CN105435852B - 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 invention discloses 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 method for preparing cyclohexanone glycerol ketals of the loaded catalyst, wherein, the spherical zeolite mesoporous composite material contains zeolite, meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture and the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture.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,
The preparation method of the loaded catalyst, the loaded catalyst prepared by this method, the loaded catalyst are in ketal reaction
In application, and using the loaded catalyst preparation 2,2- 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 expoxy propane and acetone by ketal reaction.Traditional expoxy propane
Catalyst with the ketal reaction of acetone is inorganic liquid (such as sulfuric acid, hydrochloric acid, phosphoric acid), but because its corrosiveness is big, is drawn
The side reaction of hair is more, product separation is complicated after reaction and the defect such as liquid waste processing difficulty and cause it using by certain limit
System.Attention degree increase with the whole world to Catalytic processes greenization, solid acid catalysis technique substitution liquid acid Catalytic processes are
It is imperative.Research showed in recent years, and some solid acids, Lewis hydrochlorates, molecular sieve and ionic liquid etc. are to synthesis 2,2- diformazans
The ring of base -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 of the ring preparation technology oxypropylene 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 prepare 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 the distribution of one-dimensional hexagonal hole road
Zeolite is introduced in the meso-porous molecular sieve material of structure and meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, makes boiling
Stone enters in the duct of meso-porous molecular sieve material, and the mesoporous composite material is made to be not susceptible to reunite spherical, so
The high-specific surface area of meso-porous molecular sieve material, big pore volume, large aperture and with one-dimensional hexagonal hole road distributed architecture can be retained
The features such as being distributed with two-dimentional hexagonal hole road, can reduce the reunion of meso-porous molecular sieve material again, increase its mobility so that using should
The loaded catalyst that mesoporous composite material is made can obtain turn of the reaction raw materials significantly improved when for ketal reaction
Rate, 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 one-dimensional hexagonal hole road distributed architecture and with two-dimentional hexagonal hole road distributed architecture
Meso-porous molecular sieve material, and the average grain diameter of the spherical zeolite mesoporous composite material is 30-60 microns, and specific surface area is 150-
600 meters squared per grams, pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable respectively
Aperture, the second most probable pore size and the 3rd most probable pore size, first most probable pore size are less than second most probable pore size,
Second most probable pore size is less than the 3rd most probable pore size, and first most probable pore size is 2-4 nanometers, described the
Two most probable pore sizes are 5-15 nanometers, and the 3rd most probable pore size is 10-40 nanometers.
The present invention also provides a kind of method for preparing spherical zeolite mesoporous composite material, and this method comprises the following steps：
(1) providing the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture or preparing has one-dimensional hexagonal hole
The filter cake of the meso-porous molecular sieve material of road distributed architecture, is used as component a1；
(2) providing the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparing has two-dimentional hexagonal hole
The filter cake of the meso-porous molecular sieve material of road distributed architecture, 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
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 tri-modal distribution, and
Three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size, the first most probable hole respectively
Footpath is less than second most probable pore size, and second most probable pore size is less than the 3rd most probable pore size, and described first
Most probable pore size is 2-4 nanometers, and second most probable pore size is 5-15 nanometers, and the 3rd most probable pore size is received for 10-40
Rice.
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 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, expoxy propane and acetone are contacted, with obtain 2,2- dimethyl-
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 one-dimensional hexagonal hole road distributed architecture
Meso-porous molecular sieve material, the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, zeolite and ball type carrier it is excellent
Point so that the spherical zeolite mesoporous composite material is suitable as the carrier of loaded catalyst, is particularly suitable as in ketal
The carrier of the loaded catalyst used in reaction.
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 the X-ray diffraction spectrogram of spherical zeolite mesoporous composite material according to the present invention；
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 to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment 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
Zeolite, the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture and with the mesoporous of two-dimentional hexagonal hole road distributed architecture
Molecular screen material, and the average grain diameter of the spherical zeolite mesoporous composite material is 30-60 microns, and specific surface area is 150-600
Meters squared per gram, pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable hole respectively
Footpath, the second most probable pore size and the 3rd most probable pore size, first most probable pore size are less than second most probable pore size, institute
The second most probable pore size is stated less than the 3rd most probable pore size, and first most probable pore size is 2-4 nanometers, described second
Most probable pore size is 5-15 nanometers, and the 3rd most probable pore size is 10-40 nanometers.
