CN104248986B - The preparation method of the composite mesoporous carrier of spherical attapulgite and loaded catalyst and its preparation method and application and ethyl acetate - Google Patents
The preparation method of the composite mesoporous carrier of spherical attapulgite and loaded catalyst and its preparation method and application and ethyl acetate Download PDFInfo
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Abstract
The preparation method that the invention discloses the application in the esterification reaction of a kind of composite mesoporous carrier of spherical attapulgite and preparation method thereof, a kind of loaded catalyst and preparation method thereof and this catalyst and a kind of ethyl acetate.This composite mesoporous carrier of spherical attapulgite contains attapulgite and meso-porous molecular sieve material, the mean diameter of this composite mesoporous carrier of spherical attapulgite is 30-60 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 2-4 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding.Support type benzenesulfonic acid catalyst provided by the invention not only has higher catalysis activity, and can Reusability.
Description
Technical field
The preparation method that the present invention relates to the application in the esterification reaction of a kind of composite mesoporous carrier of spherical attapulgite, the preparation method of a kind of composite mesoporous carrier of spherical attapulgite, the method composite mesoporous carrier of spherical attapulgite prepared, a kind of support type benzenesulfonic acid catalyst, the preparation method of a kind of support type benzenesulfonic acid catalyst, this support type benzenesulfonic acid catalyst and a kind of ethyl acetate.
Background technology
Attapulgite clay (abbreviation attapulgite clay) is a kind of containing Shuifu County's 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, and there is the layer chain crystal structure of uniqueness and the crystal habit of porous.Attapulgite clay has significantly high specific surface area, absorption property, catalytic action, rheological characteristic and thermostability, it is possible to be widely used in the fields such as dyeing wastewater process, deodorizer, filter aid, cleanser, decolorising agent, dytory, thixotropic agent and binding agent.Owing to the specific surface area of attapulgite clay is big, having specific channel, there is a large amount of active centre in crystal structure, therefore, attapulgite clay has the carbonium ion in organic reaction and turns the shape selective catalysis splitting action of use, concerted acid-base catalysis and molecular sieve into.
Within 1992, Mobile company synthesizes mesoporous material, and this mesoporous material has high specific surface, regular pore passage structure and narrow pore-size distribution so that mesoporous material catalysis, separation, medicine and other fields application obtain very big concern；Zhao east in 1998 unit et al. synthesizes a kind of new material-mesoporous material SBA-15 (D.Y.Zhao, J.L.Feng, Q.S.Huo, etalScience279 (1998) 548-550), this material has cube single-crystal meso-pore material aperture (6-30nm) of high-sequential, the big (1.0cm of pore volume3/ g), the high mechanical properties that keeps of thicker hole wall (4-6nm) and good catalytic adsorption performance；Zhao Dongyuan, Yu Chengzhong, remaining person of outstanding talent forever invent the preparation method (CN1341553A) of a kind of mesonic pore molecular sieve carrier material, and this mesoporous material is as heterogeneous reaction catalyst carrier, it is easy to realize separating of catalyst and product.
In existing loaded catalyst, adopt conventional meso-porous molecular sieve material as carrier.Conventional 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 surface area and the advantage such as pore volume is bigger, make to adopt the loaded catalyst that these meso-porous molecular sieve materials are made as carrier to show lot of advantages in the preparation technology of ethyl acetate, such as, catalysis activity is high, side reaction is few, post processing is simple, but, big specific surface area and high pore volume cause these meso-porous molecular sieve materials have stronger water suction, moisture absorption ability, thus can cause that these loaded catalysts are reunited in esterification reaction process, and then can seriously reduce the conversion ratio of acetic acid in ethyl acetate preparation technology.
Summary of the invention
It is an object of the invention to overcome the defect that the loaded catalyst adopting existing meso-porous molecular sieve material to make reaction raw materials conversion ratio in for esterification reaction process is relatively low, a kind of composite mesoporous carrier of spherical attapulgite being suitable as carrier is provided, and the preparation method of this composite mesoporous carrier of spherical attapulgite, the composite mesoporous carrier of spherical attapulgite obtained prepared by the method, a kind of support type benzenesulfonic acid catalyst, a kind of preparation method of support type benzenesulfonic acid catalyst, the preparation method of the application in the esterification reaction of this support type benzenesulfonic acid catalyst and a kind of ethyl acetate.
In order to achieve the above object, the present inventor is by finding after studying, meso-porous molecular sieve material introduces attapulgite, attapulgite 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, the advantages such as big pore volume and large aperture, the reunion of meso-porous molecular sieve material can be reduced again, increase its mobility, make the loaded catalyst adopting this mesopore molecular sieve to make can obtain the reaction raw materials conversion ratio significantly improved when for esterification, thus completing the present invention.
