CN104248989B - The preparation method of spherical mesoporous meerschaum complex carrier and Catalysts and its preparation method and application and ethyl acetate - Google Patents
The preparation method of spherical mesoporous meerschaum complex carrier and Catalysts and its preparation method and application and ethyl acetate Download PDFInfo
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Abstract
The preparation method that the invention provides the application in the esterification reaction of a kind of spherical mesoporous meerschaum complex carrier, the preparation method of a kind of spherical mesoporous meerschaum complex carrier, the method spherical mesoporous meerschaum complex carrier prepared, a kind of phosphoric acid loaded catalyst, the preparation method of a kind of phosphoric acid loaded catalyst, described phosphoric acid loaded catalyst and a kind of ethyl acetate.Described spherical mesoporous meerschaum complex carrier contains meerschaum and meso-porous molecular sieve material, and the average particulate diameter of described spherical mesoporous meerschaum complex carrier is 10-50 micron, specific surface area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-5 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding.Phosphoric acid loaded catalyst provided by the invention not only has higher catalysis activity, but also can Reusability.
Description
Technical field
The preparation method that the present invention relates to the application in the esterification reaction of a kind of spherical mesoporous meerschaum complex carrier, the preparation method of a kind of spherical mesoporous meerschaum complex carrier, the method spherical mesoporous meerschaum complex carrier prepared, a kind of support type phosphoric acid catalyst, the preparation method of a kind of support type phosphoric acid catalyst, described support type phosphoric acid catalyst and a kind of ethyl acetate.
Background technology
Within 1992, Mobile company synthesizes mesoporous material.This mesoporous material has high specific surface area, regular pore passage structure and narrow pore-size distribution so that its catalysis, separation, medicine and other fields application obtain very big concern.Zhao east in 1998 unit et al. has synthesized a kind of New Type of Mesoporous material SBA-15(D.Y.Zhao, J.L.Feng, Q.S.Huo, etalScience279 (1998), 548-550), this mesoporous material has cube single-crystal meso-pore material aperture (6-30 nanometer) of high-sequential, bigger pore volume (1.0cm3/ g), thicker hole wall (4-6 nanometer), higher mechanical strength and good catalytic adsorption performance.Zhao Dongyuan, Yu Chengzhong and Yu Yonghao investigated the preparation method (CN1341553A) of a kind of mesonic pore molecular sieve carrier material, and this mesonic pore molecular sieve carrier material is as heterogeneous reaction catalyst carrier, it is easy to realize separating of catalyst and product.
Meerschaum (abbreviation attapulgite clay) is a kind of moisture zeopan crystalline mineral, its basic structural unit is the elementary layer that two-layer silicon-oxy tetrahedron presss from both sides one layer of magnesia octahedron composition, in each 2:1 layer, tetrahedral sheet angle is pushed up direction at a certain distance and is overturned and cambium layer chain structure, form the duct parallel with c-axis direction at tetrahedron bar interband, there is the layer chain crystal structure of uniqueness and the crystal habit of porous.Meerschaum has significantly high specific surface area, absorption property, catalytic action, rheological characteristic and thermostability, can be used in the fields such as dyeing wastewater process, deodorizer, filter aid, cleanser, decolorising agent, dytory, thixotropic agent and binding agent, be modern age purposes the most extensively, application extend one of the most rapid mineral products.The work of exploitation natural clay mineral novel catalyst carrier is paid attention to by people always.Additionally, China's meerschaum mineral resources are relatively abundant, develop it and not only there is as catalyst carrier researching value, and have very big realistic meaning.But, meerschaum exists that surface acidity is weak, passage is little, poor heat stability and under water vapor conditions, molecular sieve component structure is had the defects such as destruction, therefore, is modified natural sepiolite being become the work that catalyst carrier must be made.
At present, industrial typically by concentrated sulphuric acid as catalyst with synthesizing ethyl acetate, it has, and equipment investment is big, side reaction is many, product separates the defects such as complicated and liquid waste processing difficulty, therefore, in order to overcome drawbacks described above, the catalyst for esterification reaction that exploitation makes new advances is to replace concentrated sulphuric acid, and people have carried out substantial amounts of research.Wherein, solid acid, solid super-strong acid and cation exchange resin etc., as the catalyst of esterification, are all more successfully explore, and it is active that these catalyst are respectively provided with higher catalysis, but the some shortcomings of there is also, as more in by-product etc..
Summary of the invention
The preparation method that the invention aims to provide the application in the esterification reaction of a kind of new spherical mesoporous meerschaum complex carrier, the preparation method of a kind of spherical mesoporous meerschaum complex carrier, the method spherical mesoporous meerschaum complex carrier prepared, a kind of support type phosphoric acid catalyst, the preparation method of a kind of support type phosphoric acid catalyst, described support type phosphoric acid catalyst and a kind of ethyl acetate.
The present inventor is by finding after studying, meso-porous molecular sieve material introduces meerschaum, meerschaum is made to enter in the duct of meso-porous molecular sieve material, and this mesoporous composite material is made and is not susceptible to the spherical of reunion, so can retain the high-specific surface area of meso-porous molecular sieve material, big pore volume, cube feature such as duct and large aperture, the reunion of meso-porous molecular sieve material can be reduced again, increase its mobility, the reaction raw materials conversion ratio significantly improved can be obtained when making the loaded catalyst adopting this meso-porous molecular sieve material to make for esterification, thus completing the present invention.
For this, the invention provides a kind of spherical mesoporous meerschaum complex carrier, wherein, this spherical mesoporous meerschaum complex carrier contains meerschaum and mesopore molecular sieve, and the average particulate diameter of spherical mesoporous meerschaum complex carrier is 10-50 micron, specific surface area is 150-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-5 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding.
The preparation method that present invention also offers a kind of spherical mesoporous meerschaum complex carrier, the method comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is carried out first contacts with acid agent, and the product crystallization obtained after contacting first filtering, obtain No. 1 mesoporous material filter cake；Cetyl trimethylammonium bromide, tetraethyl orthosilicate with ammonia, are carried out second and contact, and the product after the second contact is filtered, obtain No. 2 mesoporous material filter cakes；
(2) with mineral acid, waterglass is carried out the 3rd to contact, and the product obtained after the 3rd contact is filtered, obtain silica gel filter cake；
(3) described No. 1 mesoporous material filter cake, No. 2 mesoporous material filter cakes, silica gel filter cakes are mixed homogeneously and ball milling with meerschaum, and spray drying after the pressed powder water slurrying obtained after ball milling, will be carried out, then by the described template removal in the product that obtains.
