CN104248988A - Spherical mesoporous sepiolite composite carrier, catalyst and preparation method and application thereof and preparation method of ethyl acetate - Google Patents
Spherical mesoporous sepiolite composite carrier, catalyst and preparation method and application thereof and preparation method of ethyl acetate Download PDFInfo
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Abstract
The invention discloses a spherical mesoporous sepiolite composite carrier, a preparation method thereof, and the spherical mesoporous sepiolite composite carrier prepared by the preparation method, a phosphate supported type catalyst, a preparation method thereof, and application of the phosphate supported type catalyst in esterification, and a preparation method of ethyl acetate. The spherical mesoporous sepiolite composite carrier contains sepiolite and a mesoporous molecular sieve, the average grain diameter of the spherical mesoporous sepiolite composite carrier is 10-50 microns, the specific surface area of the spherical mesoporous sepiolite composite carrier is 200-600 m<2>/ g, the pore volume of the spherical mesoporous sepiolite composite carrier is 0.5-1.5 ml / g, the pore size distribution is double peak distribution, and most probable apertures corresponding to double peaks are respectively 6-10 nm and 20 nm-40 nm. The phosphate supported type catalyst not only has high photocatalytic activity, but also can be used repeatedly.
Description
Technical field
The present invention relates to a kind of spherical mesoporous sepiolite complex carrier, a kind of preparation method of spherical mesoporous sepiolite complex carrier, the spherical mesoporous sepiolite complex carrier prepared by the method, a kind of phosphoric acid loaded catalyst, a kind of preparation method of phosphoric acid loaded catalyst, the application in the esterification reaction of described phosphoric acid loaded catalyst and a kind of preparation method of ethyl acetate.
Background technology
Within 1992, Mobile company synthesizes mesoporous material (Beck J S, Vartuli J C, Roth W J, et al.J.Am.Chem.Soc., 1992,114 (27): 10834-10843).This mesoporous material has high specific area, regular pore passage structure and narrow pore-size distribution, makes mesoporous material obtain very large concern in the application of catalysis, separation, medicine and other fields.Within 1998, Zhao east unit waits people to synthesize a kind of novel mesoporous material SBA-15 (D.Y.Zhao, J.L.Feng, Q.S.Huo, et al Science279 (1998), 548-550), this mesoporous material has cube single-crystal meso-pore material aperture (6-30 nanometer) of high-sequential, larger pore volume (1.0cm
3/ g), thicker hole wall (4-6 nanometer), higher mechanical strength and good catalytic adsorption performance.Zhao Dongyuan, Yu Chengzhong and Yu Yonghao investigated a kind of preparation method (CN1341553A) of mesonic pore molecular sieve carrier material, and this mesonic pore molecular sieve carrier material, as heterogeneous reaction catalyst carrier, easily realizes being separated of catalyst and product.
Sepiolite (being called for short recessed soil) is a kind of moisture zeopan crystalline mineral, its basic structural unit is the elementary layer that two-layer silicon-oxy tetrahedron presss from both sides one deck magnesia octahedron composition, in each 2:1 layer, tetrahedral sheet angle is pushed up direction at a certain distance and is put upside down and form a layer chain structure, form the duct parallel with c-axis direction at tetrahedron bar interband, there is unique layer chain crystal structure and the crystal habit of porous.Sepiolite has very high specific area, absorption property, catalytic action, rheological characteristic and heat resistance, can be used in the fields such as dyeing wastewater process, deodorant, filter aid, cleanser, decolorizer, dytory, thixotropic agent and binding agent, be modern age purposes the most extensively, application expansion one of mineral products the most rapidly.The work of exploitation natural clay mineral novel catalyst carrier is always by people are paid attention to.In addition, China's sepiolite mineral resources are relatively abundant, develop it and not only have researching value as catalyst carrier, and have very large realistic meaning.But sepiolite exists that surface acidity is weak, passage is little, poor heat stability and have the defects such as destruction to molecular sieve component structure under water vapor conditions, therefore, carrying out modification to natural sepiolite is become the work that catalyst carrier must do.
At present, the industrial usual concentrated sulfuric acid as catalyst with synthesizing ethyl acetate, it has that equipment investment is large, side reaction is many, product separation is complicated and the defect such as liquid waste processing is difficult, therefore, in order to overcome above-mentioned defect, the catalyst for esterification reaction that exploitation makes new advances is to replace the concentrated sulfuric acid, and people have carried out large quantifier elimination.Wherein, solid acid, solid super-strong acid and cationic ion-exchange resin etc. are as the catalyst of esterification, and be all more successfully explore, these catalyst all have higher catalytic activity, but also come with some shortcomings, as more in accessory substance etc.
Summary of the invention
The object of this invention is to provide a kind of new spherical mesoporous sepiolite complex carrier, a kind of preparation method of spherical mesoporous sepiolite complex carrier, the spherical mesoporous sepiolite complex carrier prepared by the method, a kind of phosphoric acid loaded catalyst, a kind of preparation method of phosphoric acid loaded catalyst, the application in the esterification reaction of described phosphoric acid loaded catalyst and a kind of preparation method of ethyl acetate.
