CN105149011B - The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals - Google Patents
The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals Download PDFInfo
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- CN105149011B CN105149011B CN201410252556.XA CN201410252556A CN105149011B CN 105149011 B CN105149011 B CN 105149011B CN 201410252556 A CN201410252556 A CN 201410252556A CN 105149011 B CN105149011 B CN 105149011B
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Abstract
The present invention relates to a kind of spherical chlorite mesoporous composite material, the preparation method of the spherical chlorite mesoporous composite material, the spherical chlorite mesoporous composite material prepared by the method, loaded catalyst containing the spherical chlorite mesoporous 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 use the method for preparing cyclohexanone glycerol ketals of the loaded catalyst, wherein, the spherical chlorite mesoporous composite material contains chlorite, meso-porous molecular sieve material with three-dimensional cubic duct structure and the meso-porous molecular sieve material with hexagonal hole road 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 chlorite mesoporous composite material of the invention.
Description
Technical field
The present invention relates to a kind of spherical chlorite mesoporous composite material, the preparation side of the spherical chlorite mesoporous composite material
Method, the spherical chlorite mesoporous composite material prepared by the method, the support type containing the spherical chlorite mesoporous composite material
Catalyst, a kind of method for preparing loaded catalyst, the loaded catalyst prepared by the method, the loaded catalyst exist
Application in ketal reaction, and use the method for preparing cyclohexanone glycerol ketals of the loaded catalyst.
Background technology
Cyclohexanone glycerol ketals are that it holds compared with carbonyls with lasting with the fragrant spices of delicate fragrance, flowers and trees
Long, raw material sources are abundant, simple production process and the advantages of stable chemical nature.Generally, cyclohexanone glycerol ketals
It is obtained by ketal reaction by glycerine and cyclohexanone.Traditional cyclohexanone and the catalyst of glycerol ketals reaction are inorganic liquid
(such as sulfuric acid, hydrochloric acid, phosphoric acid etc.), but because its corrosiveness is big, the side reaction of initiation is more, after reaction product separate complexity and
The defects such as liquid waste processing difficulty and cause it using being subject to certain restrictions.As the whole world is to the attention journey of Catalytic processes greenization
Degree increases, and solid acid catalysis technique substitution liquid acid Catalytic processes are imperative.Studied in recent years and showed, some solid acids,
Lewis hydrochlorates, molecular sieve and ionic liquid etc. have good catalytic action to synthesizing cyclohexanone glycerol ketals.
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 cyclohexanone in cyclohexanone glycerol ketals preparation technology.
The content of the invention
The invention aims to overcome the loaded catalyst being made of existing meso-porous molecular sieve material in contracting
The relatively low defect of reaction raw materials conversion ratio during reactive ketone, there is provided a kind of spherical chlorite for being suitable as carrier is composite mesoporous
Material, and the spherical chlorite mesoporous composite material preparation method, by the method prepare spherical chlorite it is composite mesoporous
Material, the loaded catalyst containing the spherical chlorite mesoporous composite material, the preparation method of the loaded catalyst, by this
Loaded catalyst prepared by method, application of the loaded catalyst in ketal reaction, and use the supported catalyst
The method that agent prepares cyclohexanone glycerol ketals.
In order to achieve the above object, the present inventor's discovery after studying, with three-dimensional cubic duct structure
Meso-porous molecular sieve material and the meso-porous molecular sieve material with hexagonal hole road structure in introduce chlorite, make chlorite enter be situated between
In the duct of porous molecular sieve material, and the mesoporous composite material is made be not susceptible to reunite it is spherical, can so retain
The high-specific surface area of meso-porous molecular sieve material, big pore volume, large aperture and with three-dimensional cubic duct structure and hexagonal hole road knot
The features such as structure, the reunion of meso-porous molecular sieve material can be reduced again, increase its mobility so that be made of the mesoporous composite material
Loaded catalyst the reaction raw materials conversion ratio for significantly improving can be obtained when for ketal reaction, so as to complete this hair
It is bright.
Therefore, the invention provides a kind of spherical chlorite mesoporous composite material, wherein, the spherical chlorite is composite mesoporous
Material contains chlorite, the meso-porous molecular sieve material with three-dimensional cubic duct structure and mesoporous point with hexagonal hole road structure
Son sieve material, and the average grain diameter of the spherical chlorite mesoporous composite material is 20-50 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 bimodal distribution, and bimodal the first most probable pore size corresponding respectively
With the second most probable pore size, first most probable pore size is less than second most probable pore size, and the first most probable hole
Footpath is 2-5 nanometers, and second most probable pore size is 5-25 nanometers.
Present invention also offers a kind of method for preparing spherical chlorite mesoporous composite material, the method includes following step
Suddenly：
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure is provided or is prepared with three-dimensional cubic duct knot
The filter cake of the meso-porous molecular sieve material of structure, as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or is prepared mesoporous with hexagonal hole road 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 and chlorite are mixed and ball milling, and by after ball milling
The solid powder for obtaining water slurrying, 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 chlorite mesoporous composite material is
20-50 microns, specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and
Bimodal to correspond to the first most probable pore size and the second most probable pore size respectively, first most probable pore size most may be used less than described second
Several apertures, and first most probable pore size is 2-5 nanometers, second most probable pore size is 5-25 nanometers.