Present invention also offers the spherical mesoporous meerschaum complex carrier prepared by said method.
Present invention also offers a kind of support type phosphoric acid catalyst, wherein, this catalyst includes above-mentioned spherical mesoporous meerschaum complex carrier and the load phosphoric acid on described spherical mesoporous meerschaum complex carrier.
The preparation method that present invention also offers a kind of support type phosphoric acid catalyst, the method includes above-mentioned spherical mesoporous meerschaum complex carrier, phosphoric acid and water mix homogeneously, and the mixture obtained is carried out spray drying.
Present invention also offers the application in the esterification reaction of described support type phosphoric acid catalyst.
Additionally, the preparation method that present invention also offers a kind of ethyl acetate, the method includes: in the presence of a catalyst and when esterification, is contacted with ethanol by acetic acid, obtains ethyl acetate, and wherein, described catalyst is above-mentioned support type phosphoric acid catalyst.
The inventors found that, as a rule, the microscopic appearance of conventional ordered mesoporous material SBA-15 is bar-shaped, not only mobility is poor, and there is stronger water suction, moisture absorption ability, this will be further exacerbated by the agglomeration traits of bar-shaped ordered mesopore material SBA-15, is stored, transports, post-treatment and application are made troubles.But, on the one hand, carrier provided by the invention is spherical, it is possible to reduces the agglomeration traits of powder body, improve its mobility.On the other hand, carrier provided by the invention not only remains the feature of the high-specific surface area of ordered mesoporous material, big pore volume, large aperture and narrow ditribution, and its pore-size distribution presents the tri-modal distribution of uniqueness, is more conducive to the load of active component, thus having higher catalysis activity.
Additionally, due to meerschaum is a kind of natural clay mineral material being dirt cheap, its introducing can reduce the production cost of carrier to a great extent.Namely, the advantage of mesoporous material and meerschaum that micro-sphere structure, aperture are had tri-modal distribution by spherical mesoporous meerschaum complex carrier provided by the invention dexterously combines, thus the application for described spherical mesoporous meerschaum complex carrier provides better platform, and widen its application.
Other features and advantages of the present invention will be 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 constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.In the accompanying drawings:
Fig. 1 is X-ray diffracting spectrum (XRD figure spectrum), and wherein, a is the XRD spectra of spherical mesoporous meerschaum complex carrier (C1)；B is the XRD spectra of the spherical mesoporous meerschaum complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying method, and abscissa is 2 θ, and vertical coordinate is intensity；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM figure) of the microscopic appearance of spherical mesoporous meerschaum complex carrier (C1)；
Fig. 3 A and 3B is the scanning electron microscope (SEM) photograph of the spherical mesoporous meerschaum complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying method.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
Spherical mesoporous meerschaum complex carrier provided by the invention contains meerschaum and mesopore molecular sieve, and the average particulate diameter of described spherical mesoporous meerschaum complex carrier is 10-50 micron, specific surface area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-5 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding.Under preferable case, the average particulate diameter of described spherical mesoporous meerschaum complex carrier is 10-50 micron, specific surface area is 180-600 meters squared per gram, pore volume is 0.8-1.3 ml/g, pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-4 nanometer, 5-10 nanometer and 25-35 nanometer that described three peaks are corresponding.
In the present invention, described average particulate diameter adopts laser fineness gage to record, and specific surface area, pore volume and most probable pore size record according to nitrogen adsorption methods.
Spherical mesoporous meerschaum complex carrier according to the present invention, by the particle size of spherical mesoporous meerschaum complex carrier is controlled within above-mentioned scope, may insure that described spherical mesoporous meerschaum complex carrier is not susceptible to reunite, and the reaction raw materials conversion ratio that the loaded catalyst made used as carrier can improve in esterification reaction process.When the specific surface area of described spherical mesoporous meerschaum complex carrier less than 150 meters squared per gram and/or pore volume less than 0.5 ml/g time, the catalysis activity of the loaded catalyst made used as carrier can significantly reduce；When the specific surface area of described spherical mesoporous meerschaum complex carrier more than 600 meters squared per gram and/or pore volume more than 1.5 mls/g time, the loaded catalyst made used as carrier is susceptible to reunite in esterification reaction process, thus the reaction raw materials conversion ratio affected in esterification reaction process.
In described spherical mesoporous meerschaum complex carrier, relative to the described mesopore molecular sieve of 100 weight portions, the content of described meerschaum can be 1-50 weight portion, it is preferred to 20-50 weight portion.
In the present invention, described spherical mesoporous meerschaum complex carrier can also contain the silicon dioxide introduced by waterglass." by the silicon dioxide that waterglass introduces " refers in the preparation process of described spherical mesoporous meerschaum complex carrier, waterglass bring the silica component in the final spherical mesoporous meerschaum complex carrier prepared into as preparing raw material.In described spherical mesoporous meerschaum complex carrier, relative to the described meso-porous molecular sieve material of 100 weight portions, the content of the described silicon dioxide introduced by waterglass can be 1-200 weight portion, it is preferred to 50-150 weight portion.
In the present invention, described mesopore molecular sieve can be the conventional selection of this area, as a rule, it is mainly composed of silicon dioxide, and the average particulate diameter of described mesopore molecular sieve is 10-50 micron, specific surface area is 150-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-5 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding.Under preferable case, the average particulate diameter of described mesopore molecular sieve is 10-50 micron, specific surface area is 180-600 meters squared per gram, pore volume is 0.8-1.3 ml/g, pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-4 nanometer, 5-10 nanometer and 25-35 nanometer that described three peaks are corresponding.