For this, the present invention provides a kind of composite mesoporous carrier of spherical attapulgite, wherein, this composite mesoporous carrier of spherical attapulgite contains attapulgite and meso-porous molecular sieve material, and the mean diameter of the described composite mesoporous carrier of spherical attapulgite is 30-60 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 2-4 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding.
The preparation method that the present invention also provides for a kind of composite mesoporous carrier of spherical attapulgite, the method comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acid agent, and by the product crystallization that obtains after contact and filter, obtain No. 1 mesoporous material filter cake；Cetyl trimethylammonium bromide, tetraethyl orthosilicate are contacted with ammonia, and the product after contact is filtered, obtain No. 2 mesoporous material filter cakes；
(2) waterglass is contacted with mineral acid, and the product obtained after 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 attapulgite, 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 a kind of composite mesoporous carrier of spherical attapulgite prepared by said method.
Present invention also offers a kind of support type benzenesulfonic acid catalyst, wherein, this catalyst includes the above-mentioned composite mesoporous carrier of spherical attapulgite and the load benzenesulfonic acid on the described composite mesoporous carrier of spherical attapulgite.
The preparation method that present invention also offers a kind of support type benzenesulfonic acid catalyst, wherein, the method includes the above-mentioned composite mesoporous carrier of spherical attapulgite, benzenesulfonic 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 above-mentioned support type benzenesulfonic acid catalyst.
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 benzenesulfonic acid catalyst.
The inventors found that, including the above-mentioned composite mesoporous carrier of spherical attapulgite with certain physical property and load, the catalyst activity of the benzenesulfonic acid on the described composite mesoporous carrier of spherical attapulgite is higher, can the esterification of catalysis acetic acid and ethanol obtain higher acetic acid conversion and ethyl acetate selectivity, this is possibly due to: on the one hand, carrier provided by the invention is spherical, the reunion of powder body can be reduced, improve its mobility；On the other hand, carrier provided by the invention not only remains that the high-specific surface area of meso-porous molecular sieve material, big pore volume, aperture be big and the feature of narrowly distributing, and its pore-size distribution presents the tri-modal distribution of uniqueness, is more beneficial for the load of active component, thus having higher catalysis activity.
Additionally, cheap attapulgite is incorporated in composite, it is possible to reduce the production cost of carrier to a great extent.Namely, the advantage of meso-porous molecular sieve material and attapulgite that micro-sphere structure, aperture are had tri-modal distribution by the composite mesoporous carrier of spherical attapulgite provided by the invention dexterously combines, thus the application for the described composite mesoporous carrier of spherical attapulgite provides better platform, and expand its application.
Additionally, catalyst provided by the invention also has and does not corrode that instrument, side reaction be few and the simple advantage of aftertreatment technology.
It addition, when preparing described support type benzenesulfonic acid catalyst by the method for spray drying, described support type benzenesulfonic acid catalyst may be repeated utilization, and still can obtain higher reaction raw materials conversion ratio in recycling process.
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), wherein, a is the XRD spectra of spherical attapulgite mesoporous composite material carrier (C1), b is the XRD spectra of spherical attapulgite mesoporous composite material carrier (Cat-1) of the load benzenesulfonic acid obtained by spray drying method, abscissa is 2 θ, and vertical coordinate is intensity；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the microscopic appearance of spherical attapulgite mesoporous composite material carrier (C1)；
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the microscopic appearance of spherical attapulgite mesoporous composite material carrier (Cat-1) of the load benzenesulfonic 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.
The present invention provides a kind of composite mesoporous carrier of spherical attapulgite, wherein, this composite mesoporous carrier of spherical attapulgite contains attapulgite and meso-porous molecular sieve material, and the mean diameter of the described composite mesoporous carrier of spherical attapulgite is 30-60 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 2-4 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding.Under preferable case, the mean diameter of the described composite mesoporous carrier of spherical attapulgite is 35-40 micron, specific surface area is 180-600 meters squared per gram, pore volume is 0.8-1.5 ml/g, pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-3 nanometer, 5-10 nanometer and 20-30 nanometer that described three peaks are corresponding.
In the present invention, described mean diameter adopts laser fineness gage to record, and specific surface area, pore volume and most probable pore size record according to nitrogen adsorption methods.
The composite mesoporous carrier of spherical attapulgite according to the present invention is that three holes are uniformly distributed, by the particle size of spherical mesoporous attapulgite complex carrier is controlled within above-mentioned scope, may insure that the described composite mesoporous carrier of spherical attapulgite 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 attapulgite 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 the described composite mesoporous carrier of spherical attapulgite 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 conversion ratio of the reaction raw materials affected in esterification reaction process.