Present invention also offers the spherical chlorite mesoporous composite material 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 chlorite mesoporous composite material 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 the spherical green mud of the invention
Stone 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 a kind of preparation method of cyclohexanone glycerol ketals, the method includes：In the presence of catalyst
Under, under conditions of ketal reaction, cyclohexanone and glycerine are contacted, to obtain cyclohexanone glycerol ketals, wherein, the catalyst
It is according to above-mentioned loaded catalyst of the invention.
Spherical chlorite mesoporous composite material according to the present invention, combines Jie with three-dimensional cubic duct structure
Porous molecular sieve material, the meso-porous molecular sieve material with hexagonal hole road structure, chlorite and ball type carrier so that should
Spherical chlorite mesoporous composite material is suitable as the carrier of loaded catalyst, is particularly suitable as making in ketal reaction
The carrier of loaded catalyst.
In the loaded catalyst of the invention, have as the spherical chlorite mesoporous composite material of carrier mesoporous
The characteristics of loose structure of molecular screen material, but also it is loaded with benzene sulfonic acid so that the loaded catalyst both has support type
The advantage of catalyst such as catalysis activity is high, side reaction is few, post processing is simple etc., and with the catalytic performance of acid so that the load
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 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 chlorite mesoporous composite material according to the present invention；
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of spherical chlorite mesoporous composite material according to the present invention；
Fig. 3 is the pore size distribution curve of spherical chlorite mesoporous composite material 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 chlorite mesoporous composite material, wherein, the spherical chlorite mesoporous composite material
Contain chlorite, the meso-porous molecular sieve material with three-dimensional cubic duct structure and the mesopore molecular sieve with hexagonal hole road structure
Material, and the average grain diameter of the spherical chlorite mesoporous composite material is 20-50 microns, and specific surface area is 150-600 squares
Rice/gram, pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal corresponds to the first most probable pore size and the respectively
Two most probable pore sizes, first most probable pore size is less than second most probable pore size, and first most probable pore size is
2-5 nanometers, second most probable pore size is 5-25 nanometers.
Spherical chlorite mesoporous composite material according to the present invention has three-dimensional cubic duct structure and six sides simultaneously
Pore passage structure, 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 chlorite mesoporous composite material according to the present invention, by by spherical chlorite mesoporous composite material
Particle size is controlled within above range, it can be ensured that the spherical chlorite mesoporous composite material is not susceptible to reunite, and
And be used as the loaded catalyst that carrier is made and can improve reaction raw materials conversion ratio during ketal reaction.When described
When the specific surface area of spherical chlorite mesoporous composite material is less than 0.5 ml/g less than 150 meters squared per grams and/or pore volume,
The catalysis activity for being used as the loaded catalyst that carrier is made can be significantly reduced；When the spherical composite mesoporous material of chlorite
When the specific surface area of material is more than 1.5 mls/g more than 600 meters squared per grams and/or pore volume, be used as that carrier is made is negative
Supported catalyst is susceptible to reunite during ketal reaction, so that the reaction raw materials conversion during influenceing ketal reaction
Rate.
In the preferred case, the average grain diameter of the spherical chlorite mesoporous composite material is 20-40 microns, specific surface area
It is 210-600 meters squared per grams, pore volume is 0.8-1.5 mls/g, and first most probable pore size is 2-4 nanometers, described
Second most probable pore size is 10-24 nanometers.
In the spherical chlorite mesoporous composite material, relative to described in 100 weight portions have three-dimensional cubic duct
The total amount of the meso-porous molecular sieve material of structure and the meso-porous molecular sieve material with hexagonal hole road structure, the chlorite
Content can be 1-50 weight portions, preferably 20-50 weight portions；The mesopore molecular sieve material with three-dimensional cubic duct structure
Expect that with the weight ratio of the meso-porous molecular sieve material with hexagonal hole road structure can be 1：0.1-10, preferably 1：0.5-2.
In the present invention, the spherical chlorite mesoporous composite material can also contain the titanium dioxide introduced by silica gel
Silicon." silica being introduced into by silica gel " refers in the preparation process of the spherical chlorite mesoporous composite material, by silicon
The silica component that glue is brought into the spherical chlorite mesoporous composite material of final preparation as preparing raw material.Described spherical
In chlorite mesoporous composite material, relative to the mesopore molecular sieve material with three-dimensional cubic duct structure described in 100 weight portions
The total amount of material and the meso-porous molecular sieve material with hexagonal hole road structure, the silica introduced by silica gel is contained
Amount can be 1-200 weight portions, preferably 50-150 weight portions.
In the present invention, the meso-porous molecular sieve material with three-dimensional cubic duct structure and described with hexagonal hole road
The meso-porous molecular sieve material of structure can be each meso-porous molecular sieve material commonly used in the art, and each can basis
Conventional method is prepared.