The present inventor is by finding after research, sepiolite is introduced in meso-porous molecular sieve material, sepiolite is made to enter in the duct of meso-porous molecular sieve material, and this mesoporous composite material is made the spherical of reunion not easily occurs, the high-specific surface area of meso-porous molecular sieve material can be retained like this, large pore volume, cube feature such as duct and large aperture, the reunion of meso-porous molecular sieve material can be reduced again, increase its mobility, make the loaded catalyst adopting this meso-porous molecular sieve material to make for the reaction raw materials conversion ratio significantly improved can be obtained during esterification, thus complete the present invention.
For this reason, the invention provides a kind of spherical mesoporous sepiolite complex carrier, wherein, this spherical mesoporous sepiolite complex carrier contains sepiolite and mesopore molecular sieve, and the average particulate diameter of described spherical mesoporous sepiolite complex carrier is 10-50 micron, specific area is 200-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 6-10 nanometer and 20-40 nanometer.
Present invention also offers a kind of preparation method of spherical mesoporous sepiolite complex carrier, the method comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane and sour agent are carried out first and contacts, and the product crystallization that obtains filtering after contacting first, obtain mesoporous material filter cake;
(2) waterglass and inorganic acid are carried out second to contact, and the product obtained after contacting second filters, and obtains silica gel filter cake;
(3) described mesoporous material filter cake, silica gel filter cake to be mixed with sepiolite and ball milling, and carry out spraying dry by after the pressed powder water slurrying obtained after ball milling, then by the described template removal in the product that obtains.
Present invention also offers the spherical mesoporous sepiolite complex carrier prepared by said method.
Present invention also offers a kind of phosphoric acid loaded catalyst, wherein, this phosphoric acid loaded catalyst comprises above-mentioned spherical mesoporous sepiolite complex carrier and the phosphoric acid of load on described spherical mesoporous sepiolite complex carrier.
Present invention also offers a kind of preparation method of phosphoric acid loaded catalyst, the method comprises and above-mentioned spherical mesoporous sepiolite complex carrier, phosphoric acid and water being mixed, and the mixture obtained is carried out spraying dry.
Present invention also offers the application in the esterification reaction of described phosphoric acid loaded catalyst.
In addition, present invention also offers a kind of preparation method of ethyl acetate, the method comprises: in the presence of a catalyst and under the condition of esterification, acetic acid is contacted with ethanol, obtain ethyl acetate, wherein, described catalyst is above-mentioned phosphoric acid loaded catalyst.
The present inventor finds, as a rule, the microscopic appearance of conventional ordered mesoporous material SBA-15 is bar-shaped, not only mobility is poor, and there is stronger water suction, moisture absorption ability, this will aggravate the agglomeration traits of bar-shaped ordered mesopore material SBA-15 further, is stored, transports, aft-loaded airfoil and application make troubles.But on the one hand, carrier provided by the invention is spherical, can reduce the agglomeration traits of powder, improve its mobility.On the other hand, carrier provided by the invention not only remains the large and feature of narrowly distributing in the high-specific surface area of ordered mesoporous material, large pore volume, aperture, and its pore-size distribution presents unique bimodal distribution, is more conducive to the load of active component, thus has higher catalytic activity.
In addition, because sepiolite is a kind of natural clay mineral material be dirt cheap, its introducing can reduce the production cost of carrier to a great extent.Namely, the advantage of mesoporous material and sepiolite that micro-sphere structure, aperture are had bimodal distribution by spherical mesoporous sepiolite complex carrier provided by the invention dexterously combines, thus provide better platform for the application of described spherical mesoporous sepiolite complex carrier, and widen its application.
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 X-ray diffracting spectrum (XRD collection of illustrative plates), and wherein, a is the XRD spectra of spherical mesoporous sepiolite complex carrier (C1); B is the XRD spectra of the spherical mesoporous sepiolite complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying process, and abscissa is 2 θ, and ordinate is intensity;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM figure) of the microscopic appearance of spherical mesoporous sepiolite complex carrier (C1);
Fig. 3 A and 3B is the scanning electron microscope (SEM) photograph of the spherical mesoporous sepiolite complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying process.
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.
Spherical mesoporous sepiolite complex carrier provided by the invention contains sepiolite and mesopore molecular sieve, and the average particulate diameter of described spherical mesoporous sepiolite complex carrier is 10-50 micron, specific area is 200-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 6-10 nanometer and 20-40 nanometer.Under preferable case, the average particulate diameter of described spherical mesoporous sepiolite complex carrier is 10-50 micron, specific area is 280-600 meters squared per gram, pore volume is 0.8-1.3 ml/g, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 6-8 nanometer and 20-30 nanometer.
In the present invention, described average particulate diameter adopts laser fineness gage to record, and specific area, pore volume and most probable pore size record according to nitrogen adsorption methods.
Spherical mesoporous sepiolite complex carrier according to the present invention, by the particle size of spherical mesoporous sepiolite complex carrier is controlled within above-mentioned scope, can guarantee that described spherical mesoporous sepiolite complex carrier is not easily reunited, and the reaction raw materials conversion ratio in esterification reaction process can be improved used as the loaded catalyst that carrier is made.When the specific area of described spherical mesoporous sepiolite complex carrier is less than 200 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 sepiolite complex carrier is greater than 600 meters squared per gram and/or pore volume is greater than 1.5 mls/g, the loaded catalyst made used as carrier is easily reunited in esterification reaction process, thus affects the reaction raw materials conversion ratio in esterification reaction process.
In described spherical mesoporous sepiolite complex carrier, relative to the described mesopore molecular sieve of 100 weight portions, the content of described sepiolite can be 100-300 weight portion.