Spherical zeolite mesoporous composite material according to the present invention has the two-dimentional hole of hexagonal hole road three of a distinctive peacekeeping
Distributed architecture, the average grain diameter of its particle is measured using laser fineness gage, specific surface area, pore volume and most probable pore size root
Measured according to nitrogen adsorption methods.
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 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 less than second most probable
Aperture, second most probable pore size is less than the 3rd most probable pore size, and first most probable pore size is 2-4 nanometers,
Second most probable pore size is 5-10 nanometers, and the 3rd most probable pore size is 10-25 nanometers.
In the spherical zeolite mesoporous composite material, relative to described in 100 parts by weight there is one-dimensional hexagonal hole road to divide
The total amount of the meso-porous molecular sieve material of cloth structure and the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, institute
The content for stating zeolite can be 1-50 parts by weight, preferably 20-50 parts by weight；It is described with one-dimensional hexagonal hole road distributed architecture
The weight ratio of meso-porous molecular sieve material and the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture is 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 tool described in 100 parts by weight with one-dimensional hexagonal hole road distributed architecture
There are the total amount of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, 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 one-dimensional hexagonal hole road distributed architecture and described there is two dimension
The meso-porous molecular sieve material of hexagonal hole road distributed architecture can be each meso-porous molecular sieve material commonly used in the art, and
It can prepare according to the conventional method.
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 one-dimensional hexagonal hole road distributed architecture or preparing has one-dimensional hexagonal hole
The filter cake of the meso-porous molecular sieve material of road distributed architecture, is used as component a1；
(2) providing the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparing has two-dimentional hexagonal hole
The filter cake of the meso-porous molecular sieve material of road distributed architecture, 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
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 tri-modal distribution, and
Three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size, the first most probable hole respectively
Footpath is less than second most probable pore size, and second most probable pore size is less than the 3rd most probable pore size, and described first
Most probable pore size is 2-4 nanometers, and second most probable pore size is 5-15 nanometers, and the 3rd most probable pore size is received for 10-40
Rice.
In the preferred case, the component a1 and the component a2 cause being averaged for the spherical zeolite mesoporous composite material
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 less than second most probable pore size, second most probable pore size is less than the 3rd most probable pore size, and institute
It is 2-4 nanometers to state the first most probable pore size, and second most probable pore size is 5-10 nanometers, and the 3rd most probable pore size is
10-25 nanometers.
In step (1), the preparation of the filter cake of the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture is prepared
Process includes：In the presence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with sour agent, and will
The mixture obtained after contact carries out crystallization and filtering.
According to the present invention, the template, ethanol, the consumption of trimethylpentane and tetramethoxy-silicane are not limited particularly
It is fixed, it can be changed in wider scope, usually, the template, ethanol, trimethylpentane and tetramethoxy-silicane rub
Your ratio can be 1：100-500：200-500：50-200, preferably 1：200-400：250-400：70-150.
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.The sour agent
It is preferred that using in form of an aqueous solutions.Preferably, the sour agent is the acetic acid and sodium acetate that pH value is 1-6 (more preferably 3-5)
Cushioning liquid.
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 preferably to exist
Carried out under stirring condition.The consumption of the sour agent is preferably so that tetramethoxy-silicane and the pH value of the haptoreaction system of sour agent are
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 one-dimensional hexagonal hole road distributed architecture, pass through
Filtering can be included with the process for obtaining filter cake：After filtration, with deionized water cyclic washing, (washing times can be 2-
10) suction filtration, is then carried out.
In step (1), " providing the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture " can be direct
Weigh or choose the product of the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture or prepare with one-dimensional
The meso-porous molecular sieve material of hexagonal hole road distributed architecture.The meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture
Preparation method can implement according to the conventional method, for example, its preparation method can include：Being prepared according to the above method has
The filter cake of the meso-porous molecular sieve material of one-dimensional hexagonal hole road distributed architecture, then by gained filtration cakes torrefaction, and will be obtained after drying
Product in template removal.The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80
Hour.