Present invention also offers a kind of method for preparing spherical chlorite mesoporous composite material, the method includes following step
Suddenly：
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure is provided or is prepared with three-dimensional cubic duct knot
The filter cake of the meso-porous molecular sieve material of structure, as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or is prepared mesoporous with hexagonal hole road 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 and chlorite are mixed and ball milling, and by after ball milling
The solid powder for obtaining water slurrying, 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 chlorite mesoporous composite material is
20-50 microns, specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and
Bimodal to correspond to the first most probable pore size, the second most probable pore size respectively, first most probable pore size most may be used less than described second
Several apertures, and first most probable pore size is 2-5 nanometers, second most probable pore size is 5-25 nanometers.
Under preferable case, the component a1 and component a2 causes the average of the spherical chlorite mesoporous composite material
Particle diameter is 20-40 microns, and specific surface area is 210-600 meters squared per grams, and pore volume is 0.8-1.5 mls/g, and described first
Most probable pore size is 2-4 nanometers, and second most probable pore size is 10-24 nanometers.
In step (1), the process for preparing the filter cake of the meso-porous molecular sieve material with three-dimensional cubic duct structure can be with
Including：In the presence of template and butanol, tetraethyl orthosilicate is contacted with sour agent, and the mixture that will be obtained after contact
Carry out crystallization and filtering.
According to the present invention, the mol ratio of the template, butanol and tetraethyl orthosilicate can change in scope wider,
As long as the meso-porous molecular sieve material filter cake with three-dimensional cubic duct structure, usually, the template, fourth can be formed
The mol ratio of the consumption of alcohol and tetraethyl orthosilicate can be 1：10-100：10-90, preferably 1：60-90：50-75.
According to the present invention, the template can be various templates commonly used in the art.Most preferably, the mould
Plate agent is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, and the template can be commercially available (for example, can
So that purchased from Aldrich, trade name P123, molecular formula is EO20PO70EO20), it is also possible to by existing various method systems
It is standby to obtain.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxy
The mean molecule quantity of ethene-polyoxypropylene polyoxyethylene is calculated and obtained.
According to the present invention, the sour agent can be various routines can be used for adjust pH value material or mixture it is (such as molten
Liquid).Preferably, the sour agent is hydrochloric acid.Preferably used in form of an aqueous solutions as the hydrochloric acid of sour agent.The pH of aqueous hydrochloric acid solution
Value can be 1-6.
According to the present invention, the butanol is preferably n-butanol.
The present invention is no with the condition that sour agent is contacted to the tetraethyl orthosilicate particularly to be limited, for example, positive silicic acid second
The condition that ester is contacted with sour agent can include：Temperature is 10-60 DEG C, and the time is 10-72 hours, and pH value is 1-7.In order to more favourable
Uniform mixing between each material, the tetraethyl orthosilicate is contacted with sour agent and preferably carried out under agitation.The sour agent
Consumption is preferably so that tetraethyl orthosilicate is 1-7 with the pH value of the haptoreaction system of sour agent.
There is no particular limitation for condition of the present invention to the crystallization, and the condition of the crystallization can be that this area is conventional
Selection, for example, the condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.Under preferable case, institute
The condition for stating crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
During there is the filter cake of meso-porous molecular sieve material in three-dimensional cubic duct 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 times), then
Carry out suction filtration.
In step (1), " providing the meso-porous molecular sieve material with three-dimensional cubic duct structure " can directly be weighed
Or choose the product of the meso-porous molecular sieve material with three-dimensional cubic duct structure, or prepare with three-dimensional cubic duct
The meso-porous molecular sieve material of structure.The preparation method of the meso-porous molecular sieve material with three-dimensional cubic duct structure can be with root
Implement according to conventional method, for example, its preparation method can include：Being prepared according to the above method has three-dimensional cubic duct structure
Meso-porous molecular sieve material filter cake, then by gained filtration cakes torrefaction, and the template removal in the product that will be obtained after drying.
The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80 hours.
The process that the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure is prepared in step (2) can include：Will
Tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia haptoreaction, and the mixture that will be obtained after haptoreaction carries out crystalline substance
Change and filter.
According to the present invention, the mol ratio of the tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can be wider
In the range of change, as long as the meso-porous molecular sieve material filter cake with hexagonal hole road structure, usually, positive silicon can be formed
The mol ratio of acetoacetic ester, cetyl trimethylammonium bromide and ammonia can be 1：0.1-1：0.1-5, preferably 1：0.2-0.5：
1.5-3.5。
According to the present invention, ammonia is added preferably in the form of ammoniacal liquor.
According to the present invention, haptoreaction process the depositing in water of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia
Under carry out.Preferably, part water is introduced in the form of ammoniacal liquor, and part water is added in the form of deionized water.In positive silicic acid second
In the haptoreaction system of ester, cetyl trimethylammonium bromide and ammonia, tetraethyl orthosilicate can be 1 with the mol ratio of water：
100-200, preferably 1：120-180.
