CN105214735B - 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 mesoporous composite, the preparation method of the spherical mesoporous composite, the spherical mesoporous composite prepared by the method, loaded catalyst containing the spherical mesoporous composite, the preparation method of the loaded catalyst, the loaded catalyst prepared by the 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 mesoporous composite contains the meso-porous molecular sieve material with one-dimensional straight channels structure and with caged cubic structure.The conversion ratio of reaction raw materials can be significantly improved during ketal reaction as the loaded catalyst that carrier is made using the spherical mesoporous composite of the invention.
Description
Technical field
The present invention relates to a kind of spherical mesoporous composite, the preparation method of the spherical mesoporous composite, by the method
The spherical mesoporous composite for preparing, the loaded catalyst containing the spherical mesoporous composite, one kind prepares support type and urges
The method of agent, by the application of the loaded catalyst, the loaded catalyst of the method preparation in ketal reaction, and makes
With the method for preparing the ring of 2,2- dimethyl -4- methyl-1,3-dioxies penta of the loaded catalyst.
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 obtained 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 etc.), but because of its corrosiveness
Greatly, the side reaction of initiation is more, product separates the defects such as complicated and liquid waste processing difficulty and causes it using being subject to one after reaction
Fixed limitation.As the whole world increases the attention degree of Catalytic processes greenization, solid acid catalysis technique substitution liquid acid catalysis
Technique is imperative.In recent years research show, 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.
In existing loaded catalyst, using conventional meso-porous molecular sieve material as carrier.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 pore volume high 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 of oxidation cyclopropane 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
A kind of relatively low defect of reaction raw materials conversion ratio during reactive ketone, there is provided spherical mesoporous composite for being suitable as carrier,
And the preparation method of the spherical mesoporous composite, the spherical mesoporous composite prepared by the method, contain spherical Jie
The loaded catalyst of hole composite material, the preparation method of the loaded catalyst, the loaded catalyst prepared by the method,
Application of the loaded catalyst in ketal reaction, and the preparation 2 of the loaded catalyst is used, 2- dimethyl -4- methyl -
The method of 1,3- dioxolanes.
In order to achieve the above object, the present inventor, will be with one-dimensional straight channels structure by being found after research
Meso-porous molecular sieve material and the meso-porous molecular sieve material with caged cubic structure combine, and by the composite mesoporous material
Material is made up of spray drying process and is not susceptible to the spherical of reunion, can so retain the high-ratio surface of meso-porous molecular sieve material
Long-pending, big pore volume, large aperture and with one-dimensional straight channels structure and the features such as caged cubic structure, can reduce mesoporous molecular again
The reunion of material is sieved, increases its mobility so that the loaded catalyst being made of the mesoporous composite material is for ketal
The reaction raw materials conversion ratio for significantly improving can be obtained during reaction, so as to complete the present invention.
Therefore, the invention provides a kind of spherical mesoporous composite, wherein, the spherical mesoporous composite contains to be had
One-dimensional straight channels structure and the meso-porous molecular sieve material with caged cubic structure, and the spherical mesoporous composite is flat
Equal average grain diameter is 30-60 microns, and specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, aperture
In bimodal distribution, and bimodal corresponding respectively the first most probable pore size and the second most probable pore size, first most probable pore size is small
In second most probable pore size, the first most probable pore size is 2-6 nanometers, and second most probable pore size is 15-50 nanometers.
Present invention also offers a kind of method for preparing spherical mesoporous composite, the method is comprised the following steps：
(1) providing the meso-porous molecular sieve material with one-dimensional straight channels structure or preparing has one-dimensional straight channels knot
The filter cake of the meso-porous molecular sieve material of structure, as component a1；
(2) meso-porous molecular sieve material with caged cubic structure is provided or is prepared mesoporous with caged cubic structure
The filter cake of molecular screen material, as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, as component b；
(4) the component a1, the component a2, the component b are mixed and ball milling, and by consolidating for being obtained after ball milling
Body powder water slurrying, the slurry that then will be obtained is spray-dried；
Wherein, the component a1 and the component a2 cause that the average average grain diameter of the spherical mesoporous composite is
30-60 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, the first most probable pore size is 2-6 nanometers, and second most probable pore size is 15-50 nanometers.
Present invention also offers the spherical mesoporous composite prepared by the above method.
Present invention also offers a kind of loaded catalyst, the catalyst contains carrier and load benzene on the carrier
Sulfonic acid, wherein, the carrier is according to the spherical mesoporous composite of the invention.
Present invention also offers a kind of method for preparing loaded catalyst, the method includes：By carrier, benzene sulfonic acid and water
It is well mixed, and the mixture that will be obtained is spray-dried, wherein, the carrier is according to of the invention described spherical mesoporous
Composite.
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, the method bag
Include：In the presence of a catalyst, under conditions of ketal reaction, by oxidation cyclopropane and acetone contact, to obtain 2,2- diformazans
Base -4- methyl isophthalic acids, 3- dioxolanes, wherein, the catalyst is according to above-mentioned loaded catalyst of the invention.