In the described three equally distributed composite mesoporous carriers of spherical attapulgite in hole, relative to the described meso-porous molecular sieve material of 100 weight portions, the content of described attapulgite can be 1-50 weight portion, it is preferred to 20-50 weight portion.
In the present invention, the described composite mesoporous carrier of spherical attapulgite can also contain the silicon dioxide introduced by waterglass." by the silicon dioxide that waterglass introduces " refers in the preparation process of the described composite mesoporous carrier of spherical attapulgite, waterglass bring the silica component in the final spherical attapulgite complex carrier prepared into as preparing raw material.In the described composite mesoporous carrier of spherical attapulgite, 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 meso-porous molecular sieve material can be the conventional selection of this area, as a rule, it is mainly composed of silicon dioxide, and the mean diameter of described meso-porous molecular sieve material is 30-60 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 2-4 nanometer that described three peaks are corresponding, 5-15 nanometer and 10-40 nanometer, under preferable case, the mean diameter of described meso-porous molecular sieve material is 35-40 micron, specific surface area is 180-600 meters squared per gram, pore volume is 0.8-1.5 ml/g, pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-3 nanometer that described three peaks are corresponding, 5-10 nanometer and 20-30 nanometer.
The preparation method that the present invention also provides for a kind of composite mesoporous carrier of spherical attapulgite, the method comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acid agent, and by the product crystallization that obtains after contact and filter, obtain No. 1 mesoporous material filter cake；Cetyl trimethylammonium bromide, tetraethyl orthosilicate are contacted with ammonia, and the product after contact is filtered, obtain No. 2 mesoporous material filter cakes；
(2) waterglass is contacted with mineral acid, and the product obtained after 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 attapulgite, 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 the above-mentioned three equally distributed composite mesoporous carriers of spherical attapulgite in hole, mainly through controlling No. 1 mesoporous material filter cake, the pore-size distribution of the described composite mesoporous carrier of spherical attapulgite controls as tri-modal distribution, and makes this composite mesoporous carrier of spherical attapulgite have three holes to be uniformly distributed structure by the composition of No. 2 mesoporous material filter cakes and silica gel filter cake；And by controlling forming method (namely, first No. 1 mesoporous material filter cake, No. 2 mesoporous material filter cakes, silica gel filter cakes are mixed homogeneously and ball milling with attapulgite, then by spray drying after the pressed powder water slurrying obtained) microscopic appearance of the described composite mesoporous carrier of spherical attapulgite is controlled as spherical.
According to the present invention, to the kind of described template, there is no particular limitation, as long as can so that the composite mesoporous carrier of spherical attapulgite obtained 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 mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene and obtains.
According to the present invention, to the kind of described acid agent, there is no particular limitation, it is possible to for 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.Under preferable case, described acid agent be pH value is that 1-6(is preferably 3-5) buffer solution of acetic acid and sodium acetate.
The condition that described tetramethoxy-silicane is contacted by the present invention with acid agent does not limit especially, for instance, the condition that described tetramethoxy-silicane contacts with acid agent 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 that described tetramethoxy-silicane contacts with acid agent includes: temperature 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 tetramethoxy-silicane contacts with acid agent and preferably carries out under agitation.The consumption of described acid agent is preferably so that the pH value of described tetramethoxy-silicane and acid agent haptoreaction system is 1-7, it is preferred to 3-6.
There is no particular limitation to the condition of described crystallization for the present invention, the condition of described crystallization can be the selection that this area is conventional, such as, the condition of described crystallization may include that temperature is 30-150 DEG C, time is 10-72 hour, under preferable case, the condition of described crystallization includes: temperature is 40-80 DEG C, and the time is 20-40 hour.Described crystallization is implemented by hydrothermal crystallization method.
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 mean molecule quantity 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, by template, ethanol, acidic aqueous solution and trimethylpentane stirring mixing 6-10 hour, then adds tetramethoxy-silicane and continues stirring mixing 4-62 hour.
According to the present invention, 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, 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; the ammonia that addition is commercially available is generally difficult to and meets above mol ratio; therefore; in the process that cetyl trimethylammonium bromide, tetraethyl orthosilicate contact with ammonia; generally also need to add water, carry out haptoreaction by cetyl trimethylammonium bromide, tetraethyl orthosilicate, ammonia and extra water.The consumption of above-mentioned water includes the water of water and the extra addition contained in ammonia itself.
There is no particular limitation for the condition that cetyl trimethylammonium bromide, tetraethyl orthosilicate are contacted by the present invention with ammonia, for instance may include that the temperature of contact is 25-100 DEG C, it is preferred to 50-100 DEG C；The time of contact is 1-10 hour, it is preferred to 2-6 hour.