According to the present invention, the catalytic condition of tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia is without spy
Other restriction, as long as the meso-porous molecular sieve material filter cake with hexagonal hole road structure can be formed, usually, positive silicic acid second
The catalytic condition of ester, cetyl trimethylammonium bromide and ammonia can include：Temperature is 25-100 DEG C, and the time is 10-
72 hours.Preferably, the haptoreaction is carried out under agitation, is beneficial to the uniform mixing between each material.
According to the present invention, there is no particular limitation for condition of the present invention to the crystallization, and the condition of the crystallization can be
The conventional selection in this area, for example, the condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.
Under preferable case, the condition of the crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40 hours.The crystallization passes through hydro-thermal
Crystallization method is implemented.
During there is the filter cake of meso-porous molecular sieve material of hexagonal hole road 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 times), then
Carry out suction filtration.
In step (2), " providing the meso-porous molecular sieve material with hexagonal hole road structure " can directly be weighed or select
Take mesoporous point with hexagonal hole road structure of the product, or preparation of the meso-porous molecular sieve material with hexagonal hole road structure
Son sieve material.The preparation method of the meso-porous molecular sieve material with hexagonal hole road structure can be real according to the conventional method
Apply, for example, its preparation method can include：Meso-porous molecular sieve material with hexagonal hole road structure is prepared according to the above method
Filter cake, then by gained filtration cakes torrefaction.
In step (3), 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.
According to the present invention, there is no particular limitation for the condition that waterglass is contacted with inorganic acid, can be according to preparing silica gel
Suitably determine in common process.Under preferable case, the condition that waterglass is contacted with inorganic acid can include：Temperature is 10-60
DEG C, preferably 20-40 DEG C；Time is 1-5 hours, preferably 1.5-3 hours；PH value is 2-4.Between in order to be more beneficial for each material
Uniform mixing, waterglass preferably carries out under agitation with the catalytic process of inorganic acid.
The waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 weight %, preferably 12-30 weight %.
According to the present invention, the inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulphur
At least one in acid, nitric acid and hydrochloric acid.The inorganic acid can be used in pure form, it is also possible to the shape of its aqueous solution
Formula is used.The consumption of the inorganic 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.
During the above-mentioned filter cake for preparing silica gel, can be included with obtaining the process of filter cake by filtering：In filtering
Afterwards, it is 0.01-0.03 weight % with the content of distilled water cyclic washing to sodium ion, then carries out suction filtration.
In step (4), relative to total consumption of the component a1 and the component a2 of 100 weight portions, the component b
Consumption can be 1-200 weight portions, preferably 50-150 weight portions；The consumption of the chlorite can be 1-50 weight portions,
Preferably 20-50 weight portions；The weight ratio of the consumption of the component a1 and the component a2 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 three-dimensional cubic duct structure,
The component a2 is the filter cake of the meso-porous molecular sieve material with hexagonal hole road 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 three-dimensional cubic duct structure, step (2) is
The process of the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure is prepared, step (3) is the mistake of the filter cake for preparing silica gel
Cheng Shi, the preparation method of the spherical chlorite mesoporous composite material can also include：After the spray drying of step (4),
Removed template method in the product obtained from spray drying.The condition of the removed template method can include：Temperature is 300-600
DEG C, the time is 10-80 hours.
Present invention also offers the spherical chlorite mesoporous composite material 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 chlorite mesoporous composite material 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 reaction raw materials conversion ratio higher can be obtained during recycling, the method for preparing loaded catalyst includes：Will
Carrier, benzene sulfonic acid and water are well mixed, and the mixture that will be obtained is spray-dried, wherein, the carrier is carried for the present invention
The above-mentioned spherical chlorite mesoporous composite material for supplying.
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 a kind of preparation method of cyclohexanone glycerol ketals, the method includes：In catalyst
In the presence of, under conditions of ketal reaction, cyclohexanone and glycerine are contacted, to obtain cyclohexanone glycerol ketals, wherein, it is described to urge
The above-mentioned loaded catalyst that agent is provided for the present invention.
In the preparation method of the cyclohexanone glycerol ketals, there is no particular limitation for the consumption of cyclohexanone and glycerine, only
Can react and obtain cyclohexanone glycerol ketals, but in order to improve the utilization rate of raw material, under preferable case, cyclohexanone and sweet
The mol ratio of oil is 1：0.5-10.
In the preparation method of the cyclohexanone glycerol ketals, there is no particular limitation for the consumption of the catalyst, can be with
Suitably determined according to the conventional method for preparing cyclohexanone glycerol ketals.Under preferable case, relative to the hexamethylene of 100 weight portions
Ketone, the consumption of the catalyst is 1-15 weight portions, more preferably 2-14 weight portions.
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 in tetrafluoroethene liner reactor and under conditions of backflow, i.e. the reaction temperature is reflux temperature, the reaction temperature
Degree can be 25-100 DEG C, preferably 60-100 DEG C.Reaction time can be 1-20 hours, preferably 2-15 hours.
