CN105435850B - The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals - Google Patents
The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals Download PDFInfo
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Abstract
The present invention relates to a kind of spherical illite mesoporous composite material, the preparation method of the spherical illite mesoporous composite material, the spherical illite mesoporous composite material prepared by this method, loaded catalyst containing the spherical illite 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 illite mesoporous composite material contains illite and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture.The loaded catalyst being made using the spherical illite 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 illite mesoporous composite material, the preparation side of the spherical illite mesoporous composite material
Method, the spherical illite mesoporous composite material prepared by this method, the support type containing the spherical illite mesoporous composite material
Catalyst, a kind of method for preparing loaded catalyst, the loaded catalyst prepared by this 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 property.Generally, cyclohexanone glycerol ketals
It is made by glycerine and cyclohexanone by ketal reaction.The catalyst that traditional cyclohexanone and glycerol ketals are reacted is inorganic liquid
(such as sulfuric acid, hydrochloric acid, phosphoric acid), but because its corrosiveness is big, the side reaction of initiation is more, after reaction product separation complexity and
The defects such as liquid waste processing difficulty and cause it using being subject to certain restrictions.With attention journey of the whole world to Catalytic processes greenization
Degree increase, solid acid catalysis technique substitution liquid acid Catalytic processes are imperative.Research showed in recent years, some solid acids,
Lewis hydrochlorates, molecular sieve and ionic liquid etc. have good catalytic action to synthesizing cyclohexanone glycerol ketals.
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 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
There is provided a kind of spherical illite for being suitable as carrier is composite mesoporous for the relatively low defect of reaction raw materials conversion ratio during reactive ketone
Material, and the spherical illite mesoporous composite material preparation method, the spherical illite prepared by this method is composite mesoporous
Material, the loaded catalyst containing the spherical illite 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 after research by having found, with the distribution of one-dimensional channels diplopore
Illite is introduced in the meso-porous molecular sieve material of structure, illite is entered in the duct of meso-porous molecular sieve material, and should
Is not susceptible to reunite spherical is made in mesoporous composite material, can so retain the high-specific surface area, big of meso-porous molecular sieve material
Pore volume, large aperture and the features such as with one-dimensional channels diplopore distributed architecture, can reduce the reunion of meso-porous molecular sieve material, increase again
Plus its mobility so that the loaded catalyst being made of the mesoporous composite material can obtain bright when for ketal reaction
The aobvious reaction raw materials conversion ratio improved, so as to complete the present invention.
Therefore, the invention provides a kind of spherical illite mesoporous composite material, wherein, the spherical illite is composite mesoporous
Material contains illite and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and the spherical illite is mesoporous
The average grain diameter of composite be 30-60 micron, specific surface area be 150-600 meters squared per grams, pore volume for 0.5-1.5 milliliters/
Gram, aperture is in bimodal distribution, and bimodal corresponds to the first most probable pore size and the second most probable pore size, first most probable respectively
Aperture is less than second most probable pore size, and first most probable pore size is 1-15 nanometers, second most probable pore size
For 10-40 nanometers.
Present invention also offers a kind of method for preparing spherical illite mesoporous composite material, this method includes following step
Suddenly：
(1) meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture is provided or preparing has one-dimensional channels double
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, is used as component a；
(2) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(3) the component a, the component b and illite are mixed and ball milling, and by the solid powder obtained after ball milling
Water slurrying is used at end, is then spray-dried obtained slurry；
Wherein, the component a causes the average grain diameter of the spherical illite mesoporous composite material to be 30-60 microns, than
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 is corresponded to respectively
First most probable pore size and the second most probable pore size, first most probable pore size are less than second most probable pore size, and institute
It is 1-15 nanometers to state the first most probable pore size, and second most probable pore size is 10-40 nanometers.
Present invention also offers the spherical illite 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 illite 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 Erie according to the present 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, this 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
For the above-mentioned loaded catalyst according to the present invention.
Spherical illite mesoporous composite material according to the present invention, is combined with one-dimensional channels diplopore distributed architecture
Meso-porous molecular sieve material, the advantage of illite and ball type carrier so that the spherical illite mesoporous composite material is adapted to use
Make the carrier of loaded catalyst, be particularly suitable as the carrier of loaded catalyst used in ketal reaction.