The condition that described waterglass is contacted by the present invention with mineral acid is not particularly limited, for instance, the condition that described waterglass contacts with mineral acid 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, and pH value is 2-4.In order to be more beneficial for the Homogeneous phase mixing between each material, described waterglass contacts with mineral acid and 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 contact conditions reaction system of mineral acid is 2-4.
According to the present invention, in the preparation process of the described composite mesoporous carrier of spherical attapulgite, 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 attapulgite can select according to the component of the three equally distributed composite mesoporous carriers of spherical attapulgite in hole 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 attapulgite 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.
According to the present invention, to the concrete operation method of described ball milling and condition, there is no particular limitation, and the structure not destroy or substantially not destroy carrier is 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.
According to the present invention, by the process of pressed powder use water slurrying, to the weight ratio of described pressed powder Yu water, there is no particular limitation, it is possible to changes in wider scope, as long as the slurry of spray drying can be obtained being conducive to.Such as, described pressed powder is 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 described spray drying includes: temperature can be 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min；Under preferable case, the condition of described spray drying includes temperature and is 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min；Under most preferred case, the condition of described spray drying includes: temperature is 200 DEG C, and the rotating speed of rotation is 12000r/min.
According to the present invention, the method for removed template method is generally calcination method.The condition of described removed template method can select for this area routine, for instance, the condition of described removed template method includes: 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 composite mesoporous carrier of spherical attapulgite prepared by said method.
Present invention also offers a kind of support type benzenesulfonic acid catalyst, wherein, this catalyst includes the above-mentioned composite mesoporous carrier of spherical attapulgite and the load benzenesulfonic acid on the described composite mesoporous carrier of spherical attapulgite.
According to the present invention, in described support type benzenesulfonic acid catalyst, the content of the described composite mesoporous carrier of spherical attapulgite and benzenesulfonic acid can be the conventional selection of this area, such as, with the gross weight of described support type benzenesulfonic acid catalyst for benchmark, the content of described benzenesulfonic acid can be 1-50 weight %, it is preferred to 5-50 weight %, the content of the described composite mesoporous carrier of spherical attapulgite can be 50-99 weight %, it is preferred to 50-95 weight %.
In the present invention, described support type benzenesulfonic acid catalyst can be prepared according to various methods commonly used in the art, it is only necessary to by benzenesulfonic acid load on the carrier.
In a preferred embodiment, in order to make the support type benzenesulfonic acid 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 the above-mentioned composite mesoporous carrier of spherical attapulgite, benzenesulfonic acid and water mix homogeneously, and the mixture obtained is carried out spray drying.
Wherein, the consumption of the described composite mesoporous carrier of spherical attapulgite, benzenesulfonic acid and water reasonably can select according to the catalyst that expection obtains, such as, with total consumption of described spherical attapulgite complex carrier and benzenesulfonic acid for benchmark, the consumption of described benzenesulfonic acid can be 1-50 weight %, it is preferred to 5-50 weight %；The consumption of the described composite mesoporous carrier of spherical attapulgite can be 50-99 weight %, it is preferred to 50-95 weight %.Additionally, the mol ratio of described benzenesulfonic acid and water is 1:15-35, it is preferred to 1:20-25.
According to the present invention, the method of described spray drying is known to the skilled person, as mentioned above, it is generally and the mixture of composite mesoporous for spherical attapulgite carrier, water and benzenesulfonic 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；Under preferable case, the condition of described spray drying includes temperature and is 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min；Under most preferred case, the condition of described spray drying includes: temperature is 200 DEG C, and the rotating speed of rotation is 12000r/min.
Present invention also offers the application in the esterification reaction of above-mentioned support type benzenesulfonic acid 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 support type benzenesulfonic acid 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 support type benzenesulfonic acid 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 support type benzenesulfonic acid 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, it is centrifuged final reactant mixture separating, and by centrifugal 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 support type benzenesulfonic acid catalyst.
Below in conjunction with embodiment, the present invention is described in detail.
In following example, 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, mean molecule quantity 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 EXPERIMENTAL EXAMPLE and Experimental comparison's 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 the composite mesoporous carrier of spherical attapulgite provided by the invention and support type benzenesulfonic acid Catalysts and its preparation method are described.
(1) preparation of the composite mesoporous carrier of spherical attapulgite
1.0 grams of (0.0001mol) triblock copolymer polyethylene glycol glycerol-Polyethylene Glycol (P123) 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, afterwards by 3.43g(0.03mol) trimethylpentane join in above-mentioned solution, and after stirring 8 hours at 15 DEG C, add 2.28 grams of (0.015mol) tetramethoxy-silicanes, then at 15 DEG C, stir 20 hours when pH value is 4.5, and gained solution is transferred 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 1g, tetraethyl orthosilicate: cetyl trimethylammonium bromide: ammonia and the mol ratio of water in 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.