In the present invention, described spherical mesoporous sepiolite complex carrier can also containing the silica introduced by waterglass." silica introduced by waterglass " refers in the preparation process of described spherical mesoporous sepiolite complex carrier, to be brought into the silica component in the spherical mesoporous sepiolite complex carrier of final preparation by waterglass as raw materials.In described spherical mesoporous sepiolite complex carrier, relative to the described meso-porous molecular sieve material of 100 weight portions, the content of the described silica introduced by waterglass can be 100-300 weight portion.
In the present invention, described mesopore molecular sieve can be that the routine of this area is selected, as a rule, its main component is silica, and the average particulate diameter of described mesopore molecular sieve is 10-50 micron, specific area is 200-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 6-10 nanometer and 20-40 nanometer.Under preferable case, the average particulate diameter of described mesopore molecular sieve is 10-50 micron, and specific area is 280-600 meters squared per gram, and pore volume is 0.8-1.3 ml/g, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 6-8 nanometer and 20-30 nanometer.
The preparation method of spherical mesoporous sepiolite complex carrier provided by the invention comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane and sour agent are carried out first and contacts, and the product crystallization that obtains filtering after contacting first, obtain mesoporous material filter cake;
(2) waterglass and inorganic acid are carried out second to contact, and the product obtained after contacting second filters, and obtains silica gel filter cake;
(3) described mesoporous material filter cake, silica gel filter cake to be mixed with sepiolite and ball milling, and carry out spraying dry by after the pressed powder water slurrying obtained after ball milling, then by the described template removal in the product that obtains.
In the preparation process of above-mentioned spherical mesoporous sepiolite complex carrier, the pore-size distribution of described spherical mesoporous sepiolite complex carrier controls as bimodal distribution by the composition mainly through controlling mesoporous material filter cake, and mainly through controlling forming method (namely, first described mesoporous material filter cake, silica gel filter cake are mixed with sepiolite and ball milling, then by spraying dry after the pressed powder water slurrying obtained after ball milling) microscopic appearance of described spherical mesoporous sepiolite complex carrier is controlled as spherical.
The kind of the present invention to described template is not particularly limited, as long as the spherical mesoporous sepiolite complex carrier obtained can be made to have above described holes structure, such as, described template can be triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.Wherein, this template can be commercially available (such as, can available from Aldrich Co, commodity are called P123, and molecular formula is EO
20pO
70eO
20), also can be prepared by existing various method.When described template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of described template calculates according to the number-average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene.
According to the present invention, the kind of described sour agent can be the routine selection of this area, can be the mixture of existing various acid or acid.Wherein, the mixture of described acid or acid can use with pure state, also can use with the form of its aqueous solution, preferably use in form of an aqueous solutions.Preferably, described sour agent is pH value is that 1-6(is preferably 3-5) acetic acid and the cushioning liquid of sodium acetate.
The condition of the present invention to described first contact is not particularly limited, and such as, it can be 10-60 DEG C that the condition of described first contact generally includes temperature, and the time can be 10-72 hour, and pH value can be 1-7; Under preferable case, it is 10-30 DEG C that the condition of described first contact comprises temperature, and the time is 20-40 hour, and pH value is 3-6.In order to more be conducive to the Homogeneous phase mixing between each material, described first contact is preferably carried out under agitation.The consumption of described sour agent preferably makes the pH value of described first haptoreaction system be 1-7, is more preferably 3-6.
The condition of the present invention to described crystallization is also not particularly limited, and such as, it can be 30-150 DEG C that the condition of described crystallization generally includes temperature, and the time can be 10-72 hour; Under preferable case, it is 40-80 DEG C that the condition of described crystallization comprises temperature, and the time is 20-40 hour.
According to the present invention, in the process of the described 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, is preferably 1:200-400:250-400:70-150.Wherein, when described template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of described template calculates according to the number-average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene.
In addition, the present invention is not particularly limited described template, ethanol, sour agent, the way of contact between trimethylpentane and tetramethoxy-silicane, such as, above-mentioned five kinds of materials can be mixed contact simultaneously, also several materials wherein first can be mixed contact, remaining material be added in the mixture that obtains and continue mixing contact again.Under preferable case, the described way of contact is first at 10-60 DEG C, template, ethanol, sour agent and trimethylpentane is uniformly mixed 6-10 hour, and then adds tetramethoxy-silicane and continue to be uniformly mixed 4-62 hour.
The condition of the present invention to described second contact is not particularly limited, and such as, it can be 10-60 DEG C that the condition of described second contact generally includes temperature, is preferably 20-40 DEG C; Time can be 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, described second contact is preferably carried out under agitation.
As well known to those skilled in the art, described waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 % by weight, is preferably 12-30 % by weight.
The kind of described inorganic acid can be that the routine of this area is selected, and such as, can be one or more 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.
According to the present invention, in the preparation process of described spherical mesoporous sepiolite complex carrier, the mode of filtering described in step (1) and (2) can adopt and well known to a person skilled in the art that various mode is carried out, and is preferably suction filtration and is separated.It is a kind of mode utilizing air pressure to realize liquid to be separated with solid particle well-known to those skilled in the art that described suction filtration is separated.
In addition, preparing in the process of mesoporous material filter cake and silica gel filter cake above-mentioned, can comprise with the process obtaining filter cake by filtering: after filtration, with distilled water cyclic washing (washing times can be 2-10), then carry out suction filtration.