The preparation method of spherical mesoporous meerschaum complex carrier provided by the invention comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is carried out first contacts with acid agent, and the product crystallization obtained after contacting first filtering, obtain No. 1 mesoporous material filter cake；Cetyl trimethylammonium bromide, tetraethyl orthosilicate with ammonia, are carried out second and contact, and the product after the second contact is filtered, obtain No. 2 mesoporous material filter cakes；
(2) with mineral acid, waterglass is carried out the 3rd to contact, and the product obtained after the 3rd contact is filtered, obtain silica gel filter cake；
(3) described No. 1 mesoporous material filter cake, No. 2 mesoporous material filter cakes, silica gel filter cakes are mixed homogeneously and ball milling with meerschaum, and spray drying after the pressed powder water slurrying obtained after ball milling, will be carried out, then by the described template removal in the product that obtains.
In the preparation process of above-mentioned spherical mesoporous meerschaum complex carrier, the pore-size distribution of described spherical mesoporous meerschaum complex carrier is controlled as tri-modal distribution by the composition mainly through controlling No. 1 mesoporous material filter cake and No. 2 mesoporous material filter cakes, and mainly through controlling forming method (namely, first described No. 1 mesoporous material filter cake, No. 2 mesoporous material filter cakes, silica gel filter cakes are mixed homogeneously and ball milling with meerschaum, then by spray drying after the pressed powder water slurrying obtained after ball milling) microscopic appearance of described spherical mesoporous meerschaum complex carrier is controlled as spherical.
The kind of described template is not particularly limited by the present invention, as long as the spherical mesoporous meerschaum complex carrier enabled to has above described holes structure, for instance, described template can be triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.Wherein, this template can be commercially available that (for example, it is possible to available from Aldrich Co, commodity are called P123, and molecular formula is EO20PO70EO20), it is also possible to prepared by existing various methods.When described template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of described template calculates according to the number-average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene and obtains.
According to the present invention, the kind of described acid agent can be the conventional selection of this area, it is possible to for the mixture of existing various acid or acid.Wherein, the mixture of described acid or acid can use with pure state, it is also possible to uses with the form of its aqueous solution, it is preferable that use in form of an aqueous solutions.Preferably, described acid agent be pH value is that 1-6(is preferably 3-5) acetic acid and the buffer solution of sodium acetate.
The condition of described first contact is not particularly limited by the present invention, for instance, the condition of described first contact generally includes temperature can be 10-60 DEG C, and the time can be 10-72 hour, and pH value can be 1-7；Under preferable case, the condition of described first contact includes temperature and is 10-30 DEG C, and the time is 20-40 hour, and pH value is 3-6.In order to be more beneficial for the Homogeneous phase mixing between each material, described first contact preferably carries out under agitation.The consumption of described acid agent is preferably so that the pH value of described first haptoreaction system is 1-7, more preferably 3-6.
The present invention to the condition of described crystallization also without limiting especially, for instance, the condition of described crystallization generally includes temperature can be 30-150 DEG C, and the time can be 10-72 hour；Under preferable case, the condition of described crystallization includes temperature and is 40-80 DEG C, and the time is 20-40 hour.
According to the present invention, in the process of No. 1 mesoporous material filter cake of preparation, the consumption of each material can carry out selecting and adjusting in wider scope.Such as, the mol ratio of described template, ethanol, trimethylpentane and tetramethoxy-silicane can be 1:100-500:200-500:50-200, it is preferred to 1:200-400:250-400:70-150.Wherein, when described template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of described template calculates according to the number-average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene and obtains.
In addition, described template, ethanol, acid agent, the way of contact between trimethylpentane and tetramethoxy-silicane are not particularly limited by the present invention, such as, above-mentioned five kinds of materials can be mixed contact simultaneously, it is also possible to the mixture that several materials therein are first mixed contact, obtain for the addition of remaining material again continues mixing contact.Under preferable case, the described way of contact is first at 10-60 DEG C, template, ethanol, acid agent and trimethylpentane stirring is mixed 6-10 hour, then adds tetramethoxy-silicane and continues stirring mixing 4-62 hour.
In like manner, in the process of No. 2 mesoporous material filter cakes of preparation, the content of each material can also carry out selecting and adjusting in wider scope, such as, ammonia and the mol ratio of water in described tetraethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can be 1:0.1-1:0.1-5:100-200, it is preferred to 1:0.1-0.5:2-4:120-160.It should be noted that; in preparation process; the ammonia that addition is commercially available is generally difficult to and meets above mol ratio; therefore; in the process of described second contact; generally also need to add water, i.e. cetyl trimethylammonium bromide, tetraethyl orthosilicate, ammonia are carried out second with the extra water added and contacted.The consumption of above-mentioned water includes the water of water and the extra addition contained in ammonia itself.
The condition of described second contact is not particularly limited by the present invention, it may for example comprise the temperature of contact can be 25-100 DEG C, it is preferred to 50-100 DEG C；The time of contact can be 1-10 hour, it is preferred to 2-6 hour.
The condition of described 3rd contact is not particularly limited by the present invention, for instance, the condition of described 3rd contact generally includes temperature can be 10-60 DEG C, it is preferred to 20-40 DEG C；Time can be 1-5 hour, it is preferred to 1.5-3 hour；PH value is 2-4.In order to be more beneficial for the Homogeneous phase mixing between each material, described 3rd contact preferably carries out under agitation.
As well known to those skilled in the art, described waterglass is the aqueous solution of sodium silicate, and its concentration can be 10-50 weight %, it is preferred to 12-30 weight %.
The kind of described mineral acid can be the conventional selection of this area, for instance, it is possible to for one or more in sulphuric acid, nitric acid and hydrochloric acid.Described mineral acid can use in pure form, it is also possible to uses with the form of its aqueous solution.The consumption of described mineral acid is preferably so that the pH value of waterglass and the haptoreaction system of mineral acid is 2-4.
According to the present invention, in the preparation process of described spherical mesoporous meerschaum complex carrier, the mode filtered described in step (1) and (2) can adopt and well known to a person skilled in the art that various mode carries out, it is preferred to sucking filtration separates.It is well-known to those skilled in the art utilize air pressure to realize a kind of mode that liquid separates with solid particle that described sucking filtration separates.
In addition, in the process of No. 1 mesoporous material filter cake of above-mentioned preparation, No. 2 mesoporous material filter cakes and silica gel filter cake, be may include that after filtration by the process filtered to obtain filter cake, with distilled water cyclic washing (washing times can be 2-10), then carry out sucking filtration.
