CN105214735A - Mesoporous composite material and Catalysts and its preparation method and application and 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes - Google Patents
Mesoporous composite material and Catalysts and its preparation method and application and 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes Download PDFInfo
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Abstract
The present invention relates to a kind of spherical mesoporous composite, the preparation method of this spherical mesoporous composite, the spherical mesoporous composite prepared by the method, loaded catalyst containing this spherical mesoporous composite, the preparation method of this loaded catalyst, the loaded catalyst prepared by the method, the application of this loaded catalyst in ketal reaction, and use the preparation 2 of this loaded catalyst, 2-dimethyl-4-methyl isophthalic acid, the method of 3-dioxolanes, wherein, this spherical mesoporous composite contains the meso-porous molecular sieve material having one dimension straight channels structure He have caged cubic structure.Adopt described spherical mesoporous composite of the present invention can significantly improve the conversion ratio of reaction raw materials as the loaded catalyst that carrier is made in ketal reaction process.
Description
Technical field
The present invention relates to a kind of spherical mesoporous composite, the preparation method of this spherical mesoporous composite, the spherical mesoporous composite prepared by the method, loaded catalyst containing this spherical mesoporous composite, prepare a method for loaded catalyst, the loaded catalyst prepared by the method, the application of this loaded catalyst in ketal reaction, and use the preparation 2 of this loaded catalyst, 2-dimethyl-4-methyl isophthalic acid, the method for 3-dioxolanes.
Background technology
2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes is important organic synthesis intermediate.Generally, 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes is obtained by ketal reaction primarily of oxidation cyclopropane and acetone.The catalyst of traditional oxidation cyclopropane and the ketal reaction of acetone is inorganic liquid (such as sulfuric acid, hydrochloric acid, phosphoric acid etc.), but defects such as because its corrosiveness is large, the side reaction of initiation is many, reaction afterproduct separate complex and liquid waste processing difficulty and cause its use to be subject to certain restrictions.Along with the whole world increases the attention degree of Catalytic processes greenization, it is imperative that solid acid catalysis technique replaces liquid acid Catalytic processes.Research in recent years shows, some solid acids, Lewis hydrochlorate, molecular sieve and ionic liquid etc. are to synthesis 2,2-dimethyl-4-methyl isophthalic acid, and 3-dioxolanes has good catalytic action.
In existing loaded catalyst, adopt conventional meso-porous molecular sieve material as carrier.It is orderly that meso-porous molecular sieve material has duct, aperture is adjustable, specific area and the advantage such as pore volume is larger, lot of advantages is shown in the preparation technology of the loaded catalyst making to adopt these meso-porous molecular sieve materials to make as carrier in organic catalytic reaction, such as, catalytic activity is high, side reaction is few, post processing is simple, but, large specific area and high pore volume make these meso-porous molecular sieve materials have stronger water suction, moisture absorption ability, thus these loaded catalysts can be caused to reunite in catalytic reaction process, and then reduce by 2, 2-dimethyl-4-methyl isophthalic acid, the conversion ratio of cyclopropane is oxidized in 3-dioxolanes preparation technology.
Summary of the invention
The object of the invention is to overcome the loaded catalyst defect that reaction raw materials conversion ratio is lower in ketal reaction process adopting existing meso-porous molecular sieve material to make, a kind of spherical mesoporous composite being suitable as carrier is provided, and the preparation method of this spherical mesoporous composite, the spherical mesoporous composite prepared by the method, loaded catalyst containing this spherical mesoporous composite, the preparation method of this loaded catalyst, the loaded catalyst prepared by the method, the application of this loaded catalyst in ketal reaction, with the preparation 2 using this loaded catalyst, 2-dimethyl-4-methyl isophthalic acid, the method of 3-dioxolanes.
In order to achieve the above object, the present inventor is by finding after research, the meso-porous molecular sieve material with one dimension straight channels structure is combined with the meso-porous molecular sieve material with caged cubic structure, and this mesoporous composite material is made by spray drying process the spherical of reunion not easily occurs, the high-specific surface area of meso-porous molecular sieve material can be retained like this, large pore volume, large aperture and there is the feature such as one dimension straight channels structure and caged cubic structure, the reunion of meso-porous molecular sieve material can be reduced again, increase its mobility, the loaded catalyst making to adopt this mesoporous composite material to make is for obtaining the reaction raw materials conversion ratio significantly improved during ketal reaction, thus complete the present invention.
For this reason, the invention provides a kind of spherical mesoporous composite, wherein, this spherical mesoporous composite contains the meso-porous molecular sieve material having one dimension straight channels structure He have caged cubic structure, and the average average grain diameter of this spherical mesoporous composite is 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, first most probable pore size is 2-6 nanometer, described second most probable pore size is 15-50 nanometer.
Present invention also offers a kind of method preparing spherical mesoporous composite, the method comprises the following steps:
(1) meso-porous molecular sieve material with one dimension straight channels structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of one dimension straight channels structure, as component a1;
(2) meso-porous molecular sieve material with caged cubic structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of caged cubic structure, as component a2;
(3) silica gel is provided or prepares the filter cake of silica gel, as components b;
(4) described component a1, described component a2, described components b are carried out mixing and ball milling, and the pressed powder water slurrying will obtained after ball milling, then the slurry obtained is carried out spraying dry;
Wherein, described component a1 and described component a2 makes the average average grain diameter of described spherical mesoporous composite be 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, first most probable pore size is 2-6 nanometer, and described second most probable pore size is 15-50 nanometer.
Present invention also offers the spherical mesoporous composite prepared by said method.