During the ketal reaction, in order to be conducive to the carrying out of ketal reaction, the reaction is preferably in water entrainer
In the presence of carry out.There is no particular limitation for consumption of the present invention to the water entrainer, can be changed in scope wider, preferably
In the case of, relative to the cyclohexanone of 100 weight portions, the consumption of the water entrainer is 30-100 weight portions, more preferably 50-80 weights
Amount part.The water entrainer can be selected from one or more in hexamethylene, petroleum ether, dimethylbenzene, toluene and benzene, preferably hexamethylene
Alkane.
The preparation method of the cyclohexanone glycerol ketals is additionally may included in after ketal reaction terminates, mixed to final reaction
Compound is centrifuged, and the solid product that will be centrifugally separating to obtain is vacuum dried 1-24 hours at 25-200 DEG C, preferably
It is vacuum dried 6-10 hours 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.
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 EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio of cyclohexanone and the selectivity root of cyclohexanone glycerol ketals
It is calculated according to below equation.
The use of the conversion ratio (%) of cyclohexanone=(content of cyclohexanone in the consumption-product of cyclohexanone) ÷ cyclohexanone
Amount × 100%
The actual production ÷ cyclohexanone glycerol ketals of selectivity (the %)=cyclohexanone glycerol ketals of cyclohexanone glycerol ketals
Theoretical yield × 100%
Embodiment 1
The present embodiment be used for illustrate spherical chlorite mesoporous composite material of the invention and loaded catalyst and they
Preparation method.
(1) spherical chlorite mesoporous composite material is prepared
6g (0.001mol) triblock copolymer surfactant P123 is dissolved in the hydrochloric acid that 10ml, pH value are 4 water-soluble
In liquid and 220ml deionized water solutions, stirring 4h to P123 dissolvings form clear solution, then add in the clear solution
6g (0.08mol) n-butanols simultaneously stir 1h, are subsequently placed in 40 DEG C of water-bath, and 12.9g (0.062mol) tetraethyl orthosilicate is slow
Slowly be added drop-wise in the solution, keep the temperature at about 40 DEG C, pH value be 4.5 under conditions of stir 24h, then again at 100 DEG C
Hydro-thermal process 24h, then carry out filtering and and be washed with deionized 4 times, then suction filtration is obtained with three-dimensional cubic duct
The filter cake X1 of meso-porous molecular sieve material.
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is 1.0g, the ammonia and water in tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor
Mol ratio is 1：0.37：2.8：142, and 24h is stirred at 80 DEG C, then the hydro-thermal process 24h at 100 DEG C again, is then carried out
Filtering and and be washed with deionized 4 times, then suction filtration obtains the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure
Y1。
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 cake B1 and 5g chlorite of above-mentioned preparation is 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 400r/min.Closing ball grinder, temperature is ball milling 1 hour at 60 DEG C in the ball grinder, obtains 25g solid powders；Should
Solid powder is dissolved in 22.5 grams of deionized waters, is spray-dried under being 12000r/min in rotating speed at 200 DEG C；Spraying is dry
The product obtained after dry is calcined 24 hours in Muffle furnace at 500 DEG C, and removed template method obtains 24 grams of spherical chlorite mesoporous
Composite C1.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical chlorite mesoporous composite material C1 of 24g that will be prepared in above-mentioned steps (1) are together with benzene sulfonic acid
It is put into deionized water, stirring to dissolving, and spherical chlorite mesoporous composite material C1 and the weight ratio of benzene sulfonic acid are 50:50,
Deionized water is 25 with the mol ratio of benzene sulfonic acid:1, it is spray-dried under being 12000r/min in rotating speed at 200 DEG C, loaded
Type catalyst Cat-1.
The support type benzene sulfonic acid catalyst is entered with XRD, ESEM and U.S.'s Kang Ta companies Atsorb-1 types instrument
Row is characterized.
Fig. 1 is X-ray diffracting spectrum, is the XRD spectra of spherical chlorite mesoporous composite material C1.By going out in XRD spectra
Existing low-angle spectral peak understands that spherical chlorite mesoporous composite material C1 has orderly three-dimensional cubic duct structure and hexagonal hole
Road structure.
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of spherical chlorite mesoporous composite material C1.As seen from the figure, it is spherical
The microscopic appearance of chlorite mesoporous composite material C1 is Mesoporous Spheres that particle diameter is 50 μm.
Fig. 3 is spherical chlorite mesoporous composite material C1 pore size distribution curves.
The pore structure parameter of spherical chlorite mesoporous composite material C1 and loaded catalyst Cat-1 is as shown in table 1 below.
Table 1
| Sample | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) | |
| Composite C1 | 270 | 1.5 | 4,20 | 50 |
| Catalyst Cat-1 | 160 | 0.9 | 2.1,11 | 50 |
By the data of upper table 1 can be seen that spherical chlorite mesoporous composite material load benzene sulfonic acid after, specific surface area
Reduce with pore volume, this explanation benzene sulfonic acid during load-reaction enters into spherical chlorite mesoporous composite material
It is internal.
