at 80 DEG C again, was then carried out
Filter and and be washed with deionized 4 times, then suction filtration obtains the filter cake Y3 of the meso-porous molecular sieve material with hexagonal hole road structure.
The sulfuric acid solution that the waterglass and concentration for being 15 weight % by concentration are 12 weight % is using weight ratio as 4:1 is mixed
Merge haptoreaction 1.5 hours at 40 DEG C, then pH value is adjusted to 2 with concentration for 98 weight % sulfuric acid, then to obtaining
Reaction mass carry out suction filtration, and be washed with distilled water to sodium ions content for 0.02 weight %, obtain the filter cake B3 of silica gel.
13g filter cake X3,7g filter cake Y3,10g filter cake B3 and 8g zeolites of above-mentioned preparation are put into 100ml ball grinders together
In, wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, is turned
Speed is 300r/min.Ball grinder is closed, temperature is ball milling 0.5 hour at 80 DEG C in ball grinder, obtains 38g solid powders；Will
The solid powder is dissolved in 12 grams of deionized waters, is spray-dried at 250 DEG C in the case where rotating speed is 11000r/min；Spraying is dry
The product obtained after dry is calcined 15 hours in Muffle furnace at 550 DEG C, and removed template method obtains 35 grams of spherical zeolites mesoporous multiple
Condensation material C3.
(2) loaded catalyst is prepared
At 25 DEG C, the 35g spherical zeolite mesoporous composite materials C3 prepared in above-mentioned steps (1) is put together with benzene sulfonic acid
Enter in deionized water, stirring to dissolving, and the weight ratio of spherical zeolite mesoporous composite material C3 and benzene sulfonic acid is 95:5, deionization
The mol ratio of water and benzene sulfonic acid is 25:1, it is spray-dried at 150 DEG C in the case where rotating speed is 13000r/min, obtains supported catalyst
Agent Cat-3.
Spherical zeolite mesoporous composite material C3 and loaded catalyst Cat-3 pore structure parameter are as shown in table 2 below.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C3 | 208 | 1.2 | 3,20 | 45 |
| Catalyst Cat-3 | 190 | 1.0 | 2.8,18 | 46 |
By spherical zeolite mesoporous composite material it can be seen from the data of upper table 2 load benzene sulfonic acid after, specific surface area and
Pore volume has reduced, and this explanation benzene sulfonic acid during load-reaction is entered in spherical zeolite mesoporous composite material
Portion.
Embodiment 4
The present embodiment be used for illustrate the present invention spherical zeolite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical zeolite mesoporous composite material is prepared
By 6g (0.001mol) triblock copolymer surfactant P123 be dissolved in 10ml, pH value be 3 hydrochloric acid and
In 220ml deionized water solutions, stirring 4h to P123 dissolvings form clear solution, then add 6.75g into the clear solution
(0.09mol) n-butanol simultaneously stirs 1h, in the water-bath for being subsequently placed in 30 DEG C, and 15.6g (0.075mol) tetraethyl orthosilicate is slow
Be added drop-wise in the solution, keep the temperature at about 40 DEG C, pH value be to stir 72h under conditions of 3.5, the then hydro-thermal at 40 DEG C again
Handle 40h, then carry out filtering and and be washed with deionized 4 times, then suction filtration is obtained with the mesoporous of three-dimensional cubic duct
The filter cake X4 of molecular screen material.
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is ammonia and water in 1.0g, tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor
Mol ratio is 1：0.5：1.5：180, and stir at 40 DEG C 72h, then the hydro-thermal process 40h at 40 DEG C again, was then carried out
Filter and and be washed with deionized 4 times, then suction filtration obtains the filter cake Y4 of the meso-porous molecular sieve material with hexagonal hole road structure.
The sulfuric acid solution that the waterglass and concentration for being 15 weight % by concentration are 12 weight % is using weight ratio as 6:1 is mixed
Merge haptoreaction 3 hours at 20 DEG C, then adjust pH value to 4 with concentration for 98 weight % sulfuric acid, then to obtaining
Reaction mass carries out suction filtration, and is washed with distilled water to sodium ions content for 0.02 weight %, obtains the filter cake B4 of silica gel.
