CN105214734A - 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 this spherical illite mesoporous composite material, the spherical illite mesoporous composite material prepared by the method, loaded catalyst containing this spherical illite mesoporous composite material, the preparation method of this loaded catalyst, the loaded catalyst prepared by the method, the application of this loaded catalyst in ketal reaction, and use the method preparing cyclohexanone glycerol ketals of this loaded catalyst, wherein, described spherical illite mesoporous composite material contains illite, there is the meso-porous molecular sieve material of three-dimensional cubic duct structure and there is the meso-porous molecular sieve material of hexagonal hole road structure.Adopt described spherical illite mesoporous composite material of the present invention can significantly improve the conversion ratio of reaction raw materials as the loaded catalyst that carrier is made in ketal reaction process.
Description
Technical field
The present invention relates to a kind of spherical illite mesoporous composite material, the preparation method of this spherical illite mesoporous composite material, the spherical illite mesoporous composite material prepared by the method, loaded catalyst containing this spherical illite mesoporous composite material, a kind of method preparing loaded catalyst, the loaded catalyst prepared by the method, the application of this loaded catalyst in ketal reaction, and use the method preparing cyclohexanone glycerol ketals of this loaded catalyst.
Background technology
Cyclohexanone glycerol ketals is the spices with delicate fragrance, flowers and trees perfume (or spice), and it is compared with carbonyls, has that lasting is lasting, abundant raw material source, production technology simple and the advantage such as stable chemical nature.Generally, cyclohexanone glycerol ketals is obtained by ketal reaction by glycerine and cyclohexanone.The catalyst of traditional cyclohexanone and glycerol ketals reaction is inorganic liquid (such as sulfuric acid, hydrochloric acid, phosphoric acid etc.), but defects such as because its corrosiveness is large, the side reaction of initiation is many, reaction afterproduct separate complex and liquid waste processing difficulty and cause its use to be subject to certain restrictions.Along with the whole world increases the attention degree of Catalytic processes greenization, it is imperative that solid acid catalysis technique replaces liquid acid Catalytic processes.Research in recent years shows, some solid acids, Lewis hydrochlorate, molecular sieve and ionic liquid etc. have good catalytic action to synthesizing cyclohexanone glycerol ketals.
In existing loaded catalyst, adopt conventional meso-porous molecular sieve material as carrier.It is orderly that meso-porous molecular sieve material has duct, aperture is adjustable, specific area and the advantage such as pore volume is larger, lot of advantages is shown in the preparation technology of the loaded catalyst making to adopt these meso-porous molecular sieve materials to make as carrier in organic catalytic reaction, such as, catalytic activity is high, side reaction is few, post processing is simple, but, large specific area and high pore volume make these meso-porous molecular sieve materials have stronger water suction, moisture absorption ability, thus these loaded catalysts can be caused to reunite in catalytic reaction process, and then reduce the conversion ratio of cyclohexanone glycerol ketals preparation technology cyclohexanone.
Summary of the invention
The object of the invention is to overcome the loaded catalyst defect that reaction raw materials conversion ratio is lower in ketal reaction process adopting existing meso-porous molecular sieve material to make, a kind of spherical illite mesoporous composite material being suitable as carrier is provided, and the preparation method of this spherical illite mesoporous composite material, the spherical illite mesoporous composite material prepared by the method, loaded catalyst containing this spherical illite mesoporous composite material, the preparation method of this loaded catalyst, the loaded catalyst prepared by the method, the application of this loaded catalyst in ketal reaction, and use this loaded catalyst to prepare the method for cyclohexanone glycerol ketals.
In order to achieve the above object, the present inventor is by finding after research, illite is introduced in the meso-porous molecular sieve material with three-dimensional cubic duct structure and the meso-porous molecular sieve material with hexagonal hole road structure, illite is made to enter in the duct of meso-porous molecular sieve material, and this mesoporous composite material is made the spherical of reunion not easily occurs, the high-specific surface area of meso-porous molecular sieve material can be retained like this, large pore volume, large aperture and there is the feature such as three-dimensional cubic duct structure and hexagonal hole road structure, the reunion of meso-porous molecular sieve material can be reduced again, increase its mobility, the loaded catalyst making to adopt this mesoporous composite material to make is for obtaining the reaction raw materials conversion ratio significantly improved during ketal reaction, thus complete the present invention.
For this reason, the invention provides a kind of spherical illite mesoporous composite material, wherein, this spherical illite mesoporous composite material contains illite, there is the meso-porous molecular sieve material of three-dimensional cubic duct structure and there is the meso-porous molecular sieve material of hexagonal hole road structure, and the average grain diameter of this spherical illite mesoporous composite material is 20-50 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference, second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-5 nanometer, described second most probable pore size is 5-25 nanometer.
Present invention also offers a kind of method preparing spherical illite mesoporous composite material, the method comprises the following steps:
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of three-dimensional cubic duct structure, as component a1;
(2) meso-porous molecular sieve material with hexagonal hole road structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure, as component a2;
(3) silica gel is provided or prepares the filter cake of silica gel, as components b;
(4) described component a1, described component a2, described components b and illite are carried out mixing and ball milling, and the pressed powder water slurrying will obtained after ball milling, then the slurry obtained is carried out spraying dry;
Wherein, described component a1 and described component a2 makes the average grain diameter of described spherical illite mesoporous composite material be 20-50 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-5 nanometer, described second most probable pore size is 5-25 nanometer.
Present invention also offers the spherical illite mesoporous composite material prepared by said method.
Present invention also offers a kind of loaded catalyst, this catalyst contains carrier and load benzene sulfonic acid on the carrier, and wherein, described carrier is spherical illite mesoporous composite material according to the present invention.