Present invention also offers a kind of loaded catalyst, this catalyst contains carrier and load benzene sulfonic acid on the carrier, and wherein, described carrier is spherical mesoporous composite according to the present invention.
Present invention also offers a kind of method preparing loaded catalyst, the method comprises: carrier, benzene sulfonic acid and water are mixed, and the mixture obtained is carried out spraying dry, and wherein, described carrier is spherical mesoporous composite according to the present invention.
Present invention also offers the loaded catalyst prepared by said method.
Present invention also offers the application of above-mentioned loaded catalyst in ketal reaction.
Present invention also offers a kind of 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclopropane will be oxidized contact with acetone, to obtain 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes, wherein, described catalyst is according to above-mentioned loaded catalyst of the present invention.
Spherical mesoporous composite according to the present invention, combine there is one dimension straight channels structure meso-porous molecular sieve material, there is the meso-porous molecular sieve material of caged cubic structure and the advantage of ball type carrier, make this spherical mesoporous composite be suitable as the carrier of loaded catalyst, be particularly suitable as the carrier of the loaded catalyst used in organic reaction.
In described loaded catalyst of the present invention, spherical mesoporous composite as carrier has the feature of the loose structure of meso-porous molecular sieve material, but also load has benzene sulfonic acid, this loaded catalyst had both been had, and the advantage of loaded catalyst is as high in catalytic activity, side reaction is few, post processing is simple, there is again the catalytic performance of acid, not only can not cause equipment corrosion when making this loaded catalyst in for organic reaction process, but also the conversion ratio of reaction raw materials can be significantly improved.
In addition, when preparing described loaded catalyst by spray-dired method, described loaded catalyst can reuse, and still can obtain higher reaction raw materials conversion ratio in recycling process.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of spherical mesoporous composite according to the present invention;
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical mesoporous composite according to the present invention;
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical mesoporous composite according to the present invention;
Fig. 4 is the pore size distribution curve of spherical mesoporous composite according to the present invention.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of spherical mesoporous composite, wherein, this spherical mesoporous composite contains the meso-porous molecular sieve material with one dimension straight channels structure and the meso-porous molecular sieve material with caged cubic structure, and the average average grain diameter of this spherical mesoporous composite is 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-6 nanometer, described second most probable pore size is 15-50 nanometer.
Spherical mesoporous composite according to the present invention has one dimension straight channels structure and caged cubic structure simultaneously, and the average grain diameter of its particle adopts laser fineness gage to record, and specific area, pore volume and most probable pore size record according to nitrogen adsorption methods.
Spherical mesoporous composite according to the present invention, by the particle size of spherical mesoporous composite is controlled within above-mentioned scope, can guarantee that described spherical mesoporous composite is not easily reunited, and the conversion ratio of the reaction raw materials in ketal reaction process can be improved used as the loaded catalyst that carrier is made.When the specific area of described spherical mesoporous composite is less than 150 meters squared per gram and/or pore volume is less than 0.5 ml/g, the catalytic activity of the loaded catalyst made used as carrier can significantly reduce; When the specific area of described spherical mesoporous composite is greater than 600 meters squared per gram and/or pore volume is greater than 1.5 mls/g, the loaded catalyst made used as carrier is easily reunited in ketal reaction process, thus affects the conversion ratio of the reaction raw materials in ketal reaction process.
In the preferred case, the average average grain diameter of described spherical mesoporous composite is 35-55 micron, and specific area is 180-600 meters squared per gram, and pore volume is 0.8-1.2 ml/g, described first most probable pore size is 2-4 nanometer, and described second most probable pore size is 20-30 nanometer.
In described spherical mesoporous composite, described in there is the meso-porous molecular sieve material of one dimension straight channels structure and the described weight ratio with the meso-porous molecular sieve material of caged cubic structure can be 1:0.1-10, be preferably 1:0.5-2.
In the present invention, described spherical mesoporous composite can also containing the silica introduced by silica gel." silica introduced by silica gel " refers in the preparation process of described spherical mesoporous composite, to be brought into the silica component in the spherical mesoporous composite of final preparation by silica gel as raw materials.In described spherical mesoporous composite, relative to having the meso-porous molecular sieve material of one dimension straight channels and the described total amount with the meso-porous molecular sieve material of caged cubic structure described in 100 weight portions, the content of the described silica introduced by silica gel can be 1-200 weight portion, is preferably 50-150 weight portion.
In the present invention, described there is one dimension straight channels structure meso-porous molecular sieve material and the described meso-porous molecular sieve material with the caged cubic structure meso-porous molecular sieve material that can use for this area routine separately, and can to prepare according to the method for routine separately.
Present invention also offers a kind of method preparing spherical mesoporous composite, the method comprises the following steps:
(1) meso-porous molecular sieve material with one dimension straight channels structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of one dimension straight channels structure, as component a1;
(2) meso-porous molecular sieve material with caged cubic structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of caged cubic structure, as component a2;
(3) silica gel is provided or prepares the filter cake of silica gel, as components b;
(4) described component a1, described component a2, described components b are carried out mixing and ball milling, and the pressed powder water slurrying will obtained after ball milling, then the slurry obtained is carried out spraying dry;
Wherein, described component a1 and described component a2 makes the average average grain diameter of described spherical mesoporous composite be 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-6 nanometer, described second most probable pore size is 15-50 nanometer.
In the preferred case, described component a1 and described component a2 makes the average average grain diameter of described spherical mesoporous composite be 35-55 micron, specific area is 180-600 meters squared per gram, pore volume is 0.8-1.2 ml/g, described first most probable pore size is 2-4 nanometer, and described second most probable pore size is 20-30 nanometer.