According to the present invention, in step (3), the consumption of described mesoporous material filter cake, silica gel filter cake and sepiolite can according to expecting that the component of the spherical mesoporous sepiolite complex carrier obtained is selected, such as, relative to the described mesoporous material filter cake of 100 weight portions, the consumption of described silica gel filter cake can be 100-300 weight portion, and the consumption of described sepiolite can be 100-300 weight portion.
To the concrete operation method of ball milling and condition, there is no particular limitation in the present invention, with do not destroy or substantially do not destroy carrier structure and make silica gel, sepiolite enters in carrier duct and is as the criterion.Those skilled in the art can select various suitable condition to implement the present invention according to mentioned above principle.Particularly, 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 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 comprises: 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 addition, by the process of pressed powder use water slurrying, the consumption of described pressed powder and water is not particularly limited, as long as can obtain being conducive to spray-dired slurry, such as, the weight ratio of described pressed powder and water can be 1:0.5-5, is preferably 1:1-2.
According to the present invention, described spray-dired concrete operation method and condition are known to the skilled person.Particularly, the slurry be made into by described pressed powder and water to be joined in atomizer High Rotation Speed to realize spraying dry.Wherein, it can be 100-300 DEG C that spray-dired condition comprises temperature, and the rotating speed of rotation can be 10000-15000r/min; Particularly preferably in situation, it is 200 DEG C that described spray-dired condition comprises temperature, and the rotating speed of rotation is 12000r/min.
According to the present invention, the method for removed template method is generally calcination method.Wherein, it can be 300-600 DEG C that the condition of described calcination method comprises temperature, is preferably 350-550 DEG C, most preferably is 500 DEG C; Time can be 10-80 hour, is preferably 20-30 hour, most preferably is 24 hours.
Present invention also offers the spherical mesoporous sepiolite complex carrier prepared by said method.
Present invention also offers a kind of phosphoric acid loaded catalyst, wherein, this phosphoric acid loaded catalyst comprises above-mentioned spherical mesoporous sepiolite complex carrier and the phosphoric acid of load on above-mentioned spherical mesoporous sepiolite complex carrier.
Wherein, the content of described spherical mesoporous sepiolite complex carrier and phosphoric acid can be the routine selection of this area, and such as, with the gross weight of described catalyst for benchmark, the content of described phosphoric acid can be 1-50 % by weight, is preferably 5-50 % by weight; The content of described spherical mesoporous sepiolite complex carrier can be 50-99 % by weight, is preferably 50-95 % by weight.
In the present invention, the various method preparations that described phosphoric acid loaded catalyst can use according to this area routine, only need by phosphoric acid load on the carrier.
In a preferred embodiment, can reuse to make the phosphoric acid loaded catalyst of preparation, and in recycling process, still can obtain higher reaction raw materials conversion ratio, the method preparing loaded catalyst comprises: above-mentioned spherical mesoporous sepiolite complex carrier, phosphoric acid and water are mixed, and the mixture obtained is carried out spraying dry.
Wherein, the consumption of described spherical mesoporous sepiolite complex carrier, phosphoric acid and water can according to expecting that the catalyst obtained reasonably is selected, such as, with total consumption of described spherical mesoporous sepiolite complex carrier and phosphoric acid for benchmark, the consumption of described phosphoric acid can be 1-50 % by weight, is preferably 5-50 % by weight; The consumption of described spherical mesoporous sepiolite complex carrier can be 50-99 % by weight, is preferably 50-95 % by weight.In addition, the weight ratio of described spherical mesoporous sepiolite complex carrier and water can be 1:15-35, is preferably 1:20-25.
Described spray-dired method is known to the skilled person, as mentioned above, be generally and the mixture of described spherical mesoporous sepiolite complex carrier, water and phosphoric acid joined in atomizer High Rotation Speed to realize spraying dry, wherein, it can be 100-300 DEG C that spray-dired condition comprises temperature, and the rotating speed of rotation can be 10000-15000r/min; Particularly preferably in situation, it is 200 DEG C that described spray-dired condition comprises temperature, and the rotating speed of rotation is 12000r/min.
Present invention also offers the application in the esterification reaction of above-mentioned phosphoric acid loaded catalyst.
In addition, present invention also offers a kind of preparation method of ethyl acetate, the method comprises: in the presence of a catalyst and under the condition of esterification, acetic acid is contacted with ethanol, obtain ethyl acetate, wherein, described catalyst is above-mentioned phosphoric acid loaded catalyst.
The consumption of the present invention to described acetic acid and ethanol is not particularly limited, as long as can be obtained by reacting ethyl acetate, but in order to improve the utilization rate of raw material, under preferable case, the mol ratio of described acetic acid and ethanol is 1:0.5-10.
In addition, the consumption of the present invention to described phosphoric acid loaded catalyst is also not particularly limited, can come suitably to select according to the addition of acetic acid in course of reaction and/or ethanol, as a rule, relative to the acetic acid of 100 weight portions, the consumption of described phosphoric acid loaded catalyst can be 1-15 weight portion, is preferably 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 reaction time.Wherein, in order to more be conducive to the carrying out of esterification, described reaction is preferably under reflux conditions carried out, that is, described reaction temperature is reflux temperature.The prolongation in reaction time can improve the conversion ratio of reactant and the yield of product within the specific limits, but the amplitude that the reaction time is long improves reaction-ure conversion-age and product yield is also not obvious, therefore, consider effect and efficiency, under preferable case, the described reaction time is 1-10 hour, is more preferably 2-8 hour.