Present invention also offers a kind of method preparing loaded catalyst, the method comprises: carrier, benzene sulfonic acid and water are mixed, and the mixture obtained is carried out spraying dry, wherein, described carrier is spherical illite mesoporous composite material according to the present invention.
Present invention also offers the loaded catalyst prepared by said method.
Present invention also offers the application of above-mentioned loaded catalyst in ketal reaction.
Present invention also offers a kind of preparation method of cyclohexanone glycerol ketals, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclohexanone is contacted with glycerine, to obtain cyclohexanone glycerol ketals, wherein, described catalyst is according to above-mentioned loaded catalyst of the present invention.
Spherical illite mesoporous composite material according to the present invention, combine the advantage of the meso-porous molecular sieve material with three-dimensional cubic duct structure, the meso-porous molecular sieve material with hexagonal hole road structure, illite and ball type carrier, make this spherical illite mesoporous composite material be suitable as the carrier of loaded catalyst, be particularly suitable as the carrier of the loaded catalyst used in ketal reaction.
In described loaded catalyst of the present invention, spherical illite mesoporous composite material as carrier has the feature of the loose structure of meso-porous molecular sieve material, but also load has benzene sulfonic acid, this loaded catalyst had both been had, and the advantage of loaded catalyst is as high in catalytic activity, side reaction is few, post processing is simple, there is again the catalytic performance of acid, not only can not cause equipment corrosion when making this loaded catalyst in for ketal reaction process, but also the conversion ratio of reaction raw materials can be significantly improved.
In addition, when preparing described loaded catalyst by spray-dired method, described loaded catalyst can reuse, and still can obtain higher reaction raw materials conversion ratio in recycling process.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.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) photograph of the microscopic appearance of spherical illite mesoporous composite material according to the present invention.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of spherical illite mesoporous composite material, wherein, this spherical illite mesoporous composite material contains illite, there is the meso-porous molecular sieve material of three-dimensional cubic duct structure and there is the meso-porous molecular sieve material of hexagonal hole road structure, and the average grain diameter of this spherical illite mesoporous composite material is 20-50 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-5 nanometer, described second most probable pore size is 5-25 nanometer.
Spherical illite mesoporous composite material according to the present invention has three-dimensional cubic duct structure and hexagonal hole road structure simultaneously, the average grain diameter of its particle adopts laser fineness gage to record, and specific area, pore volume and most probable pore size record according to nitrogen adsorption methods.
Spherical illite mesoporous composite material according to the present invention, by the particle size of spherical illite mesoporous composite material is controlled within above-mentioned scope, can guarantee that described spherical illite mesoporous composite material is not easily reunited, and the reaction raw materials conversion ratio in ketal reaction process can be improved used as the loaded catalyst that carrier is made.When the specific area of described spherical illite mesoporous composite material is less than 150 meters squared per gram and/or pore volume is less than 0.5 ml/g, the catalytic activity of the loaded catalyst made used as carrier can significantly reduce; When the specific area of described spherical illite mesoporous composite material is greater than 600 meters squared per gram and/or pore volume is greater than 1.5 mls/g, the loaded catalyst made used as carrier is easily reunited in ketal reaction process, thus affects the reaction raw materials conversion ratio in ketal reaction process.
In the preferred case, the average grain diameter of described spherical illite mesoporous composite material is 20-40 micron, and specific area is 210-600 meters squared per gram, and pore volume is 0.8-1.5 ml/g, and described first most probable pore size is 2-3 nanometer, described second most probable pore size is 10-24 nanometer.
In described spherical illite mesoporous composite material, relative to having the meso-porous molecular sieve material of three-dimensional cubic duct structure and the described total amount with the meso-porous molecular sieve material of hexagonal hole road structure described in 100 weight portions, described illitic content can be 1-50 weight portion, is preferably 20-50 weight portion; Described there is three-dimensional cubic duct structure meso-porous molecular sieve material and the described weight ratio with the meso-porous molecular sieve material of hexagonal hole road structure can be 1:0.1-10, be preferably 1:0.5-2.
In the present invention, described spherical illite mesoporous composite material can also containing the silica introduced by silica gel." silica introduced by silica gel " refers in the preparation process of described spherical illite mesoporous composite material, to be brought into the silica component in the spherical illite mesoporous composite material of final preparation by silica gel as raw materials.In described spherical illite mesoporous composite material, relative to having the meso-porous molecular sieve material of three-dimensional cubic duct structure and the described total amount with the meso-porous molecular sieve material of hexagonal hole road structure described in 100 weight portions, the content of the described silica introduced by silica gel can be 1-200 weight portion, is preferably 50-150 weight portion.
In the present invention, described there is three-dimensional cubic duct structure meso-porous molecular sieve material and the described meso-porous molecular sieve material with the hexagonal hole road structure meso-porous molecular sieve material that can use for this area routine separately, and can to prepare according to the method for routine separately.
Present invention also offers a kind of method preparing spherical illite mesoporous composite material, the method comprises the following steps:
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of three-dimensional cubic duct structure, as component a1;
(2) meso-porous molecular sieve material with hexagonal hole road structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure, as component a2;
(3) silica gel is provided or prepares the filter cake of silica gel, as components b;
(4) described component a1, described component a2, described components b and illite are carried out mixing and ball milling, and the pressed powder water slurrying will obtained after ball milling, then the slurry obtained is carried out spraying dry;
Wherein, described component a1 and described component a2 makes the average grain diameter of described spherical illite mesoporous composite material be 20-50 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference, the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-5 nanometer, described second most probable pore size is 5-25 nanometer.