In the loaded catalyst of the present invention, have as the spherical illite 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 catalytic activity is high, side reaction is few, post processing is simple etc., has the catalytic performance of acid again 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 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 illite mesoporous composite material according to the present invention；
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of spherical illite mesoporous composite material according to the present invention.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of spherical illite mesoporous composite material, wherein, the spherical illite mesoporous composite material
Meso-porous molecular sieve material containing illite and with one-dimensional channels diplopore distributed architecture, and the spherical illite is composite mesoporous
The average grain diameter of material is 30-60 microns, and specific surface area is 150-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g,
Aperture is in bimodal distribution, and bimodal corresponds to the first most probable pore size and the second most probable pore size, the first most probable hole respectively
Footpath is less than second most probable pore size, and first most probable pore size is 1-15 nanometers, and second most probable pore size is
10-40 nanometers.
Spherical illite mesoporous composite material according to the present invention has one-dimensional channels diplopore distributed architecture, its particle
Average grain diameter measured using laser fineness gage, specific surface area, pore volume and most probable pore size are surveyed according to nitrogen adsorption methods
.
Spherical illite mesoporous composite material according to the present invention, by by spherical illite mesoporous composite material
Particle size is controlled within above range, it can be ensured that the spherical illite mesoporous composite material is not susceptible to reunite, and
And be used as the loaded catalyst that carrier is made and can improve the reaction raw materials conversion ratio during ketal reaction.When described
When the specific surface area of spherical illite mesoporous composite material is less than 150 meters squared per grams and/or pore volume less than 0.5 ml/g,
Being used as the catalytic activity for the loaded catalyst that carrier is made can significantly reduce；When the spherical composite mesoporous material of illite
When the specific surface area of material is more than 600 meters squared per grams and/or pore volume and is more than 1.5 mls/g, be used as that carrier is made is negative
Supported catalyst is easily reunited 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 illite mesoporous composite material is 35-55 microns, specific surface area
For 180-600 meters squared per grams, pore volume is 0.8-1.2 mls/g, and first most probable pore size is 3-12 nanometers, described the
Two most probable pore sizes are 25-35 nanometers.
In the spherical illite mesoporous composite material, relative to described in 100 parts by weight have one-dimensional channels diplopore
The meso-porous molecular sieve material of distributed architecture, the illitic content can be 1-50 parts by weight, preferably 20-50 parts by weight.
In the present invention, the spherical illite 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 illite mesoporous composite material, by silicon
The silica component that glue is brought into as preparing raw material in the spherical illite mesoporous composite material finally prepared.Described spherical
In illite mesoporous composite material, relative to the mesoporous molecular described in 100 parts by weight with one-dimensional channels diplopore distributed architecture
Material is sieved, 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 channels diplopore distributed architecture can be normal for this area
The meso-porous molecular sieve material used is advised, and can be prepared according to the conventional method.
Present invention also offers a kind of method for preparing spherical illite mesoporous composite material, this method includes following step
Suddenly：
(1) meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture is provided or preparing has one-dimensional channels double
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, is used as component a；
(2) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(3) the component a, the component b and illite are mixed and ball milling, and by the solid powder obtained after ball milling
Water slurrying is used at end, is then spray-dried obtained slurry；
Wherein, the component a causes the average grain diameter of the spherical illite mesoporous composite material to be 30-60 microns, than
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 is corresponded to respectively
First most probable pore size and the second most probable pore size, first most probable pore size are less than second most probable pore size, and institute
It is 1-15 nanometers to state the first most probable pore size, and second most probable pore size is 10-40 nanometers.
In the preferred case, the component a causes the average grain diameter of the spherical illite mesoporous composite material to be 35-55
Micron, specific surface area is 180-600 meters squared per grams, and pore volume is 0.8-1.2 mls/g, and first most probable pore size is 3-
12 nanometers, second most probable pore size is 25-35 nanometers.
In step (1), the process of the filter cake of the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture is prepared
It can include：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, trimethylpentane and tetramethoxy-silicane mol ratio can be wider
In the range of change, as long as the filter cake of the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture can be formed,
Usually, the mol ratio of the template, ethanol, trimethylpentane and tetramethoxy-silicane can be 1：100-500：200-
500：50-200, preferably 1：200-400：250-400：70-150.
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), existing various method systems can also be passed through
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 material or mixture that the sour agent can be used for adjusting pH value for various routines are (such as molten
Liquid).The sour agent is preferably used in form of an aqueous solutions, and its pH value can be 1-6, preferably 3-5.It is highly preferred that the acid
Agent is the cushioning liquid of the acetic acid that pH value is 1-6 (more preferably 3-5) and sodium acetate.