In step (2), the process of the filter cake of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture is prepared
Including：In the presence of template, tetraethyl orthosilicate is contacted with sour agent, and the mixture obtained after contact is subjected to crystallization
And filtering.
According to the present invention, there is no particular limitation for the consumption of the template and tetraethyl orthosilicate, can be in wider model
Interior variation is enclosed, usually, the mol ratio of the template and tetraethyl orthosilicate is 1：1-2.5, preferably 1：1-2.
Preferably, preparing the process of the filter cake of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture also includes
In presence of water, tetraethyl orthosilicate is contacted with sour agent.
There is no particular limitation for the consumption of the water, can be changed in wider scope, as long as dissolving institute can be played
The effect of template is stated, usually, the mol ratio of the template and water can be 1：40-250, preferably 1：90-
130。
The water is preferably redistilled water.It should be noted that the mole of above-mentioned water refers to be drawn by redistilled water
Enter the mole of the water in reaction system.
According to the present invention, it can be various templates commonly used in the art that the template, which is, most preferably, described
Template is cetyl trimethylammonium bromide (CTAB)；The sour agent can be used for the thing for adjusting pH value for various routines
Matter or mixture (such as solution).The sour agent is preferably used in form of an aqueous solutions.Preferably, the sour agent is that pH value is 0-1
Hydrochloric acid solution.
According to the present invention, the condition that tetraethyl orthosilicate is contacted with the sour agent includes：Temperature is 10-60 DEG C, and the time is 10-
72 hours, pH value was 0-1；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is 10-72 hours, preferable case
Under, the condition of the crystallization includes：Temperature is 80-140 DEG C, and the time is 20-40 hours.The crystallization passes through hydrothermal crystallizing method
To implement.
According to the present invention, to template, tetraethyl orthosilicate, sour agent and the mode of water contact, there is no particular limitation, preferably
In the case of, first template is dissolved in water and is sufficiently stirred for forming homogeneous phase solution, then the pH of resulting solution is adjusted (preferably with sour agent
0-1), then into resulting solution tetraethyl orthosilicate is slowly added dropwise.
During the filter cake of meso-porous molecular sieve material in above-mentioned preparation with two-dimentional hexagonal hole road distributed architecture, pass through
Filtering can be included with the process for obtaining filter cake：After filtration, with deionized water cyclic washing, (washing times can be 2-
10) suction filtration, is then carried out.
In step (2), " providing the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture " can be direct
Weighing or choose the product of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparing has two dimension
The meso-porous molecular sieve material of hexagonal hole road distributed architecture.The meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture
Preparation method can implement according to the conventional method, for example, its preparation method can include：Being prepared according to the above method has
The filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, then by gained filtration cakes torrefaction, and will be obtained after drying
Product in template removal.The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80
Hour.
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.
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 component a1 and the component a2 weight ratio are 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 component a1 is the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture
Filter cake, the component a2 is the filter cake of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, and the component b is silicon
During the filter cake of glue, namely when filter cake of the step (1) for meso-porous molecular sieve material of the preparation with one-dimensional hexagonal hole road distributed architecture
Process, step (2) for the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture filter cake process, step (3)
During process to prepare the filter cake of silica gel, the preparation method of the spherical zeolite mesoporous composite material can also include：In step
(4) after spray drying, removed template method in the product obtained from spray drying.The condition of the removed template method can be wrapped
Include：Temperature is 300-600 DEG C, and the 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, expoxy propane and acetone are contacted, to obtain 2,2- bis-
Methyl -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 consumption of expoxy propane and acetone
There is no particular limitation, and 2,2- dimethyl -4- methyl isophthalic acids are obtained as long as can react, 3- dioxolanes, but in order to improve
Under the utilization rate of raw material, preferable case, the mol ratio of expoxy propane 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 expoxy propane of 100 parts by weight, the consumption of the catalyst is 1-15 parts by weight, more preferably
For 2-14 parts by weight.