By waterglass that concentration is 15 weight % and sulfuric acid solution that concentration is 12 weight %, and be that 5:1 is mixed homogeneously by waterglass and the weight ratio of sulphuric acid, then stirring reaction 3 hours at 20 DEG C, and the sulphuric acid that product concentration is 98 weight % that obtains is adjusted pH is 3, then through sucking filtration, distilled water wash, reaction mass 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 dielectric material filter cakes, 20 grams of silica gel filter cakes and 10 grams of attapulgites 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 50 grams of deionized waters, and at 200 DEG C, is spray drying under 12000r/min at rotating speed；Then the product obtained after spray drying being calcined 24 hours in the Muffle furnace of 500 DEG C with removed template method, target product three hole obtaining 49 grams of removed template methods is uniformly distributed the composite mesoporous carrier of spherical attapulgite, called after C1.
(2) preparation of support type benzenesulfonic acid catalyst
At 25 DEG C, above-mentioned 49 grams of composite mesoporous carriers of spherical attapulgite are put in deionized water together with benzenesulfonic acid, stirring is to dissolving, and three hole be uniformly distributed the weight ratio 50:50 of spherical attapulgite mesoporous composite material support C 1 and benzenesulfonic acid, the mol ratio of deionized water and benzenesulfonic acid is 25:1, then by the mixture of gained at 200 DEG C, is carry out spray drying under 12000r/min at rotating speed, obtain support type benzenesulfonic acid catalyst, called after Cat-1.
The composite mesoporous carrier of spherical attapulgite and this support type benzenesulfonic acid catalyst that this three hole are all distributed with XRD, scanning electron microscope and U.S. Kang Ta company Atsorb-1 type nitrogen adsorption desorption instrument characterize.
Fig. 1 is X-ray diffracting spectrum (XRD figure), wherein, a is the XRD spectra of the composite mesoporous carrier of spherical attapulgite (C1), and b is the XRD spectra of the composite mesoporous carrier of the spherical attapulgite (Cat-1) of the load benzenesulfonic acid obtained by spray drying method, abscissa is 2 θ, and vertical coordinate is intensity.Can be seen that from the result of Fig. 1, the XRD spectra a of the composite mesoporous carrier of spherical attapulgite (C1) and the XRD spectra b of the composite mesoporous carrier of the spherical attapulgite (Cat-1) of load benzenesulfonic acid obtained by spray drying method all occurs in that low-angle spectral peak, thereby it is assumed that, the three holes composite mesoporous carrier of equally distributed spherical attapulgite (C1) and support type benzenesulfonic acid catalyst (Cat-1) are respectively provided with the hexagonal hole road structure of 2D specific to meso-porous molecular sieve material.
Fig. 2 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the composite mesoporous carrier of spherical attapulgite (C1), by the result of Fig. 2 it can be seen that the microscopic appearance of the composite mesoporous carrier of spherical attapulgite (C1) is particle diameter is the Mesoporous Spheres of 30-60 μm.
Fig. 3 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the composite mesoporous carrier of the spherical attapulgite (Cat-1) of the load benzenesulfonic acid obtained by spray drying method.By the result of Fig. 3 it can be seen that the microscopic appearance of the composite mesoporous carrier of the spherical attapulgite (Cat-1) of the load benzenesulfonic acid obtained by spray drying method is still basic keeps spherical, particle diameter is 30-60 μm.
Table 1 is the pore structure parameter of spherical attapulgite mesoporous composite material carrier (C1) and the composite mesoporous carrier of the spherical attapulgite (Cat-1) of load benzenesulfonic acid.
Table 1
Be can be seen that by the data of table 1, the composite mesoporous carrier of spherical attapulgite is after load benzenesulfonic acid, pore volume and specific surface area and average pore size all reduce to some extent, and this illustrates that benzenesulfonic acid enters into the inside of the composite mesoporous carrier of spherical attapulgite in load-reaction process.
Comparative example 1
This comparative example is for illustrating spherical mesoporous complex carrier and the support type benzenesulfonic acid Catalysts and its preparation method of reference.
The composite mesoporous carrier of spherical attapulgite and the preparation of support type benzenesulfonic acid catalyst is carried out according to the method for embodiment 1, institute the difference is that, in the process of the preparation three equally distributed composite mesoporous carriers of spherical attapulgite in hole, it is added without attapulgite, obtains composite mesoporous carrier (DC1) and support type benzenesulfonic acid catalyst (DCat-1).