Spherical mesoporous composite according to the present invention, combines the mesoporous molecular with one-dimensional straight channels structure
Sieve material, there is the meso-porous molecular sieve material and ball type carrier of caged cubic structure so that this is spherical mesoporous compound
Material is suitable as the carrier of loaded catalyst, the loaded catalyst for being particularly suitable as being used in organic reaction
Carrier.
In the loaded catalyst of the invention, the spherical mesoporous composite as carrier has mesopore molecular sieve
The characteristics of loose structure of material, but also it is loaded with benzene sulfonic acid so that the loaded catalyst both has loaded catalyst
Advantage such as catalysis activity it is high, side reaction is few, post processing is simple etc., and with the catalytic performance of acid so that the supported catalyst
Agent will not only cause equipment corrosion when during for organic reaction, but also can significantly improve the conversion of reaction raw materials
Rate.
In addition, when the method by being spray-dried prepares the loaded catalyst, the loaded catalyst can be with
Reused, and reaction raw materials conversion ratio higher still can be obtained during recycling.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the X-ray diffraction spectrogram of spherical mesoporous composite according to the present invention；
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of spherical mesoporous composite according to the present invention；
Fig. 3 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of spherical mesoporous composite according to the present invention；
Fig. 4 is the pore size distribution curve of spherical mesoporous composite according to the present invention.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of spherical mesoporous composite, wherein, the spherical mesoporous composite contains with one-dimensional
The meso-porous molecular sieve material of straight channels structure and the meso-porous molecular sieve material with caged cubic structure, and this is spherical mesoporous
The average average grain diameter of composite is 30-60 microns, and specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5
Ml/g, aperture is in bimodal distribution, and bimodal corresponding respectively the first most probable pore size and the second most probable pore size, described first
Most probable pore size is less than second most probable pore size, and first most probable pore size is 2-6 nanometers, second most probable
Aperture is 15-50 nanometers.
There is spherical mesoporous composite according to the present invention one-dimensional straight channels structure and caged cube to tie simultaneously
Structure, the average grain diameter of its particle is measured using laser fineness gage, and specific surface area, pore volume and most probable pore size are according to nitrogen
Absorption method is measured.
Spherical mesoporous composite according to the present invention, controls by by the particle size of spherical mesoporous composite
Within above range, it can be ensured that the spherical mesoporous composite is not susceptible to reunite, and is used as carrier and is made
Loaded catalyst can improve the conversion ratio of the reaction raw materials during ketal reaction.When the spherical mesoporous composite
Specific surface area when being less than 0.5 ml/g less than 150 meters squared per grams and/or pore volume, be used as the load that carrier is made
The catalysis activity of type catalyst can be significantly reduced；When the specific surface area of the spherical mesoporous composite is more than 600 meters squared per grams
And/or pore volume is when being more than 1.5 mls/g, it is used as the loaded catalyst that carrier is made and holds during ketal reaction
Easily reunite, so that the conversion ratio of the reaction raw materials during influenceing ketal reaction.
In the preferred case, the average average grain diameter of the spherical mesoporous composite is 35-55 microns, and specific surface area is
180-600 meters squared per grams, pore volume is 0.8-1.2 mls/g, and first most probable pore size is 2-4 nanometers, described second
Most probable pore size is 20-30 nanometers.
In the spherical mesoporous composite, the meso-porous molecular sieve material and institute with one-dimensional straight channels structure
The weight ratio for stating the meso-porous molecular sieve material with caged cubic structure can be 1:0.1-10, preferably 1:0.5-2.
In the present invention, the spherical mesoporous composite can also contain the silica introduced by silica gel." pass through
The silica that silica gel is introduced into " refers in the preparation process of the spherical mesoporous composite, by silica gel as preparing raw material
The silica component brought into the spherical mesoporous composite of final preparation.In the spherical mesoporous composite, relatively
In described in 100 weight portions with the meso-porous molecular sieve material of one-dimensional straight channels and described with the mesoporous of caged cubic structure
The total amount of molecular screen material, the content of the silica introduced by silica gel can be 1-200 weight portions, preferably 50-
150 weight portions.
In the present invention, the meso-porous molecular sieve material with one-dimensional straight channels structure and described with caged cube
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 mesoporous composite, the method is comprised the following steps：
(1) providing the meso-porous molecular sieve material with one-dimensional straight channels structure or preparing has one-dimensional straight channels knot
The filter cake of the meso-porous molecular sieve material of structure, as component a1；
(2) meso-porous molecular sieve material with caged cubic structure is provided or is prepared mesoporous with caged cubic structure
The filter cake of molecular screen material, as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, as component b；
(4) the component a1, the component a2, the component b are mixed and ball milling, and by consolidating for being obtained after ball milling
Body powder water slurrying, the slurry that then will be obtained is spray-dried；
Wherein, the component a1 and the component a2 cause that the average average grain diameter of the spherical mesoporous composite is
30-60 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 2-6 nanometers, second most probable pore size is 15-50 nanometers.
In the preferred case, the component a1 and the component a2 cause the average of the spherical mesoporous composite
Particle diameter is 35-55 microns, and specific surface area is 180-600 meters squared per grams, and pore volume is 0.8-1.2 mls/g, and described first most
Can several apertures be 2-4 nanometer, second most probable pore size be 20-30 nanometers.