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 quantity
For 5800.
In following examples and comparative example, X-ray diffraction analysis are in the model D8 purchased from German Bruker AXS companies
Carried out on Advance X-ray diffractometer；Scanning electricity of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on sub- microscope；Pore structure parameter analyzes the nitrogen adsorption desorption in the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on instrument, wherein, before being tested, sample is deaerated 4 hours at 200 DEG C；The analysis of reaction product liquid phase ingredient is in purchase
Carried out 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 expoxy propane, 3-
The selectivity of dioxolanes is calculated according to below equation and obtained.
The conversion ratio (%) of expoxy propane=(content of the consumption of expoxy propane-reaction product oxypropylene) ÷ epoxies
Consumption × 100% of propane
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
1.0g (0.0002mol) triblock copolymer surfactant P123 and 2.76g (0.06mol) ethanol is added to
28ml, pH value in 4 acetic acid and the buffer solution of sodium acetate, to stir to P123 and being completely dissolved at 15 DEG C, obtain backward
6g (0.053mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then adds 2.13g (0.014mol) four thereto
Methoxy silane, stirs 20h under conditions of 15 DEG C, pH value is 4.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reactor of lining, the crystallization 24h at 60 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is had
There is the filter cake A1 of the meso-porous molecular sieve material of one-dimensional hexagonal hole road single hole distributed architecture；
1g (0.003mol) cetyl trimethylammonium bromide (CTAB) is added in a certain amount of redistilled water, filled
Divide and stir to obtain homogeneous phase solution, adjusted the pH value of the solution to 0.2 for 0.4 aqueous hydrochloric acid solution with 10mL, pH value.Above-mentioned molten
Liquid is heated to after 15 DEG C, and tetraethyl orthosilicate (TEOS) is slowly added dropwise, wherein, cetyl trimethylammonium bromide：Tetraethyl orthosilicate：
The mol ratio of redistilled water is 1：1：90.Then continue at 15 DEG C after stirring 25 hours, this solution is transferred to poly- four
PVF is in the kettle of lining, static hydrothermal crystallizing handles 40h at 80 DEG C.Then filtered and be washed with deionized 4
Secondary, then suction filtration obtains the filter cake A2 of the meso-porous molecular sieve material with two-dimentional hexagonal hole road single hole distributed architecture.
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 A1,5g filter cake A2,10g 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 in Muffle furnace at 500 DEG C calcine 24 hours, removed template method, obtain 24 grams have one-dimensional hexagonal hole road and
The spherical zeolite mesoporous composite material C1 of the two-dimentional pore size distribution structure of hexagonal hole road three.
(2) loaded catalyst is prepared
At 25 DEG C, the 24g 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.
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, spherical zeolite mesoporous composite material C1 has one-dimensional hexagonal hole road and two dimension specific to mesoporous material
The pore size distribution structure of hexagonal hole road three.
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 30-60 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 tri-modal distribution.
Spherical zeolite mesoporous composite material C1 and loaded catalyst Cat-1 pore structure parameter are as shown in table 1 below.
Table 1
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) meso-porous molecular sieve material filter cake A1 and A2 are replaced, so that mesoporous composite material D2 and support type be made respectively
Catalyst 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 is used for the spherical zeolite mesoporous composite material and loaded catalyst for illustrating the present invention and its preparation
Method.
(1) spherical zeolite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethanol is added to
28ml, pH value in 5 acetic acid and the buffer solution of sodium acetate, to stir to P123 and being completely dissolved at 15 DEG C, obtain backward
9.12g (0.08mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then adds 3.04g (0.02mol) thereto
Tetramethoxy-silicane, stirs 15h under conditions of 25 DEG C, pH value is 5.5, obtained solution then is transferred into polytetrafluoroethylene (PTFE)
In the reactor of liner, the crystallization 10h at 100 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is obtained
To the filter cake A3 of the meso-porous molecular sieve material with one-dimensional hexagonal hole road single hole distributed architecture.