According to the present invention, the preparation method of described ethyl acetate is also preferably included in after esterification terminates, suction filtration separation is carried out to final reactant mixture, and suction filtration is separated the solid product vacuum drying 1-24 hour at 25-200 DEG C obtained, preferably vacuum drying 6-10 hour at 50-120 DEG C, to reclaim phosphoric acid loaded catalyst.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples and comparative example, template polyoxyethylene-poly-oxypropylene polyoxyethylene available from Aldrich Co, is abbreviated as P123, and molecular formula is EO
20pO
70eO
20, be the material of 9003-11-6 in the registration number of U.S. chemical abstract, number-average molecular weight Mn is 5800.
In following examples and comparative example, X-ray diffraction analysis is that the X-ray diffractometer of D8Advance carries out in the model purchased from German Bruker AXS company; Scanning electron microscope analysis is that the SEM of XL-30 is carried out in the model of purchased from American FEI Co.; Pore structure parameter analysis is that the nitrogen adsorption desorption instrument of Autosorb-1 carries out in the model of purchased from American Kang Ta company, wherein, before testing, sample is degassed 4 hours at 200 DEG C; The analysis of product liquid phase ingredient is being carried out purchased from Britain Agilent company 7890A/5973N gas chromatograph-mass spectrometer.
In following examples and comparative example, consumption × 100% of the conversion ratio (%) of the acetic acid=content of acetic acid (in the consumption-product of acetic acid) ÷ acetic acid; Theoretical yield × 100% of the actual production ÷ ethyl acetate of selective (the %)=ethyl acetate of ethyl acetate.
Embodiment 1
This embodiment is for illustration of spherical mesoporous sepiolite complex carrier provided by the invention and Catalysts and its preparation method.
(1) preparation of spherical mesoporous sepiolite complex carrier:
1.0 grams of triblock copolymer P123s and 1.69 grams of ethanol (0.037mol) are joined 28mL, pH value be 4 acetic acid and sodium acetate cushioning liquid in, at 15 DEG C, be stirred to P123 dissolve completely, add 6g(0.053mol afterwards) trimethylpentane, and stirring added 2.13 grams of (0.014mol) tetramethoxy-silicanes after 8 hours at 15 DEG C, then at 15 DEG C, pH value is stir 20 hours under the condition of 4.5, and solution is transferred in teflon-lined reactor, baking oven crystallization 24 hours at 60 DEG C, and by the crystallization product suction filtration that obtains and with distilled water washing washing, obtain mesoporous material filter cake.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution be that 5:1 mixes by waterglass and the weight ratio of sulfuric acid, then stirring reaction 1.5 hours at 15 DEG C, and the sulfuric acid solution adjusted to ph being 98 % by weight by the product concentration obtained is 3, then reaction mass suction filtration, distilled water being washed till sodium ions content is 0.02 % by weight, obtains silica gel filter cake.
10 grams of mesoporous material filter cakes, 10 grams of silica gel filter cakes are put into 100mL ball grinder (wherein together with 10 grams of sepiolites, ball grinder material is polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate, 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 30 grams of pressed powders.This pressed powder is dissolved in 30 grams of deionized waters, and at 200 DEG C, under rotating speed is 12000r/min spraying dry, then the product obtained after spraying dry is calcined 24 hours with removed template method in the Muffle furnace of 500 DEG C, obtain the spherical mesoporous sepiolite complex carrier of target product of 28 grams of removed template methods, called after C1.
(2) preparation of phosphoric acid loaded catalyst:
At 25 DEG C, above-mentioned 28 grams of spherical mesoporous sepiolite complex carriers are put into deionized water together with phosphoric acid, be stirred to dissolving, the weight ratio controlling spherical sepiolite clay mineral complex carrier, deionized water and phosphoric acid is 1:25:1, then the mixture obtained is carried out spraying dry at 200 DEG C, under rotating speed is 12000r/min, obtain the spherical mesoporous sepiolite complex carrier (i.e. phosphoric acid loaded catalyst) of load phosphoric acid, called after Cat-1.
Characterize with X-ray diffractometer, SEM and the nitrogen adsorption desorption instrument spherical mesoporous sepiolite complex carrier to this spherical mesoporous sepiolite complex carrier and load phosphoric acid.
Fig. 1 is X-ray diffracting spectrum (XRD spectra), and wherein, a is the XRD spectra of spherical mesoporous sepiolite complex carrier (C1); B is the XRD spectra of the spherical mesoporous sepiolite complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying process, and abscissa is 2 θ, and ordinate is intensity.As can be seen from the result of Fig. 1, all there is low-angle spectrum peak in the XRD spectra a of spherical mesoporous sepiolite complex carrier (C1), the XRD spectra b of the spherical mesoporous sepiolite complex carrier (Cat-1) of load phosphoric acid obtained by spray drying process, can infer thus, this bi-material all has hexagonal hole road structure specific to mesoporous material.
Fig. 2 is the scanning electron microscope (SEM) photograph of the microscopic appearance of spherical mesoporous sepiolite complex carrier (C1).As can be seen from the result of Fig. 2, the microscopic appearance of spherical mesoporous sepiolite complex carrier (C1) to be diameter the be Mesoporous Spheres of 10-50 μm.