In step (1), the process that preparation has the filter cake of the meso-porous molecular sieve material of one dimension straight channels structure can comprise: under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
In step (1), the mol ratio of described template, ethanol, trimethylpentane and tetramethoxy-silicane can be 1:100-500:200-500:50-200, is preferably 1:200-400:250-400:70-150.
The various templates that described template can use for the preparation of the meso-porous molecular sieve material with one dimension straight channels structure for this area is conventional.Most preferably, described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, this template can be commercially available (such as, can available from Aldrich Co, commodity are called P123, molecular formula is EO20PO70EO20), also can be prepared by existing various method.When described template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of described template calculates according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene and obtains.
Described sour agent can be material or the mixture (as solution) that various routine may be used for adjust ph.Described sour agent preferably uses in form of an aqueous solutions, and its pH value can be 1-6, is preferably 3-5.More preferably, described sour agent is pH value is the acetic acid of 1-6 (more preferably 3-5) and the cushioning liquid of sodium acetate.
The condition that tetramethoxy-silicane contacts with described sour agent can comprise: temperature is 10-60 DEG C, and the time is 10-72 hour, and pH value is 1-7.In order to more be conducive to the Homogeneous phase mixing between each material, described tetramethoxy-silicane contacts with sour agent and preferably carries out under agitation.The consumption of described sour agent preferably makes the pH value of the haptoreaction system of tetramethoxy-silicane and sour agent be 1-7.
The condition of described crystallization can comprise: temperature is 30-150 DEG C, and the time is 10-72 hour.Under preferable case, the condition of described crystallization comprises: temperature is 40-100 DEG C, and the time is 10-48 hour.Described crystallization is implemented by hydrothermal crystallization method.
Have in the process of the filter cake of the meso-porous molecular sieve material of one-dimensional tunnel structure in above-mentioned preparation, can comprise with the process obtaining filter cake by filtering: after filtration, with deionized water cyclic washing (washing times can be 2-10), then carry out suction filtration.
In step (1), " providing the meso-porous molecular sieve material with one dimension straight channels structure " can be the product directly taking or choose the meso-porous molecular sieve material with one dimension straight channels structure, also can be the meso-porous molecular sieve material that preparation has one dimension straight channels structure.The described preparation method with the meso-porous molecular sieve material of one dimension straight channels structure can implement according to the method for routine, such as, its preparation method can comprise: the filter cake according to said method preparation with the meso-porous molecular sieve material of one-dimensional tunnel structure, then by gained filtration cakes torrefaction, and by the template removal in the product that obtains after drying.The condition of described removed template method can comprise: temperature is 300-600 DEG C, and the time is 10-80 hour.
In step (2), prepare the process with the filter cake of the meso-porous molecular sieve material of caged cubic structure can comprise: under the existence of template, potassium chloride and dimethylbenzene, ethyl orthosilicate is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
In step (2), the mol ratio of described template, potassium chloride, dimethylbenzene and ethyl orthosilicate is 1:100-500:400-600:200-400, is preferably 1:200-450:400-500:200-300.
In step (2), described template can be the various templates that this area routine uses for the preparation of the meso-porous molecular sieve material of caged cubic structure.Most preferably, described template is triblock copolymer Pluronic F-127 ether-polycyclic oxypropylene ether-Pluronic F-127 ether, this template can be commercially available (such as, can available from Aldrich Co, commodity are called F127, molecular formula is EO106PO70EO106), also can be prepared by existing various method.When described template is Pluronic F-127 ether-polycyclic oxypropylene ether-Pluronic F-127 ether, the molal quantity of described template calculates according to the mean molecule quantity of Pluronic F-127 ether-polycyclic oxypropylene ether-Pluronic F-127 ether and obtains.
Described sour agent can be material or the mixture (as solution) that various routine may be used for adjust ph.Under preferable case, described sour agent can be hydrochloric acid.Described hydrochloric acid preferably uses with the form of aqueous hydrochloric acid solution.To the concentration of hydrochloric acid and consumption, there is no particular limitation in the present invention, can change, generally in wider scope, the concentration of hydrochloric acid can be 1-5mol/L, and the consumption of hydrochloric acid can be 50-80mL, under preferable case, the concentration of hydrochloric acid is 1-2mol/L, and the consumption of hydrochloric acid is 50-60mL.
In step (2), ethyl orthosilicate and the catalytic condition of described sour agent can comprise: temperature is 5-100 DEG C, and the time is 10-72 hour.In order to more be conducive to the Homogeneous phase mixing between each material, the contact of described ethyl orthosilicate and sour agent is preferably carried out under agitation.
In step (2), the condition of described crystallization can comprise: temperature is 30-150 DEG C, and the time is 10-72 hour.Under preferable case, the condition of described crystallization comprises: temperature is 40-130 DEG C, and the time is 20-50 hour.Described crystallization is implemented by hydrothermal crystallization method.
Have in the process of the filter cake of the meso-porous molecular sieve material of caged cubic structure in above-mentioned preparation, can comprise with the process obtaining filter cake by filtering: after filtration, with deionized water cyclic washing (washing times can be 2-10), then carry out suction filtration.
In step (2), " providing the meso-porous molecular sieve material with caged cubic structure " can be the product directly taking or choose the meso-porous molecular sieve material with caged cubic structure, also can be the meso-porous molecular sieve material that preparation has caged cubic structure.The described preparation method with the meso-porous molecular sieve material of caged cubic structure can implement according to the method for routine, such as, its preparation method can comprise: the filter cake according to said method preparation with the meso-porous molecular sieve material of caged cubic structure, then by gained filtration cakes torrefaction, and by the template removal in the product that obtains after drying.It is 300-600 DEG C that the condition of described removed template method can comprise temperature, and the time is 10-80 hour.
