CN104248987A - Spherical montmorillonite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate - Google Patents
Spherical montmorillonite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate Download PDFInfo
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Abstract
The invention relates to a spherical montmorillonite mesoporous composite material, a preparation method thereof, the spherical montmorillonite mesoporous composite material prepared by the preparation method, a supported catalyst containing the spherical montmorillonite mesoporous composite material, a preparation method of the supported catalyst, the supported catalyst prepared by the preparation method, application of the supported catalyst in esterification reaction, and a preparation method of ethyl acetate by use of the supported catalyst. The spherical montmorillonite mesoporous composite material contains montmorillonite, a mesoporous molecular sieve material with a three-dimensional cubic channel structure and a mesoporous molecular sieve material with a hexagonal channel structure. The supported catalyst prepared from the spherical montmorillonite mesoporous composite material as a carrier can significantly increase the conversion rate of reaction raw materials in the esterification process.
Description
Technical field
The present invention relates to a kind of spherical montmorillonite mesoporous composite material, the preparation method of this spherical montmorillonite mesoporous composite material, the spherical montmorillonite mesoporous composite material prepared by the method, loaded catalyst containing this spherical montmorillonite mesoporous composite material, the preparation method of this loaded catalyst, the loaded catalyst prepared by the method, the application in the esterification reaction of this loaded catalyst, and the method preparing ethyl acetate using this loaded catalyst.
Background technology
Ethyl acetate is also known as ethyl acetate.Pure ethyl acetate is the liquid that water white transparency has aromatic odor, it is a kind of broad-spectrum fine chemical product, there is excellent dissolubility, quick-drying, of many uses, be a kind of very important Organic Chemicals and fabulous industrial solvent, be widely used in the production process of acetate fiber, ethyl cellulose, vinyl, acetate fiber resin, chlorinated rubber, synthetic rubber, coating and paint etc.Its main application has: as industrial solvent, in the products such as coating, adhesive, ethyl cellulose, artificial leather, malthoid colouring agent, staple fibre; As adhesive, for the production of printing-ink, olivet; As extractant, for the production of the products such as medicine, organic acid.
In the traditional synthesis of ethyl acetate, usually adopt the concentrated sulfuric acid as catalyst, its shortcoming be that equipment corrosion is serious, side reaction is many, product separation is complicated and liquid waste processing difficult etc.In order to replace the catalyst of the concentrated sulfuric acid as esterification, people have carried out large quantifier elimination.Loaded catalyst is adopted to be one of more successful probing direction as the catalyst of esterification.
In existing loaded catalyst, adopt conventional meso-porous molecular sieve material as carrier.Typical meso-porous molecular sieve material has bar-shaped mesoporous silicon oxide SBA-15.Although it is orderly that the meso-porous molecular sieve material of these routines has duct, aperture is adjustable, specific area and the advantage such as pore volume is larger, the loaded catalyst adopting these meso-porous molecular sieve materials to make as carrier is made to show lot of advantages in the preparation technology of ethyl acetate, 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 esterification reaction process, and then can the serious conversion ratio reducing acetic acid in ethyl acetate 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 esterification reaction process adopting existing meso-porous molecular sieve material to make, a kind of spherical montmorillonite mesoporous composite material being suitable as carrier is provided, and the preparation method of this spherical montmorillonite mesoporous composite material, the spherical montmorillonite mesoporous composite material prepared by the method, loaded catalyst containing this spherical montmorillonite mesoporous composite material, the preparation method of this loaded catalyst, the loaded catalyst prepared by the method, the application in the esterification reaction of this loaded catalyst, with the method preparing ethyl acetate using this loaded catalyst.
In order to achieve the above object, the present inventor is by finding after research, montmorillonite 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, montmorillonite 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 esterification, thus complete the present invention.
