CN105435852A - Mesoporous composite material and catalyst and preparation method and application thereof and 2,2-dimethyl-4-methyl-1,3-dioxolane preparation method - Google Patents
Mesoporous composite material and catalyst and preparation method and application thereof and 2,2-dimethyl-4-methyl-1,3-dioxolane preparation method Download PDFInfo
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Abstract
The invention relates to a spherical zeolite mesoporous composite material, a preparation method thereof, the spherical zeolite mesoporous composite material prepared by the preparation method, a supported catalyst containing the spherical zeolite mesoporous composite material, a preparation method of the supported catalyst, the supported catalyst prepared by the preparation method, application of the supported catalyst in ketalization reaction, and a preparation method of cyclohexanone glyceryl ketal by use of the supported catalyst. The spherical zeolite mesoporous composite material contains zeolite, a mesoporous molecular sieve material with a one-dimensional hexagonal-channel distribution structure and a mesoporous molecular sieve material with a two-dimensional hexagonal-channel distribution structure. The supported catalyst prepared from the zeolite mesoporous composite material as a carrier can significantly increase the conversion rate of reaction raw materials in the ketalization reaction process.
Description
Technical field
The present invention relates to a kind of spherical zeolite mesoporous composite material, the preparation method of this spherical zeolite mesoporous composite material, the spherical zeolite mesoporous composite material prepared by the method, loaded catalyst containing this spherical zeolite 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 preparation 2 of this loaded catalyst, 2-dimethyl-4-methyl isophthalic acid, the method for 3-dioxolanes.
Background technology
2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes is important organic synthesis intermediate.Generally, 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes is obtained by ketal reaction primarily of oxidation cyclopropane and acetone.The catalyst of traditional oxidation cyclopropane and the ketal reaction of acetone 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. are to synthesis 2,2-dimethyl-4-methyl isophthalic acid, and 3-dioxolanes has good catalytic action.
Natural zeolite is the porous aluminosilicate mineral material of moisture rack-like structure, is the general name of zeolite race mineral.Zeolite chemistry composition is primarily of SiO
2, Al
2o
3, H
2o and alkali, alkaline-earth metal ions four part composition, great changes have taken place for this four fraction, thus constitute multiple zeolite group mineral.Finding 40 kinds of natural zeolite mineral, comparatively common with analcime, chabasie, clinoptilolite, heulandite, erionite, ferrierite, laumontite, modenite, phillipsite.Current China finds that there is more than the 10 kind of natural zeolite mineral products such as analcime, clinoptilolite, modenite, ferrierite, phillipsite, epidesmine.A large amount of utilization, mainly clinoptilolite, modenite, next has analcime, epidesmine.The specific physical character of zeolite depends on the lattice structure of zeolite, and zeolite is by SiO
2and Al
2o
3tetrahedron element is staggered to spatial network.Due to the opening of crystal structure, zeolite contains the uneven duct of many sizes and cavity.And the needs of compensation positive charge that cause uneven due to aluminium displacement silicon electricity price in tetrahedron, in these ducts and cavity often occupied by alkali metal or alkaline-earth metal ions and zeolite water molecule.The structures shape of zeolite it possess unique physical and chemical performance such as ion exchangeable and adsorptive selectivity.In addition, zeolite also have good heat endurance, acid resistance, can dehydration property, the catalytic cracking of chemical reaction, the characteristic such as radiation resistance and low bulk density, porous.
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 by 2, 2-dimethyl-4-methyl isophthalic acid, the conversion ratio of cyclopropane is oxidized in 3-dioxolanes preparation technology.
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 zeolite mesoporous composite material being suitable as carrier is provided, and the preparation method of this spherical zeolite mesoporous composite material, the spherical zeolite mesoporous composite material prepared by the method, loaded catalyst containing this spherical zeolite 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 2, 2-dimethyl-4-methyl isophthalic acid, the method of 3-dioxolanes.