Comparative example 2
This comparative example is for illustrating the composite mesoporous carrier of spherical attapulgite and the support type benzenesulfonic acid Catalysts and its preparation method of reference.
The composite mesoporous carrier of spherical attapulgite and the preparation of support type benzenesulfonic acid catalyst is carried out according to the method for embodiment 1, the difference is that, in the process of the preparation three equally distributed composite mesoporous carriers of spherical attapulgite in hole, do not include being dissolved in pressed powder in 50 grams of deionized waters, and be the step of spray drying under 12000r/min at rotating speed at 200 DEG C, but directly pressed powder is calcined 24 hours in the Muffle furnace of 500 DEG C, removed template method.Obtain the three hole composite mesoporous carrier DCat-2 of equally distributed spherical attapulgite of three hole equally distributed spherical attapulgite composite mesoporous carrier DC2 and load benzenesulfonic acid.
Comparative example 3
This comparative example is for illustrating the composite mesoporous carrier of spherical attapulgite and the support type benzenesulfonic acid Catalysts and its preparation method of reference.
The composite mesoporous carrier of spherical attapulgite and the preparation of support type benzenesulfonic acid catalyst is carried out according to the method for embodiment 1, the difference is that, in the process preparing the composite mesoporous carrier of spherical attapulgite, 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 composite mesoporous carrier DCat-3 of spherical attapulgite of spherical attapulgite composite mesoporous carrier DC3 and load benzenesulfonic acid).
Embodiment 2
This embodiment is used for the composite mesoporous carrier of spherical attapulgite provided by the invention and support type benzenesulfonic acid Catalysts and its preparation method are described.
(1) preparation of the composite mesoporous carrier of spherical attapulgite
1.0 grams of triblock copolymer P123s and 0.92 gram of ethanol (0.02mol) are joined 28mL, pH value is in the acetic acid of 5 and the buffer solution of sodium acetate, stir at 20 DEG C to P123 and be completely dissolved, afterwards by 2.86g(0.025mol) trimethylpentane join in above-mentioned solution, and after stirring 1 hour at 20 DEG C, add 1.07 grams of (0.007mol) tetramethoxy-silicanes, then at 20 DEG C, stir 30 hours when pH value is 5.5, and gained solution is transferred in teflon-lined reactor, baking oven crystallization 40 hours at 40 DEG C, and 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 1g, and the ammonia in tetraethyl orthosilicate, cetyl trimethylammonium bromide, ammonia, the mol ratio of water 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 1.5 hours at 40 DEG C, and the sulphuric acid that product concentration is 98 weight % that obtains is adjusted pH is 2, then through sucking filtration, distilled water wash, reaction mass 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 dielectric material filter cakes, 10 grams of silica gel filter cakes and 4 grams of attapulgites 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 51 grams of deionized waters, and at 150 DEG C, is spray drying under 11000r/min at rotating speed；Then the product obtained after spray drying being calcined 24 hours in the Muffle furnace of 500 DEG C with removed template method, target product three hole obtaining 32 grams of removed template methods is uniformly distributed the composite mesoporous carrier of spherical attapulgite, called after C2.
(2) preparation of support type benzenesulfonic acid catalyst
At 25 DEG C, above-mentioned 32 gram of three hole is uniformly distributed the composite mesoporous carrier of spherical attapulgite put into together with benzenesulfonic acid in deionized water, stirring is to dissolving, and three to be uniformly distributed the weight ratio of spherical attapulgite mesoporous composite material carrier and benzenesulfonic acid be 95:5 in hole, the mol ratio of deionized water and benzenesulfonic acid is 20:1, then by the mixture of gained at 150 DEG C, it is under 11000r/min, carry out spray drying at rotating speed, obtain the composite mesoporous carrier of spherical attapulgite (i.e. support type benzenesulfonic acid catalyst) of load benzenesulfonic acid, called after Cat-2.
Table 2 is the pore structure parameter of the composite mesoporous carrier of spherical attapulgite (C2) and the mesoporous composite mesoporous carrier (Cat-2) of spherical attapulgite of load benzenesulfonic acid.
Table 2
From the data of table 2 it can be seen that the composite mesoporous carrier of spherical attapulgite is after load benzenesulfonic acid, pore volume and specific surface area all reduce to some extent, it can be said that bright, and in load-reaction process, benzenesulfonic acid has entered into the inside of the composite mesoporous carrier of spherical attapulgite.
Embodiment 3
This embodiment is used for the composite mesoporous carrier of spherical attapulgite provided by the invention and support type benzenesulfonic acid Catalysts and its preparation method are described.