The condition that tetramethoxy-silicane is contacted with sour agent can include：Temperature is 10-60 DEG C, and the time is 10-72 hours, pH
It is worth for 1-7.In order to be more beneficial for the uniform mixing between each material, the tetramethoxy-silicane is contacted preferably in stirring bar with sour agent
Carried out under part.The consumption of the sour agent is preferably so that the pH value of tetramethoxy-silicane and the haptoreaction system of sour agent is 1-7.
The condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.It is described under preferable case
The condition of crystallization includes：Temperature is 40-100 DEG C, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
During the filter cake of meso-porous molecular sieve material in above-mentioned preparation with one-dimensional channels diplopore 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
It is secondary), then carry out suction filtration.
In step (1), " providing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture " can be direct
Weigh or choose the product of the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture or prepare with one-dimensional
The meso-porous molecular sieve material of duct diplopore distributed architecture.The meso-porous molecular sieve material with one-dimensional channels diplopore 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 channels diplopore 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), 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 (2), " offer silica gel " can directly be weighed or choose silica gel product or prepare silica gel.
Preparing the method for silica gel can implement according to the conventional method, for example, can include：The filter cake of silica gel is prepared according to the above method,
Then by gained filtration cakes torrefaction.
It is above-mentioned prepare the filter cake of silica gel during, can be included with the process for obtaining filter cake by filtering：In filtering
Afterwards, it is 0.01-0.03 weight % with the content of distilled water cyclic washing to sodium ion, then carries out suction filtration.
In step (3), relative to the component a of 100 parts by weight consumption, the consumption of the component b can be 1-
200 parts by weight, preferably 50-150 parts by weight；The illitic consumption can be 1-50 parts by weight, preferably 20-50 weight
Part.
In step (3), 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 (3), 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 (3), 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 (3), when the filter that the component a is the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture
Cake, when the component b is the filter cake of silica gel, namely it is mesoporous with one-dimensional channels diplopore distributed architecture to prepare when step (1)
The process of the filter cake of molecular screen material, when step (2) is the process for the filter cake for preparing silica gel, the spherical illite is composite mesoporous
The preparation method of material can also include：After the spray drying of step (3), mould is removed in the product obtained from spray drying
Plate agent.The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80 hours.
Present invention also offers the spherical illite 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 illite 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 illite 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 a kind of preparation method of cyclohexanone glycerol ketals, this 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 provides 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
It can react and obtain cyclohexanone glycerol ketals, but in order to improve under the utilization rate of raw material, preferable case, cyclohexanone and sweet
The mol ratio of oil is 1：0.5-10.
In the preparation method of the cyclohexanone glycerol ketals, also there is no particular limitation for the consumption of the catalyst, can
Suitably to be determined according to conventional cyclohexanone glycerol ketals preparation technology.Under preferable case, relative to 100 parts by weight
Cyclohexanone, the consumption of the catalyst is 1-15 parts by weight, more preferably 2-14 parts by weight.
During the ketal reaction, in order to be more beneficial for the progress 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, and preferably 60-100 DEG C, the reaction time can be 1-20 hours, preferably 2-15 hours.
During the ketal reaction, in order to be conducive to the progress 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 wider scope, preferably
In the case of, relative to the cyclohexanone of 100 parts by weight, the consumption of the water entrainer is 30-100 parts by weight, more preferably 50-80 weights
Measure part.The water entrainer can be selected from the 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 being centrifugally separating to obtain is dried in vacuo into 1-24 hours at 25-200 DEG C, preferably
It is dried in vacuo 6-10 hours 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 purchased from German Bruker AXS companies
Carried out on D8Advance X-ray diffractometer；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on electron microscope；Pore structure parameter analysis inhales de- in the nitrogen of the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on attached instrument, wherein, before being tested, sample is deaerated 4 hours at 200 DEG C；The analysis of reaction product liquid phase ingredient exists
Carried out purchased from Agilent companies of Britain 7890A/5973N gas chromatograph-mass spectrometers.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio of cyclohexanone and the selectivity root of cyclohexanone glycerol ketals
Calculate and obtain according to below equation.