Comparative example 1
Method according to embodiment 1 prepares spherical chlorite mesoporous composite material and loaded catalyst, different,
Chlorite is added without during preparing the mesoporous composite material as carrier, so as to mesoporous composite material D1 be obtained respectively and bear
Supported catalyst Cat-D-1.
Comparative example 2
Method according to embodiment 1 prepares spherical chlorite mesoporous composite material and loaded catalyst, different,
During preparing loaded catalyst, (Jilin University's high-tech is purchased from the bar-shaped mesoporous silicon oxide SBA-15 of identical weight
Skill limited company) replace the filter cake X1 and filter cake Y1, so as to mesoporous composite material D2 and support type be obtained respectively
Catalyst Cat-D-2.
Embodiment 2
The present embodiment be used for illustrate spherical chlorite mesoporous composite material of the invention and loaded catalyst and they
Preparation method.
Method according to embodiment 1 prepares spherical chlorite mesoporous composite material and loaded catalyst, different,
The step of not being spray-dried during preparing loaded catalyst, and benzene sulfonic acid is supported on ball by the method only by impregnating
On shape chlorite mesoporous composite material, so as to loaded catalyst Cat-2 is obtained.
Embodiment 3
The present embodiment be used for illustrate spherical chlorite mesoporous composite material of the invention and loaded catalyst and they
Preparation method.
(1) spherical chlorite mesoporous composite material is prepared
6g (0.001mol) triblock copolymer surfactant P123 is dissolved in the hydrochloric acid that 10ml, pH value are 5 water-soluble
In liquid and 220ml deionized water solutions, stirring 4h to P123 dissolvings form clear solution, then add in the clear solution
4.5g (0.06mol) n-butanols simultaneously stir 1h, are subsequently placed in 40 DEG C of water-bath, and 10.4g (0.05mol) tetraethyl orthosilicate is slow
Slowly be added drop-wise in the solution, keep the temperature at about 60 DEG C, pH value be to stir 48h under conditions of 5.5, the then water at 80 DEG C again
Heat treatment 20h, then carry out filtering and and be washed with deionized 4 times, then suction filtration obtains Jie with three-dimensional cubic duct
The filter cake X3 of porous molecular sieve material.
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is 1.0g, the ammonia and water in tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor
Mol ratio is 1：0.2：3.5：120, and 48h is stirred at 60 DEG C, then the hydro-thermal process 20h at 80 DEG C again, was then carried out
Filter and and be washed with deionized 4 times, then suction filtration obtains the filter cake Y3 of the meso-porous molecular sieve material with hexagonal hole road structure.
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 cake B3 and 8g chlorite of above-mentioned preparation is 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.Closing ball grinder, temperature is ball milling 0.5 hour at 80 DEG C in the ball grinder, obtains 38g solid powders；Will
The solid powder is dissolved in 12 grams of deionized waters, is spray-dried under being 11000r/min in rotating speed at 250 DEG C；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 chlorite mesoporous
Composite C3.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical chlorite mesoporous composite material C3 of 35g that will be prepared in above-mentioned steps (1) are together with benzene sulfonic acid
It is put into deionized water, stirring to dissolving, and spherical chlorite mesoporous composite material C3 and the weight ratio of benzene sulfonic acid are 95:5, go
Ionized water is 25 with the mol ratio of benzene sulfonic acid:1, it is spray-dried under being 13000r/min in rotating speed at 150 DEG C, obtain support type
Catalyst Cat-3.
The pore structure parameter of spherical chlorite mesoporous composite material C3 and loaded catalyst Cat-3 is as shown in table 2 below.
Table 2
| Sample | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) | |
| Composite C3 | 200 | 1.2 | 3,22 | 45 |
| Catalyst Cat-3 | 185 | 1.0 | 2.0,18 | 46 |
By the data of upper table 2 can be seen that spherical chlorite mesoporous composite material load benzene sulfonic acid after, specific surface area
Reduce with pore volume, this explanation benzene sulfonic acid during load-reaction enters into spherical chlorite mesoporous composite material
It is internal.
Embodiment 4
The present embodiment be used for illustrate spherical chlorite mesoporous composite material of the invention and loaded catalyst and they
Preparation method.
(1) spherical chlorite mesoporous composite material is prepared
By 6g (0.001mol) triblock copolymer surfactant P123 be dissolved in hydrochloric acid that 10ml, pH value are 3 and
In 220ml deionized water solutions, stirring 4h to P123 dissolvings form clear solution, then to adding 6.75g in the clear solution
(0.09mol) n-butanol simultaneously stirs 1h, is subsequently placed in 30 DEG C of water-bath, and 15.6g (0.075mol) tetraethyl orthosilicate is slow
Be added drop-wise in the solution, keep the temperature at about 40 DEG C, pH value be to stir 72h under conditions of 3.5, the then hydro-thermal at 40 DEG C again
Treatment 40h, then carry out filtering and and be washed with deionized 4 times, then suction filtration is obtained with the mesoporous of three-dimensional cubic duct
The filter cake X4 of molecular screen material.