According to the present invention, in step (3), the consumption of described No. 1 mesoporous material filter cake, No. 2 mesoporous material filter cakes, silica gel filter cake and meerschaum can select according to the component of the spherical mesoporous meerschaum complex carrier that expection obtains, such as, with total consumption of the described No. 1 mesoporous material filter cake of 100 weight portions and No. 2 mesoporous material filter cakes for benchmark, the consumption of described silica gel filter cake can be 1-200 weight portion, it is preferred to 50-150 weight portion；The consumption of described meerschaum can be 1-50 weight portion, it is preferred to 20-50 weight portion；The weight ratio of described No. 1 mesoporous material filter cake and No. 2 mesoporous material filter cakes can be 0.5-1.5:1.
There is no particular limitation to the concrete operation method of ball milling and condition for the present invention, not destroy or substantially not destroy carrier structure and to make silica gel, meerschaum enter in carrier duct to be as the criterion.Those skilled in the art can select various suitable condition to implement the present invention according to mentioned above principle.Specifically, described ball milling carries out in ball mill, and wherein, in ball mill, the diameter of abrading-ball can be 2-3mm；The quantity of abrading-ball reasonably can select according to the size of ball grinder, for being sized to the ball grinder of 50-150mL, generally can use 1 abrading-ball；The material of described abrading-ball can be Achates, politef etc., it is preferred to Achates.The condition of described ball milling includes: 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.
Additionally, by the process of pressed powder use water slurrying, the consumption of described pressed powder and water is not particularly limited, as long as the slurry of spray drying can be obtained being conducive to, such as, described pressed powder can be 1:0.5-5 with the weight ratio of water, it is preferred to 1:1-2.
According to the present invention, concrete operation method and the condition of described spray drying are known to the skilled person.Specifically, described pressed powder and water the slurry being made into is joined in nebulizer high speed rotating to realize spray drying.Wherein, the condition of spray drying includes temperature can be 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min；Particularly preferably in situation, it is 200 DEG C that the condition of described spray drying includes temperature, and the rotating speed of rotation is 12000r/min.
According to the present invention, the method for removed template method is generally calcination method.Wherein, the condition of described calcination method include temperature can be 300-600 DEG C, it is preferred to 350-550 DEG C, it is most preferred that be 500 DEG C；Time can be 10-80 hour, it is preferred to 20-30 hour, it is most preferred that is 24 hours.
Present invention also offers the spherical mesoporous meerschaum complex carrier prepared by said method.
Present invention also offers a kind of phosphoric acid loaded catalyst, wherein, this phosphoric acid loaded catalyst includes above-mentioned spherical mesoporous meerschaum complex carrier and the load phosphoric acid on described spherical mesoporous meerschaum complex carrier.
Wherein, the content of described spherical mesoporous meerschaum complex carrier and phosphoric acid can be the conventional selection of this area, for instance, with the gross weight of described catalyst for benchmark, the content of described phosphoric acid can be 1-50 weight %, it is preferred to 5-50 weight %；The content of described spherical mesoporous meerschaum complex carrier can be 50-99 weight %, it is preferred to 50-95 weight %.
In the present invention, described phosphoric acid loaded catalyst can be prepared according to various methods commonly used in the art, it is only necessary to by phosphoric acid load on the carrier.
In a preferred embodiment, in order to make the phosphoric acid loaded catalyst of preparation may be repeated utilization, and in recycling process, still can obtain higher reaction raw materials conversion ratio, the method preparing loaded catalyst includes: by above-mentioned spherical mesoporous meerschaum complex carrier, phosphoric acid and water mix homogeneously, and the mixture obtained is carried out spray drying.
Wherein, the consumption of described spherical mesoporous meerschaum complex carrier, phosphoric acid and water reasonably can select according to the catalyst that expection obtains, such as, with total consumption of described spherical mesoporous meerschaum complex carrier and phosphoric acid for benchmark, the consumption of described phosphoric acid can be 1-50 weight %, it is preferred to 5-50 weight %；The consumption of described spherical mesoporous meerschaum complex carrier can be 50-99 weight %, it is preferred to 50-95 weight %.Additionally, the weight ratio of described spherical mesoporous meerschaum complex carrier and water can be 1:15-35, it is preferred to 1:20-25.
The method of described spray drying is known to the skilled person, as mentioned above, it is generally and the mixture of described spherical mesoporous meerschaum complex carrier, water and phosphoric acid is joined in nebulizer high speed rotating to realize spray drying, wherein, the condition of spray drying includes temperature can be 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min；Particularly preferably in situation, it is 200 DEG C that the condition of described spray drying includes temperature, and the rotating speed of rotation is 12000r/min.
Present invention also offers the application in the esterification reaction of above-mentioned phosphoric acid loaded catalyst.
Additionally, the preparation method that present invention also offers a kind of ethyl acetate, wherein, the method includes: in the presence of a catalyst and when esterification, is contacted with ethanol by acetic acid, obtains ethyl acetate, wherein, described catalyst is above-mentioned phosphoric acid loaded catalyst.
The consumption of described acetic acid and ethanol is not particularly limited by the present invention, as long as ethyl acetate can be obtained by reacting, but in order to improve the utilization rate of raw material, it is preferable that in situation, the mol ratio of described acetic acid and ethanol is 1:0.5-10.
In addition, the present invention to the consumption of described phosphoric acid loaded catalyst also without limiting especially, suitably can select according to the addition of acetic acid in course of reaction and/or ethanol, as a rule, acetic acid relative to 100 weight portions, the consumption of described phosphoric acid loaded catalyst can be 1-15 weight portion, it is preferred to 2-14 weight portion.
According to the present invention, the condition of described esterification is conventionally known to one of skill in the art, generally includes reaction temperature and response time.Wherein, in order to be more beneficial for the carrying out of esterification, described reaction preferably under reflux conditions carries out, i.e. described reaction temperature is reflux temperature.The prolongation in response time can improve the conversion ratio of reactant and the yield of product within the specific limits, but the response time long amplitude that reaction-ure conversion-age and product yield are improved is also inconspicuous, therefore, consider effect and efficiency, under preferable case, the described response time is 1-10 hour, more preferably 2-8 hour.