In step (1), the process for preparing the filter cake of the meso-porous molecular sieve material with one-dimensional straight channels structure can be with
Including：In the presence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with sour agent, and will contact
The mixture for obtaining afterwards carries out crystallization and filtering.
In step (1), the mol ratio of the template, ethanol, trimethylpentane and tetramethoxy-silicane can be 1：
100-500：200-500：50-200, preferably 1：200-400：250-400：70-150.
The template can be commonly used in the art for preparing the mesoporous molecular with one-dimensional straight channels structure
Sieve the various templates of material.Most preferably, the template is triblock copolymer PULLRONIC F68-polyoxy second
Alkene, the template can be commercially available (for example, can be purchased from Aldrich, trade name P123, molecular formula is
EO20PO70EO20), it is also possible to prepared by existing various methods.When the template is polyoxyethylene-polyoxy third
During alkene-polyoxyethylene, the average molecular weight of the molal quantity of the template according to polyoxyethylene-poly-oxypropylene polyoxyethylene
Obtain.
The sour agent can be the material or mixture (such as solution) that various routines can be used for adjusting pH value.The sour agent
It is preferred that using in form of an aqueous solutions, its pH value can be 1-6, preferably 3-5.It is highly preferred that it is 1-6 that the sour agent is pH value
The acetic acid of (more preferably 3-5) and the cushioning liquid of sodium acetate.
The condition that tetramethoxy-silicane is contacted with the sour agent can include：Temperature is 10-60 DEG C, and the time is that 10-72 is small
When, pH value is 1-7.In order to be more beneficial for the uniform mixing between each material, the tetramethoxy-silicane is contacted with sour agent and preferably existed
Carried out under stirring condition.The consumption of the sour agent is preferably so that tetramethoxy-silicane is with the pH value of the haptoreaction system of sour agent
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 10-48 hours.The crystallization is implemented by hydrothermal crystallization method.
During there is the filter cake of meso-porous molecular sieve material of one-dimensional tunnel structure in above-mentioned preparation, obtained by filtering
The process for obtaining 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 one-dimensional straight channels structure " can directly be weighed
Or choose the product of the meso-porous molecular sieve material with one-dimensional straight channels structure, or prepare with one-dimensional straight channels
The meso-porous molecular sieve material of structure.The preparation method of the meso-porous molecular sieve material with one-dimensional straight channels structure can be with root
Implement according to conventional method, for example, its preparation method can include：Jie with one-dimensional tunnel structure is prepared according to the above method
The filter cake of porous molecular sieve material, then by gained filtration cakes torrefaction, and the template removal in the product that will be obtained after drying.It is described
The condition of removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80 hours.
The process that the filter cake of the meso-porous molecular sieve material with caged cubic structure is prepared in step (2) can include：
In the presence of template, potassium chloride and dimethylbenzene, tetraethyl orthosilicate is contacted with sour agent, and it is mixed by what is obtained after contact
Compound carries out crystallization and filtering.
In step (2), the mol ratio of the template, potassium chloride, dimethylbenzene and tetraethyl orthosilicate is 1：100-500：
400-600：200-400, preferably 1：200-450：400-500：200-300.
In step (2), the template can be mesoporous point for preparing caged cubic structure commonly used in the art
The various templates of son sieve material.Most preferably, the template is triblock copolymer Pluronic F-127 ether-polycyclic oxypropylene
Ether-Pluronic F-127 ether, the template can be commercially available (for example, can be purchased from Aldrich, trade name
F127, molecular formula is EO106PO70EO106), it is also possible to prepared by existing various methods.When the template is
During Pluronic F-127 ether-polycyclic oxypropylene ether-Pluronic F-127 ether, the molal quantity of the template according to Pluronic F-127 ether-
The mean molecule quantity of polycyclic oxypropylene ether-Pluronic F-127 ether is calculated and obtained.
The sour agent can be the material or mixture (such as solution) that various routines can be used for adjusting pH value.Preferable case
Under, the sour agent can be hydrochloric acid.The hydrochloric acid is preferably used in the form of aqueous hydrochloric acid solution.The present invention to the concentration of hydrochloric acid and
There is no particular limitation for consumption, can be changed in scope wider, and generally, the concentration of hydrochloric acid can be 1-5mol/
L, the consumption of hydrochloric acid can be 50-80mL, and under preferable case, the concentration of hydrochloric acid is 1-2mol/L, and the consumption of hydrochloric acid is 50-
60mL。
In step (2), tetraethyl orthosilicate and the catalytic condition of sour agent can include：Temperature is 5-100 DEG C, when
Between be 10-72 hours.In order to be more beneficial for the uniform mixing between each material, the tetraethyl orthosilicate is preferred with the contact of sour agent
Carry out under agitation.
In step (2), the condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.It is preferred that
In the case of, the condition of the crystallization includes：Temperature is 40-130 DEG C, and the time is 20-50 hours.The crystallization passes through hydrothermal crystallizing
Method is implemented.