Fig. 3 A and 3B is the scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical mesoporous sepiolite complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying process.Wherein, Fig. 3 A is the scanning electron microscope (SEM) photograph of the spherical mesoporous sepiolite complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying process; Fig. 3 B is the scanning electron microscope (SEM) photograph of the high-amplification-factor of the spherical mesoporous sepiolite complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying process.As seen from the figure, the microscopic appearance of the spherical mesoporous sepiolite complex carrier (Cat-1) of the load phosphoric acid obtained by spray drying process is still basic keeps spherical, and particle diameter is 10-50 μm.
Table 1 is the pore structure parameter of the spherical mesoporous sepiolite complex carrier (Cat-1) of spherical mesoporous sepiolite complex carrier (C1) and load phosphoric acid.
Table 1
As can be seen from the data of table 1, spherical mesoporous sepiolite complex carrier is after load phosphoric acid, and pore volume and specific area reduce all to some extent, it can be said that bright, and in load-reaction process, phosphoric acid has entered into the inside of spherical mesoporous sepiolite complex carrier.
Comparative example 1
This comparative example is for illustration of the spherical mesoporous sepiolite complex carrier of reference and Catalysts and its preparation method.
Spherical mesoporous sepiolite complex carrier and phosphoric acid loaded catalyst is prepared according to the method for embodiment 1, unlike, in the preparation process of spherical mesoporous sepiolite complex carrier, do not add sepiolite, obtain the spherical mesoporous sepiolite complex carrier DCat-1 of spherical mesoporous sepiolite complex carrier DC1 and support type phosphoric acid.
Comparative example 2
This comparative example is for illustration of the spherical mesoporous sepiolite complex carrier of reference and Catalysts and its preparation method.
The preparation of spherical mesoporous sepiolite complex carrier and phosphoric acid loaded catalyst is prepared according to the method for embodiment 1, unlike, in the preparation process of spherical mesoporous sepiolite complex carrier, do not comprise and this pressed powder is dissolved in 30 grams of deionized waters, and at 200 DEG C, under rotating speed is 12000r/min spray-dired step, but directly described pressed powder is calcined 24 hours with removed template method in the Muffle furnace of 500 DEG C, obtain the catalyst DCat-2 of spherical mesoporous sepiolite complex carrier DC2 and support type phosphoric acid.
Comparative example 3
This comparative example is for illustration of the spherical mesoporous sepiolite complex carrier of reference and Catalysts and its preparation method.
Spherical mesoporous sepiolite complex carrier and phosphoric acid loaded catalyst is prepared according to the method for embodiment 1, unlike, in the preparation process of spherical mesoporous sepiolite complex carrier, the bar-shaped mesoporous silicon oxide SBA-15 filter cake (being purchased from high-tech limited company of Changchun Jilin University) of mesoporous material filter cake identical weight part substitutes, and obtains the spherical mesoporous sepiolite complex carrier DCat-3 of spherical mesoporous sepiolite complex carrier DC3 and support type phosphoric acid.
Embodiment 2
This embodiment is for illustration of spherical mesoporous sepiolite complex carrier provided by the invention and Catalysts and its preparation method.
(1) preparation of spherical mesoporous sepiolite complex carrier:
1.0 grams of triblock copolymer P123s and 3.69 grams of (0.08mol) ethanol are joined 28mL, pH value be 5 acetic acid and sodium acetate cushioning liquid in, at 60 DEG C, be stirred to P123 dissolve completely, add 9.14g(0.08mol afterwards) trimethylpentane, and stirring added 4.68 grams of (0.03mol) tetramethoxy-silicanes after 1 hour at 60 DEG C, then at 60 DEG C, pH value is stir 10 hours under the condition of 5.5, and solution is transferred in teflon-lined reactor, baking oven crystallization 72 hours at 30 DEG C, the crystallization product suction filtration obtained is washed four times with distilled water, obtain mesoporous material filter cake.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution be that 5:1 mixes by waterglass and the weight ratio of sulfuric acid, then stirring reaction 1 hour at 60 DEG C, and the sulfuric acid solution adjusted to ph being 98 % by weight by the product concentration obtained is 2, then reaction mass suction filtration, distilled water being washed till sodium ions content is 0.02 % by weight, obtains silica gel filter cake.
10 grams of mesoporous material filter cakes, 30 grams of silica gel filter cakes are put into 100mL ball grinder (wherein together with 30 grams of sepiolites, ball grinder material is polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate, 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 70 grams of pressed powders.This pressed powder is dissolved in 100 grams of deionized waters, and at 200 DEG C, under rotating speed is 12000r/min spraying dry, then the product obtained after spraying dry is calcined 24 hours with removed template method in the Muffle furnace of 500 DEG C, obtain the spherical mesoporous sepiolite complex carrier of target product of 68 grams of removed template methods, called after C2.
(2) preparation of support type phosphoric acid catalyst:
At 25 DEG C, above-mentioned 68 grams of spherical mesoporous sepiolite complex carriers are put into deionized water together with phosphoric acid, be stirred to dissolving, the weight ratio controlling spherical sepiolite clay mineral complex carrier, deionized water and phosphoric acid is 1:25:1, then the mixture obtained is carried out spraying dry at 200 DEG C, under rotating speed is 12000r/min, obtain the spherical mesoporous sepiolite complex carrier (i.e. support type phosphoric acid catalyst) of load phosphoric acid, called after Cat-2.