According to the present invention, the preparation method of described ethyl acetate is it is also preferred that include after esterification terminates, final reactant mixture is carried out sucking filtration separation, and sucking filtration is separated solid product vacuum drying 1-24 hour at 25-200 DEG C obtained, preferably in vacuum drying at 50-120 DEG C 6-10 hour, to reclaim phosphoric acid loaded catalyst.
Below in conjunction with embodiment, the present invention is described in detail.
In following example and comparative example, template polyoxyethylene-poly-oxypropylene polyoxyethylene available from Aldrich Co, it is abbreviated as P123, molecular formula is EO20PO70EO20, at the material that registration number is 9003-11-6 of U.S. chemical abstract, number-average molecular weight Mn is 5800.
In following example and comparative example, X-ray diffraction analysis carries out on the X-ray diffractometer that model is D8Advance purchased from BrukerAXS company of Germany；Scanning electron microscope analysis carries out in the scanning electron microscope that model is XL-30 of purchased from American FEI Co.；Pore structure parameter analysis carries out on the nitrogen adsorption desorption instrument that model is Autosorb-1 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 carrying out purchased from Agilent company of Britain 7890A/5973N gas chromatograph-mass spectrometer.
In following example and comparative example, consumption × 100% of the conversion ratio (%) of acetic acid=(in the consumption-product of acetic acid the content of acetic acid) ÷ acetic acid；Theoretical yield × 100% of the actual production ÷ ethyl acetate of selectivity (the %)=ethyl acetate of ethyl acetate.
Embodiment 1
This embodiment is used for spherical mesoporous meerschaum complex carrier provided by the invention and Catalysts and its preparation method are described.
(1) preparation of spherical mesoporous meerschaum complex carrier:
1.0 grams of triblock copolymer P123s and 1.69 grams of (0.037mol) ethanol are joined 28mL, pH value is in the acetic acid of 4 and the buffer solution of sodium acetate, stir at 15 DEG C to P123 and be completely dissolved, add 6g(0.053mol afterwards) trimethylpentane, and after stirring 8 hours at 15 DEG C, add 2.13 grams of (0.014mol) tetramethoxy-silicanes, then at 15 DEG C, stir 20 hours when pH value is 4.5, and transfer the solution in teflon-lined reactor, baking oven crystallization 24 hours at 60 DEG C, by the crystallization product sucking filtration obtained and with distilled water wash four times, obtain No. 1 mesoporous material filter cake.
At 80 DEG C, cetyl trimethylammonium bromide and tetraethyl orthosilicate are joined in the ammonia spirit that concentration is 25 weight %, add deionized water, wherein, the addition of tetraethyl orthosilicate is 1 gram, and ammonia and the mol ratio of water in tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammonia are 1:0.37:2.8:142, and stirs 4 hours at 80 DEG C of temperature, then by solution sucking filtration and with distilled water wash four times, No. 2 mesoporous material filter cakes are obtained.
It is that 5:1 is mixed homogeneously by waterglass that concentration is 15 weight % and sulfuric acid solution that concentration is 12 weight % by waterglass and the weight ratio of sulphuric acid, then stirring reaction 1.5 hours at 15 DEG C, and the sulfuric acid solution that product concentration is 98 weight % that obtains is adjusted pH value is 3, then reaction mass sucking filtration, distilled water wash being washed till sodium ions content is 0.02 weight %, obtains silica gel filter cake.
10 grams of No. 1 mesoporous material filter cakes, 10 grams of No. 2 mesoporous material filter cakes, 20 grams of silica gel filter cakes and 10 grams of meerschaums are put into together in 100mL ball grinder (wherein, ball grinder material is politef, Material quality of grinding balls is Achates, the diameter of abrading-ball is 3mm, 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 50 grams of pressed powders.This pressed powder is dissolved in 100 grams of deionized waters, and be spray drying under 12000r/min at 200 DEG C, at rotating speed, then the product obtained after spray drying is calcined 24 hours with removed template method in the Muffle furnace of 500 DEG C, obtain the spherical mesoporous meerschaum complex carrier of target product of 49 grams of removed template methods, called after C1.
(2) preparation of phosphoric acid loaded catalyst:
At 25 DEG C, above-mentioned 49 grams of spherical mesoporous meerschaum complex carriers are put in deionized water together with phosphoric acid, stirring is to dissolving, the weight ratio controlling spherical sepiolite clay mineral complex carrier, deionized water and phosphoric acid is 1:25:1, then by the mixture obtained at 200 DEG C, be under 12000r/min, carry out spray drying at rotating speed, obtain the spherical mesoporous meerschaum complex carrier (i.e. phosphoric acid loaded catalyst) of load phosphoric acid, called after Cat-1.
With X-ray diffractometer, scanning electron microscope and nitrogen adsorption desorption instrument, the spherical mesoporous meerschaum complex carrier of this spherical mesoporous meerschaum complex carrier and load phosphoric acid is characterized.
Fig. 1 is X-ray diffracting spectrum (XRD spectra), and wherein, a is the XRD spectra of spherical mesoporous meerschaum complex carrier (C1)；B is the XRD spectra of the spherical mesoporous meerschaum complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying method, and abscissa is 2 θ, and vertical coordinate is intensity.Can be seen that from the result of Fig. 1, the XRD spectra a of spherical mesoporous meerschaum complex carrier (C1), the load phosphoric acid obtained by spray drying method the XRD spectra b of spherical mesoporous meerschaum complex carrier (Cat-1) all occur in that low-angle spectral peak, thereby it is assumed that, both materials are respectively provided with hexagonal hole road structure specific to mesoporous material.
Fig. 2 is the scanning electron microscope (SEM) photograph of the microscopic appearance of spherical mesoporous meerschaum complex carrier (C1).From the result of Fig. 2 it can be seen that the microscopic appearance of spherical mesoporous meerschaum complex carrier (C1) is diameter is the Mesoporous Spheres of 10-50 μm.
Fig. 3 A and 3B is the scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical mesoporous meerschaum complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying method.Wherein, Fig. 3 A is the scanning electron microscope (SEM) photograph of the spherical mesoporous meerschaum complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying method；Fig. 3 B is the scanning electron microscope (SEM) photograph of the high-amplification-factor of the spherical mesoporous meerschaum complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying method.As seen from the figure, the microscopic appearance of the spherical mesoporous meerschaum complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying method is still basic keeps spherical, and particle diameter is 10-50 μm.