1g (0.003mol) cetyl trimethylammonium bromide is added in a certain amount of redistilled water, is sufficiently stirred for
Homogeneous phase solution is obtained, is adjusted the pH value of the solution to 0.1 for 0.3 aqueous hydrochloric acid solution with 7mL, pH value.The heating of above-mentioned solution
To after 30 DEG C, tetraethyl orthosilicate is slowly added dropwise, wherein, cetyl trimethylammonium bromide：Tetraethyl orthosilicate：Redistilled water
Mol ratio is 1：1.5：130.Then continue at 30 DEG C after stirring 40 hours, this solution is transferred to using polytetrafluoroethylene (PTFE) as lining
In kettle in, in 100 DEG C of static hydrothermal crystallizings processing 20h.Then filtered and be washed with deionized 4 times, then suction filtration
Obtain the filter cake A4 of the meso-porous molecular sieve material with two-dimentional hexagonal hole road single hole distributed architecture.
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 A3,7g filter cake A4,10g 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
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
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethanol is added to
28ml, pH value in 3 acetic acid and the buffer solution of sodium acetate, to stir to P123 and being completely dissolved at 15 DEG C, obtain backward
5.7g (0.05mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then adds 4.56g (0.03mol) four thereto
Methoxy silane, stirs 10h under conditions of 40 DEG C, pH value is 3.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reactor of lining, the crystallization 48h at 40 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is had
There is the filter cake A5 of the meso-porous molecular sieve material of one-dimensional hexagonal hole road single hole distributed architecture.
1g (0.003mol) cetyl trimethylammonium bromide is added in a certain amount of redistilled water, is sufficiently stirred for
Homogeneous phase solution is obtained, is adjusted the pH value of the solution to 0.1 for 0.5 aqueous hydrochloric acid solution with pH value.Above-mentioned solution is heated to 50
After DEG C, tetraethyl orthosilicate is slowly added dropwise, wherein, cetyl trimethylammonium bromide：Tetraethyl orthosilicate：Mole of redistilled water
Than for 1：2：110.Then continue at 50 DEG C after stirring 30 hours, this solution is transferred to the kettle using polytetrafluoroethylene (PTFE) as lining
In, in 140 DEG C of static hydrothermal crystallizing processing 30h.Then filtered and be washed with deionized 4 times, then suction filtration is had
There is the filter cake A6 of the meso-porous molecular sieve material of two-dimentional hexagonal hole road single hole distributed architecture.
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 A5,13g filter cake A6,30g 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 | 1.0 | 2.0,5,20 | 55 |
| Catalyst Cat-4 | 160 | 0.7 | 1.7,3,16 | 59 |
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, is sequentially placed into 5g expoxy propane and 20g acetone in 100mL high pressure polytetrafluoroethyllining lining reactor,
Under conditions of stirring, reacted 6 hours in 75 DEG C of oil baths, be subsequently cooled to room temperature and centrifuge, solid catalyst Cat-1 exists
It is dried in vacuo 6 hours, is cooled to after room temperature at 150 DEG C, is recycled after recovery.Using gas chromatographic analysis reaction product liquid into
Point, the conversion ratio 99% of expoxy propane, 2,2- dimethyl -4- methyl isophthalic acids, the selectivity 99% 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, 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 obtained expoxy propane 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
According to the method for embodiment 5 prepare 2,2- dimethyl -4- methyl isophthalic acids, 3- dioxolanes, except that, use respectively
The loaded catalyst Cat-1 is replaced from the embodiment 5-8 and comparative example 3-4 catalyst reclaimed.As a result, each calculate and obtain
Expoxy propane conversion ratio and 2,2- dimethyl -4- penta ring selective datas of methyl-1,3-dioxy it is 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, had
The meso-porous molecular sieve material of one-dimensional hexagonal hole road distributed architecture and the mesopore molecular sieve material with two-dimentional hexagonal hole road distributed architecture
Material, zeolite enters in the duct of meso-porous molecular sieve material, and the average grain diameter of the spherical zeolite mesoporous composite material is 30-60
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 tri-modal distribution, and three
Peak corresponds to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size respectively, and first most probable pore size is small
In second most probable pore size, second most probable pore size is less than the 3rd most probable pore size, and described first most may be used
Several apertures are 2-4 nanometers, and second most probable pore size is 5-15 nanometers, and the 3rd most probable pore size is 10-40 nanometers.