In step (3), the process preparing the filter cake of silica gel can comprise: contacted with inorganic acid by waterglass, and is filtered by the mixture obtained after contact.
There is no particular limitation for the condition that waterglass contacts with inorganic acid, suitably can determine according in the common process preparing silica gel.Under preferable case, the condition that waterglass contacts with inorganic acid can comprise: temperature is 10-60 DEG C, is preferably 20-40 DEG C; Time is 1-5 hour, is preferably 1.5-3 hour; PH value is 2-4.
In order to more be conducive to the Homogeneous phase mixing between each material, waterglass and the catalytic process of inorganic acid are preferably carried out under agitation.
Described waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 % by weight, is preferably 12-30 % by weight.
Described inorganic acid can be the various inorganic acids that this area routine uses, and such as, can be at least one in sulfuric acid, nitric acid and hydrochloric acid.Described inorganic acid can use in pure form, also can use with the form of its aqueous solution.The consumption of described inorganic acid preferably makes the pH value of the haptoreaction system of waterglass and inorganic acid be 2-4.
In step (3), " providing silica gel " can be directly take or choose silica gel product, also can be prepare silica gel.The method preparing silica gel can be implemented according to the method for routine, such as, can comprise: the filter cake preparing silica gel according to said method, then by gained filtration cakes torrefaction.
In step (4), relative to the described component a1 of 100 weight portions and total consumption of described component a2, the consumption of described components b can be 1-200 weight portion, the weight ratio being preferably the consumption of component a1 and described component a2 described in 50-150 weight portion can be 1:0.1-10, is preferably 1:0.5-2.
In step (4), described ball milling can carry out in ball mill, and in described ball mill, the inwall of ball grinder is preferably polytetrafluoroethyllining lining, and the diameter of the abrading-ball in ball mill can be 2-3mm; The quantity of abrading-ball reasonably can be selected according to the size of ball grinder, is the ball grinder of 50-150ml for size, usually can use 1 abrading-ball; The material of described abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., is preferably agate.The condition of described ball milling can comprise: the rotating speed of abrading-ball can be 300-500r/min, and the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hour.
In step (4), the process of the pressed powder water slurrying obtained after ball milling can be carried out at 25-60 DEG C.In pulping process, the weight ratio of the consumption of pressed powder and water can be 1:0.1-2, is preferably 1:0.3-0.9.
In step (4), described spraying dry can be implemented according to the mode of routine, such as, can carry out in atomizer.Described spray-dired condition can comprise: temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min; Under preferable case, described spray-dired condition comprises: temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min.
In step (4), when the filter cake that described component a1 is the meso-porous molecular sieve material with one dimension straight channels structure, described component a2 is the filter cake of the meso-porous molecular sieve material with caged cubic structure, and described components b is when being the filter cake of silica gel, also namely when step (1) is the process that preparation has the filter cake of the meso-porous molecular sieve material of one dimension straight channels structure, step (2) is the process that preparation has the filter cake of the meso-porous molecular sieve material of caged cubic structure, when step (3) is for preparing the process of the filter cake of silica gel, the preparation method of described spherical mesoporous composite can also comprise: after the spraying dry of step (4), removed template method from the product that spraying dry obtains.The condition of described removed template method can comprise: temperature is 300-600 DEG C, and the time is 10-80 hour.
Present invention also offers the spherical mesoporous composite prepared by said method.
Present invention also offers a kind of loaded catalyst, this catalyst contains carrier and load benzene sulfonic acid on the carrier, and wherein, described carrier is above-mentioned spherical mesoporous composite provided by the invention.
In described loaded catalyst, there is no particular limitation for the content of described carrier and benzene sulfonic acid, suitably can determine according to the loaded catalyst of this area routine, such as, with the gross weight of described loaded catalyst for benchmark, the content of benzene sulfonic acid can be 1-50 % by weight, is preferably 5-50 % by weight; The content of described carrier is 50-99 % by weight, is preferably 50-95 % by weight.
In the present invention, the various method preparations that described loaded catalyst can use according to this area routine, only need by benzene sulfonic acid load on the carrier.
In a preferred embodiment, can reuse to make the loaded catalyst of preparation, and in recycling process, still can obtain the conversion ratio of higher reaction raw materials, the method preparing loaded catalyst comprises: carrier, benzene sulfonic acid and water are mixed, and the mixture obtained is carried out spraying dry, wherein, described carrier is above-mentioned spherical mesoporous composite provided by the invention.
Prepare in the process of loaded catalyst above-mentioned, with total consumption of described carrier and benzene sulfonic acid for benchmark, the consumption of benzene sulfonic acid can be 1-50 % by weight, is preferably 5-50 % by weight; The consumption of described carrier can be 50-99 % by weight, is preferably 50-95 % by weight.
Described spraying dry can be implemented according to the mode of routine, such as, can carry out in atomizer.Described spray-dired condition can comprise: temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min; Under preferable case, described spray-dired condition comprises: temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min.
Present invention also offers the loaded catalyst prepared by above-mentioned spray drying process.
Present invention also offers the application of above-mentioned loaded catalyst in ketal reaction.
In addition, present invention also offers a kind of 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclopropane will be oxidized and contact with acetone, to obtain 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes, wherein, described catalyst is above-mentioned loaded catalyst provided by the invention.