Table 1 is the pore structure parameter of spherical mesoporous meerschaum complex carrier (C1) and the spherical mesoporous meerschaum complex carrier (Cat-1) of load phosphoric acid.
Table 1
From the data of table 1 it can be seen that spherical mesoporous meerschaum complex carrier is after load phosphoric acid, pore volume and specific surface area all reduce to some extent, it can be said that bright, and in load-reaction process, phosphoric acid has entered into the inside of spherical mesoporous meerschaum complex carrier.
Comparative example 1
This comparative example is for illustrating spherical mesoporous meerschaum complex carrier and the Catalysts and its preparation method of reference.
Spherical mesoporous meerschaum complex carrier and phosphoric acid loaded catalyst is prepared according to the method for embodiment 1, the difference is that, in the preparation process of spherical mesoporous meerschaum complex carrier, it is added without meerschaum, obtains the spherical mesoporous meerschaum complex carrier DCat-1 of spherical mesoporous meerschaum complex carrier DC1 and support type phosphoric acid.
Comparative example 2
This comparative example is for illustrating spherical mesoporous meerschaum complex carrier and the Catalysts and its preparation method of reference.
Spherical mesoporous meerschaum complex carrier and phosphoric acid loaded catalyst is prepared according to the method for embodiment 1, the difference is that, in the preparation process of spherical mesoporous meerschaum complex carrier, do not include being dissolved in by this pressed powder in 100 grams of deionized waters, and be the step of spray drying under 12000r/min at 200 DEG C, at rotating speed, but directly described pressed powder is calcined 24 hours with removed template method in the Muffle furnace of 500 DEG C, obtain the spherical mesoporous meerschaum complex carrier DCat-2 of spherical mesoporous meerschaum complex carrier DC2 and support type phosphoric acid.
Comparative example 3
This comparative example is for illustrating spherical mesoporous meerschaum complex carrier and the Catalysts and its preparation method of reference.
The preparation of spherical mesoporous meerschaum complex carrier and phosphoric acid loaded catalyst is carried out according to the method for embodiment 1, the difference is that, in the preparation process of spherical mesoporous meerschaum complex carrier, No. 1 mesoporous material filter cake and No. 2 mesoporous material filter cakes are used that the bar-shaped mesoporous silicon oxide SBA-15 filter cake (commercially available from high-tech limited company of Changchun Jilin University) of identical weight part substitutes, and obtain the spherical mesoporous meerschaum complex carrier DCat-3 of spherical mesoporous meerschaum complex carrier DC3 and support type phosphoric acid.
Embodiment 2
This embodiment is used for spherical mesoporous meerschaum complex carrier provided by the invention and Catalysts and its preparation method are described.
(1) preparation of spherical mesoporous meerschaum complex carrier:
1.0 grams of triblock copolymer P123s and 3.69 grams of (0.08mol) ethanol are joined 28mL, pH value is in the acetic acid of 5 and the buffer solution of sodium acetate, stir at 60 DEG C to P123 and be completely dissolved, add 9.14g(0.08mol afterwards) trimethylpentane, and after stirring 1 hour at 60 DEG C, add 4.68 grams of (0.03mol) tetramethoxy-silicanes, then at 60 DEG C, stir 10 hours when pH value is 5.5, and transfer the solution in teflon-lined reactor, baking oven crystallization 72 hours at 30 DEG C, by the crystallization product sucking filtration obtained and with distilled water wash four times, obtain No. 1 mesoporous material filter cake.
At 100 DEG C, cetyl trimethylammonium bromide and tetraethyl orthosilicate are joined in the ammonia spirit that concentration is 25 weight %, add deionized water, wherein, the addition of tetraethyl orthosilicate is 1 gram, and ammonia and the mol ratio of water in tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammonia are 1:0.1:2:120, and stirs 2 hours at 100 DEG C of temperature, then by solution sucking filtration and with distilled water wash four times, No. 2 mesoporous material filter cakes are obtained.
It is that 5:1 is mixed homogeneously by waterglass that concentration is 15 weight % and sulfuric acid solution that concentration is 12 weight % by waterglass and the weight ratio of sulphuric acid, then stirring reaction 1 hour at 60 DEG C, and the sulfuric acid solution that product concentration is 98 weight % that obtains is adjusted pH value is 2, then reaction mass sucking filtration, distilled water wash being washed till sodium ions content is 0.02 weight %, obtains silica gel filter cake.
12 grams of No. 1 mesoporous material filter cakes, 8 grams of No. 2 mesoporous material filter cakes, 10 grams of silica gel filter cakes and 4 grams of meerschaums are put into together in 100mL ball grinder (wherein, ball grinder material is politef, Material quality of grinding balls is Achates, the diameter of abrading-ball is 3mm, 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 34 grams of pressed powders.This pressed powder is dissolved in 100 grams of deionized waters, and be spray drying under 12000r/min at 200 DEG C, at rotating speed, then the product obtained after spray drying is calcined 24 hours with removed template method in the Muffle furnace of 500 DEG C, obtain the spherical mesoporous meerschaum complex carrier of target product of 32 grams of removed template methods, called after C2.
(2) preparation of phosphoric acid loaded catalyst:
At 25 DEG C, above-mentioned 32 grams of spherical mesoporous meerschaum complex carriers are put in deionized water together with phosphoric acid, stirring is to dissolving, the weight ratio controlling spherical sepiolite clay mineral complex carrier, deionized water and phosphoric acid is 1:25:1, then by the mixture obtained at 200 DEG C, be under 12000r/min, carry out spray drying at rotating speed, obtain the spherical mesoporous meerschaum complex carrier (i.e. phosphoric acid loaded catalyst) of load phosphoric acid, called after Cat-2.
Table 2 is the pore structure parameter of spherical mesoporous meerschaum complex carrier (C2) and the spherical mesoporous meerschaum complex carrier (Cat-2) of load phosphoric acid.