In order to achieve the above object, the present inventor is by finding after research, zeolite is introduced in the meso-porous molecular sieve material with one dimension hexagonal hole road distributed architecture and the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, zeolite 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 features such as one dimension hexagonal hole road distributed architecture and two-dimentional hexagonal hole road distribution, the reunion of meso-porous molecular sieve material can be reduced again, increase its mobility, make the loaded catalyst adopting this mesoporous composite material to make at the conversion ratio for the reaction raw materials significantly improved can be obtained during ketal reaction, thus complete the present invention.
For this reason, the invention provides a kind of spherical zeolite mesoporous composite material, wherein, this spherical zeolite mesoporous composite material contains zeolite, there is the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture and there is the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, and the average grain diameter of this spherical zeolite mesoporous composite material is 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is three peak distributions, and three peak corresponding first most probable pore size respectively, second most probable pore size and the 3rd most probable pore size, described first most probable pore size is less than described second most probable pore size, described second most probable pore size is less than described 3rd most probable pore size, and described first most probable pore size is 2-4 nanometer, described second most probable pore size is 5-15 nanometer, described 3rd most probable pore size is 10-40 nanometer.
The present invention also provides a kind of method preparing spherical zeolite mesoporous composite material, and the method comprises the following steps:
(1) meso-porous molecular sieve material with one dimension hexagonal hole road distributed architecture or preparation is provided to have the filter cake of the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture, as component a1;
(2) meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparation is provided to have the filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, 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 zeolite 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 zeolite mesoporous composite material be 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is three peak distributions, and three peak corresponding first most probable pore size respectively, second most probable pore size and the 3rd most probable pore size, described first most probable pore size is less than described second most probable pore size, described second most probable pore size is less than described 3rd most probable pore size, and described first most probable pore size is 2-4 nanometer, described second most probable pore size is 5-15 nanometer, described 3rd most probable pore size is 10-40 nanometer.
Present invention also offers the spherical zeolite 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 zeolite 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 zeolite 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 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclopropane will be oxidized contact with acetone, to obtain 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes, wherein, described catalyst is according to above-mentioned loaded catalyst of the present invention.
Spherical zeolite mesoporous composite material according to the present invention, combine the advantage of the meso-porous molecular sieve material with one dimension hexagonal hole road distributed architecture, the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, zeolite and ball type carrier, make this spherical zeolite 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 zeolite 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 zeolite mesoporous composite material according to the present invention;
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical zeolite mesoporous composite material according to the present invention;
Fig. 3 is the pore size distribution curve of spherical zeolite mesoporous composite material according to the present invention.
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 zeolite mesoporous composite material, wherein, this spherical zeolite mesoporous composite material contains zeolite, there is the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture and there is the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, and the average grain diameter of this spherical zeolite mesoporous composite material is 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is three peak distributions, and three peak corresponding first most probable pore size respectively, second most probable pore size and the 3rd most probable pore size, described first most probable pore size is less than described second most probable pore size, described second most probable pore size is less than described 3rd most probable pore size, and described first most probable pore size is 2-4 nanometer, described second most probable pore size is 5-15 nanometer, described 3rd most probable pore size is 10-40 nanometer.
Spherical zeolite mesoporous composite material according to the present invention has a distinctive peacekeeping two dimension hexagonal hole road three pore size distribution structure, 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 zeolite mesoporous composite material according to the present invention, by the particle size of spherical zeolite mesoporous composite material is controlled within above-mentioned scope, can guarantee that described spherical zeolite 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 zeolite 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 zeolite 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 zeolite mesoporous composite material is 35-55 micron, specific area is 180-600 meters squared per gram, pore volume is 0.8-1.2 ml/g, described first most probable pore size is less than described second most probable pore size, and described second most probable pore size is less than described 3rd most probable pore size, and described first most probable pore size is 2-4 nanometer, described second most probable pore size is 5-10 nanometer, and described 3rd most probable pore size is 10-25 nanometer.
In described spherical zeolite mesoporous composite material, relative to having the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture and the described total amount with the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture described in 100 weight portions, the content of described zeolite can be 1-50 weight portion, is preferably 20-50 weight portion; Described there is one dimension hexagonal hole road distributed architecture meso-porous molecular sieve material and the described weight ratio with the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture be 1:0.1-10, be preferably 1:0.5-2.