Described 2,2-dimethyl-4-methyl isophthalic acid, in the preparation method of 3-dioxolanes, there is no particular limitation, as long as can be obtained by reacting 2,2-dimethyl-4-methyl isophthalic acid for the consumption of oxidation cyclopropane and acetone, 3-dioxolanes, but in order to improve the utilization rate of raw material, under preferable case, the mol ratio of oxidation cyclopropane and acetone is 1:0.5-10.
At described 2,2-dimethyl-4-methyl isophthalic acids, in the preparation method of 3-dioxolanes, also there is no particular limitation for the consumption of described catalyst, can according to 2,2-dimethyl-4-methyl isophthalic acids of routine, and the preparation technology of 3-dioxolanes suitably determines.Under preferable case, relative to the oxidation cyclopropane of 100 weight portions, the consumption of described catalyst is 1-15 weight portion, is more preferably 2-14 weight portion.
In described ketal reaction process, in order to more be conducive to the carrying out of ketal reaction, described reaction is preferably carried out under high pressure polytetrafluoroethyllining lining reactor condition.The condition of described ketal reaction can comprise: reaction temperature is 25-100 DEG C, is preferably 60-100 DEG C; Reaction time is 1-20 hour, is preferably 2-15 hour.
Described 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes can also be included in after ketal reaction terminates, centrifugation is carried out to final reactant mixture, and the solid product that centrifugation is obtained vacuum drying 1-24 hour at 25-200 DEG C, preferably vacuum drying 6-10 hour at 50-150 DEG C, to reclaim catalyst.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene available from Aldrich Co, is abbreviated as P123, and molecular formula is EO20PO70EO20, is the material of 9003-11-6 in the registration number of U.S. chemical abstract, and mean molecule quantity is 5800.Pluronic F-127 ether-polycyclic oxypropylene ether-Pluronic F-127 ether available from Aldrich Co, is abbreviated as F127, and molecular formula is EO106PO70EO106, and mean molecule quantity is 12600.
In following examples and comparative example, X-ray diffraction analysis is that the X-ray diffractometer of D8Advance carries out in the model purchased from German BrukerAXS company; Scanning electron microscope analysis is that the SEM of XL-30 is carried out in the model of purchased from American FEI Co.; Pore structure parameter analysis is that the nitrogen adsorption desorption instrument of Autosorb-1 carries out in the model of purchased from American Kang Ta company, wherein, before testing, sample is degassed 4 hours at 200 DEG C; The analysis of product liquid phase ingredient is being carried out purchased from Britain Agilent company 7890A/5973N gas chromatograph-mass spectrometer.
In following examples and comparative example, the conversion ratio of oxidation cyclopropane and 2,2-dimethyl-4-methyl isophthalic acid, the selective of 3-dioxolanes obtains according to following formulae discovery.
Conversion ratio (%)=(being oxidized the content of cyclopropane in the consumption-product of oxidation cyclopropane) ÷ of oxidation cyclopropane is oxidized consumption × 100% of cyclopropane
2,2-dimethyl-4-methyl isophthalic acid, selective (%)=2, the 2-dimethyl-4-methyl isophthalic acid of 3-dioxolanes, actual production ÷ 2, the 2-dimethyl-4-methyl isophthalic acid of 3-dioxolanes, theoretical yield × 100% of 3-dioxolanes
Embodiment 1
The present embodiment is for illustration of spherical mesoporous composite of the present invention and loaded catalyst and their preparation method.
(1) spherical mesoporous composite is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 2.76g (0.06mol) ethanol is joined 28ml, pH value be 4 acetic acid and sodium acetate buffer in, at 15 DEG C, be stirred to P123 dissolve completely, the backward solution obtained in add 6g (0.053mol) trimethylpentane, 8h is stirred at 15 DEG C, add 2.13g (0.014mol) tetramethoxy-silicane more wherein, at 15 DEG C, pH value is stir 20h under the condition of 4.5, then the solution obtained is transferred in teflon-lined reactor, crystallization 24h at 60 DEG C, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake X1 of the meso-porous molecular sieve material with one dimension straight channels.
It is 2molL that the KCl of PluronicF127 and the 2.5g (0.034mol) of 1.0g (0.0001mol) is dissolved in 60mL concentration
-1hCl solution in, and be placed on magnetic agitation in flask, then add the dimethylbenzene of 5.2g (0.049mol), at 14 DEG C, stir 24h with the rotating speed of 350r/min.And then add the ethyl orthosilicate (TEOS) of 4.5g (0.022mol) wherein, continue to react 50h at 14 DEG C, then the solution obtained is proceeded to high pressure polytetrafluoroethyllining lining reactor, crystallization 48h at 130 DEG C.Then carry out filtration and and spend deionized water 5 times, then suction filtration obtains having the filter cake Y1 of the meso-porous molecular sieve material of caged cubic structure diplopore distribution.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution with weight ratio be 5:1 carry out mixed be incorporated in 30 DEG C at haptoreaction 2 hours, then be the sulfuric acid adjusted to ph to 3 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B1 of silica gel.
By 5g filter cake X1,5g filter cake Y1 of above-mentioned preparation, 10g filter cake B1 puts into 100ml ball grinder together, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 1 hour at 60 DEG C, obtains 20g pressed powder; This pressed powder is dissolved in 10 grams of deionized waters, at 200 DEG C under rotating speed is 12000r/min spraying dry; Calcined 24 hours at 500 DEG C in Muffle furnace by the product obtained after spraying dry, removed template method P123 and F127, obtains 18 grams of spherical mesoporous composite C1.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical mesoporous composite C1 of 18g of preparation in above-mentioned steps (1) is put into deionized water together with benzene sulfonic acid, be stirred to dissolving, and the weight ratio of spherical mesoporous composite C1 and benzene sulfonic acid is 50:50, the mol ratio of deionized water and benzene sulfonic acid is 25:1, at 200 DEG C under rotating speed is 12000r/min spraying dry, obtain loaded catalyst Cat-1.