In the preferred case, described component a1 and described component a2 makes the average grain diameter of described spherical illite mesoporous composite material be 20-40 micron, specific area is 210-600 meters squared per gram, pore volume is 0.8-1.5 ml/g, and described first most probable pore size is 2-3 nanometer, described second most probable pore size is 10-24 nanometer.
In step (1), the process that preparation has a filter cake of the meso-porous molecular sieve material of three-dimensional cubic duct structure can comprise: under the existence of template and butanols, ethyl orthosilicate is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
According to the present invention, the mol ratio of described template, butanols and ethyl orthosilicate can change in wider scope, as long as the meso-porous molecular sieve material filter cake with three-dimensional cubic duct structure can be formed, usually, the mol ratio of the consumption of described template, butanols and ethyl orthosilicate can be 1:10-100:10-90, is preferably 1:60-90:50-75.
According to the present invention, described template can be the various templates that this area routine uses.Most preferably, described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, this template can be commercially available (such as, can available from Aldrich Co, commodity are called P123, and molecular formula is EO
20pO
70eO
20), also can be prepared by existing various method.When described template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of described template calculates according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene and obtains.
According to the present invention, described sour agent can be material or the mixture (as solution) that various routine may be used for adjust ph.Preferably, described sour agent is hydrochloric acid.Hydrochloric acid as sour agent preferably uses in form of an aqueous solutions.The pH value of aqueous hydrochloric acid solution can be 1-6.
According to the present invention, described butanols is preferably n-butanol.
The present invention does not limit especially to the condition that described ethyl orthosilicate contacts with sour agent, and such as, the condition that ethyl orthosilicate contacts with sour agent can comprise: temperature is 10-60 DEG C, and the time is 10-72 hour, and pH value is 1-7.In order to more be conducive to the Homogeneous phase mixing between each material, described ethyl orthosilicate contacts with sour agent and preferably carries out under agitation.The consumption of described sour agent preferably makes the pH value of the haptoreaction system of ethyl orthosilicate and sour agent be 1-7.
To the condition of described crystallization, there is no particular limitation in the present invention, and the condition of described crystallization can be the selection of this area routine, and such as, the condition of described crystallization can comprise: temperature is 30-150 DEG C, and the time is 10-72 hour.Under preferable case, the condition of described crystallization comprises: temperature is 40-100 DEG C, and the time is 20-40 hour.Described crystallization is implemented by hydrothermal crystallization method.
Have in the process of the filter cake of the meso-porous molecular sieve material in three-dimensional cubic duct in above-mentioned preparation, can comprise with the process obtaining filter cake by filtering: after filtration, with deionized water cyclic washing (washing times can be 2-10 time), then carry out suction filtration.
In step (1), " providing the meso-porous molecular sieve material with three-dimensional cubic duct structure " can be the product directly taking or choose the meso-porous molecular sieve material with three-dimensional cubic duct structure, also can be the meso-porous molecular sieve material that preparation has three-dimensional cubic duct structure.The described preparation method with the meso-porous molecular sieve material of three-dimensional cubic duct structure can implement according to the method for routine, such as, its preparation method can comprise: the filter cake according to said method preparation with the meso-porous molecular sieve material of three-dimensional cubic duct structure, then by gained filtration cakes torrefaction, and by the template removal in the product that obtains after drying.The condition of described removed template method can comprise: temperature is 300-600 DEG C, and the time is 10-80 hour.
The process in step (2) preparation with the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure can comprise: by ethyl orthosilicate, softex kw and ammonia haptoreaction, and the mixture obtained after haptoreaction is carried out crystallization and filtration.
According to the present invention, the mol ratio of described ethyl orthosilicate, softex kw and ammonia can change in wider scope, as long as the meso-porous molecular sieve material filter cake with hexagonal hole road structure can be formed, usually, the mol ratio of ethyl orthosilicate, softex kw and ammonia can be 1:0.1-1:0.1-5, is preferably 1:0.2-0.5:1.5-3.5.
According to the present invention, ammonia preferably adds with the form of ammoniacal liquor.
According to the present invention, the haptoreaction process of ethyl orthosilicate, softex kw and ammonia is carried out in presence of water.Preferably, part water is introduced with the form of ammoniacal liquor, and part water adds with the form of deionized water.In the haptoreaction system of ethyl orthosilicate, softex kw and ammonia, the mol ratio of ethyl orthosilicate and water can be 1:100-200, is preferably 1:120-180.
According to the present invention, there is no particular limitation for the catalytic condition of ethyl orthosilicate, softex kw and ammonia, as long as the meso-porous molecular sieve material filter cake with hexagonal hole road structure can be formed, usually, the catalytic condition of ethyl orthosilicate, softex kw and ammonia can comprise: temperature is 25-100 DEG C, and the time is 10-72 hour.Preferably, this haptoreaction is under agitation carried out, and is beneficial to the Homogeneous phase mixing between each material.
According to the present invention, to the condition of described crystallization, there is no particular limitation in the present invention, and the condition of described crystallization can be the selection of this area routine, and such as, the condition of described crystallization can comprise: temperature is 30-150 DEG C, and the time is 10-72 hour.Under preferable case, the condition of described crystallization comprises: temperature is 40-100 DEG C, and the time is 20-40 hour.Described crystallization is implemented by hydrothermal crystallization method.
Have in the process of the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure in above-mentioned preparation, can comprise with the process obtaining filter cake by filtering: after filtration, with deionized water cyclic washing (washing times can be 2-10 time), then carry out suction filtration.