7g filter cake X4,13g filter cake Y4,30g filter cake B4 and 5g zeolites of above-mentioned preparation are put into 100ml ball grinders together
In, wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, is turned
Speed is 500r/min.Ball grinder is closed, temperature is ball milling 10 hours at 40 DEG C in ball grinder, obtains 55g solid powders；Should
Solid powder is dissolved in 30 grams of deionized waters, is spray-dried at 150 DEG C in the case where rotating speed is 13000r/min；Will spray drying
The product obtained afterwards is calcined 70 hours in Muffle furnace at 450 DEG C, and removed template method obtains 53 grams of spherical zeolites composite mesoporous
Material C 4.
(2) loaded catalyst is prepared
At 25 DEG C, the 53g spherical zeolite mesoporous composite materials C4 prepared in above-mentioned steps (1) is put together with benzene sulfonic acid
Enter in deionized water, stirring to dissolving, and the weight ratio of spherical zeolite mesoporous composite material C4 and benzene sulfonic acid is 85:15, go from
The mol ratio of sub- water and benzene sulfonic acid is 25:1, it is spray-dried at 250 DEG C in the case where rotating speed is 11000r/min, obtains support type and urge
Agent Cat-4.
Spherical zeolite mesoporous composite material C4 and loaded catalyst Cat-4 pore structure parameter are as shown in table 3 below.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C4 | 270 | 1.2 | 2.7,20 | 40 |
| Catalyst Cat-4 | 195 | 1.0 | 2.0,18 | 40 |
By spherical zeolite mesoporous composite material it can be seen from the data of upper table 3 load benzene sulfonic acid after, specific surface area and
Pore volume has reduced, and this explanation benzene sulfonic acid during load-reaction is entered in spherical zeolite mesoporous composite material
Portion.
Embodiment 5
The present embodiment is used for application and the 2,2- dimethyl -4- first for illustrating the loaded catalyst that the present invention is provided
The preparation method of base -1,3- dioxolanes.
Loaded catalyst Cat-1 prepared by embodiment 1 is dried in vacuo 6 hours at 150 DEG C, is cooled to after room temperature,
0.5 gram is weighed, cyclopropane is aoxidized with 5g and 20g acetone is sequentially added in 100ml polytetrafluoroethyllining lining reactors, in stirring
Under conditions of, reacted 6 hours in 75 DEG C of oil baths, be subsequently cooled to room temperature and centrifuge, solid catalyst Cat-1 is 150
It is dried in vacuo 6 hours, is cooled to after room temperature at DEG C, is recycled after recovery.Utilize gas chromatographic analysis reaction product liquid composition, oxygen
Change the conversion ratio 98.5% of cyclopropane, 2,2- dimethyl -4- methyl isophthalic acids, the selectivity 100% of 3- dioxolanes, yield 100%.
Embodiment 6-8 and comparative example 3-4
According to the method for embodiment 5 prepare 2,2- dimethyl -4- methyl isophthalic acids, 3- dioxolanes, except that,
Respectively the support type is replaced with the embodiment 2-4 and comparative example 1-2 of the identical weight loaded catalyst prepared
Catalyst Cat-1.As a result, the conversion ratio and 2,2- diformazan of obtained oxidation cyclopropane are each calculated
The selective data of the ring of base -4- methyl-1,3-dioxies penta is as shown in table 4 below.
Table 4
Embodiment 9-12 and comparative example 5-6
According to the method for embodiment 5 prepare 2,2- dimethyl -4- methyl isophthalic acids, 3- dioxolanes, except that, use respectively
The catalyst from embodiment 5-8 and comparative example 3-4 recovery of identical weight replaces the loaded catalyst Cat-1.As a result, respectively
From the conversion ratio and the selective data of the ring of 2,2- dimethyl -4- methyl-1,3-dioxies penta for calculating obtained oxidation cyclopropane such as
Shown in table 5 below.