In the present invention, described spherical zeolite 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 zeolite mesoporous composite material, to be brought into the silica component in the spherical zeolite mesoporous composite material of final preparation by silica gel as raw materials.In described spherical zeolite mesoporous composite material, relative to there is described in 100 weight portions the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture and there is the total amount of meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, 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 one dimension hexagonal hole road distributed architecture meso-porous molecular sieve material and the described meso-porous molecular sieve material with the two-dimentional hexagonal hole road distributed architecture meso-porous molecular sieve material that can use for this area routine separately, and can to prepare according to the method for routine.
Present invention also offers a kind of method preparing spherical zeolite mesoporous composite material, the method comprises the following steps:
(1) meso-porous molecular sieve material with one dimension hexagonal hole road distributed architecture or preparation is provided to have the filter cake of the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture, as component a1;
(2) meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparation is provided to have the filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, 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 zeolite 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 zeolite mesoporous composite material be 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is three peak distributions, and three peak corresponding first most probable pore size respectively, second most probable pore size and the 3rd most probable pore size, described first most probable pore size is less than described second most probable pore size, described second most probable pore size is less than described 3rd most probable pore size, and described first most probable pore size is 2-4 nanometer, described second most probable pore size is 5-15 nanometer, described 3rd most probable pore size is 10-40 nanometer.
In the preferred case, described component a1 and described component a2 makes the average grain diameter of described spherical zeolite mesoporous composite material be 35-55 micron, specific area is 180-600 meters squared per gram, pore volume is 0.8-1.2 ml/g, described first most probable pore size is less than described second most probable pore size, described second most probable pore size is less than described 3rd most probable pore size, and described first most probable pore size is 2-4 nanometer, described second most probable pore size is 5-10 nanometer, and described 3rd most probable pore size is 10-25 nanometer.
In step (1), the preparation process that preparation has the filter cake of the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture comprises: under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
According to the present invention, there is no particular limitation for the consumption of described template, ethanol, trimethylpentane and tetramethoxy-silicane, can change in wider scope, usually, the mol ratio of described template, ethanol, trimethylpentane and tetramethoxy-silicane can be 1:100-500:200-500:50-200, is preferably 1:200-400:250-400:70-150.
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.
Described sour agent can be material or the mixture (as solution) that various routine may be used for adjust ph.Described sour agent preferably uses in form of an aqueous solutions.Preferably, described sour agent is pH value is the acetic acid of 1-6 (more preferably 3-5) and the cushioning liquid of sodium acetate.
The condition that tetramethoxy-silicane contacts with described 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 tetramethoxy-silicane 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 tetramethoxy-silicane and sour agent be 1-7.
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 one dimension hexagonal hole road distributed architecture 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), then carry out suction filtration.
In step (1), " providing the meso-porous molecular sieve material with one dimension hexagonal hole road distributed architecture " can be the product directly taking or choose the meso-porous molecular sieve material with one dimension hexagonal hole road distributed architecture, also can be the meso-porous molecular sieve material that preparation has one dimension hexagonal hole road distributed architecture.The described preparation method with the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture 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 one dimension hexagonal hole road distributed architecture, 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.
In step (2), the process that preparation has the filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture comprises: under template exists, ethyl orthosilicate is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
According to the present invention, there is no particular limitation for the consumption of described template and ethyl orthosilicate, can change in wider scope, and usually, the mol ratio of described template and ethyl orthosilicate is 1:1-2.5, is preferably 1:1-2.
Preferably, the process that preparation has the filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture also comprises in presence of water, is contacted by ethyl orthosilicate with sour agent.
There is no particular limitation for the consumption of described water, can change in wider scope, as long as can play the effect of dissolving described template, usually, the mol ratio of described template and water can be 1:40-250, is preferably 1:90-130.
Described water is preferably redistilled water.It should be noted that, the mole of above-mentioned water refers to the mole being introduced the water in reaction system by redistilled water.