Table 2
From the data of table 2 it can be seen that spherical mesoporous meerschaum complex carrier is after load phosphoric acid, pore volume and specific surface area all reduce to some extent, it can be said that bright, and in load-reaction process, phosphoric acid has entered into the inside of spherical mesoporous meerschaum complex carrier.
Embodiment 3
This embodiment is used for spherical mesoporous meerschaum complex carrier provided by the invention and Catalysts and its preparation method are described.
(1) preparation of spherical mesoporous meerschaum complex carrier:
1.0 grams of triblock copolymer P123s and 2.76 grams of (0.06mol) ethanol are joined 28mL, pH value is in the acetic acid of 3 and the buffer solution of sodium acetate, stir at 40 DEG C to P123 and be completely dissolved, add 6.85g(0.06mol afterwards) trimethylpentane, and after stirring 8 hours at 40 DEG C, add 3.12 grams of (0.02mol) tetramethoxy-silicanes, then at 40 DEG C, stir 30 hours when pH value is 3.5, and transfer the solution in teflon-lined reactor, baking oven crystallization 10 hours at 150 DEG C, by the crystallization product sucking filtration obtained and with distilled water wash four times, obtain No. 1 mesoporous material filter cake.
At 50 DEG C, cetyl trimethylammonium bromide and tetraethyl orthosilicate are joined in the ammonia spirit that concentration is 25 weight %, add deionized water, wherein, the addition of tetraethyl orthosilicate is 1 gram, and ammonia and the mol ratio of water in tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammonia are 1:0.5:4:160, and stirs 6 hours at 50 DEG C of temperature, then by solution sucking filtration and with distilled water wash four times, No. 2 mesoporous material filter cakes are obtained.
It is that 5:1 is mixed homogeneously by waterglass that concentration is 15 weight % and sulfuric acid solution that concentration is 12 weight % by waterglass and the weight ratio of sulphuric acid, then stirring reaction 5 hours at 30 DEG C, and the sulfuric acid solution that product concentration is 98 weight % that obtains is adjusted pH value is 4, then reaction mass sucking filtration, distilled water wash being washed till sodium ions content is 0.02 weight %, obtains silica gel filter cake.
8 grams of No. 1 mesoporous material filter cakes, 12 grams of No. 2 mesoporous material filter cakes, 30 grams of silica gel filter cakes and 8 grams of meerschaums are put into together in 100mL ball grinder (wherein, ball grinder material is politef, Material quality of grinding balls is Achates, the diameter of abrading-ball is 3mm, 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 58 grams of pressed powders.This pressed powder is dissolved in 100 grams of deionized waters, and be spray drying under 12000r/min at 200 DEG C, at rotating speed, then the product obtained after spray drying is calcined 24 hours with removed template method in the Muffle furnace of 500 DEG C, obtain the spherical mesoporous meerschaum complex carrier of target product of 57 grams of removed template methods, called after C3.
(2) preparation of phosphoric acid loaded catalyst:
At 25 DEG C, above-mentioned 57 grams of spherical mesoporous meerschaum complex carriers are put in deionized water together with phosphoric acid, stirring is to dissolving, the weight ratio controlling spherical sepiolite clay mineral complex carrier, deionized water and phosphoric acid is 1:25:1, then by the mixture obtained at 200 DEG C, be under 12000r/min, carry out spray drying at rotating speed, obtain the spherical mesoporous meerschaum complex carrier (i.e. phosphoric acid loaded catalyst) of load phosphoric acid, called after Cat-3.
Table 3 is the pore structure parameter of spherical mesoporous meerschaum complex carrier (C3) and the spherical mesoporous meerschaum complex carrier (Cat-3) of load phosphoric acid.
Table 3
From the data of table 3 it can be seen that spherical mesoporous meerschaum complex carrier is after load phosphoric acid, pore volume and specific surface area all reduce to some extent, it can be said that bright, and in load-reaction process, phosphoric acid has entered into the inside of spherical mesoporous meerschaum complex carrier.
Embodiment 4
This embodiment is used for spherical mesoporous meerschaum complex carrier provided by the invention and Catalysts and its preparation method are described.
Spherical mesoporous meerschaum complex carrier and phosphoric acid loaded catalyst is prepared according to the method for embodiment 1, the difference is that, the process preparing phosphoric acid loaded catalyst does not have the step of spray drying, and only by impregnate method by phosphoric acid load on spherical mesoporous meerschaum complex carrier, thus prepare phosphoric acid loaded catalyst Cat-4.
Embodiment 5
This embodiment is used for the preparation method that ethyl acetate provided by the invention is described.
By phosphoric acid loaded catalyst Cat-1 vacuum drying 6 hours at 150 DEG C in embodiment 1,0.5 gram is weighed after being cooled to room temperature 25 DEG C, it is sequentially added in 100mL there-necked flask with 11.5 grams of ethanol and 15 grams of acetic acid, stirring reaction 3 hours under heated reflux condition, it is subsequently cooled to room temperature 25 DEG C and sucking filtration separates, utilize the liquid phase ingredient of gas chromatograph-mass spectrometer analytical reactions product, and by calculating the conversion ratio of acetic acid and the selectivity of ethyl acetate, result is as shown in table 4.
Embodiment 6-8
Embodiment 6-8 is used for the preparation method that ethyl acetate provided by the invention is described.
Prepare ethyl acetate according to the method for embodiment 5, institute the difference is that, replace described loaded catalyst Cat-1 with the embodiment 2-4 loaded catalyst prepared respectively.As a result, each calculating the conversion ratio of acetic acid and the selectivity of ethyl acetate, result is as shown in table 4.
Comparative example 4-6
Comparative example 4-6 is used for illustrating the reference preparation method of ethyl acetate.
Ethyl acetate is prepared according to the method for embodiment 5, the difference is that, replace described loaded catalyst Cat-1 with the comparative example 1-3 loaded catalyst prepared respectively.As a result, the conversion ratio of respective calculated acetic acid and the selectivity of ethyl acetate, result is as shown in table 4.