Table 5
Load is used as using the spherical zeolite mesoporous composite material of the present invention it can be seen from the data of above-mentioned table 4 and 5
System into loaded catalyst the conversion ratio of reaction raw materials can be significantly improved during ketal reaction.Pass through moreover, working as
When the method for spray drying prepares the loaded catalyst, the loaded catalyst may be repeated utilization, and
Still higher reaction raw materials conversion ratio can be obtained during recycling.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (29)
1. a kind of spherical zeolite mesoporous composite material, it is characterised in that the spherical zeolite mesoporous composite material contains zeolite, tool
There are the meso-porous molecular sieve material of three-dimensional cubic duct structure and the meso-porous molecular sieve material with hexagonal hole road structure, and it is described
The average grain diameter of spherical zeolite mesoporous composite material is 20-50 microns, and specific surface area is 150-600 meters squared per grams, and pore volume is
0.5-1.5 mls/g, aperture is in bimodal distribution, and bimodal corresponds to the first most probable pore size and the second most probable pore size, institute respectively
The first most probable pore size is stated less than second most probable pore size, and first most probable pore size is 2-5 nanometers, described second
Most probable pore size is 5-25 nanometers.
2. composite according to claim 1, wherein, relative to having three-dimensional cubic duct described in 100 parts by weight
The total amount of the meso-porous molecular sieve material of structure and the meso-porous molecular sieve material with hexagonal hole road structure, the zeolite contains
Measure as 1-50 parts by weight；The meso-porous molecular sieve material with three-dimensional cubic duct structure has hexagonal hole road structure with described
Meso-porous molecular sieve material weight ratio be 1：0.1-10.
3. composite according to claim 2, wherein, relative to having three-dimensional cubic duct described in 100 parts by weight
The total amount of the meso-porous molecular sieve material of structure and the meso-porous molecular sieve material with hexagonal hole road structure, the zeolite contains
Measure as 20-50 parts by weight；The meso-porous molecular sieve material with three-dimensional cubic duct structure has hexagonal hole road knot with described
The weight ratio of the meso-porous molecular sieve material of structure is 1：0.5-2.
4. a kind of method for preparing spherical zeolite mesoporous composite material, this method comprises the following steps：
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure is provided or prepared with three-dimensional cubic duct structure
The filter cake of meso-porous molecular sieve material, is used as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or the mesoporous molecular with hexagonal hole road structure is prepared
The filter cake of material is sieved, component a2 is used as；
(3) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(4) the component a1, the component a2, the component b and zeolite are mixed and ball milling, and will be obtained after ball milling
Obtained slurry, is then spray-dried by solid powder water slurrying；
Wherein, the component a1 and the component a2 cause the average grain diameter of the spherical zeolite mesoporous composite material to be 20-50
Micron, specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal
The first most probable pore size and the second most probable pore size are corresponded to respectively, and first most probable pore size is less than the second most probable hole
Footpath, and first most probable pore size is 2-5 nanometers, second most probable pore size is 5-25 nanometers.
5. method according to claim 4, wherein, in step (4), relative to 100 parts by weight the component a1 and
Total consumption of the component a2, the consumption of the component b is 1-200 parts by weight；The consumption of the zeolite is 1-50 parts by weight；Institute
The weight ratio for stating component a1 and the component a2 consumption is 1：0.1-10.
6. method according to claim 5, wherein, in step (4), relative to 100 parts by weight the component a1 and
Total consumption of the component a2, the consumption of the component b is 50-150 parts by weight；The consumption of the zeolite is 20-50 parts by weight；
The weight ratio of the component a1 and the component a2 consumption is 1：0.5-2.
7. method according to claim 4, wherein, in step (1), prepare mesoporous with three-dimensional cubic duct structure
The process of the filter cake of molecular screen material includes：In the presence of template and butanol, tetraethyl orthosilicate is contacted with sour agent,
And the mixture obtained after contact is subjected to crystallization and filtering.
8. method according to claim 7, wherein, the mol ratio of the template, butanol and tetraethyl orthosilicate is 1：10-
100：10-90.
9. method according to claim 8, wherein, the mol ratio of the template, butanol and tetraethyl orthosilicate is 1：60-
90：50-75.
10. the method according to any one in claim 7-9, wherein, the template is triblock copolymer polyoxy
Ethene-polyoxypropylene polyoxyethylene；The sour agent is hydrochloric acid；The condition that tetraethyl orthosilicate is contacted with sour agent includes：Temperature is
10-60 DEG C, the time is 10-72 hours, and pH value is 1-7；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is 10-
72 hours.