The use of the conversion ratio (%) of cyclohexanone=(content of cyclohexanone in consumption-reaction product of cyclohexanone) ÷ cyclohexanone
Amount × 100%
The actual production ÷ cyclohexanone glycerol ketals of selectivity (%)=cyclohexanone glycerol ketals of cyclohexanone glycerol ketals
Theoretical yield × 100%
Embodiment 1
The present embodiment be used for illustrate the present invention spherical illite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical illite 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 for 4 acetic acid and sodium acetate buffer in, stir to P123 and be completely dissolved at 15 DEG C, obtain backward it is molten
6g (0.053mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then adds 2.13g (0.014mol) tetramethyl thereto
TMOS, stirs 20h under conditions of 15 DEG C, pH value is 4.5, obtained solution then is transferred into polytetrafluoroethyllining lining
Reactor in, the crystallization 24h at 60 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is had
The filter cake A1 of the meso-porous molecular sieve material of one-dimensional channels diplopore 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.
10g filter cake A1,10g filter cake B1 and 2g illites 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 22g solid powders；The solid powder is molten
Solution is spray-dried in 19.8 grams of deionized waters at 200 DEG C in the case where rotating speed is 12000r/min；By what is obtained after spray drying
Product is calcined 24 hours in Muffle furnace at 500 DEG C, removed template method, and obtaining 20 grams has one-dimensional channels diplopore distributed architecture
Spherical illite mesoporous composite material C1.
(2) loaded catalyst is prepared
At 25 DEG C, by the spherical illite mesoporous composite material C1 of 20g prepared in above-mentioned steps (1) together with benzene sulfonic acid
It is put into deionized water, stirring to dissolving, and the weight ratio of spherical illite mesoporous composite material C1 and benzene sulfonic acid is 50:50,
Deionized water and the mol ratio of benzene sulfonic acid are 25:1, it is spray-dried, is loaded in the case where rotating speed is 12000r/min at 200 DEG C
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 spherical illite mesoporous composite material C1 XRD spectra.Go out in XRD spectra
Existing low-angle spectral peak understands that spherical illite mesoporous composite material C1 has one-dimensional channels diplopore specific to mesoporous material point
Cloth structure.
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of spherical illite mesoporous composite material C1 microscopic appearance.As seen from the figure, it is spherical
Illite mesoporous composite material C1 microscopic appearance is the Mesoporous Spheres that particle diameter is 30-60 μm.
Spherical illite mesoporous composite material C1 and loaded catalyst Cat-1 pore structure parameter are as shown in table 1 below.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C1 | 301 | 1.0 | 3,40 | 50 |
| Catalyst Cat-1 | 150 | 0.9 | 2,25 | 50 |
Spherical illite mesoporous composite material is after load benzene sulfonic acid it can be seen from the data of upper table 1, specific surface area
Reduce with pore volume, this explanation benzene sulfonic acid during load-reaction enters spherical illite mesoporous composite material
It is internal.
Comparative example 1
Spherical illite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different,
Illite is added without during preparing the mesoporous composite material as carrier, so that mesoporous composite material D1 is made respectively and negative
Supported catalyst Cat-D-1.
Comparative example 2
Spherical illite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is 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) instead of the filter cake A1 of the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, so that respectively
Mesoporous composite material D2 and loaded catalyst Cat-D-2 is made.
Embodiment 2
The present embodiment be used for illustrate the present invention spherical illite mesoporous composite material and loaded catalyst and they
Preparation method.
Spherical illite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different,
The step of not being spray-dried during preparing loaded catalyst, and benzene sulfonic acid is only supported on by ball by the method for dipping
On shape illite mesoporous composite material, so that loaded catalyst Cat-2 is made.
Embodiment 3
The present embodiment be used for illustrate the present invention spherical illite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical illite 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 for 5 acetic acid and sodium acetate buffer in, stir to P123 and be completely dissolved at 15 DEG C, obtain backward it is molten
9.12g (0.08mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then adds 3.04g (0.02mol) four thereto
Methoxy silane, stirs 15h under conditions of 25 DEG C, pH value is 5.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reactor of lining, the crystallization 30h at 100 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is obtained
The filter cake A3 of meso-porous molecular sieve material with one-dimensional channels diplopore 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.