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %, its
In, the addition of tetraethyl orthosilicate is 1.0g, the ammonia and water in tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammoniacal liquor
Mol ratio is 1：0.5：1.5：180, and 72h is stirred at 40 DEG C, then the hydro-thermal process 40h at 40 DEG C again, was then carried out
Filter and and be washed with deionized 4 times, then suction filtration obtains the filter cake Y4 of the meso-porous molecular sieve material with hexagonal hole road structure.
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 cake B4 and 5g chlorite of above-mentioned preparation is 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.Closing ball grinder, temperature is ball milling 10 hours at 40 DEG C in the ball grinder, obtains 55g solid powders；Should
Solid powder is dissolved in 30 grams of deionized waters, is spray-dried under being 13000r/min in rotating speed at 150 DEG C；Will spray drying
The product for obtaining afterwards is calcined 70 hours in Muffle furnace at 450 DEG C, and removed template method obtains 53 grams of spherical chlorite mesoporous multiple
Condensation material C4.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical chlorite mesoporous composite material C4 of 53g that will be prepared in above-mentioned steps (1) are together with benzene sulfonic acid
It is put into deionized water, stirring to dissolving, and spherical chlorite mesoporous composite material C4 and the weight ratio of benzene sulfonic acid are 85:15,
Deionized water is 25 with the mol ratio of benzene sulfonic acid:1, it is spray-dried under being 11000r/min in rotating speed at 250 DEG C, loaded
Type catalyst Cat-4.
The pore structure parameter of spherical chlorite mesoporous composite material C4 and loaded catalyst Cat-4 is as shown in table 3 below.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C4 | 270 | 1.2 | 2.5,20 | 49 |
| Catalyst Cat-4 | 176 | 0.9 | 1.9,18 | 48 |
By the data of upper table 3 can be seen that spherical chlorite mesoporous composite material load benzene sulfonic acid after, specific surface area
Reduce with pore volume, this explanation benzene sulfonic acid during load-reaction enters into spherical chlorite mesoporous composite material
It is internal.
Embodiment 5
The present embodiment is used for application and the cyclohexanone glycerol ketals of the loaded catalyst for illustrating present invention offer
Preparation method.
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, 100ml polytetrafluoroethyllining lining reactors are sequentially added with the hexamethylene of 5g cyclohexanone, 6g glycerine and 2.5g
In, at 100 DEG C, under reflux conditions, 0.5h is reacted, room temperature and centrifugation are subsequently cooled to, solid catalyst Cat-1 exists
It is vacuum dried 6 hours at 150 DEG C, after being cooled to room temperature, is recycled after recovery.Using gas chromatographic analysis reaction product liquid into
Point, and by calculating, cyclohexanone conversion ratio is 99.9%, the selectivity of cyclohexanone glycerol ketals is 100%, and yield is
100%.
Embodiment 6-8 and comparative example 3-4
Method according to embodiment 5 prepares cyclohexanone glycerol ketals, except that, respectively with embodiment 2-4 and contrast
Loaded catalyst prepared by example 1-2 replaces the loaded catalyst Cat-1.As a result, the cyclohexanone being each calculated
The selective data of conversion ratio and cyclohexanone glycerol ketals is as shown in table 4 below.
Table 4
Embodiment 9-12 and comparative example 5-6
Method according to embodiment 5 prepares cyclohexanone glycerol ketals, except that, respectively with from embodiment 5-8 and right
The catalyst that ratio 3-4 is reclaimed replaces the loaded catalyst Cat-1.As a result, the conversion of the cyclohexanone being each calculated
The selective data of rate and cyclohexanone glycerol ketals is as shown in table 5 below.
Table 5
Be can be seen that using the spherical chlorite mesoporous composite material conduct of the invention by the data of above-mentioned table 4 and 5
The loaded catalyst that carrier is made can significantly improve the conversion ratio of reaction raw materials during ketal reaction.And, when logical
When the method for crossing spray drying prepares the loaded catalyst, the loaded catalyst may be repeated utilization, and
Reaction raw materials conversion ratio higher still can be obtained during recycling.
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 chlorite mesoporous composite material, it is characterised in that the spherical chlorite mesoporous composite material contains green
Mudstone, the meso-porous molecular sieve material with three-dimensional cubic duct structure and the meso-porous molecular sieve material with hexagonal hole road structure,
And the average grain diameter of the spherical chlorite mesoporous composite material be 20-50 micron, specific surface area for 150-600 square metres/
Gram, pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal the first most probable pore size and second corresponding respectively is most
Can several apertures, first most probable pore size is less than second most probable pore size, and first most probable pore size is received for 2-5
Rice, second most probable pore size is 5-25 nanometers.
2. composite according to claim 1, wherein, relative to having three-dimensional cubic duct described in 100 weight portions
The total amount of the meso-porous molecular sieve material of structure and the meso-porous molecular sieve material with hexagonal hole road structure, the chlorite
Content is 1-50 weight portions；The meso-porous molecular sieve material with three-dimensional cubic duct structure is with described with hexagonal hole road knot
The weight ratio of the meso-porous molecular sieve material of structure is 1：0.1-10.