For this reason, the invention provides a kind of spherical montmorillonite mesoporous composite material, wherein, this spherical montmorillonite mesoporous composite material contains montmorillonite, 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 montmorillonite 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 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 the 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 a kind of method preparing spherical montmorillonite 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 montmorillonite 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 montmorillonite 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 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 the 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 montmorillonite 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 montmorillonite 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 montmorillonite 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 in the esterification reaction of above-mentioned loaded catalyst.
Present invention also offers a kind of preparation method of ethyl acetate, the method comprises: in the presence of a catalyst, under the condition of esterification, acetic acid is contacted with ethanol, to obtain ethyl acetate, wherein, described catalyst is loaded catalyst according to the present invention.
Spherical montmorillonite 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, montmorillonite and ball type carrier, make this spherical montmorillonite mesoporous composite material be suitable as the carrier of loaded catalyst, be particularly suitable as the carrier of the loaded catalyst used in the esterification reaction.
In described loaded catalyst of the present invention, spherical montmorillonite 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 esterification 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 montmorillonite mesoporous composite material according to the present invention and described loaded catalyst;
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical montmorillonite mesoporous composite material according to the present invention;
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of loaded catalyst according to the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, 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 montmorillonite mesoporous composite material, wherein, this spherical montmorillonite mesoporous composite material contains montmorillonite, 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 montmorillonite 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 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 the 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 montmorillonite 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 montmorillonite mesoporous composite material according to the present invention, by the particle size of spherical montmorillonite mesoporous composite material is controlled within above-mentioned scope, can guarantee that described spherical montmorillonite mesoporous composite material is not easily reunited, and the reaction raw materials conversion ratio in esterification reaction process can be improved used as the loaded catalyst that carrier is made.When the specific area of described spherical montmorillonite 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 montmorillonite 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 esterification reaction process, thus affects the reaction raw materials conversion ratio in esterification reaction process.
In the preferred case, the average grain diameter of described spherical montmorillonite mesoporous composite material is 20-40 micron, specific area is 210-600 meters squared per gram, pore volume is 0.8-1.5 ml/g, described first most probable pore size is 2-4, described second most probable pore size is 6-12 nanometer, and described 3rd most probable pore size is 25-35 nanometer.
In described spherical montmorillonite 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 described montmorillonite 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 montmorillonite 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 montmorillonite mesoporous composite material, to be brought into the silica component in the spherical montmorillonite mesoporous composite material of final preparation by silica gel as raw materials.In described spherical montmorillonite 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 montmorillonite 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 montmorillonite 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 montmorillonite 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 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 the 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 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.
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.
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.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.
Described butanols is preferably n-butanol.
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.
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.
Having in above-mentioned preparation in the process of the filter cake of the meso-porous molecular sieve material in three-dimensional cubic duct, 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 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.
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.
Ammonia preferably adds with the form of ammoniacal liquor.
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.
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.
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.
Having in above-mentioned preparation in the process of the filter cake of the meso-porous molecular sieve material of hexagonal hole road structure, 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 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.
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 montmorillonite 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 (1) 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 montmorillonite 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 montmorillonite 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 montmorillonite 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 montmorillonite 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 in the esterification reaction of above-mentioned loaded catalyst.
In addition, present invention also offers a kind of preparation method of ethyl acetate, the method comprises: in the presence of a catalyst, under the condition of esterification, acetic acid is contacted with ethanol, to obtain ethyl acetate, it is characterized in that, described catalyst is above-mentioned loaded catalyst provided by the invention.
In the preparation method of described ethyl acetate, there is no particular limitation for the consumption of acetic acid and ethanol, as long as can be obtained by reacting ethyl acetate, but in order to improve the utilization rate of raw material, under preferable case, the mol ratio of acetic acid and ethanol is 1:0.5-10.
Also there is no particular limitation for the consumption of described catalyst, suitably can determine according to the ethyl acetate preparation technology of routine.Under preferable case, relative to the acetic acid of 100 weight portions, the consumption of described catalyst is 1-15 weight portion, is more preferably 2-14 weight portion.