Table 2 is the pore structure parameter of the spherical mesoporous sepiolite complex carrier (Cat-2) of spherical mesoporous sepiolite complex carrier (C2) and load phosphoric acid.
Table 2
As can be seen from the data of table 2, spherical mesoporous sepiolite complex carrier is after load phosphoric acid, and pore volume and specific area reduce all to some extent, it can be said that bright, and in load-reaction process, phosphoric acid has entered into the inside of spherical mesoporous sepiolite complex carrier.
Embodiment 3
This embodiment is for illustration of spherical mesoporous sepiolite complex carrier provided by the invention and Catalysts and its preparation method.
(1) preparation of spherical mesoporous sepiolite complex carrier:
1.0 grams of triblock copolymer P123s and 2.76 grams of (0.06mol) ethanol are joined 28mL, pH value be 3 acetic acid and sodium acetate cushioning liquid in, at 40 DEG C, be stirred to P123 dissolve completely, add 6.85g(0.06mol afterwards) trimethylpentane, and stirring added 3.12 grams of (0.02mol) tetramethoxy-silicanes after 8 hours at 40 DEG C, then at 40 DEG C, pH value is stir 30 hours under the condition of 3.5, and solution is transferred in teflon-lined reactor, baking oven crystallization 10 hours at 150 DEG C, the crystallization product suction filtration obtained is washed four times with distilled water, obtain mesoporous material filter cake.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution be that 5:1 mixes by waterglass and the weight ratio of sulfuric acid, then stirring reaction 5 hours at 30 DEG C, and the sulfuric acid solution adjusted to ph being 98 % by weight by the product concentration obtained is 4, then reaction mass suction filtration, distilled water being washed till sodium ions content is 0.02 % by weight, obtains silica gel filter cake.
10 grams of mesoporous material filter cakes, 20 grams of silica gel filter cakes are put into 100mL ball grinder (wherein together with 20 grams of sepiolites, ball grinder material is polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, quantity is 1, and rotating speed is 400r/min), closure ball grinding jar, in ball grinder, temperature is ball milling 1 hour at 60 DEG C, obtains 50 grams of pressed powders.This pressed powder is dissolved in 100 grams of deionized waters, and at 200 DEG C, under rotating speed is 12000r/min spraying dry, then the product obtained after spraying dry is calcined 24 hours with removed template method in the Muffle furnace of 500 DEG C, obtain the spherical mesoporous sepiolite complex carrier of target product of 49 grams of removed template methods, called after C3.
(2) preparation of support type phosphoric acid catalyst:
At 25 DEG C, above-mentioned 49 grams of spherical mesoporous sepiolite complex carriers are put into deionized water together with phosphoric acid, be stirred to dissolving, the weight ratio controlling spherical sepiolite clay mineral complex carrier, deionized water and phosphoric acid is 1:25:1, then the mixture obtained is carried out spraying dry at 200 DEG C, under rotating speed is 12000r/min, obtain the spherical mesoporous sepiolite complex carrier (i.e. support type phosphoric acid catalyst) of load phosphoric acid, called after Cat-3.
Table 3 is the pore structure parameter of the spherical mesoporous sepiolite complex carrier (Cat-3) of spherical mesoporous sepiolite complex carrier (C3) and load phosphoric acid.
Table 3
As can be seen from the data of table 3, spherical mesoporous sepiolite complex carrier is after load phosphoric acid, and pore volume and specific area reduce all to some extent, it can be said that bright, and in load-reaction process, phosphoric acid has entered into the inside of spherical mesoporous sepiolite complex carrier.
Embodiment 4
This embodiment is for illustration of spherical mesoporous sepiolite complex carrier provided by the invention and Catalysts and its preparation method.
Spherical mesoporous sepiolite complex carrier and phosphoric acid loaded catalyst is prepared according to the method for embodiment 1, unlike, spray-dired step is not had in the process preparing phosphoric acid loaded catalyst, and by means of only the method for dipping by phosphoric acid load on spherical mesoporous sepiolite complex carrier, thus obtained phosphoric acid loaded catalyst Cat-4.
Embodiment 5
This embodiment is used for illustrating the preparation method of ethyl acetate provided by the invention.
By the vacuum drying 6 hours at 150 DEG C of the phosphoric acid loaded catalyst Cat-1 in embodiment 1,0.5 gram is taken after being cooled to room temperature 25 DEG C, add in 100mL there-necked flask successively with 11.5 grams of ethanol and 15 grams of acetic acid, stirring reaction 3 hours under heated reflux condition, then room temperature 25 DEG C is cooled to and suction filtration separation, utilize the liquid phase ingredient of gas chromatograph-mass spectrometer analytical reactions product, and by calculating the conversion ratio of acetic acid and the selective of ethyl acetate, result is as shown in table 4.
Embodiment 6-8
Embodiment 6-8 is used for illustrating the preparation method of ethyl acetate provided by the invention.
Ethyl acetate is prepared according to the method for embodiment 5, unlike, replace described loaded catalyst Cat-1 with loaded catalyst prepared by embodiment 2-4 respectively.As a result, calculate the conversion ratio of acetic acid and the selective of ethyl acetate separately, result is as shown in table 4.
Comparative example 4-6
Comparative example 4-6 is used for the reference preparation method of ethyl acetate is described.