Table 4
| Numbering | Catalyst | The conversion ratio of acetic acid | The selectivity of ethyl acetate |
| Embodiment 5 | Cat-1 | 99.7% | 100% |
| Embodiment 6 | Cat-2 | 99.9% | 100% |
| Embodiment 7 | Cat-3 | 99.8% | 100% |
| Embodiment 8 | Cat-4 | 99.6% | 100% |
| Comparative example 4 | DCat-1 | 91% | 99% |
| Comparative example 5 | DCat-2 | 92% | 99% |
| Comparative example 6 | DCat-3 | 90% | 99% |
Embodiment 9-12 and comparative example 7-9
Ethyl acetate is prepared according to the method for embodiment 5, the difference is that, replace described loaded catalyst Cat-1 with from embodiment 5-8 and the comparative example 4-6 catalyst reclaimed respectively.As a result, the conversion ratio of respective calculated acetic acid and the selectivity of ethyl acetate, result is as shown in table 5.
Table 5
| Numbering | Catalyst | The conversion ratio of acetic acid | The selectivity of ethyl acetate |
| Embodiment 9 | The Cat-1 reclaimed | 99.5% | 100% |
| Embodiment 10 | The Cat-2 reclaimed | 99.4% | 99% |
| Embodiment 11 | The Cat-3 reclaimed | 99.1% | 100% |
| Embodiment 12 | The Cat-4 reclaimed | 97.5% | 99% |
| Comparative example 7 | The DCat-1 reclaimed | 89% | 98% |
| Comparative example 8 | The DCat-2 reclaimed | 90% | 97% |
| Comparative example 9 | The DCat-3 reclaimed | 88% | 98% |
As can be seen from the above results, adopting support preparation method provided by the invention can obtain average particulate diameter is 10-50 micron, specific surface area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, pore-size distribution is tri-modal distribution, and the spherical mesoporous meerschaum complex carrier of most probable pore size respectively 2-5 nanometer, 5-15 nanometer and 10-40 nanometer corresponding to described three peaks.Additionally, when phosphoric acid loaded catalyst provided by the invention is used for the preparation of ethyl acetate, not only there is higher acetic acid conversion and ethyl acetate selectivity, and also can by reclaiming and Reusability, aftertreatment technology is simple.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode.In order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a spherical mesoporous meerschaum complex carrier, it is characterized in that, this spherical mesoporous meerschaum complex carrier contains meerschaum and mesopore molecular sieve, and the average particulate diameter of described spherical mesoporous meerschaum complex carrier is 10-50 micron, specific surface area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, and pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-5 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding.
2. carrier according to claim 1, wherein, relative to the described mesopore molecular sieve of 100 weight portions, the content of described meerschaum is 1-50 weight portion.
3. a preparation method for spherical mesoporous meerschaum complex carrier, the method comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is carried out first contacts with acid agent, and the product crystallization obtained after contacting first filtering, obtain No. 1 mesoporous material filter cake；Cetyl trimethylammonium bromide, tetraethyl orthosilicate with ammonia, are carried out second and contact, and the product after the second contact is filtered, obtain No. 2 mesoporous material filter cakes；
(2) with mineral acid, waterglass is carried out the 3rd to contact, and the product obtained after the 3rd contact is filtered, obtain silica gel filter cake；
(3) described No. 1 mesoporous material filter cake, No. 2 mesoporous material filter cakes, silica gel filter cakes are mixed homogeneously and ball milling with meerschaum, and spray drying after the pressed powder water slurrying obtained after ball milling, will be carried out, then by the described template removal in the product that obtains.
4. preparation method according to claim 3, wherein, in step (3), with total consumption of the described No. 1 mesoporous material filter cake of 100 weight portions and No. 2 mesoporous material filter cakes for benchmark, the consumption of described silica gel filter cake is 1-200 weight portion, and the consumption of described meerschaum is 1-50 weight portion；The weight ratio of described No. 1 mesoporous material filter cake and No. 2 mesoporous material filter cakes is 0.5-1.5:1.
5. preparation method according to claim 3, wherein, in step (1), the mol ratio of described template, ethanol, trimethylpentane and tetramethoxy-silicane is 1:100-500:200-500:50-200；Ammonia and the mol ratio of water in described tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammonia are 1:0.1-1:0.1-5:100-200.
6. the preparation method according to claim 3 or 5, wherein, described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；The acetic acid of described acid agent to be pH value be 1-6 and the buffer solution of sodium acetate.
7. the preparation method according to claim 3 or 5, wherein, the condition of described first contact includes temperature and is 10-60 DEG C, and the time is 10-72 hour, and pH value is 1-7.
8. preparation method according to claim 7, wherein, the condition of described crystallization includes temperature and is 30-150 DEG C, and the time is 10-72 hour.
9. preparation method according to claim 7, wherein, the condition of described second contact includes temperature and is 25-100 DEG C, and the time is 1-10 hour.
10. preparation method according to claim 3, wherein, in step (2), the condition of described 3rd contact includes temperature and is 10-60 DEG C, and the time is 1-5 hour, and pH value is 2-4；Described mineral acid is one or more in sulphuric acid, nitric acid and hydrochloric acid.
11. preparation method according to claim 3, wherein, in step (3), the condition of described ball milling includes: the rotating speed of abrading-ball is 300-500r/min, and the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hour.
12. preparation method according to claim 11, wherein, the condition of described spray drying includes: temperature is 100-300 DEG C, and rotating speed is 10000-15000r/min.
13. preparation method according to claim 11, wherein, the condition of removed template method includes: temperature is 300-600 DEG C, and the time is 10-80 hour.
14. the spherical mesoporous meerschaum complex carrier that the method described in any one in claim 3-13 prepares.
15. a support type phosphoric acid catalyst, it is characterised in that this support type phosphoric acid catalyst includes the spherical mesoporous meerschaum complex carrier described in claim 1,2 or 14 and the load phosphoric acid on described spherical mesoporous meerschaum complex carrier.
16. a preparation method for support type phosphoric acid catalyst, the method includes the spherical mesoporous meerschaum complex carrier described in claim 1,2 or 14, phosphoric acid and water mix homogeneously, and the mixture obtained is carried out spray drying.
17. the application that the support type phosphoric acid catalyst described in claim 15 is in the esterification reaction.
18. the preparation method of an ethyl acetate, the method includes: in the presence of a catalyst and when esterification, is contacted with ethanol by acetic acid, obtains ethyl acetate, it is characterized in that, described catalyst is the support type phosphoric acid catalyst described in claim 15.
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