With XRD, ESEM and U.S. Kang Ta company Atsorb-1 type instrument, this carrier and support type benzene sulfonic acid catalyst are characterized.
Fig. 1 is X-ray diffracting spectrum, and compose peak from the low-angle occurred in XRD spectra, spherical mesoporous composite C1 and loaded catalyst Cat-1 all has orderly one dimension straight channels structure and caged cubic structure.
Fig. 2 and Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical mesoporous composite C1.As seen from the figure, the microscopic appearance of spherical mesoporous composite C1 to be particle diameter the be Mesoporous Spheres of 30-60 μm.
Fig. 4 is the pore size distribution curve of spherical mesoporous composite according to the present invention, and as seen from the figure, spherical mesoporous composite C1 is diplopore distribution.
The pore structure parameter of spherical mesoporous composite C1 and loaded catalyst Cat-1 is as shown in table 1 below.
Table 1
As can be seen from the data of upper table 1, spherical mesoporous composite is after load benzene sulfonic acid, and specific area and pore volume reduce all to some extent, and this illustrates that benzene sulfonic acid enters into the inside of spherical mesoporous composite in load-reaction process.
Comparative example 1
Spherical mesoporous composite and loaded catalyst is prepared according to the method for embodiment 1, difference, in the process preparing loaded catalyst, replace described filter cake X1 and described filter cake Y1 with the bar-shaped mesoporous silicon oxide SBA-15 (purchased from high-tech limited company of Jilin University) of identical weight, thus obtain mesoporous composite material D2 and loaded catalyst Cat-D-2 respectively.
Embodiment 2
The present embodiment is for illustration of spherical mesoporous composite of the present invention and loaded catalyst and their preparation method.
Spherical mesoporous composite and loaded catalyst is prepared according to the method for embodiment 1, difference, spray-dired step is not had in the process preparing loaded catalyst, and by means of only the method for dipping by benzene sulfonic acid load on spherical mesoporous composite, thus obtained loaded catalyst Cat-2.
Embodiment 3
The present embodiment is for illustration of spherical mesoporous composite of the present invention and loaded catalyst and their preparation method.
(1) spherical mesoporous composite is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethanol is joined 28ml, pH value be 5 acetic acid and sodium acetate buffer in, at 15 DEG C, be stirred to P123 dissolve completely, the backward solution obtained in add 9.12g (0.08mol) trimethylpentane, 8h is stirred at 15 DEG C, add 3.04g (0.02mol) tetramethoxy-silicane more wherein, at 25 DEG C, pH value is stir 15h under the condition of 5.5, then the solution obtained is transferred in high pressure teflon-lined reactor, crystallization 10h at 100 DEG C, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake X3 of the meso-porous molecular sieve material with one dimension straight channels.
It is 1molL that the KCl of PluronicF127 and the 1.49g (0.02mol) of 1.0g (0.0001mol) is dissolved in 55mL concentration
-1hCl solution in, and be placed on magnetic agitation in flask, then add the dimethylbenzene of 4.25g (0.04mol), at 14 DEG C, stir 24h with the rotating speed of 350r/min.And then add the ethyl orthosilicate (TEOS) of 6.25g (0.03mol) wherein, continue to react 30h at 50 DEG C, then the solution obtained is proceeded to high pressure polytetrafluoroethyllining lining reactor, crystallization 20h at 100 DEG C.Then carry out filtration and and spend deionized water 5 times, then suction filtration obtains having the filter cake Y3 of the meso-porous molecular sieve material of caged cubic structure diplopore distribution.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution with weight ratio be 4:1 carry out mixed be incorporated in 40 DEG C at haptoreaction 1.5 hours, then be the sulfuric acid adjusted to ph to 2 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B3 of silica gel.
13g filter cake X3,7g filter cake Y3,10g filter cake B3 of above-mentioned preparation is put into 100ml ball grinder together, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 300r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 0.5 hour at 80 DEG C, obtains 30g pressed powder; This pressed powder is dissolved in 9 grams of deionized waters, at 250 DEG C under rotating speed is 11000r/min spraying dry; Calcined 15 hours at 550 DEG C in Muffle furnace by the product obtained after spraying dry, removed template method, obtains 28 grams of spherical mesoporous composite C3.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical mesoporous composite C3 of 28g of preparation in above-mentioned steps (1) is put into deionized water together with benzene sulfonic acid, be stirred to dissolving, and the weight ratio of spherical mesoporous composite C3 and benzene sulfonic acid is 95:5, the mol ratio of deionized water and benzene sulfonic acid is 25:1, at 150 DEG C under rotating speed is 13000r/min spraying dry, obtain loaded catalyst Cat-3.
The pore structure parameter of spherical mesoporous composite C3 and loaded catalyst Cat-3 is as shown in table 2 below.
Table 2
Embodiment 4
The present embodiment is for illustration of spherical mesoporous composite of the present invention and loaded catalyst and their preparation method.