During there is the filter cake of meso-porous molecular sieve material of caged cubic structure in above-mentioned preparation, obtained by filtering
The process for obtaining 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 caged cubic structure " can directly be weighed or select
Take mesoporous point with caged cubic structure of the product, or preparation of the meso-porous molecular sieve material with caged cubic structure
Son sieve material.The preparation method of the meso-porous molecular sieve material with caged cubic structure can be real according to the conventional method
Apply, for example, its preparation method can include：Meso-porous molecular sieve material with caged cubic structure is prepared according to the above method
Filter cake, then by gained filtration cakes torrefaction, and the template removal in the product that will be obtained after drying.The bar of the removed template method
Part can include that temperature is 300-600 DEG C, and the time is 10-80 hours.
In step (3), the process for preparing 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 determines.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
In at least one.The inorganic acid can be used in pure form, it is also possible to be used in the form of its aqueous solution.The nothing
The consumption of machine acid is preferably so that waterglass is 2-4 with the pH value of the haptoreaction system of inorganic acid.
In step (3), " offer silica gel " can directly be weighed or choose silica gel product, or prepare silica gel.
The method for preparing silica gel can be implemented 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.
In step (4), relative to total consumption of the component a1 and the component a2 of 100 weight portions, the component b
Consumption can be 1-200 weight portions, the weight of the consumption of component a1 and the component a2 preferably described in 50-150 weight portions
Than that 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
Polytetrafluoroethyllining lining, the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can be according to the size of ball grinder
Reasonably selected, be the ball grinder of 50-150ml for size, can generally be used 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
300-500r/min, the temperature in 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 that will be obtained after ball milling can be entered at 25-60 DEG C
OK.In pulping process, solid powder can be 1 with the weight ratio of the consumption of water: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 one-dimensional straight channels structure,
The component a2 is the filter cake of the meso-porous molecular sieve material with caged cubic structure, and the component b for silica gel filter cake when,
Namely when the process that step (1) is the filter cake for preparing the meso-porous molecular sieve material with one-dimensional straight channels structure, step (2) is
The process of the filter cake of the meso-porous molecular sieve material with caged cubic structure is prepared, step (3) is the mistake of the filter cake for preparing silica gel
Cheng Shi, the preparation method of the spherical mesoporous composite can also include：After the spray drying of step (4), from spraying
Removed template method in the product being dried to obtain.The condition of the removed template method can include：Temperature is 300-600 DEG C, time
It is 10-80 hours.
Present invention also offers the spherical mesoporous composite prepared by the above method.
Present invention also offers a kind of loaded catalyst, the catalyst contains carrier and load benzene on the carrier
Sulfonic acid, wherein, the above-mentioned spherical mesoporous composite that the carrier is provided 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
It is 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 for preparing may be repeated utilization, and
Still the conversion ratio of reaction raw materials higher can be obtained during recycling, the method for preparing loaded catalyst includes：
Carrier, benzene sulfonic acid and water are well mixed, and the mixture that will be obtained is spray-dried, wherein, the carrier is the present invention
The above-mentioned spherical mesoporous composite for providing.
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.
Additionally, 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, by oxidation cyclopropane and acetone contact, to obtain 2,2-
Dimethyl -4- methyl isophthalic acids, 3- dioxolanes, wherein, the above-mentioned loaded catalyst that the catalyst is provided for the present invention.
In 2, the 2- dimethyl -4- methyl isophthalic acids, in the preparation method of 3- dioxolanes, the use of oxidation cyclopropane and acetone
There is no particular limitation for amount, as long as can react that 2,2- dimethyl -4- methyl isophthalic acids are obtained, 3- dioxolanes, but in order to carry
The utilization rate of raw material high, under preferable case, the mol ratio of oxidation cyclopropane and acetone is 1：0.5-10.
In 2, the 2- dimethyl -4- methyl isophthalic acids, in 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 weight portions, the consumption of the catalyst is 1-15 weight portions, more excellent
Elect 2-14 weight portions as.
During the ketal reaction, in order to be more beneficial for the carrying out of ketal reaction, the reaction is preferably poly- in high pressure
Carried out under the conditions of tetrafluoroethene liner reactor.The condition of the ketal reaction can include：Reaction temperature is 25-100 DEG C, excellent
Elect 60-100 DEG C as；Reaction time is 1-20 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 terminates
Afterwards, final reactant mixture is centrifuged, and the solid product that will be centrifugally separating to obtain vacuum at 25-200 DEG C
Dry 1-24 hours, be vacuum dried 6-10 hours preferably at 50-150 DEG C, to reclaim catalyst.
Below will the present invention will be described in detail by embodiment.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, writes a Chinese character in simplified form
It is P123, molecular formula is EO20PO70EO20, is the material of 9003-11-6, mean molecule in the registration number of U.S. chemical abstract
Measure is 5800.Pluronic F-127 ether-polycyclic oxypropylene ether-Pluronic F-127 ether is purchased from Aldrich, is abbreviated as F127, point
Minor is EO106PO70EO106, and mean molecule quantity is 12600.
In following examples and comparative example, X-ray diffraction analysis are in the model purchased from German Bruker AXS companies
Carried out on the X-ray diffractometer of D8Advance；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 is analyzed de- in the nitrogen suction 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 product liquid phase ingredient exists
Purchased from being carried out on Agilent companies of Britain 7890A/5973N gas chromatograph-mass spectrometers.