In step (2), " providing the meso-porous molecular sieve material with hexagonal hole road structure " can be the product directly taking or choose the meso-porous molecular sieve material with hexagonal hole road structure, also can be the meso-porous molecular sieve material that preparation has hexagonal hole road structure.The described preparation method with the meso-porous molecular sieve material of hexagonal hole road structure can implement according to the method for routine, such as, its preparation method can comprise: the filter cake according to said method preparation with the meso-porous molecular sieve material of hexagonal hole road structure, then by gained filtration cakes torrefaction.
In step (3), the process preparing the filter cake of silica gel can comprise: contacted with inorganic acid by waterglass, and is filtered by the mixture obtained after contact.
According to the present invention, there is no particular limitation for the condition that waterglass contacts with inorganic acid, suitably can determine according in the common process preparing silica gel.Under preferable case, the condition that waterglass contacts with inorganic acid can comprise: temperature is 10-60 DEG C, is preferably 20-40 DEG C; Time is 1-5 hour, is preferably 1.5-3 hour; PH value is 2-4.In order to more be conducive to the Homogeneous phase mixing between each material, waterglass and the catalytic process of inorganic acid are preferably carried out under agitation.
Described waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 % by weight, is preferably 12-30 % by weight.
According to the present invention, described inorganic acid can be the various inorganic acids that this area routine uses, and such as, can be at least one in sulfuric acid, nitric acid and hydrochloric acid.Described inorganic acid can use in pure form, also can use with the form of its aqueous solution.The consumption of described inorganic acid preferably makes the pH value of the haptoreaction system of waterglass and inorganic acid be 2-4.
In step (3), " providing silica gel " can be directly take or choose silica gel product, also can be prepare silica gel.The method preparing silica gel can be implemented according to the method for routine, such as, can comprise: the filter cake preparing silica gel according to said method, then by gained filtration cakes torrefaction.
Prepare in the process of the filter cake of silica gel above-mentioned, can comprise with the process obtaining filter cake by filtering: after filtration, being 0.01-0.03 % by weight with distilled water cyclic washing to the content of sodium ion, then carrying out suction filtration.
In step (4), relative to the described component a1 of 100 weight portions and total consumption of described component a2, the consumption of described components b can be 1-200 weight portion, is preferably 50-150 weight portion; Described illitic consumption can be 1-50 weight portion, is preferably 20-50 weight portion; The weight ratio of the consumption of described component a1 and described component a2 can be 1:0.1-10, is preferably 1:0.5-2.
In step (4), described ball milling can carry out in ball mill, and in described ball mill, the inwall of ball grinder is preferably polytetrafluoroethyllining lining, and the diameter of the abrading-ball in ball mill can be 2-3mm; The quantity of abrading-ball reasonably can be selected according to the size of ball grinder, is the ball grinder of 50-150ml for size, usually can use 1 abrading-ball; The material of described abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., is preferably agate.The condition of described ball milling can comprise: the rotating speed of abrading-ball can be 300-500r/min, and the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hour.
In step (4), the process of the pressed powder water slurrying obtained after ball milling can be carried out at 25-60 DEG C.In pulping process, the weight ratio of the consumption of pressed powder and water can be 1:0.1-2, is preferably 1:0.3-0.9.
In step (4), described spraying dry can be implemented according to the mode of routine, such as, can carry out in atomizer.Described spray-dired condition can comprise: temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min; Under preferable case, described spray-dired condition comprises: temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min.
In step (4), when the filter cake that described component a1 is the meso-porous molecular sieve material with three-dimensional cubic duct structure, described component a2 is the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure, and described components b is when being the filter cake of silica gel, also namely when step (1) is the process that preparation has the filter cake of the meso-porous molecular sieve material of three-dimensional cubic duct structure, step (2) is the process that preparation has the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure, when step (3) is for preparing the process of the filter cake of silica gel, the preparation method of described spherical illite mesoporous composite material can also comprise: after the spraying dry of step (4), removed template method from the product that spraying dry obtains.The condition of described removed template method can comprise: temperature is 300-600 DEG C, and the time is 10-80 hour.
Present invention also offers the spherical illite mesoporous composite material prepared by said method.
Present invention also offers a kind of loaded catalyst, this catalyst contains carrier and load benzene sulfonic acid on the carrier, and wherein, described carrier is above-mentioned spherical illite mesoporous composite material provided by the invention.
In described loaded catalyst, there is no particular limitation for the content of described carrier and benzene sulfonic acid, suitably can determine according to the loaded catalyst of this area routine, such as, with the gross weight of described loaded catalyst for benchmark, the content of benzene sulfonic acid can be 1-50 % by weight, is preferably 5-50 % by weight; The content of described carrier is 50-99 % by weight, is preferably 50-95 % by weight.
In the present invention, the various method preparations that described loaded catalyst can use according to this area routine, only need by benzene sulfonic acid load on the carrier.
In a preferred embodiment, can reuse to make the loaded catalyst of preparation, and in recycling process, still can obtain higher reaction raw materials conversion ratio, the method preparing loaded catalyst comprises: carrier, benzene sulfonic acid and water are mixed, and the mixture obtained is carried out spraying dry, wherein, described carrier is above-mentioned spherical illite mesoporous composite material provided by the invention.
Prepare in the process of loaded catalyst above-mentioned, with total consumption of described carrier and benzene sulfonic acid for benchmark, the consumption of benzene sulfonic acid can be 1-50 % by weight, is preferably 5-50 % by weight; The consumption of described carrier can be 50-99 % by weight, is preferably 50-95 % by weight.
Described spraying dry can be implemented according to the mode of routine, such as, can carry out in atomizer.Described spray-dired condition can comprise: temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min; Under preferable case, described spray-dired condition comprises: 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 the application of above-mentioned loaded catalyst in ketal reaction.