According to the present invention, described template is the various templates that can use for this area routine, and most preferably, described template is softex kw (CTAB); Described sour agent can be material or the mixture (as solution) that various routine may be used for adjust ph.Described sour agent preferably uses in form of an aqueous solutions.Preferably, the hydrochloric acid solution of described sour agent to be pH value be 0-1.
According to the present invention, 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 0-1; The condition of described crystallization comprises: temperature is 30-150 DEG C, and the time is 10-72 hour, and under preferable case, the condition of described crystallization comprises: temperature is 80-140 DEG C, and the time is 20-40 hour.Described crystallization is implemented by hydrothermal crystallizing method.
According to the present invention, there is no particular limitation for the mode contacted with water template, ethyl orthosilicate, sour agent, under preferable case, first template is dissolved in water fully to stir and forms homogeneous phase solution, then regulate the pH (preferred 0-1) of gained solution with sour agent, more slowly drip ethyl orthosilicate in gained solution.
Have in the process of the filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture 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), then carry out suction filtration.
In step (2), " providing the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture " can be the product directly taking or choose the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, also can be the meso-porous molecular sieve material that preparation has two-dimentional hexagonal hole road distributed architecture.The described preparation method with the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture 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 two-dimentional hexagonal hole road distributed architecture, 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.
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.
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.
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.
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; The consumption of described zeolite can be 1-50 weight portion, and be preferably 20-50 weight portion, the weight ratio of described component a1 and described component a2 is 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 one dimension hexagonal hole road distributed architecture, described component a2 is the filter cake of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, when described components b is 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 one dimension hexagonal hole road distributed architecture, step (2) is for having the process of the filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, when step (3) is for preparing the process of the filter cake of silica gel, the preparation method of described spherical zeolite 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 zeolite 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 zeolite 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 zeolite 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 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclopropane will be oxidized and contact with acetone, to obtain 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes, wherein, described catalyst is above-mentioned loaded catalyst provided by the invention.
Described 2,2-dimethyl-4-methyl isophthalic acid, in the preparation method of 3-dioxolanes, there is no particular limitation, as long as can be obtained by reacting 2,2-dimethyl-4-methyl isophthalic acid for the consumption of oxidation cyclopropane and acetone, 3-dioxolanes, but in order to improve the utilization rate of raw material, under preferable case, the mol ratio of oxidation cyclopropane and acetone is 1:0.5-10.
At described 2,2-dimethyl-4-methyl isophthalic acids, in the preparation method of 3-dioxolanes, also there is no particular limitation for the consumption of described catalyst, can according to 2,2-dimethyl-4-methyl isophthalic acids of routine, and the preparation technology of 3-dioxolanes suitably determines.Under preferable case, relative to the oxidation cyclopropane of 100 weight portions, the consumption of described catalyst is 1-15 weight portion, is more preferably 2-14 weight portion.
At described 2,2-dimethyl-4-methyl isophthalic acids, in the preparation method of 3-dioxolanes, in order to more be conducive to the carrying out of ketal reaction, described reaction is preferably carried out in high pressure polytetrafluoroethyllining lining reactor, and described reaction temperature can be 25-100 DEG C, is preferably 60-100 DEG C.Reaction time can be 0.5-20 hour, is preferably 2-15 hour.
Described 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes 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 EO
20pO
70eO
20, be the material of 9003-11-6 in the registration number of U.S. chemical abstract, 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 oxidation cyclopropane and 2,2-dimethyl-4-methyl isophthalic acid, the selective of 3-dioxolanes obtains according to following formulae discovery.