In following examples and comparative example, the conversion ratio and 2,2- dimethyl -4- methyl isophthalic acids of cyclopropane, 3- dioxies penta are aoxidized
The selectivity of ring is calculated according to below equation.
Aoxidize conversion ratio (%)=(content of cyclopropane is aoxidized in the consumption-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 is used to illustrate spherical mesoporous composite of the invention and loaded catalyst and their preparation
Method.
(1) spherical mesoporous composite is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 2.76g (0.06mol) ethanol is added to
During 28ml, pH value are 4 acetic acid and sodium acetate buffer, are stirred to P123 at 15 DEG C and be completely dissolved, it is it is backward obtain it is molten
6g (0.053mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then be added thereto to 2.13g (0.014mol) tetramethyl
TMOS, 20h is stirred under conditions of 15 DEG C, pH value are for 4.5, and the solution that then will be obtained is transferred to polytetrafluoroethyllining lining
Reactor in, the crystallization 24h at 60 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is had
The filter cake X1 of the meso-porous molecular sieve material of one-dimensional straight channels.
The KCl of the Pluronic F127 and 2.5g (0.034mol) of 1.0g (0.0001mol) is dissolved in into 60mL concentration is
2mol·L-1HCl solution in, and be placed on magnetic agitation in flask, the dimethylbenzene of 5.2g (0.049mol) is added, at 14 DEG C
Under 24h is stirred with the rotating speed of 350r/min.Then the tetraethyl orthosilicate (TEOS) of 4.5g (0.022mol) is added thereto to again, after
Continue and 50h is reacted at 14 DEG C, the solution that then will be obtained is transferred to high pressure polytetrafluoroethyllining lining reactor, the crystallization at 130 DEG C
48h.Then carry out filtering and and be washed with deionized 5 times, then suction filtration is obtained with the distribution of caged cubic structure diplopore
The filter cake Y1 of meso-porous molecular sieve material.
By sulfuric acid solution that waterglass and concentration that concentration is 15 weight % are 12 weight % with weight ratio be 5:1 is mixed
Merge haptoreaction 2 hours at 30 DEG C, then adjust pH value to 3 with sulfuric acid that concentration is 98 weight %, 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 cakes B1 of above-mentioned preparation is put into 100ml ball grinders together, wherein, ball
The material of grinding jar 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.Closing ball grinder, temperature is ball milling 1 hour at 60 DEG C in the ball grinder, obtains 20g solid powders；The solid powder is molten
Solution is spray-dried in 10 grams of deionized waters under being 12000r/min in rotating speed at 200 DEG C；The product that will be obtained after spray drying
Thing is calcined 24 hours in Muffle furnace at 500 DEG C, and removed template method P123 and F127 obtain 18 grams of spherical mesoporous composites
C1。
(2) loaded catalyst is prepared
At 25 DEG C, the spherical mesoporous composite C1 of 18g prepared in above-mentioned steps (1) are put into together with benzene sulfonic acid
In ionized water, stirring to dissolving, and spherical mesoporous composite C1 and the weight ratio of benzene sulfonic acid are 50:50, deionized water and benzene
The mol ratio of sulfonic acid is 25:1, it is spray-dried under being 12000r/min in rotating speed at 200 DEG C, obtain loaded catalyst Cat-
1。
The carrier and support type benzene sulfonic acid are urged with XRD, ESEM and U.S.'s Kang Ta companies Atsorb-1 types instrument
Agent is characterized.
Fig. 1 is X-ray diffracting spectrum, from the low-angle spectral peak occurred in XRD spectra, spherical mesoporous composite
C1 and loaded catalyst Cat-1 are respectively provided with orderly one-dimensional straight channels structure and caged cubic structure.
Fig. 2 and Fig. 3 are the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of spherical mesoporous composite C1.As seen from the figure, spherical Jie
The microscopic appearance of hole composite material C1 is the Mesoporous Spheres that particle diameter is 30-60 μm.
Fig. 4 is the pore size distribution curve of spherical mesoporous composite according to the present invention, as seen from the figure, spherical mesoporous
Composite C1 is distributed for diplopore.
The pore structure parameter of spherical mesoporous composite C1 and loaded catalyst Cat-1 is as shown in table 1 below.
Table 1
Spherical mesoporous composite is can be seen that by the data of upper table 1 after benzene sulfonic acid is loaded, specific surface area and hole body
Product has reduced, and this explanation benzene sulfonic acid during load-reaction enters into the inside of spherical mesoporous composite.
Comparative example 1
Method according to embodiment 1 prepares spherical mesoporous composite and loaded catalyst, different, negative preparing
During supported catalyst, (Jilin University's high-tech share is purchased from the bar-shaped mesoporous silicon oxide SBA-15 of identical weight
Co., Ltd) replace the filter cake X1 and filter cake Y1, so as to mesoporous composite material D2 and loaded catalyst be obtained respectively
Cat-D-2。
Embodiment 2
The present embodiment is used to illustrate spherical mesoporous composite of the invention and loaded catalyst and their preparation
Method.