In described esterification reaction process, in order to more be conducive to the carrying out of esterification, described reaction is preferably under reflux conditions carried out, that is, described reaction temperature is reflux temperature.Reaction time can be 1-10 hour, is preferably 2-8 hour.
The preparation method of described ethyl acetate can also be included in after esterification terminates, suction filtration separation is carried out to final reactant mixture, and suction filtration is separated the solid product vacuum drying 1-24 hour at 25-200 DEG C obtained, preferably vacuum drying 6-10 hour at 50-120 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, average molecular mass Mn 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 Bruker AXS 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 acetic acid and the selective of ethyl acetate obtain according to following formulae discovery.
Consumption × 100% of the conversion ratio (%) of the acetic acid=content of acetic acid (in the consumption-product of acetic acid) ÷ acetic acid
Theoretical yield × 100% of the actual production ÷ ethyl acetate of selective (the %)=ethyl acetate of ethyl acetate
Embodiment 1
The present embodiment is for illustration of spherical montmorillonite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
(1) spherical montmorillonite mesoporous composite material is prepared
By 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, 6g(0.08mol is added again in described clear solution) n-butanol stir 1h, then the water-bath of 40 DEG C is placed in, by 12.9g(0.062) 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 10g montmorillonite, 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 30g pressed powder; This pressed powder is dissolved in 30 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 30 grams of spherical montmorillonite mesoporous composite material C1.
(2) loaded catalyst is prepared
At 25 DEG C, the 30g spherical montmorillonite 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 montmorillonite 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, and wherein, a is the XRD spectra of spherical montmorillonite mesoporous composite material C1, and b is the XRD spectra of loaded catalyst Cat-1.Compose peak from the low-angle occurred in XRD spectra, spherical montmorillonite mesoporous composite material C1 and loaded catalyst Cat-1 all 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 montmorillonite mesoporous composite material C1.As seen from the figure, the microscopic appearance of spherical montmorillonite mesoporous composite material C1 to be particle diameter the be Mesoporous Spheres of 20-50 μm.
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of loaded catalyst Cat-1.As seen from the figure, the microscopic appearance of loaded catalyst Cat-1 keeps spherical substantially, and its particle diameter is 20-50 μm.
The pore structure parameter of spherical montmorillonite 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 | 251 | 1.0 | 2.2，8，15 | 20-50 |
| Catalyst Cat-1 | 159 | 0.9 | 2.1，7，11 | 20-40 |
As can be seen from the data of upper table 1, spherical montmorillonite 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 montmorillonite mesoporous composite material in load-reaction process.
Comparative example 1
Spherical montmorillonite mesoporous composite material and loaded catalyst is prepared according to the method for embodiment 1, difference, be used as in preparation not add montmorillonite 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 montmorillonite mesoporous composite material and loaded catalyst is prepared according to the method for embodiment 1, difference, in the process preparing loaded catalyst, with the bar-shaped mesoporous silicon oxide SBA-15(of identical weight purchased from high-tech limited company of Jilin University) replace described filter cake X1 and described filter cake Y1, thus obtained mesoporous composite material D2 and loaded catalyst Cat-D-2 respectively.
Embodiment 2
The present embodiment is for illustration of spherical montmorillonite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
Spherical montmorillonite 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 montmorillonite mesoporous composite material, thus obtained loaded catalyst Cat-2.
Embodiment 3
The present embodiment is for illustration of spherical montmorillonite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
(1) spherical montmorillonite mesoporous composite material is prepared
By 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, 4.5g(0.06mol is added again in described clear solution) n-butanol stir 1h, then the water-bath of 40 DEG C is placed in, by 10.4g(0.05) 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 Y3,15g filter cake B3 of above-mentioned preparation is put into 100ml ball grinder together with 15g montmorillonite, 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 50g pressed powder; This pressed powder is dissolved in 36 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 30 grams of spherical montmorillonite mesoporous composite material C3.