Conversion ratio (%)=(being oxidized the content of cyclopropane in the consumption-product of oxidation cyclopropane) ÷ of oxidation cyclopropane is oxidized consumption × 100% of cyclopropane
2,2-dimethyl-4-methyl isophthalic acid, selective (%)=2, the 2-dimethyl-4-methyl isophthalic acid of 3-dioxolanes, actual production ÷ 2, the 2-dimethyl-4-methyl isophthalic acid of 3-dioxolanes, theoretical yield × 100% of 3-dioxolanes
Embodiment 1
The present embodiment is for illustration of spherical zeolite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
(1) spherical zeolite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 2.76g (0.06mol) ethanol is joined 28ml, pH value be 4 acetic acid and sodium acetate buffer solution in, at 15 DEG C, be stirred to P123 dissolve completely, the backward solution obtained in add 6g (0.053mol) trimethylpentane, 8h is stirred at 15 DEG C, add 2.13g (0.014mol) tetramethoxy-silicane more wherein, at 15 DEG C, pH value is stir 20h under the condition of 4.5, then the solution obtained is transferred in teflon-lined reactor, crystallization 24h at 60 DEG C, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake A1 of the meso-porous molecular sieve material with one dimension hexagonal hole road single hole distributed architecture,
The softex kw (CTAB) of 1g (0.003mol) is added in a certain amount of redistilled water, fully stirs to obtain homogeneous phase solution, with the aqueous hydrochloric acid solution that 10mL, pH value are 0.4, the pH value of this solution is adjusted to 0.2.After above-mentioned solution is heated to 15 DEG C, slowly drip ethyl orthosilicate (TEOS), wherein, softex kw: ethyl orthosilicate: the mol ratio of redistilled water is 1:1:90.Then at 15 DEG C, continue stirring after 25 hours, this solution is transferred to polytetrafluoroethylene (PTFE) be lining still in, stationary water thermal crystallisation process 40h at 80 DEG C.Then carry out filtering and spend deionized water 4 times, then suction filtration obtains the filter cake A2 of the meso-porous molecular sieve material with two-dimentional hexagonal hole road single hole distributed architecture.
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 A1,5g filter cake A2,10g filter cake B1 of above-mentioned preparation is put into 100ml ball grinder together with 5g zeolite, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and 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 the spherical zeolite mesoporous composite material C1 that 24 grams have one dimension hexagonal hole road and two-dimentional hexagonal hole road three pore size distribution structure.
(2) loaded catalyst is prepared
At 25 DEG C, the 24g spherical zeolite 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 zeolite 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.
Fig. 1 is X-ray diffracting spectrum, is the XRD spectra of spherical zeolite mesoporous composite material C1.Compose peak from the low-angle occurred in XRD spectra, spherical zeolite mesoporous composite material C1 has one dimension hexagonal hole road specific to mesoporous material and two-dimentional hexagonal hole road three pore size distribution structure.
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical zeolite mesoporous composite material C1.As seen from the figure, the microscopic appearance of spherical zeolite mesoporous composite material C1 to be particle diameter the be Mesoporous Spheres of 30-60 μm.
Fig. 3 is the pore size distribution curve of spherical zeolite mesoporous composite material C1.As seen from the figure, the pore size distribution curve of material is three peak distributions.
The pore structure parameter of spherical zeolite mesoporous composite material C1 and loaded catalyst Cat-1 is as shown in table 1 below.
Table 1
As can be seen from the data of upper table 1, spherical zeolite 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 zeolite mesoporous composite material in load-reaction process.
Comparative example 1
Spherical zeolite mesoporous composite material and loaded catalyst is prepared according to the method for embodiment 1, difference, be used as in preparation not add zeolite 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 zeolite mesoporous composite material and loaded catalyst is prepared according to the method for embodiment 1, difference, in the process preparing loaded catalyst, replace meso-porous molecular sieve material filter cake A1 and A2 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 zeolite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
Spherical zeolite 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 zeolite mesoporous composite material, thus obtained loaded catalyst Cat-2.
Embodiment 3
The present embodiment for illustration of spherical zeolite mesoporous composite material of the present invention and loaded catalyst with and preparation method thereof.
(1) spherical zeolite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethanol is joined 28ml, pH value be 5 acetic acid and sodium acetate buffer solution in, at 15 DEG C, be stirred to P123 dissolve completely, the backward solution obtained in add 9.12g (0.08mol) trimethylpentane, 8h is stirred at 15 DEG C, add 3.04g (0.02mol) tetramethoxy-silicane more wherein, at 25 DEG C, pH value is stir 15h under the condition of 5.5, then the solution obtained is transferred in teflon-lined reactor, crystallization 10h at 100 DEG C, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake A3 of the meso-porous molecular sieve material with one dimension hexagonal hole road single hole distributed architecture.