In addition, present invention also offers a kind of preparation method of cyclohexanone glycerol ketals, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclohexanone is contacted with glycerine, to obtain cyclohexanone glycerol ketals, wherein, described catalyst is above-mentioned loaded catalyst provided by the invention.
In the preparation method of described cyclohexanone glycerol ketals, there is no particular limitation for the consumption of cyclohexanone and glycerine, as long as can be obtained by reacting cyclohexanone glycerol ketals, but in order to improve the utilization rate of raw material, under preferable case, the mol ratio of cyclohexanone and glycerine is 1:0.5-10.
In the preparation method of described cyclohexanone glycerol ketals, there is no particular limitation for the consumption of described catalyst, suitably can determine according to the method preparing cyclohexanone glycerol ketals of routine.Under preferable case, relative to the cyclohexanone of 100 weight portions, the consumption of described catalyst is 1-15 weight portion, is more preferably 10-12 weight portion.
In described ketal reaction process, described reaction is preferably under reflux conditions carried out, that is, described reaction temperature is reflux temperature.Described reaction temperature can be 25-100 DEG C, is preferably 60-100 DEG C.Reaction time can be 0.5-24 hour, is preferably 0.5-12 hour.
In described ketal reaction process, in order to be conducive to the carrying out of ketal reaction, described reaction is preferably carried out under the existence of water entrainer.To the consumption of described water entrainer, there is no particular limitation in the present invention, can change in wider scope, and under preferable case, relative to the cyclohexanone of 100 weight portions, the consumption of described water entrainer is 30-100 weight portion, is more preferably 50-80 weight portion.Described water entrainer be selected from cyclohexane, benzinum, dimethylbenzene, toluene and benzene one or more, preferred cyclohexane.
The preparation method of described cyclohexanone glycerol ketals can also be included in after ketal reaction terminates, centrifugation is carried out to final reactant mixture, and the solid product that centrifugation is obtained vacuum drying 1-24 hour at 25-200 DEG C, preferably vacuum drying 6-10 hour at 50-150 DEG C, to reclaim catalyst.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene available from Aldrich Co, is abbreviated as P123, and molecular formula is EO20PO70EO20, is the material of 9003-11-6 in the registration number of U.S. chemical abstract, and mean molecule quantity is 5800.
In following examples and comparative example, X-ray diffraction analysis is that the X-ray diffractometer of D8Advance carries out in the model purchased from German BrukerAXS company; Scanning electron microscope analysis is that the SEM of XL-30 is carried out in the model of purchased from American FEI Co.; Pore structure parameter analysis is that the nitrogen adsorption desorption instrument of Autosorb-1 carries out in the model of purchased from American Kang Ta company, wherein, before testing, sample is degassed 4 hours at 200 DEG C; The analysis of product liquid phase ingredient is being carried out purchased from Britain Agilent company 7890A/5973N gas chromatograph-mass spectrometer.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio of cyclohexanone and the selective of cyclohexanone glycerol ketals obtain according to following formulae discovery.
Consumption × 100% of conversion ratio (%)=(content of the consumption-product cyclohexanone of cyclohexanone) ÷ cyclohexanone of cyclohexanone
Theoretical yield × 100% of the actual production ÷ cyclohexanone glycerol ketals of selective (%)=cyclohexanone glycerol ketals of cyclohexanone glycerol ketals
Embodiment 1
The present embodiment is for illustration of spherical illite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
(1) spherical illite mesoporous composite material is prepared
6g (0.001mol) triblock copolymer surfactant P123 is dissolved in 10ml, pH value be 4 aqueous hydrochloric acid solution and 220ml deionized water solution in, stir 4h to P123 to dissolve, form clear solution, in described clear solution, add 6g (0.08mol) n-butanol again and stir 1h, then the water-bath of 40 DEG C is placed in, 12.9g (0.062mol) ethyl orthosilicate is slowly added drop-wise in this solution, temperature is maintained at about 40 DEG C, pH value is stir 24h under the condition of 4.5, and then at 100 DEG C hydrothermal treatment consists 24h, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake X1 of the meso-porous molecular sieve material with three-dimensional cubic duct.
Softex kw and ethyl orthosilicate being joined concentration is in the ammonia spirit of 25 % by weight, wherein, the addition of ethyl orthosilicate is 1.0g, ammonia in ethyl orthosilicate, softex kw, ammoniacal liquor and the mol ratio of water are 1:0.37:2.8:142, and 24h is stirred at 80 DEG C, and then at 100 DEG C hydrothermal treatment consists 24h, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake Y1 of the meso-porous molecular sieve material with hexagonal hole road structure.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution with weight ratio be 5:1 carry out mixed be incorporated in 30 DEG C at haptoreaction 2 hours, then be the sulfuric acid adjusted to ph to 3 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B1 of silica gel.
5g filter cake X1,5g filter cake Y1,10g filter cake B1 of above-mentioned preparation is put into 100ml ball grinder together with 5g illite, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 1 hour at 60 DEG C, obtains 25g pressed powder; This pressed powder is dissolved in 22.5 grams of deionized waters, at 200 DEG C under rotating speed is 12000r/min spraying dry; Calcined 24 hours at 500 DEG C in Muffle furnace by the product obtained after spraying dry, removed template method, obtains 24 grams of spherical illite mesoporous composite material C1.
(2) loaded catalyst is prepared
At 25 DEG C, the 24g spherical illite mesoporous composite material C1 of preparation in above-mentioned steps (1) is put into deionized water together with benzene sulfonic acid, be stirred to dissolving, and the weight ratio of spherical illite mesoporous composite material C1 and benzene sulfonic acid is 50:50, the mol ratio of deionized water and benzene sulfonic acid is 25:1, at 200 DEG C under rotating speed is 12000r/min spraying dry, obtain loaded catalyst Cat-1.