Method according to embodiment 1 prepares spherical mesoporous composite and loaded catalyst, different, negative preparing
The step of during supported catalyst without spray drying, and be only supported on benzene sulfonic acid by the method for dipping spherical mesoporous
On composite, so as to loaded catalyst Cat-2 is obtained.
Embodiment 3
The present embodiment is used to illustrate spherical mesoporous composite of the invention and loaded catalyst and their preparation
Method.
(1) spherical mesoporous composite is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethanol is added to
During 28ml, pH value are 5 acetic acid and sodium acetate buffer, are stirred to P123 at 15 DEG C and be completely dissolved, it is it is backward obtain it is molten
9.12g (0.08mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then be added thereto to 3.04g (0.02mol) four
Methoxy silane, 15h is stirred under conditions of 25 DEG C, pH value are for 5.5, and the solution that then will be obtained is transferred to high pressure polytetrafluoroethyl-ne
In the reactor of alkene liner, the crystallization 10h at 100 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration
Obtain the filter cake X3 of the meso-porous molecular sieve material with one-dimensional straight channels.
The KCl of the Pluronic F127 and 1.49g (0.02mol) of 1.0g (0.0001mol) is dissolved in into 55mL concentration is
1mol·L-1HCl solution in, and be placed on magnetic agitation in flask, the dimethylbenzene of 4.25g (0.04mol) is added, at 14 DEG C
Under 24h is stirred with the rotating speed of 350r/min.Then the tetraethyl orthosilicate (TEOS) of 6.25g (0.03mol) is added thereto to again, after
Continue and 30h is reacted at 50 DEG C, the solution that then will be obtained is transferred to high pressure polytetrafluoroethyllining lining reactor, the crystallization at 100 DEG C
20h.Then carry out filtering and and be washed with deionized 5 times, then suction filtration is obtained with the distribution of caged cubic structure diplopore
The filter cake Y3 of meso-porous molecular sieve material.
By sulfuric acid solution that waterglass and concentration that concentration is 15 weight % are 12 weight % with weight ratio be 4:1 is mixed
Merge haptoreaction 1.5 hours at 40 DEG C, then pH value is adjusted to 2 with the sulfuric acid that concentration is 98 weight %, 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 cakes B3 of above-mentioned preparation is put into 100ml ball grinders together, wherein, ball
The material of grinding jar 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 300r/
min.Closing ball grinder, temperature is ball milling 0.5 hour at 80 DEG C in the ball grinder, obtains 30g solid powders；By the solid powder
It is dissolved in 9 grams of deionized waters, is spray-dried under being 11000r/min in rotating speed at 250 DEG C；By what is obtained after spray drying
Product is calcined 15 hours in Muffle furnace at 550 DEG C, and removed template method obtains 28 grams of spherical mesoporous composite C3.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical mesoporous composite C3 of 28g prepared in above-mentioned steps (1) are put into together with benzene sulfonic acid
In ionized water, stirring to dissolving, and spherical mesoporous composite C3 and the weight ratio of benzene sulfonic acid are 95:5, deionized water and benzene sulphur
The mol ratio of acid is 25:1, it is spray-dried under being 13000r/min in rotating speed at 150 DEG C, obtain loaded catalyst Cat-3.
The pore structure parameter of spherical mesoporous composite C3 and loaded catalyst Cat-3 is as shown in table 2 below.
Table 2
Embodiment 4
The present embodiment is used to illustrate spherical mesoporous composite of the invention and loaded catalyst and their preparation
Method.
(1) spherical mesoporous composite is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethanol is added to
During 28ml, pH value are 3 acetic acid and sodium acetate buffer, are stirred to P123 at 15 DEG C and be completely dissolved, it is it is backward obtain it is molten
5.7g (0.05mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then be added thereto to 4.56g (0.03mol) tetramethyl
TMOS, 10h is stirred under conditions of 40 DEG C, pH value are for 3.5, and the solution that then will be obtained is transferred to high pressure polytetrafluoroethylene (PTFE)
In the reactor of liner, the crystallization 48h at 40 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is obtained
The filter cake X4 of the meso-porous molecular sieve material with one-dimensional channels.
The KCl of the Pluronic F127 of 1.0g (0.0001mol) and 3.35g (0.045mol) is dissolved in 50mL concentration
It is 2molL-1HCl solution in, and be placed on magnetic agitation in flask, the dimethylbenzene of 4.78g (0.045mol) is added, 14
24h is stirred with the rotating speed of 350r/min at DEG C.Then the tetraethyl orthosilicate (TEOS) of 4.17g (0.02mol) is added thereto to again,
15h is reacted in continuation at 70 DEG C, and the solution that then will be obtained is transferred to high pressure polytetrafluoroethyllining lining reactor, the crystallization at 40 DEG C
40h.Then carry out filtering and and be washed with deionized 5 times, then suction filtration is obtained with the distribution of caged cubic structure diplopore
The filter cake Y1 of meso-porous molecular sieve material.