(2) loaded catalyst is prepared
At 25 DEG C, the 20g spherical montmorillonite 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 montmorillonite 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 montmorillonite 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 | 455 | 1.3 | 3，10，28 | 20-50 |
| Catalyst Cat-3 | 218 | 1.2 | 2.8，8.1，20 | 20-40 |
Embodiment 4
The present embodiment is for illustration of spherical montmorillonite mesoporous composite material of the present invention and loaded catalyst and their preparation method.
(1) spherical montmorillonite mesoporous composite material is prepared
By 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, 6.75g(0.09mol is added again in described clear solution) n-butanol stir 1h, then the water-bath of 40 DEG C is placed in, by 15.6g(0.075) ethyl orthosilicate is slowly added drop-wise in this solution, temperature is maintained at about 30 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 montmorillonite, 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 montmorillonite mesoporous composite material C4.
(2) loaded catalyst is prepared
At 25 DEG C, the 20g spherical montmorillonite 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 montmorillonite 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 montmorillonite 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 | 561 | 1.5 | 3.9，16，34 | 20-50 |
| Catalyst Cat-4 | 433 | 1.4 | 3.7，14，32 | 20-40 |
Embodiment 5
The present embodiment is for illustration of the application of described loaded catalyst provided by the invention and the preparation method of ethyl acetate.
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, put into 100ml there-necked flask successively with 11.5 grams of ethanol and 15 grams of acetic acid, stir 3 hours under heated reflux condition, be then cooled to room temperature and suction filtration separation, utilize the liquid phase ingredient of gas chromatograph-mass spectrometer analytical reactions product, and by calculating, the conversion ratio of acetic acid is 99.5%, ethyl acetate is selective is 100%.
Embodiment 6-8 and comparative example 3-4
Method according to embodiment 5 prepares ethyl acetate, and 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 ethyl acetate selective data of the acetic acid calculated separately are as shown in table 4 below.
Table 4
| ? | Catalyst | The conversion ratio of acetic acid | Ethyl acetate is selective |
| Embodiment 5 | Cat-1 | 99.9% | 100% |
| Embodiment 6 | Cat-2 | 93.0% | 100% |
| Embodiment 7 | Cat-3 | 99.8% | 100% |
| Embodiment 8 | Cat-4 | 99.9% | 100% |
| Comparative example 3 | Cat-D-1 | 85.6% | 99% |
| Comparative example 4 | Cat-D-2 | 89.1% | 99% |
Embodiment 9-12 and comparative example 5-6
Method according to embodiment 5 prepares ethyl acetate, and 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 ethyl acetate selective data of the acetic acid calculated separately are as shown in table 5 below.
Table 5
| ? | Catalyst | The conversion ratio of acetic acid | Ethyl acetate is selective |
| Embodiment 9 | The Cat-1 reclaimed | 99.8% | 100% |
| Embodiment 10 | The Cat-2 reclaimed | 81.0% | 99% |
| Embodiment 11 | The Cat-3 reclaimed | 98.9% | 100% |
| Embodiment 12 | The Cat-4 reclaimed | 98.7% | 100% |
| Comparative example 5 | The Cat-D-1 reclaimed | 81.7% | 99% |
| Comparative example 6 | The Cat-D-2 reclaimed | 80.5% | 99% |
As can be seen from above-mentioned table 4 and 5 data, adopt described spherical montmorillonite 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 esterification 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.
Claims (22)
1. a spherical montmorillonite mesoporous composite material, it is characterized in that, this spherical montmorillonite mesoporous composite material contains montmorillonite, 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 montmorillonite 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 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 the 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 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 described montmorillonite 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 montmorillonite 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 montmorillonite 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 montmorillonite 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 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 the 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 montmorillonite 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 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 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 montmorillonite 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 montmorillonite 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 montmorillonite 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.
Loaded catalyst application in the esterification reaction in 21. claims 16,17 and 20 described in any one.
The preparation method of 22. 1 kinds of ethyl acetate, the method comprises: in the presence of a catalyst, under the condition of esterification, acetic acid is contacted with ethanol, to obtain ethyl acetate, 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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