With XRD, ESEM and U.S. Kang Ta company Atsorb-1 type instrument, this support type benzene sulfonic acid catalyst is characterized.
Fig. 1 is X-ray diffracting spectrum, is the XRD spectra of spherical illite mesoporous composite material C1.Compose peak from the low-angle occurred in XRD spectra, spherical illite 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) photograph of the microscopic appearance of spherical illite mesoporous composite material C1.As seen from the figure, the microscopic appearance of spherical illite mesoporous composite material C1 to be particle diameter the be Mesoporous Spheres of 50 μm.
The pore structure parameter of spherical illite mesoporous composite material C1 and loaded catalyst Cat-1 is as shown in table 1 below.
Table 1
| Sample | Specific area (m 2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C1 | 255 | 1.5 | 3，22 | 50 |
| Catalyst Cat-1 | 130 | 0.5 | 2，15 | 50 |
As can be seen from the data of upper table 1, spherical illite mesoporous composite material is after load benzene sulfonic acid, and specific area and pore volume reduce all to some extent, and this illustrates that benzene sulfonic acid enters into the inside of spherical illite mesoporous composite material in load-reaction process.
Comparative example 1
Spherical illite mesoporous composite material and loaded catalyst is prepared according to the method for embodiment 1, difference, be used as in preparation not add illite in the process of the mesoporous composite material of carrier, thus obtain mesoporous composite material D1 and loaded catalyst Cat-D-1 respectively.
Comparative example 2
Spherical illite mesoporous composite material and loaded catalyst is prepared according to the method for embodiment 1, difference, in the process preparing loaded catalyst, replace described filter cake X1 and described filter cake Y1 with the bar-shaped mesoporous silicon oxide SBA-15 (purchased from high-tech limited company of Jilin University) of identical weight, thus obtain mesoporous composite material D2 and loaded catalyst Cat-D-2 respectively.
Embodiment 2
The present embodiment is for illustration of spherical illite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
Spherical illite mesoporous composite material and loaded catalyst is prepared according to the method for embodiment 1, difference, spray-dired step is not had in the process preparing loaded catalyst, and by means of only the method for dipping by benzene sulfonic acid load on spherical illite mesoporous composite material, thus obtained loaded catalyst Cat-2.
Embodiment 3
The present embodiment is for illustration of spherical illite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
(1) spherical illite mesoporous composite material is prepared
6g (0.001mol) triblock copolymer surfactant P123 is dissolved in 10ml, pH value be 5 aqueous hydrochloric acid solution and 220ml deionized water solution in, stir 4h to P123 to dissolve, form clear solution, in described clear solution, add 4.5g (0.06mol) n-butanol again and stir 1h, then the water-bath of 40 DEG C is placed in, 10.4g (0.05mol) ethyl orthosilicate is slowly added drop-wise in this solution, temperature is maintained at about 60 DEG C, pH value is stir 48h under the condition of 5.5, and then at 80 DEG C hydrothermal treatment consists 20h, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake X3 of the meso-porous molecular sieve material with three-dimensional cubic duct.
Softex kw and ethyl orthosilicate being joined concentration is in the ammonia spirit of 25 % by weight, wherein, the addition of ethyl orthosilicate is 1.0g, ammonia in ethyl orthosilicate, softex kw, ammoniacal liquor and the mol ratio of water are 1:0.2:3.5:120, and 48h is stirred at 60 DEG C, and then at 80 DEG C hydrothermal treatment consists 20h, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake Y3 of the meso-porous molecular sieve material with hexagonal hole road structure.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution with weight ratio be 4:1 carry out mixed be incorporated in 40 DEG C at haptoreaction 1.5 hours, then be the sulfuric acid adjusted to ph to 2 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B3 of silica gel.
13g filter cake X3,7g filter cake Y3,10g filter cake B3 of above-mentioned preparation is put into 100ml ball grinder together with 8g illite, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 300r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 0.5 hour at 80 DEG C, obtains 38g pressed powder; This pressed powder is dissolved in 12 grams of deionized waters, at 250 DEG C under rotating speed is 11000r/min spraying dry; Calcined 15 hours at 550 DEG C in Muffle furnace by the product obtained after spraying dry, removed template method, obtains 35 grams of spherical illite mesoporous composite material C3.
(2) loaded catalyst is prepared
At 25 DEG C, the 35g spherical illite mesoporous composite material C3 of preparation in above-mentioned steps (1) is put into deionized water together with benzene sulfonic acid, be stirred to dissolving, and the weight ratio of spherical illite mesoporous composite material C3 and benzene sulfonic acid is 95:5, the mol ratio of deionized water and benzene sulfonic acid is 25:1, at 150 DEG C under rotating speed is 13000r/min spraying dry, obtain loaded catalyst Cat-3.
The pore structure parameter of spherical illite mesoporous composite material C3 and loaded catalyst Cat-3 is as shown in table 2 below.
Table 2
| Sample | Specific area (m 2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C3 | 211 | 1.1 | 3，23 | 45 |
| Catalyst Cat-3 | 180 | 1.0 | 2.0，18 | 46 |
As can be seen from the data of upper table 2, spherical illite mesoporous composite material is after load benzene sulfonic acid, and specific area and pore volume reduce all to some extent, and this illustrates that benzene sulfonic acid enters into the inside of spherical illite mesoporous composite material in load-reaction process.