20g filter cake A3,10g filter cake B3 and 10g illites 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 300r/
min.Ball grinder is closed, temperature is ball milling 0.5 hour at 80 DEG C in ball grinder, obtains 40g solid powders；By the solid powder
It is dissolved in 12 grams of deionized waters, is spray-dried at 250 DEG C in the case where rotating speed is 11000r/min；By what is obtained after spray drying
Product is calcined 15 hours in Muffle furnace at 550 DEG C, and removed template method obtains 38 grams of spherical illite mesoporous composite materials
C3。
(2) loaded catalyst is prepared
At 25 DEG C, by the spherical illite mesoporous composite material C3 of 38g prepared in above-mentioned steps (1) together with benzene sulfonic acid
It is put into deionized water, stirring to dissolving, and the weight ratio of spherical illite mesoporous composite material C3 and benzene sulfonic acid is 95:5, go
The mol ratio of ionized 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 support type
Catalyst Cat-3.
Spherical illite mesoporous composite material C3 and loaded catalyst Cat-3 pore structure parameter are as shown in table 2 below.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C3 | 257 | 1.3 | 3,25 | 59 |
| Catalyst Cat-3 | 220 | 1.2 | 1.1,22 | 58 |
Spherical illite mesoporous composite material is after load benzene sulfonic acid it can be seen from the data of upper table 2, specific surface area
Reduce with pore volume, this explanation benzene sulfonic acid during load-reaction enters spherical illite mesoporous composite material
It is internal.
Embodiment 4
The present embodiment be used for illustrate the present invention spherical illite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical illite 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 for 3 acetic acid and sodium acetate buffer in, stir to P123 and be completely dissolved at 15 DEG C, obtain backward it is molten
5.7g (0.05mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then adds 4.56g (0.03mol) tetramethyl thereto
TMOS, stirs 10h under conditions of 40 DEG C, pH value is 3.5, obtained solution then is transferred into polytetrafluoroethyllining lining
Reactor in, the crystallization 40h at 40 DEG C, then carry out filtering and and be washed with deionized 4 times, then suction filtration is had
The filter cake A4 of the meso-porous molecular sieve material of one-dimensional channels diplopore 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.
20g filter cake A4,30g filter cake B4 and 5g illites 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 500r/
min.Ball grinder is closed, temperature is ball milling 10 hours at 40 DEG C in ball grinder, obtains 55g solid powders；By the solid powder
It is dissolved in 30 grams of deionized waters, is spray-dried at 150 DEG C in the case where rotating speed is 13000r/min；By what is obtained after spray drying
Product is calcined 70 hours in Muffle furnace at 450 DEG C, and removed template method obtains 53 grams of spherical illite mesoporous composite materials
C4。
(2) loaded catalyst is prepared
At 25 DEG C, by the spherical illite mesoporous composite material C4 of 53g prepared in above-mentioned steps (1) together with benzene sulfonic acid
It is put into deionized water, stirring to dissolving, and the weight ratio of spherical illite mesoporous composite material C4 and benzene sulfonic acid is 85:15,
Deionized water and the mol ratio of benzene sulfonic acid are 25:1, it is spray-dried, is loaded in the case where rotating speed is 11000r/min at 250 DEG C
Type catalyst Cat-4.
Spherical illite 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 | 300 | 0.8 | 5,32 | 59 |
| Catalyst Cat-4 | 155 | 0.7 | 3,30 | 59 |
Spherical illite mesoporous composite material is after load benzene sulfonic acid it can be seen from the data of upper table 3, specific surface area
Reduce with pore volume, this explanation benzene sulfonic acid during load-reaction enters spherical illite mesoporous composite material
It is internal.
Embodiment 5
The present embodiment is used for application and the cyclohexanone glycerol ketals for illustrating the loaded catalyst that the present invention is provided
Preparation method.
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, 100ml polytetrafluoroethyllining lining reactors are sequentially placed into the hexamethylene of 5g cyclohexanone, 6g glycerine and 2.5g
In, at 100 DEG C, under reflux conditions, 0.5h is reacted, room temperature is subsequently cooled to and centrifuges, 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.Coordinated using gas chromatographic analysis reaction product liquid
Point, cyclohexanone conversion ratio is 99.9%, and cyclohexanone glycerol ketals are selectively 100%, and yield is 100%.
Embodiment 6-8 and comparative example 3-4
Cyclohexanone glycerol ketals are prepared according to the method for embodiment 5, 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, obtained cyclohexanone is each calculated
Conversion ratio and the selective data of cyclohexanone glycerol ketals are as shown in table 4 below.