2. composite according to claim 1, wherein, relative to having one-dimensional hexagonal hole road described in 100 parts by weight
The total amount of the meso-porous molecular sieve material of distributed architecture and meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, it is described
The content of zeolite is 1-50 parts by weight；The meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture has with described
The weight ratio of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture is 1：0.1-10.
3. composite according to claim 2, wherein, relative to having one-dimensional hexagonal hole road described in 100 parts by weight
The total amount of the meso-porous molecular sieve material of distributed architecture and meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, it is described
The content of zeolite is 20-50 parts by weight；The meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture and the tool
The weight ratio for having the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture is 1：0.5-2.
4. 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 one-dimensional hexagonal hole road distributed architecture or preparing has one-dimensional hexagonal hole road point
The filter cake of the meso-porous molecular sieve material of cloth structure, is used as component a1；
(2) providing the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparing has two-dimentional hexagonal hole road point
The filter cake of the meso-porous molecular sieve material of cloth structure, 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 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 30-60
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 tri-modal distribution, and three
Peak corresponds to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size respectively, and first most probable pore size is small
In second most probable pore size, second most probable pore size is less than the 3rd most probable pore size, and described first most may be used
Several apertures are 2-4 nanometers, and second most probable pore size is 5-15 nanometers, and the 3rd most probable pore size is 10-40 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 the component a1 and component a2 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 component a1 and component a2 weight ratio is 1：0.5-2.
7. method according to claim 4, wherein, it is described with one-dimensional hexagonal hole road distributed architecture in step (1)
The preparation process of the filter cake of meso-porous molecular sieve material includes：In the presence of template, trimethylpentane and ethanol, by four methoxies
Base silane is contacted with sour agent, and the mixture obtained after contact is carried out into 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 claim 7 or 8, wherein, the template is triblock copolymer polyoxyethylene-polyoxy
Proplyene-polyoxyethylene；The sour agent is the cushioning liquid of the acetic acid that pH value is 1-6 and sodium acetate；Tetramethoxy-silicane with it is described
The condition of sour agent contact includes：Temperature is 10-60 DEG C, and the time is 10-72 hours, and pH value is 1-7；The condition bag of the crystallization
Include：Temperature is 30-150 DEG C, and the time is 10-72 hours.
11. method according to claim 4, wherein, prepare the mesopore molecular sieve with two-dimentional hexagonal hole road distributed architecture
The process of the filter cake of material includes：In the presence of template, tetraethyl orthosilicate is contacted with sour agent, and will be obtained after contact
Mixture carry out crystallization and filtering.
12. method according to claim 11, wherein, the mol ratio of the template and tetraethyl orthosilicate is 1：1-2.5.
13. method according to claim 12, wherein, the mol ratio of the template and tetraethyl orthosilicate is 1：1-2.
14. the method according to claim 11 or 12, wherein, the template is cetyl trimethylammonium bromide；Institute
It is the hydrochloric acid that pH value is 0-1 to state sour agent；The condition that tetraethyl orthosilicate is contacted with the sour agent includes：Temperature is 10-60 DEG C, time
For 10-72 hours, pH value was 0-1；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 and 11, wherein, in step (4), the bar of the ball milling
Part includes：The rotating speed of abrading-ball is that the temperature in 300-500r/min, ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100
Hour；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 one-dimensional hexagonal hole road distributed architecture
The filter cake of meso-porous molecular sieve material, the component a2 is the filter of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture
Cake, the component b is the filter cake of silica gel, and methods described also includes：It is dry from spraying after the spray-drying process of step (4)
Removed template method in dry obtained product.
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, expoxy propane 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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| CN101239322A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing montmorillonite/molecular sieve composite material |
| CN103055933A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrocracking catalyst as well as preparation method and application thereof |
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| CN103055933A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrocracking catalyst as well as preparation method and application thereof |
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