By sulfuric acid solution that waterglass and concentration that concentration is 15 weight % are 12 weight % with weight ratio be 6:1 is mixed
Merge haptoreaction 3 hours at 20 DEG C, then adjust pH value to 4 with sulfuric acid that concentration is 98 weight %, 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 cakes B4 of above-mentioned preparation is put into 100ml ball grinders together, wherein, ball
The material of grinding jar 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 500r/
min.Closing ball grinder, temperature is ball milling 10 hours at 40 DEG C in the ball grinder, obtains 50g solid powders；By the solid powder
It is dissolved in 45 grams of deionized waters, is spray-dried under being 13000r/min in rotating speed at 150 DEG C；By what is obtained after spray drying
Product is calcined 70 hours in Muffle furnace at 450 DEG C, and removed template method obtains 48 grams of spherical mesoporous composite C4.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical mesoporous composite C4 of 48g prepared in above-mentioned steps (1) are put into together with benzene sulfonic acid
In ionized water, stirring to dissolving, and spherical mesoporous composite C4 and the weight ratio of benzene sulfonic acid are 85:15, deionized water and benzene
The mol ratio of sulfonic acid is 25:1, it is spray-dried under being 11000r/min in rotating speed at 250 DEG C, obtain loaded catalyst Cat-
4。
The pore structure parameter of spherical mesoporous composite C4 and loaded catalyst Cat-4 is as shown in table 3 below.
Table 3
Embodiment 5
The present embodiment is used for application and the 2,2- dimethyl -4- first of the loaded catalyst for illustrating present invention offer
The preparation method of base -1,3- dioxolanes.
Loaded catalyst Cat-1 prepared by embodiment 1 is vacuum dried 6 hours at 150 DEG C, after being cooled to room temperature,
0.5 gram is weighed, is aoxidized during cyclopropane and 20g acetone sequentially adds 100ml polytetrafluoroethyllining lining reactors with 5g, in stirring
Under conditions of, reacted 6 hours in 75 DEG C of oil baths, room temperature and centrifugation are subsequently cooled to, solid catalyst Cat-1 is 150
It is vacuum dried 6 hours at DEG C, after being cooled to room temperature, is recycled after recovery.Using gas chromatographic analysis reaction product liquid composition, oxygen
Change cyclopropane conversion ratio 99.9%, 2,2- dimethyl -4- methyl isophthalic acids, the selectivity 100% of 3- dioxolanes, yield 99%.
Embodiment 6-8 and comparative example 3-4
Method preparation 2,2- dimethyl -4- methyl isophthalic acids according to embodiment 5,3- dioxolanes, except that, use respectively
Loaded catalyst prepared by embodiment 2-4 and comparative example 1-2 replaces the loaded catalyst Cat-1.As a result, each calculate
The conversion ratio of the oxidation cyclopropane for obtaining and the selective data such as table 4 below institute of the ring of 2,2- dimethyl -4- methyl-1,3-dioxies penta
Show.
Table 4
Embodiment 9-12 and comparative example 5-6
Method preparation 2,2- dimethyl -4- methyl isophthalic acids according to embodiment 5,3- dioxolanes, except that, use respectively
The catalyst reclaimed from embodiment 5-8 and comparative example 3-4 replaces the loaded catalyst Cat-1.As a result, each it is calculated
Oxidation cyclopropane conversion ratio and the ring of 2,2- dimethyl -4- methyl-1,3-dioxies penta selective data it is as shown in table 5 below.
Table 5
Be can be seen that using the spherical mesoporous composite of the invention as carrier system by the data of above-mentioned table 4 and 5
Into loaded catalyst the conversion ratio of reaction raw materials can be significantly improved during ketal reaction.And, when by spraying
When dry method prepares the loaded catalyst, the loaded catalyst may be repeated utilization, and repeat
Still reaction raw materials conversion ratio higher can be obtained during utilization.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various 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 specific embodiment, in not lance
In the case of shield, 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 is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, 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 mesoporous composite, it is characterised in that the spherical mesoporous composite contains with one-dimensional straight channels
The meso-porous molecular sieve material of structure and the meso-porous molecular sieve material with caged cubic structure, and the spherical mesoporous composite
Average grain diameter be 30-60 micron, specific surface area be 150-600 meters squared per grams, pore volume be 0.5-1.5 mls/g, aperture
In bimodal distribution, and bimodal corresponding respectively the first most probable pore size and the second most probable pore size, first most probable pore size is small
In second most probable pore size, and first most probable pore size is 2-6 nanometers, and second most probable pore size is 15-50
Nanometer.
2. composite according to claim 1, wherein, the mesopore molecular sieve material with one-dimensional straight channels structure
Material is 1 with the weight ratio of the meso-porous molecular sieve material of caged cubic structure：0.1-10.
3. composite according to claim 2, wherein, the mesopore molecular sieve material with one-dimensional straight channels structure
Material is 1 with the weight ratio of the meso-porous molecular sieve material of caged cubic structure：0.5-2.