Table 4
| Catalyst | The conversion ratio of cyclohexanone | The selectivity of cyclohexanone glycerol ketals | |
| Embodiment 5 | Cat-1 | 99.9% | 100% |
| Embodiment 6 | Cat-2 | 95.0% | 100% |
| Embodiment 7 | Cat-3 | 99.3% | 100% |
| Embodiment 8 | Cat-4 | 99.8% | 100% |
| Comparative example 3 | Cat-D-1 | 88.1% | 99% |
| Comparative example 4 | Cat-D-2 | 83.5% | 99% |
Embodiment 9-12 and comparative example 5-6
Cyclohexanone glycerol ketals are prepared according to the method for embodiment 5, 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 obtained cyclohexanone is each calculated
The selective data of rate and cyclohexanone glycerol ketals is as shown in table 5 below.
Table 5
Using the spherical illite mesoporous composite material conduct of the present invention it can be seen from 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.Moreover, when logical
When the method for crossing spray drying prepares the loaded catalyst, the loaded catalyst may be repeated utilization, and
The conversion ratio of higher reaction raw materials still 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 (25)
1. a kind of spherical illite mesoporous composite material, it is characterised in that the spherical illite mesoporous composite material contains Erie
Stone and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, illite enter the duct of meso-porous molecular sieve material
It is interior, and the spherical illite mesoporous composite material average grain diameter be 30-60 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 be less than second most probable pore size, and first most probable pore size be 1-15
Nanometer, second most probable pore size is 10-40 nanometers.
2. composite according to claim 1, wherein, relative to having one-dimensional channels diplopore described in 100 parts by weight
The meso-porous molecular sieve material of distributed architecture, the illitic content is 1-50 parts by weight.
3. composite according to claim 2, wherein, relative to having one-dimensional channels diplopore described in 100 parts by weight
The meso-porous molecular sieve material of distributed architecture, the illitic content is 20-50 parts by weight.
4. a kind of method for preparing spherical illite mesoporous composite material, this method comprises the following steps：
(1) providing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture or preparing has one-dimensional channels diplopore point
The filter cake of the meso-porous molecular sieve material of cloth structure, is used as component a；
(2) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(3) the component a, the component b and illite are mixed and ball milling, and the solid powder obtained after ball milling is used
Obtained slurry, is then spray-dried by water slurrying；
Wherein, the component a make it that the average grain diameter of the spherical illite mesoporous composite material is 30-60 microns, compares surface
Product be 150-600 meters squared per grams, pore volume be 0.5-1.5 mls/g, aperture be in bimodal distribution, and it is bimodal respectively correspond to first
Most probable pore size and the second most probable pore size, first most probable pore size are less than second most probable pore size, and described the
One most probable pore size is 1-15 nanometers, and second most probable pore size is 10-40 nanometers.
5. method according to claim 4, wherein, in step (3), relative to the component a of 100 parts by weight use
Amount, the consumption of the component b is 1-200 parts by weight；The illitic consumption is 1-50 parts by weight.
6. method according to claim 5, wherein, in step (3), relative to the component a of 100 parts by weight use
Amount, the consumption of the component b is 50-150 parts by weight；The illitic consumption is 20-50 parts by weight.
7. method according to claim 4, wherein, in step (1), prepare with one-dimensional channels diplopore distributed architecture
The process of the filter cake of meso-porous molecular sieve material includes：In the presence of template, trimethylpentane and ethanol, by tetramethoxy-silicane
Alkane 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, in step (2), 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.
12. method according to claim 11, 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.
13. the method according to any one in claim 4-7 and 11, wherein, in step (3), 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.
14. the method according to claim 4 or 5, wherein, the component a is with one-dimensional channels diplopore distributed architecture
The filter cake of meso-porous molecular sieve material, the component b is the filter cake of silica gel, and methods described also includes：Spray drying in step (3)
After process, removed template method in the product obtained from spray drying.
15. method according to claim 14, wherein, the condition of the removed template method includes：Temperature is 300-600
DEG C, the time is 10-80 hours.
16. the spherical illite mesoporous composite material prepared as the method described in any one in claim 4-15.
17. 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 illite mesoporous composite material described in any one in claim 1-3 and 16.
18. catalyst according to claim 17, 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 %.
19. catalyst according to claim 18, 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 %.
20. 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 Erie described in any one in claim 1-3 and 16
Stone mesoporous composite material.
21. method according to claim 20, 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 %.
22. method according to claim 21, 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 %.
23. the loaded catalyst prepared as the method described in any one in claim 20-22.
24. application of the loaded catalyst in claim 17-19 and 23 described in any one in ketal reaction.
25. a kind of preparation method of cyclohexanone glycerol ketals, this 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 17-19 and 23.
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