3. composite according to claim 2, wherein, relative to having three-dimensional cubic duct described in 100 weight portions
The total amount of the meso-porous molecular sieve material of structure and the meso-porous molecular sieve material with hexagonal hole road structure, the chlorite
Content is 20-50 weight portions；The meso-porous molecular sieve material with three-dimensional cubic duct structure is with described with hexagonal hole road
The weight ratio of the meso-porous molecular sieve material of structure is 1：0.5-2.
4. a kind of method for preparing spherical chlorite mesoporous composite material, the method is comprised the following steps：
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure is provided or is prepared with three-dimensional cubic duct structure
The filter cake of meso-porous molecular sieve material, as component a1；
(2) meso-porous molecular sieve material with hexagonal hole road structure is provided or the mesoporous molecular with hexagonal hole road structure is prepared
The filter cake of material is sieved, 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 and chlorite are mixed and ball milling, and will be obtained after ball milling
Solid 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 grain diameter of the spherical chlorite mesoporous composite material is 20-
50 microns, specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and double
Peak corresponds to the first most probable pore size and the second most probable pore size respectively, and first most probable pore size is less than second most probable
Aperture, and first most probable pore size is 2-5 nanometers, second most probable pore size is 5-25 nanometers.
5. method according to claim 4, wherein, in step (4), relative to 100 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 chlorite is 1-50 weight portions；
The weight ratio of the consumption of the component a1 and the component a2 is 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 chlorite is 20-50 weight
Part；The weight ratio of the consumption of the component a1 and the component a2 is 1：0.5-2.
7. method according to claim 4, wherein, in step (1), prepare mesoporous with three-dimensional cubic duct structure
The process of the filter cake of molecular screen material includes：In the presence of template and butanol, tetraethyl orthosilicate is contacted with sour agent,
And the mixture that will be obtained after contact carries out crystallization and filtering.
8. method according to claim 7, wherein, the mol ratio of the template, butanol and tetraethyl orthosilicate is 1：10-
100：10-90.
9. method according to claim 8, wherein, the mol ratio of the template, butanol and tetraethyl orthosilicate is 1：60-
90：50-75.
10. the method according to any one in claim 7-9, wherein, the template is triblock copolymer polyoxy
Ethene-polyoxypropylene polyoxyethylene；The sour agent is hydrochloric acid；The condition that tetraethyl orthosilicate is contacted with the sour agent includes：Temperature
It it is 10-60 DEG C, the time is 10-72 hours, and pH value is 1-7；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is
10-72 hours.
11. methods according to claim 4, wherein, in step (2), prepare mesoporous point with hexagonal hole road structure
The process of the filter cake of son sieve material includes：By tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia haptoreaction, and will connect
Touching the mixture obtained after reaction carries out crystallization and filtering.
12. methods according to claim 11, wherein, tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia rub
You are than being 1：0.1-1：0.1-5.
13. methods according to claim 12, wherein, tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia rub
You are than being 1：0.2-0.5：1.5-3.5.
14. method according to any one in claim 11-13, wherein, the catalytic condition includes：Temperature
It it is 25-100 DEG C, the time is 10-72 hours；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is 10-72 hours.
15. 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 any one in claim 4-6, wherein, the component a1 is with three-dimensional cubic duct
The filter cake of the meso-porous molecular sieve material of structure, the component a2 is the filter of the meso-porous molecular sieve material with hexagonal hole road structure
Cake, and the component b is the filter cake of silica gel, methods described also includes：After the spray-drying process of step (4), from spraying
Removed template method in the product being dried to obtain.
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 chlorite mesoporous composite material 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 chlorite mesoporous composite material 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 the spherical green mud described in any one in claim 1-3 and 20
Stone mesoporous composite material.
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.
A kind of 29. preparation methods of cyclohexanone glycerol ketals, the method includes：In the presence of a catalyst, in ketal reaction
Under the conditions of, cyclohexanone and glycerine are contacted, to obtain cyclohexanone glycerol ketals, it is characterised in that the catalyst will for right
Seek the loaded catalyst described in any one in 21-23 and 27.
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| CN108855197B (en) * | 2017-05-10 | 2019-09-27 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109382129B (en) * | 2017-08-07 | 2019-11-12 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109382131B (en) * | 2017-08-07 | 2019-11-12 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109382134B (en) * | 2017-08-07 | 2019-11-12 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109382133B (en) * | 2017-08-07 | 2019-11-12 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN110732342A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with chlorite composite material with three-dimensional cubic and hexagonal pore channel structure as carrier and preparation method and application thereof |
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| GB2474119A (en) * | 2009-09-28 | 2011-04-06 | China Petroleum & Chemical | A catalytic conversion process for producing more diesel and propylene |
| CN102049285B (en) * | 2010-11-10 | 2012-07-11 | 上海师范大学 | Multistage pore-structure molecular sieve catalyst and preparation method thereof |
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