Embodiment 4
The present embodiment is for illustration of spherical illite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
(1) spherical illite mesoporous composite material is prepared
6g (0.001mol) triblock copolymer surfactant P123 is dissolved in 10ml, pH value be 3 hydrochloric acid and 220ml deionized water solution in, stir 4h to P123 to dissolve, form clear solution, in described clear solution, add 6.75g (0.09mol) n-butanol again and stir 1h, then the water-bath of 30 DEG C is placed in, 15.6g (0.075mol) ethyl orthosilicate is slowly added drop-wise in this solution, temperature is maintained at about 40 DEG C, pH value is stir 72h under the condition of 3.5, and then at 40 DEG C hydrothermal treatment consists 40h, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake X4 of the meso-porous molecular sieve material with three-dimensional cubic duct.
Softex kw and ethyl orthosilicate being joined concentration is in the ammonia spirit of 25 % by weight, wherein, the addition of ethyl orthosilicate is 1.0g, ammonia in ethyl orthosilicate, softex kw, ammoniacal liquor and the mol ratio of water are 1:0.5:1.5:180, and 72h is stirred at 40 DEG C, and then at 40 DEG C hydrothermal treatment consists 40h, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake Y4 of the meso-porous molecular sieve material with hexagonal hole road structure.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution with weight ratio be 6:1 carry out mixed be incorporated in 20 DEG C at haptoreaction 3 hours, then be the sulfuric acid adjusted to ph to 4 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B4 of silica gel.
7g filter cake X4,13g filter cake Y4,30g filter cake B4 of above-mentioned preparation is put into 100ml ball grinder together with 5g illite, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 500r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 10 hours at 40 DEG C, obtains 55g pressed powder; This pressed powder is dissolved in 30 grams of deionized waters, at 150 DEG C under rotating speed is 13000r/min spraying dry; Calcined 70 hours at 450 DEG C in Muffle furnace by the product obtained after spraying dry, removed template method, obtains 33 grams of spherical illite mesoporous composite material C4.
(2) loaded catalyst is prepared
At 25 DEG C, the 20g spherical illite mesoporous composite material C4 of preparation in above-mentioned steps (1) is put into deionized water together with benzene sulfonic acid, be stirred to dissolving, and the weight ratio of spherical illite mesoporous composite material C4 and benzene sulfonic acid is 85:15, the mol ratio of deionized water and benzene sulfonic acid is 25:1, at 250 DEG C under rotating speed is 11000r/min spraying dry, obtain loaded catalyst Cat-4.
The pore structure parameter of spherical illite mesoporous composite material C4 and loaded catalyst Cat-4 is as shown in table 3 below.
Table 3
| Sample | Specific area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C4 | 256 | 1.1 | 2.0，19 | 40 |
| Catalyst Cat-4 | 175 | 0.9 | 1.8，17 | 40 |
As can be seen from the data of upper table 3, spherical illite mesoporous composite material is after load benzene sulfonic acid, and specific area and pore volume reduce all to some extent, and this illustrates that benzene sulfonic acid enters into the inside of spherical illite mesoporous composite material in load-reaction process.
Embodiment 5
The application of the present embodiment for illustration of described loaded catalyst provided by the invention and the preparation method of cyclohexanone glycerol ketals.
Loaded catalyst Cat-1 prepared by embodiment 1 vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 0.5 gram, add in 100ml polytetrafluoroethylene (PTFE) ethene liner reactor successively, at 100 DEG C with the cyclohexane of 5g cyclohexanone and 6g glycerine and 2.5g, under reflux conditions, reaction 0.5h, is then cooled to room temperature and centrifugation, solid catalyst Cat-1 vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, recycling after reclaiming.Utilize gas chromatographic analysis reaction product liquid composition, and by calculating, cyclohexanone conversion ratio 99.9%, selective 100% of cyclohexanone glycerol ketals, yield 100%.
Embodiment 6-8 and comparative example 3-4
Prepare cyclohexanone glycerol ketals according to the method for embodiment 5, difference is, replaces described loaded catalyst Cat-1 respectively with loaded catalyst prepared by embodiment 2-4 and comparative example 1-2.As a result, conversion ratio and the cyclohexanone glycerol ketals selective data of the cyclohexanone calculated separately are as shown in table 4 below.
Table 4
Embodiment 9-12 and comparative example 5-6
Prepare cyclohexanone glycerol ketals according to the method for embodiment 5, difference is, replaces described loaded catalyst Cat-1 respectively with the catalyst reclaimed from embodiment 5-8 and comparative example 3-4.As a result, conversion ratio and the cyclohexanone glycerol ketals selective data of the cyclohexanone calculated separately are as shown in table 5 below.
Table 5
As can be seen from above-mentioned table 4 and 5 data, adopt described spherical illite mesoporous composite material of the present invention can significantly improve the conversion ratio of reaction raw materials as the loaded catalyst that carrier is made in ketal reaction process.And when preparing described loaded catalyst by spray-dired method, described loaded catalyst can reuse, and still can obtain higher reaction raw materials conversion ratio in recycling process.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (22)
1. a spherical illite mesoporous composite material, it is characterized in that, described spherical illite mesoporous composite material contains illite, there is the meso-porous molecular sieve material of three-dimensional cubic duct structure and there is the meso-porous molecular sieve material of hexagonal hole road structure, and the average grain diameter of described spherical illite mesoporous composite material is 20-50 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-5 nanometer, described second most probable pore size is 5-25 nanometer.
2. material according to claim 1, wherein, relative to having the meso-porous molecular sieve material of three-dimensional cubic duct structure and the described total amount with the meso-porous molecular sieve material of hexagonal hole road structure described in 100 weight portions, described illitic content is 1-50 weight portion, is preferably 20-50 weight portion; Described there is three-dimensional cubic duct structure meso-porous molecular sieve material and the described weight ratio with the meso-porous molecular sieve material of hexagonal hole road structure be 1:0.1-10, be preferably 1:0.5-2.