The softex kw of 1g (0.003mol) is added in a certain amount of redistilled water, fully stirs to obtain homogeneous phase solution, with the aqueous hydrochloric acid solution that 7mL, pH value are 0.3, the pH value of this solution is adjusted to 0.1.After above-mentioned solution is heated to 30 DEG C, slowly drip ethyl orthosilicate, wherein, softex kw: ethyl orthosilicate: the mol ratio of redistilled water is 1:1.5:130.Then at 30 DEG C, continue stirring after 40 hours, this solution is transferred to polytetrafluoroethylene (PTFE) be lining still in, at 100 DEG C of stationary water thermal crystallisation process 20h.Then carry out filtering and spend deionized water 4 times, then suction filtration obtains the filter cake A4 of the meso-porous molecular sieve material with two-dimentional hexagonal hole road single hole distributed architecture.
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 A3,7g filter cake A4,10g filter cake B3 of above-mentioned preparation is put into 100ml ball grinder together with 8g zeolite, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and 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 zeolite mesoporous composite material C3.
(2) loaded catalyst is prepared
At 25 DEG C, the 35g spherical zeolite 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 zeolite 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 zeolite mesoporous composite material C3 and loaded catalyst Cat-3 is as shown in table 2 below.
Table 2
Embodiment 4
The present embodiment is for illustration of spherical zeolite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
(1) spherical zeolite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethanol is joined 28ml, pH value be 3 acetic acid and sodium acetate buffer solution in, at 15 DEG C, be stirred to P123 dissolve completely, the backward solution obtained in add 5.7g (0.05mol) trimethylpentane, 8h is stirred at 15 DEG C, add 4.56g (0.03mol) tetramethoxy-silicane more wherein, at 40 DEG C, pH value is stir 10h under the condition of 3.5, then the solution obtained is transferred in teflon-lined reactor, crystallization 48h at 40 DEG C, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake A5 of the meso-porous molecular sieve material with one dimension hexagonal hole road single hole distributed architecture.
Being added in a certain amount of redistilled water by the softex kw of 1g (0.003mol), fully stirring to obtain homogeneous phase solution, is that the pH value of this solution is adjusted to 0.1 by the aqueous hydrochloric acid solution of 0.5 by pH value.After above-mentioned solution is heated to 50 DEG C, slowly drip ethyl orthosilicate, wherein, softex kw: ethyl orthosilicate: the mol ratio of redistilled water is 1:2:110.Then at 50 DEG C, continue stirring after 30 hours, this solution is transferred to polytetrafluoroethylene (PTFE) be lining still in, at 140 DEG C of stationary water thermal crystallisation process 30h.Then carry out filtering and spend deionized water 4 times, then suction filtration obtains the filter cake A6 of the meso-porous molecular sieve material with two-dimentional hexagonal hole road single hole distributed architecture.
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 A5,13g filter cake A6,30g filter cake B4 of above-mentioned preparation is put into 100ml ball grinder together with 5g zeolite, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and 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 53 grams of spherical zeolite mesoporous composite material C4.
(2) loaded catalyst is prepared
At 25 DEG C, the 53g spherical zeolite 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 zeolite 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 zeolite mesoporous composite material C4 and loaded catalyst Cat-4 is as shown in table 3 below.
Table 3
| Sample | Specific area (m 2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C4 | 270 | 1.0 | 2.0，5，20 | 55 |
| Catalyst Cat-4 | 160 | 0.7 | 1.7，3，16 | 59 |
Embodiment 5
The present embodiment for illustration of the application of described loaded catalyst provided by the invention and 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes.
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, be oxidized with 5g the high pressure polytetrafluoroethyllining lining reactor that cyclopropane and 20g acetone put into 100mL successively, under the condition stirred, react 6 hours in 75 DEG C of oil baths, then room temperature is cooled to 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, conversion ratio 99%, 2, the 2-dimethyl-4-methyl isophthalic acid of oxidation cyclopropane, selective 99% of 3-dioxolanes, yield 100%.