(1) preparation of the composite mesoporous carrier of spherical attapulgite
1.0 grams of triblock copolymer P123s and 1.38 grams of (0.03mol) ethanol are joined 28mL, pH value is in the acetic acid of 3 and the buffer solution of sodium acetate, stir at 30 DEG C to P123 and be completely dissolved, afterwards by 4.57g(0.04mol) trimethylpentane join in above-mentioned solution, and after stirring 8 hours at 30 DEG C, add 1.52 grams of (0.01mol) tetramethoxy-silicanes, then at 30 DEG C, stir 40 hours when pH value is 3.5, and gained solution is transferred in teflon-lined reactor, baking oven crystallization 20 hours at 80 DEG C, and 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 1g, 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 4:1 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 2 hours at 30 DEG C, and the sulphuric acid that product concentration is 98 weight % that obtains is adjusted pH is 4, then through sucking filtration, distilled water wash, reaction mass being washed till sodium ions content is 0.02 weight %, obtains silica gel filter cake.
The 8 of above-mentioned preparation grams of No. 1 mesoporous material filter cakes, 12 grams of No. 2 dielectric material filter cakes, 30 grams of silica gel filter cakes and 8 grams of attapulgites 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 at 250 DEG C, is spray drying under 13000r/min at rotating speed；Then the product obtained after spray drying being calcined 24 hours in the Muffle furnace of 500 DEG C with removed template method, target product three hole obtaining 55 grams of removed template methods is uniformly distributed the composite mesoporous carrier of spherical attapulgite, called after C3.
(2) preparation of support type benzenesulfonic acid catalyst
At 25 DEG C, above-mentioned 55 gram of three hole is uniformly distributed the composite mesoporous carrier of spherical attapulgite put into together with benzenesulfonic acid in deionized water, stirring is to dissolving, and three to be uniformly distributed the weight ratio of the composite mesoporous carrier of spherical attapulgite and benzenesulfonic acid be 85:15 in hole, the mol ratio of deionized water and benzenesulfonic acid is 22:1, then by the mixture of gained at 250 DEG C, it is under 13000r/min, carry out spray drying at rotating speed, obtain the three equally distributed composite mesoporous carriers of spherical attapulgite in hole of load benzenesulfonic acid, called after Cat-3.
Table 3 is the pore structure parameter of the composite mesoporous carrier of spherical attapulgite (C3) and the composite mesoporous carrier of the spherical attapulgite (Cat-3) of load benzenesulfonic acid.
Table 3
From the data of table 3 it can be seen that the composite mesoporous carrier of spherical attapulgite is after load benzenesulfonic acid, pore volume and specific surface area all reduce to some extent, it can be said that bright, and in load-reaction process, benzenesulfonic acid has entered into the inside of the composite mesoporous carrier of spherical attapulgite.
Embodiment 4
This embodiment is used for the composite mesoporous carrier of spherical attapulgite provided by the invention and Catalysts and its preparation method are described.
Method according to embodiment 1 prepares the composite mesoporous carrier of spherical attapulgite and support type benzenesulfonic acid catalyst, different, the process preparing support type benzenesulfonic acid catalyst does not have the step of spray drying, and only by impregnate method by benzenesulfonic acid load on the composite mesoporous carrier of spherical attapulgite, thus prepare support type benzenesulfonic acid catalyst Cat-4.
Embodiment 5
This EXPERIMENTAL EXAMPLE is used for the preparation method that ethyl acetate provided by the invention is described.
By support type benzenesulfonic acid catalyst (Cat-1) vacuum drying 6 hours at 120 DEG C in embodiment 1, after being cooled to room temperature 25 DEG C, weigh 0.5 gram, it is sequentially placed in 100mL there-necked flask with 11.5 grams of ethanol and 15 grams of acetic acid, stir 3 hours under heated reflux condition, be 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 ethyl acetate selectivity.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.
Method according to embodiment 5 prepares ethyl acetate, institute the difference is that, replace described loaded catalyst Cat-1 with the embodiment 2-4 loaded catalyst prepared respectively.As a result, the conversion ratio of respective calculated acetic acid and ethyl acetate selective data are as shown in table 4 below.
Comparative example 4-6
Comparative example 4-6 is used for illustrating the reference preparation method of ethyl acetate.
Method according to embodiment 5 prepares ethyl acetate, institute 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 ethyl acetate selective data are as shown in table 4 below.
Table 4
| Numbering | Catalyst | The conversion ratio of acetic acid | Ethyl acetate selectivity |
| Embodiment 5 | Cat-1 | 99.8% | 100% |
| Embodiment 6 | Cat-2 | 99.9% | 100% |
| Embodiment 7 | Cat-3 | 99.7% | 100% |
| Embodiment 8 | Cat-4 | 97.6% | 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
Method according to embodiment 5 prepares ethyl acetate, institute 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 ethyl acetate selective data are as shown in table 5 below.