(1) spherical mesoporous composite is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethanol is joined 28ml, pH value be 3 acetic acid and sodium acetate buffer in, at 15 DEG C, be stirred to P123 dissolve completely, the backward solution obtained in add 5.7g (0.05mol) trimethylpentane, 8h is stirred at 15 DEG C, add 4.56g (0.03mol) tetramethoxy-silicane more wherein, at 40 DEG C, pH value is stir 10h under the condition of 3.5, then the solution obtained is transferred in high pressure teflon-lined reactor, crystallization 48h at 40 DEG C, then carry out filtration and and spend deionized water 4 times, then suction filtration obtains the filter cake X4 of the meso-porous molecular sieve material with one-dimensional channels.
It is 2molL that the KCl of PluronicF127 and the 3.35g (0.045mol) of 1.0g (0.0001mol) is dissolved in 50mL concentration
-1hCl solution in, and be placed on magnetic agitation in flask, then add the dimethylbenzene of 4.78g (0.045mol), at 14 DEG C, stir 24h with the rotating speed of 350r/min.And then add the ethyl orthosilicate (TEOS) of 4.17g (0.02mol) wherein, continue to react 15h at 70 DEG C, then the solution obtained is proceeded to high pressure polytetrafluoroethyllining lining reactor, crystallization 40h at 40 DEG C.Then carry out filtration and and spend deionized water 5 times, then suction filtration obtains having the filter cake Y1 of the meso-porous molecular sieve material of caged cubic structure diplopore distribution.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution with weight ratio be 6:1 carry out mixed be incorporated in 20 DEG C at haptoreaction 3 hours, then be the sulfuric acid adjusted to ph to 4 of 98 % by weight by concentration, then suction filtration is carried out to the reaction mass obtained, and to be washed with distilled water to sodium ions content be 0.02 % by weight, obtain the filter cake B4 of silica gel.
7g filter cake X4,13g filter cake Y4,30g filter cake B4 of above-mentioned preparation is put into 100ml ball grinder together, and wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 500r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 10 hours at 40 DEG C, obtains 50g pressed powder; This pressed powder is dissolved in 45 grams of deionized waters, at 150 DEG C under rotating speed is 13000r/min spraying dry; Calcined 70 hours at 450 DEG C in Muffle furnace by the product obtained after spraying dry, removed template method, obtains 48 grams of spherical mesoporous composite C4.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical mesoporous composite C4 of 48g of preparation in above-mentioned steps (1) is put into deionized water together with benzene sulfonic acid, be stirred to dissolving, and the weight ratio of spherical mesoporous composite C4 and benzene sulfonic acid is 85:15, the mol ratio of deionized water and benzene sulfonic acid is 25:1, at 250 DEG C under rotating speed is 11000r/min spraying dry, obtain loaded catalyst Cat-4.
The pore structure parameter of spherical mesoporous composite C4 and loaded catalyst Cat-4 is as shown in table 3 below.
Table 3
Embodiment 5
The present embodiment for illustration of the application of described loaded catalyst provided by the invention and 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes.
Loaded catalyst Cat-1 prepared by embodiment 1 vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 0.5 gram, be oxidized cyclopropane with 5g and 20g acetone adds in 100ml polytetrafluoroethyllining lining reactor successively, under the condition stirred, react 6 hours in 75 DEG C of oil baths, then room temperature is cooled to and centrifugation, solid catalyst Cat-1 vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, recycling after reclaiming.Utilize gas chromatographic analysis reaction product liquid composition, oxidation cyclopropane conversion ratio 99.9%, 2,2-dimethyl-4-methyl isophthalic acid, selective 100% of 3-dioxolanes, yield 99%.
Embodiment 6-8 and comparative example 3-4
Prepare 2,2-dimethyl-4-methyl isophthalic acid according to the method for embodiment 5,3-dioxolanes, difference is, replaces described loaded catalyst Cat-1 respectively with loaded catalyst prepared by embodiment 2-4 and comparative example 1-2.As a result, the conversion ratio of the oxidation cyclopropane calculated separately and 2,2-dimethyl-4-methyl isophthalic acid, the selective data of 3-dioxolanes is as shown in table 4 below.
Table 4
Embodiment 9-12 and comparative example 5-6
Prepare 2,2-dimethyl-4-methyl isophthalic acid according to the method for embodiment 5,3-dioxolanes, difference is, replaces described loaded catalyst Cat-1 respectively with the catalyst reclaimed from embodiment 5-8 and comparative example 3-4.As a result, the conversion ratio of the oxidation cyclopropane calculated separately and 2,2-dimethyl-4-methyl isophthalic acid, the selective data of 3-dioxolanes is as shown in table 5 below.
Table 5
As can be seen from above-mentioned table 4 and 5 data, adopt described spherical mesoporous composite of the present invention can significantly improve the conversion ratio of reaction raw materials as the loaded catalyst that carrier is made in ketal reaction process.And when preparing described loaded catalyst by spray-dired method, described loaded catalyst can reuse, and still can obtain higher reaction raw materials conversion ratio in recycling process.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (22)
1. a spherical mesoporous composite, it is characterized in that, this spherical mesoporous composite contains the meso-porous molecular sieve material with one dimension straight channels structure and the meso-porous molecular sieve material with caged cubic structure, and the average grain diameter of this spherical mesoporous composite is 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-6 nanometer, described second most probable pore size is 15-50 nanometer.
2. composite according to claim 1, wherein, described in there is the meso-porous molecular sieve material of one dimension straight channels structure and the meso-porous molecular sieve material of caged cubic structure weight ratio be 1:0.1-10, be preferably 1:0.5-2.