Embodiment 6-8 and comparative example 3-4
Prepare 2,2-dimethyl-4-methyl isophthalic acid according to the method for embodiment 5,3-dioxolanes, 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, the conversion ratio of the oxidation cyclopropane calculated separately and 2,2-dimethyl-4-methyl isophthalic acid, the selective data of 3-dioxolanes is as shown in table 4 below.
Table 4
Embodiment 9-12 and comparative example 5-6
Prepare 2,2-dimethyl-4-methyl isophthalic acid according to the method for embodiment 5,3-dioxolanes, 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, the conversion ratio of the oxidation cyclopropane calculated separately and 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes selective data is as shown in table 5 below.
Table 5
As can be seen from above-mentioned table 4 and 5 data, adopt described spherical zeolite 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 zeolite mesoporous composite material, it is characterized in that, this spherical zeolite mesoporous composite material contains zeolite, there is the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture and there is the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, and the average grain diameter of this spherical zeolite mesoporous composite material is 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is three peak distributions, and three peak corresponding first most probable pore size respectively, second most probable pore size and the 3rd most probable pore size, described first most probable pore size is less than described second most probable pore size, described second most probable pore size is less than described 3rd most probable pore size, and described first most probable pore size is 2-4 nanometer, described second most probable pore size is 5-15 nanometer, described 3rd most probable pore size is 10-40 nanometer.
2. composite according to claim 1, wherein, relative to there is described in 100 weight portions the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture and there is the total amount of meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, the content of described zeolite is 1-50 weight portion, is preferably 20-50 weight portion; Described there is one dimension hexagonal hole road distributed architecture meso-porous molecular sieve material and the described weight ratio with the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture be 1:0.1-10, be preferably 1:0.5-2.
3. prepare a method for spherical zeolite mesoporous composite material, the method comprises the following steps:
(1) meso-porous molecular sieve material with one dimension hexagonal hole road distributed architecture or preparation is provided to have the filter cake of the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture, as component a1;
(2) meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture or preparation is provided to have the filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture, 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 zeolite 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 zeolite mesoporous composite material be 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is three peak distributions, and three peak corresponding first most probable pore size respectively, second most probable pore size and the 3rd most probable pore size, described first most probable pore size is less than described second most probable pore size, described second most probable pore size is less than described 3rd most probable pore size, and described first most probable pore size is 2-4 nanometer, described second most probable pore size is 5-15 nanometer, described 3rd most probable pore size is 10-40 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; The consumption of described zeolite is 1-50 weight portion, and be preferably 20-50 weight portion, the weight ratio 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 described preparation process with the filter cake of the meso-porous molecular sieve material of one dimension hexagonal hole road distributed architecture comprises: under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane 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, ethanol, trimethylpentane and tetramethoxy-silicane is 1:100-500:200-500:50-200, is preferably 1:200-400:250-400:70-150.
7. the method according to claim 5 or 6, wherein, described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene; Described sour agent is pH value is the acetic acid of 1-6 and the cushioning liquid of sodium acetate; The condition that tetramethoxy-silicane 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, the process that preparation has the filter cake of the meso-porous molecular sieve material of two-dimentional hexagonal hole road distributed architecture comprises: under template exists, contacted by ethyl orthosilicate with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
9. method according to claim 8, wherein, the mol ratio of described template and ethyl orthosilicate is 1:1-2.5, is preferably 1:1-2.
10. method according to claim 8 or claim 9, wherein, described template is softex kw; The hydrochloric acid of described sour agent to be pH value be 0-1; 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 0-1; 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 and 8 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 one dimension hexagonal hole road distributed architecture, described component a2 is the filter cake of the meso-porous molecular sieve material with two-dimentional hexagonal hole road distributed architecture, 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 zeolite 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 zeolite 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 zeolite 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.
22. a kind 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclopropane will be oxidized contact with acetone, to obtain 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes, 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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| CN108855054A (en) * | 2017-05-10 | 2018-11-23 | 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 |
| CN110614115A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical tri-mesoporous composite material as carrier and preparation method and application thereof |
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| CN105435852B (en) | 2017-10-03 |
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