Table 5
| Numbering | Catalyst | The conversion ratio of acetic acid | Ethyl acetate selectivity |
| Embodiment 9 | The Cat-1 reclaimed | 99.3% | 100% |
| Embodiment 10 | The Cat-2 reclaimed | 99.6% | 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 | 87% | 98% |
| Comparative example 8 | The DCat-2 reclaimed | 90% | 97% |
| Comparative example 9 | The DCat-3 reclaimed | 86% | 98% |
Be can be seen that by above result, it is 30-60 micron that the preparation method adopting carrier provided by the invention can obtain mean diameter, 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 three equally distributed composite mesoporous carriers of spherical attapulgite in hole of most probable pore size respectively 2-4 nanometer, 5-15 nanometer and 10-40 nanometer corresponding to described three peaks.In addition, the catalytic performance of support type benzenesulfonic acid catalyst provided by the invention is better, when applying the esterification that this catalyst comes catalysis acetic acid and ethanol, there is higher acetic acid conversion and ethyl acetate selectivity, and support type benzenesulfonic acid catalyst provided by the invention can through and recovery and Reusability, and 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 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 (13)
1. the composite mesoporous carrier of spherical attapulgite, it is characterized in that, this composite mesoporous carrier of spherical attapulgite contains attapulgite and meso-porous molecular sieve material, and the mean diameter of the described composite mesoporous carrier of spherical attapulgite is 30-60 micron, specific surface area is 150-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and pore-size distribution is tri-modal distribution, and the most probable pore size respectively 2-4 nanometer, 5-15 nanometer and 10-40 nanometer that described three peaks are corresponding
The preparation method of the described composite mesoporous carrier of spherical attapulgite comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acid agent, and by the product crystallization that obtains after contact and filter, obtain No. 1 mesoporous material filter cake；Cetyl trimethylammonium bromide, tetraethyl orthosilicate are contacted with ammonia, and the product after contact is filtered, obtain No. 2 mesoporous material filter cakes；
(2) waterglass is contacted with mineral acid, and the product obtained after 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 attapulgite, and spray drying will carry out after the pressed powder water slurrying obtained after ball milling, then by the described template removal in the product that obtains.
2. carrier according to claim 1, wherein, relative to the described meso-porous molecular sieve material of 100 weight portions, the content of described attapulgite is 1-50 weight portion.
3. carrier according to claim 2, wherein, relative to the described meso-porous molecular sieve material of 100 weight portions, the content of described attapulgite is 20-50 weight portion.
4. carrier according to claim 1, 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 attapulgite 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. carrier according to claim 1, 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. carrier according to claim 1 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. carrier according to claim 1 or 5, wherein, the condition that described tetramethoxy-silicane contacts with acid agent includes temperature and is 10-60 DEG C, and the time is 10-72 hour, and pH value is 1-7；The condition of described crystallization includes: temperature is 30-150 DEG C, and the time is 10-72 hour；The condition that described cetyl trimethylammonium bromide, tetraethyl orthosilicate contact with ammonia includes: temperature is 25-100 DEG C, and the time is 1-10 hour.
8. carrier according to claim 1, wherein, in step (2), the condition that described waterglass contacts with mineral acid includes: temperature 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.
9. carrier according to claim 1, 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；The condition of described spray drying includes: temperature is 100-300 DEG C, and rotating speed is 10000-15000r/min；The condition of removed template method includes: temperature is 300-600 DEG C, and the time is 10-80 hour.
10. a support type benzenesulfonic acid catalyst, it is characterised in that this catalyst includes in claim 1-9 the composite mesoporous carrier of spherical attapulgite described in any one and load benzenesulfonic acid on the described composite mesoporous carrier of spherical attapulgite.
11. the preparation method of a support type benzenesulfonic acid catalyst, it is characterised in that the method includes the composite mesoporous carrier of spherical attapulgite described in any one in claim 1-9, benzenesulfonic acid and water mix homogeneously, and the mixture obtained is carried out spray drying.
12. the application that the support type benzenesulfonic acid catalyst described in claim 10 is in the esterification reaction.
13. 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 benzenesulfonic acid catalyst described in claim 10.
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| CN110614111A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical tri-mesoporous attapulgite composite material as carrier and preparation method and application thereof |
| CN114515597B (en) * | 2020-11-19 | 2023-05-09 | 中国石油化工股份有限公司 | Esterification catalyst, preparation method thereof and application thereof in esterification synthesis reaction of acetic acid and alcohol |
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