3. prepare a method for spherical illite mesoporous composite material, the method comprises the following steps:
(1) meso-porous molecular sieve material with three-dimensional cubic duct structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of three-dimensional cubic duct structure, as component a1;
(2) meso-porous molecular sieve material with hexagonal hole road structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure, as component a2;
(3) silica gel is provided or prepares the filter cake of silica gel, as components b;
(4) described component a1, described component a2, described components b and illite are carried out mixing and ball milling, and the pressed powder water slurrying will obtained after ball milling, then the slurry obtained is carried out spraying dry;
Wherein, described component a1 and described component a2 makes the average grain diameter of described spherical illite mesoporous composite material be 20-50 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-5 nanometer, described second most probable pore size is 5-25 nanometer.
4. method according to claim 3, wherein, in step (4), relative to the described component a1 of 100 weight portions and total consumption of described component a2, the consumption of described components b is 1-200 weight portion, is preferably 50-150 weight portion; Described illitic consumption is 1-50 weight portion, is preferably 20-50 weight portion; The weight ratio of the consumption of described component a1 and described component a2 is 1:0.1-10, is preferably 1:0.5-2.
5. method according to claim 3, wherein, in step (1), the process that preparation has a filter cake of the meso-porous molecular sieve material of three-dimensional cubic duct structure comprises: under the existence of template and butanols, ethyl orthosilicate is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
6. method according to claim 5, wherein, the mol ratio of described template, butanols and ethyl orthosilicate is 1:10-100:10-90, is preferably 1:60-90:50-75.
7. the method according to claim 5 or 6, wherein, described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene; Described sour agent is hydrochloric acid; The condition that ethyl orthosilicate contacts with described sour agent comprises: temperature is 10-60 DEG C, and the time is 10-72 hour, and pH value is 1-7; The condition of described crystallization comprises: temperature is 30-150 DEG C, and the time is 10-72 hour.
8. method according to claim 3, wherein, in step (2), the process that preparation has the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure comprises: by ethyl orthosilicate, softex kw and ammonia haptoreaction, and the mixture obtained after haptoreaction is carried out crystallization and filtration.
9. method according to claim 8, wherein, the mol ratio of ethyl orthosilicate, softex kw and ammonia is 1:0.1-1:0.1-5, is preferably 1:0.2-0.5:1.5-3.5.
10. method according to claim 8 or claim 9, wherein, described catalytic condition comprises: temperature is 25-100 DEG C, and the time is 10-72 hour; The condition of described crystallization comprises: temperature is 30-150 DEG C, and the time is 10-72 hour.
11. methods according to claim 3, wherein, in step (3), the process preparing the filter cake of silica gel comprises: contacted with inorganic acid by waterglass, and is filtered by the mixture obtained after contact.
12. methods according to claim 11, wherein, the condition that waterglass contacts with inorganic acid comprises: temperature is 10-60 DEG C, and the time is 1-5 hour, and pH value is 2-4; Described inorganic acid is one or more in sulfuric acid, nitric acid and hydrochloric acid.
13. according to the method in claim 3-5,8-9 and 11-12 described in any one, wherein, in step (4), the condition of described ball milling comprises: the rotating speed of abrading-ball is 300-500r/min, temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hour; Described spray-dired condition comprises: temperature 100-300 DEG C, and rotating speed is 10000-15000r/min.
14. methods according to claim 3 or 4, wherein, described component a1 is the filter cake of the meso-porous molecular sieve material with three-dimensional cubic duct structure, described component a2 is the filter cake of the meso-porous molecular sieve material with hexagonal hole road structure, and described components b is the filter cake of silica gel, described method also comprises: after the spray-drying process of step (4), removed template method from the product that spraying dry obtains; Preferably, the condition of described removed template method comprises: temperature is 300-600 DEG C, and the time is 10-80 hour.
The 15. spherical illite mesoporous composite materials prepared by the method in claim 3-14 described in any one.
16. 1 kinds of loaded catalysts, this catalyst contains carrier and load benzene sulfonic acid on the carrier, it is characterized in that, described carrier is the spherical illite mesoporous composite material in claim 1-2 and 15 described in any one.
17. catalyst according to claim 16, wherein, with the gross weight of described loaded catalyst for benchmark, the content of benzene sulfonic acid is 1-50 % by weight, is preferably 5-50 % by weight; The content of described carrier is 50-99 % by weight, is preferably 50-95 % by weight.
18. 1 kinds of methods preparing loaded catalyst, the method comprises: carrier, benzene sulfonic acid and water are mixed, and the mixture obtained is carried out spraying dry, wherein, described carrier is the spherical illite mesoporous composite material in claim 1-2 and 15 described in any one.
19. methods according to claim 18, wherein, with total consumption of described carrier and benzene sulfonic acid for benchmark, the consumption of benzene sulfonic acid is 1-50 % by weight, is preferably 5-50 % by weight; The consumption of described carrier is 50-99 % by weight, is preferably 50-95 % by weight.
20. loaded catalysts prepared by the method described in claim 18 or 19.
The application of loaded catalyst in ketal reaction in 21. claims 16,17 and 20 described in any one.
The preparation method of 22. 1 kinds of cyclohexanone glycerol ketals, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclohexanone is contacted with glycerine, to obtain cyclohexanone glycerol ketals, it is characterized in that, described catalyst is the loaded catalyst in claim 16,17 and 20 described in any one.
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| CN108855068B (en) * | 2017-05-10 | 2019-08-20 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855198B (en) * | 2017-05-10 | 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 |
| CN110732344A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with illite composite material with three-dimensional cubic and hexagonal pore channel structure as carrier, and preparation method and application thereof |
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