11. method according to claim 4, wherein, in step (2), prepare mesoporous point with hexagonal hole road structure
The process of the filter cake of son sieve material includes：By tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia haptoreaction, and it will connect
Touch the mixture obtained after reaction and carry out crystallization and filtering.
12. method according to claim 11, wherein, tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia rub
You are than being 1：0.1-1：0.1-5.
13. method according to claim 12, wherein, tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia rub
You are than being 1：0.2-0.5：1.5-3.5.
14. the method according to claim 11 or 12, wherein, the catalytic condition includes：Temperature is 25-100
DEG C, the time is 10-72 hours；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is 10-72 hours.
15. method according to claim 4, wherein, in step (3), preparing the process of the filter cake of silica gel includes：By water
Glass is contacted with inorganic acid, and the mixture obtained after contact is filtered.
16. method according to claim 15, wherein, the condition that waterglass is contacted with inorganic acid includes：Temperature is 10-60
DEG C, the time is 1-5 hours, and pH value is 2-4；The inorganic acid is the one or more in sulfuric acid, nitric acid and hydrochloric acid.
17. the method according to any one in claim 4-7,11-13 and 15-16, wherein, it is described in step (4)
The condition of ball milling includes：The rotating speed of abrading-ball is 300-500r/min, and the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is
0.1-100 hours；The condition of the spray drying includes：100-300 DEG C of temperature, rotating speed is 10000-15000r/min.
18. the method according to claim 4 or 5, wherein, the component a1 is with the mesoporous of three-dimensional cubic duct structure
The filter cake of molecular screen material, the component a2 is the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure, and described group
Divide the filter cake that b is silica gel, methods described also includes：After the spray-drying process of step (4), the production obtained from spray drying
Removed template method in thing.
19. method according to claim 18, wherein, the condition of the removed template method includes：Temperature is 300-600
DEG C, the time is 10-80 hours.
20. the spherical zeolite mesoporous composite material prepared as the method described in any one in claim 4-19.
21. a kind of loaded catalyst, the catalyst contains the benzene sulfonic acid of carrier and load on the carrier, its feature exists
In the carrier is the spherical zeolite mesoporous composite material described in any one in claim 1-3 and 20.
22. catalyst according to claim 21, wherein, on the basis of the gross weight of the loaded catalyst, benzene sulphur
The content of acid is 1-50 weight %；The content of the carrier is 50-99 weight %.
23. catalyst according to claim 22, wherein, on the basis of the gross weight of the loaded catalyst, benzene sulphur
The content of acid is 5-50 weight %；The content of the carrier is 50-95 weight %.
24. a kind of method for preparing loaded catalyst, this method includes：Carrier, benzene sulfonic acid and water are well mixed, and will
To mixture be spray-dried, wherein, the carrier is the spherical zeolite described in any one in claim 1-3 and 20
Mesoporous composite material.
25. method according to claim 24, wherein, on the basis of total consumption of the carrier and benzene sulfonic acid, benzene sulfonic acid
Consumption be 1-50 weight %；The consumption of the carrier is 50-99 weight %.
26. method according to claim 25, wherein, on the basis of total consumption of the carrier and benzene sulfonic acid, benzene sulfonic acid
Consumption be 5-50 weight %；The consumption of the carrier is 50-95 weight %.
27. the loaded catalyst prepared as the method described in any one in claim 24-26.
28. application of the loaded catalyst in claim 21-23 and 27 described in any one in ketal reaction.
29. one kind 2,2- dimethyl -4- methyl isophthalic acids, the preparation method of 3- dioxolanes, this method includes：In the presence of catalyst
Under, under conditions of ketal reaction, oxidation cyclopropane and acetone are contacted, to obtain 2,2- dimethyl -4- methyl isophthalic acids, 3- dioxies
Penta ring, it is characterised in that the catalyst is the loaded catalyst described in any one in claim 21-23 and 27.
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| CN102039177A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Zinc trifluoromethanesulfonate-loaded spherical mesoporous material, and preparation method and application thereof |
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| CN102039177A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Zinc trifluoromethanesulfonate-loaded spherical mesoporous material, and preparation method and application thereof |
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