3. prepare a method for spherical mesoporous composite, the method comprises the following steps:
(1) meso-porous molecular sieve material with one dimension straight channels structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of one dimension straight channels structure, as component a1;
(2) meso-porous molecular sieve material with caged cubic structure or preparation is provided to have the filter cake of the meso-porous molecular sieve material of caged cubic structure, as component a2;
(3) silica gel is provided or prepares the filter cake of silica gel, as components b;
(4) described component a1, described component a2, described components b are carried out mixing and ball milling, and the pressed powder water slurrying will obtained after ball milling, then the slurry obtained is carried out spraying dry;
Wherein, described component a1 and described component a2 makes the average grain diameter of described spherical mesoporous composite be 30-60 micron, specific area is 150-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, aperture is bimodal distribution, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and described first most probable pore size is 2-6 nanometer, described second most probable pore size is 15-50 nanometer.
4. method according to claim 3, wherein, in step (4), relative to the described component a1 of 100 weight portions and total consumption of described component a2, the consumption of described components b is 1-200 weight portion, is preferably 50-150 weight portion; The weight ratio of the consumption of described component a1 and described component a2 is 1:0.1-10, is preferably 1:0.5-2.
5. method according to claim 3, wherein, in step (1), the process that preparation has the filter cake of the meso-porous molecular sieve material of one dimension straight channels structure comprises: under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
6. method according to claim 5, wherein, the mol ratio of described template, ethanol, trimethylpentane and tetramethoxy-silicane is 1:100-500:200-500:50-200, is preferably 1:200-400:250-400:70-150.
7. the method according to claim 5 or 6, wherein, described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene; Described sour agent is pH value is the acetic acid of 1-6 and the cushioning liquid of sodium acetate; The condition that tetramethoxy-silicane contacts with described sour agent comprises: temperature is 10-60 DEG C, and the time is 10-72 hour, and pH value is 1-7; The condition of described crystallization comprises: temperature is 30-150 DEG C, and the time is 10-72 hour.
8. method according to claim 3, wherein, in step (2), the process that preparation has the filter cake of the meso-porous molecular sieve material of caged cubic structure comprises: under the existence of template, potassium chloride and dimethylbenzene, ethyl orthosilicate is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtration.
9. method according to claim 8, wherein, the mol ratio of described template, potassium chloride, dimethylbenzene and ethyl orthosilicate is 1:100-500:400-600:200-400, is preferably 1:200-450:400-500:200-300.
10. method according to claim 8 or claim 9, wherein, described template is triblock copolymer Pluronic F-127 ether-polycyclic oxypropylene ether-Pluronic F-127 ether; Described sour agent is hydrochloric acid; The condition that ethyl orthosilicate contacts with described sour agent comprises: temperature is 5-100 DEG C, and the time is 10-72 hour; The condition of described crystallization comprises: temperature is 30-150 DEG C, and the time is 10-72 hour.
11. methods according to claim 3, wherein, in step (3), the process preparing the filter cake of silica gel comprises: contacted with inorganic acid by waterglass, and is filtered by the mixture obtained after contact.
12. methods according to claim 11, wherein, the condition that waterglass contacts with inorganic acid comprises: temperature is 10-60 DEG C, and the time is 1-5 hour, and pH value is 2-4; Described inorganic acid is one or more in sulfuric acid, nitric acid and hydrochloric acid.
13. according to the method in claim 3-5,8-9 and 11-12 described in any one, wherein, in step (4), the condition of described ball milling comprises: the rotating speed of abrading-ball is 300-500r/min, temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hour; Described spray-dired condition comprises: temperature 100-300 DEG C, and rotating speed is 10000-15000r/min.
14. methods according to claim 3 or 4, wherein, described component a1 is the filter cake of the meso-porous molecular sieve material with one dimension straight channels structure, described component a2 is the filter cake of the meso-porous molecular sieve material with caged cubic structure, and described components b is the filter cake of silica gel, described method also comprises: after the spray-drying process of step (4), removed template method from the product that spraying dry obtains; Preferably, the condition of described removed template method comprises: temperature is 300-600 DEG C, and the time is 10-80 hour.
The 15. spherical mesoporous composites prepared by the method in claim 3-14 described in any one.
16. 1 kinds of loaded catalysts, this catalyst contains carrier and load benzene sulfonic acid on the carrier, it is characterized in that, described carrier is the spherical mesoporous composite in claim 1-2 and 15 described in any one.
17. catalyst according to claim 16, wherein, with the gross weight of described loaded catalyst for benchmark, the content of benzene sulfonic acid is 1-50 % by weight, is preferably 5-50 % by weight; The content of described carrier is 50-99 % by weight, is preferably 50-95 % by weight.
18. 1 kinds of methods preparing loaded catalyst, the method comprises: carrier, benzene sulfonic acid and water are mixed, and the mixture obtained is carried out spraying dry, wherein, described carrier is the spherical mesoporous composite in claim 1-2 and 15 described in any one.
19. methods according to claim 18, wherein, with total consumption of described carrier and benzene sulfonic acid for benchmark, the consumption of benzene sulfonic acid is 1-50 % by weight, is preferably 5-50 % by weight; The consumption of described carrier is 50-99 % by weight, is preferably 50-95 % by weight.
20. loaded catalysts prepared by the method described in claim 18 or 19.
The application of loaded catalyst in ketal reaction in 21. claims 16,17 and 20 described in any one.
22. a kind 2,2-dimethyl-4-methyl isophthalic acid, the preparation method of 3-dioxolanes, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclopropane will be oxidized contact with acetone, to obtain 2,2-dimethyl-4-methyl isophthalic acid, 3-dioxolanes, it is characterized in that, described catalyst is the loaded catalyst in claim 16,17 and 20 described in any one.
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