4. a kind of method for preparing spherical mesoporous composite, the method is comprised the following steps：
(1) meso-porous molecular sieve material with one-dimensional straight channels structure is provided or is prepared with one-dimensional straight channels structure
The filter cake of meso-porous molecular sieve material, as component a1；
(2) meso-porous molecular sieve material with caged cubic structure is provided or the mesoporous molecular with caged cubic structure is prepared
The filter cake of material is sieved, as component a2；
(3) provide silica gel or prepare the filter cake of silica gel, as component b；
(4) the component a1, the component a2, the component b are mixed and ball milling, and the solid powder that will be obtained after ball milling
Water slurrying is used at end, and the slurry that then will be obtained is spray-dried；
Wherein, the component a1 and the component a2 cause that the average grain diameter of the spherical mesoporous composite is 30-60 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 right respectively
The first most probable pore size and the second most probable pore size, first most probable pore size is answered to be less than second most probable pore size, and
First most probable pore size is 2-6 nanometers, and second most probable pore size is 15-50 nanometers.
5. method according to claim 4, wherein, in step (4), relative to 100 weight portions the component a1 and
Total consumption of the component a2, the consumption of the component b is 1-200 weight portions；The consumption of the component a1 and the component a2
Weight ratio be 1：0.1-10.
6. method according to claim 5, wherein, in step (4), relative to 100 weight portions the component a1 and
Total consumption of the component a2, the consumption of the component b is 50-150 weight portions；The consumption of the component a1 and the component a2
Weight ratio be 1：0.5-2.
7. method according to claim 4, wherein, in step (1), prepare mesoporous with one-dimensional straight channels structure
The process of the filter cake of molecular screen material includes：In the presence of template, trimethylpentane and ethanol, by tetramethoxy-silicane with
Sour agent is contacted, and the mixture that will be obtained after contact carries out crystallization and filtering.
8. method according to claim 7, wherein, the template, ethanol, trimethylpentane and tetramethoxy-silicane
Mol ratio is 1：100-500：200-500：50-200.
9. method according to claim 8, wherein, the template, ethanol, trimethylpentane and tetramethoxy-silicane
Mol ratio is 1：200-400：250-400：70-150.
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 that pH value is the acetic acid of 1-6 and the cushioning liquid of sodium acetate；Tetramethoxy-silicane
The condition that alkane is contacted with the sour agent includes：Temperature is 10-60 DEG C, and the time is 10-72 hours, and pH value is 1-7；The crystallization
Condition includes：Temperature is 30-150 DEG C, and the time is 10-72 hours.
11. methods according to claim 4, wherein, in step (2), prepare mesoporous point with caged cubic structure
The process of the filter cake of son sieve material includes：In the presence of template, potassium chloride and dimethylbenzene, tetraethyl orthosilicate is entered with sour agent
Row contact, and the mixture that will be obtained after contact carries out crystallization and filtering.
12. methods according to claim 11, wherein, the template, potassium chloride, dimethylbenzene and tetraethyl orthosilicate rub
You are than being 1：100-500：400-600：200-400.
13. methods according to claim 12, wherein, the template, potassium chloride, dimethylbenzene and tetraethyl orthosilicate rub
You are than being 1：200-450：400-500：200-300.
14. method according to any one in claim 11-13, wherein, the template is poly- for triblock copolymer
Oxireme ether-polycyclic oxypropylene ether-Pluronic F-127 ether；The sour agent is hydrochloric acid；Tetraethyl orthosilicate is contacted with the sour agent
Condition include：Temperature is 5-100 DEG C, and the time is 10-72 hours；The condition of the crystallization includes：Temperature is 30-150 DEG C, when
Between be 10-72 hours.
15. methods according to claim 4, wherein, in step (3), the process for preparing the filter cake of silica gel includes：By water
Glass is contacted with inorganic acid, and the mixture obtained after contact is filtered.
16. methods 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 one or more in sulfuric acid, nitric acid and hydrochloric acid.
17. 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 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. method according to claim 4 or 5, wherein, the component a1 is with the mesoporous of one-dimensional straight channels structure
The filter cake of molecular screen material, the component a2 is the filter cake of the meso-porous molecular sieve material with caged cubic structure, and described group
B is divided to be the filter cake of silica gel, methods described also includes：After the spray-drying process of step (4), from the product that spray drying is obtained
Removed template method in thing.
19. methods 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.
Spherical mesoporous composite prepared by 20. method as described in any one in claim 4-19.
A kind of 21. loaded catalysts, the catalyst contains carrier and load benzene sulfonic acid on the carrier, and its feature exists
In spherical mesoporous composite of the carrier 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 %.
A kind of 24. methods for preparing loaded catalyst, the method includes：Carrier, benzene sulfonic acid and water are well mixed, and will
To mixture be spray-dried, wherein, the carrier is spherical mesoporous described in any one in claim 1-3 and 20
Composite.
25. methods 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. methods 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 %.
Loaded catalyst prepared by 27. method as described in any one in claim 24-26.
The application of loaded catalyst in 28. 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, the method includes：In the presence of catalyst
Under, under conditions of ketal reaction, expoxy propane and acetone are contacted, to obtain 2,2- dimethyl -4- methyl isophthalic acids, 3- dioxies penta
Ring, it is characterised in that loaded catalyst of the catalyst described in any one in claim 21-23 and 27.
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| CN102952209A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN103586076A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and ethyl acetate preparation method |
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| CN102453144A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN102952209A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN103586076A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and ethyl acetate preparation method |
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