Ethyl acetate is prepared according to the method for embodiment 5, unlike, replace described loaded catalyst Cat-1 with loaded catalyst prepared by comparative example 1-3 respectively.As a result, calculate the conversion ratio of acetic acid and the selective of ethyl acetate separately, result is as shown in table 4.
Table 4
| Numbering | Catalyst | The conversion ratio of acetic acid | Ethyl acetate selective |
| Embodiment 5 | Cat-1 | 99.5% | 99% |
| Embodiment 6 | Cat-2 | 99.7% | 100% |
| Embodiment 7 | Cat-3 | 99.4% | 99% |
| Embodiment 8 | Cat-4 | 99.1% | 98% |
| Comparative example 4 | DCat-1 | 90% | 99% |
| Comparative example 5 | DCat-2 | 91% | 99% |
| Comparative example 6 | DCat-3 | 90% | 99% |
Embodiment 9-12 and comparative example 7-9
Ethyl acetate is prepared according to the method for embodiment 5, unlike, replace described loaded catalyst Cat-1 with the catalyst reclaimed from embodiment 5-8 and comparative example 4-6 respectively.As a result, calculate the conversion ratio of acetic acid and the selective of ethyl acetate separately, result is as shown in table 5.
Table 5
| Numbering | Catalyst | The conversion ratio of acetic acid | Ethyl acetate selective |
| Embodiment 9 | The Cat-1 reclaimed | 99.5% | 99% |
| Embodiment 10 | The Cat-2 reclaimed | 99.6% | 99% |
| Embodiment 11 | The Cat-3 reclaimed | 99.3% | 99% |
| Embodiment 12 | The Cat-4 reclaimed | 97.5% | 98% |
| Comparative example 7 | The DCat-1 reclaimed | 89% | 98% |
| Comparative example 8 | The DCat-2 reclaimed | 90% | 97% |
| Comparative example 9 | The DCat-3 reclaimed | 88% | 98% |
As can be seen from the above results, adopting support preparation method provided by the invention can obtain average particulate diameter is 10-50 micron, specific area is 200-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively the spherical mesoporous sepiolite complex carrier of 6-10 nanometer and 20-40 nanometer.In addition, when phosphoric acid loaded catalyst provided by the invention is used for the preparation of ethyl acetate, not only there is higher acetic acid conversion and ethyl acetate selective, and can by reclaim and Reusability, aftertreatment technology is simple.
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 (14)
1. a spherical mesoporous sepiolite complex carrier, it is characterized in that, this spherical mesoporous sepiolite complex carrier contains sepiolite and mesopore molecular sieve, and the average particulate diameter of described spherical mesoporous sepiolite complex carrier is 10-50 micron, specific area is 200-600 meters squared per gram, pore volume is 0.5-1.5 ml/g, and pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 6-10 nanometer and 20-40 nanometer.
2. carrier according to claim 1, wherein, relative to the described mesopore molecular sieve of 100 weight portions, the content of described sepiolite is 100-300 weight portion.
3. a preparation method for spherical mesoporous sepiolite complex carrier, the method comprises the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane and sour agent are carried out first and contacts, and the product crystallization that obtains filtering after contacting first, obtain mesoporous material filter cake;
(2) waterglass and inorganic acid are carried out second to contact, and the product obtained after contacting second filters, and obtains silica gel filter cake;
(3) described mesoporous material filter cake, silica gel filter cake to be mixed with sepiolite and ball milling, and carry out spraying dry by after the pressed powder water slurrying obtained after ball milling, then by the described template removal in the product that obtains.
4. preparation method according to claim 3, wherein, in step (3), relative to the described mesoporous material filter cake of 100 weight portions, the consumption of described silica gel filter cake is 100-300 weight portion, and the consumption of described sepiolite is 100-300 weight portion.
5. preparation method according to claim 3, wherein, in step (1), the mol ratio of described template, ethanol, trimethylpentane and tetramethoxy-silicane is 1:100-500:200-500:50-200.
6. according to claim 3 or described preparation method, wherein, in step (1), described template is triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide; Described sour agent is pH value is the acetic acid of 1-6 and the cushioning liquid of sodium acetate.
7. the preparation method according to claim 3 or 6, wherein, it is 10-60 DEG C that the condition of described first contact comprises temperature, and the time is 10-72 hour, and pH value is 1-7; It is 30-150 DEG C that the condition of described crystallization comprises temperature, and the time is 10-72 hour.
8. preparation method according to claim 3, wherein, in step (2), it is 10-60 DEG C that the condition of described second contact comprises temperature, 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.
9. preparation method according to claim 3, wherein, in step (3), the condition of described ball milling comprises: 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; Preferably, described spray-dired condition comprises: temperature is 100-300 DEG C, and rotating speed is 10000-15000r/min; Preferably, the condition of removed template method comprises: temperature is 300-600 DEG C, and the time is 10-80 hour.
10. the spherical mesoporous sepiolite complex carrier prepared by the method in claim 3-9 described in any one.
11. 1 kinds of phosphoric acid loaded catalysts, is characterized in that, this phosphoric acid loaded catalyst comprises spherical mesoporous sepiolite complex carrier described in claim 1,2 or 10 and the phosphoric acid of load on described spherical mesoporous sepiolite complex carrier.
The preparation method of 12. 1 kinds of phosphoric acid loaded catalysts, the method comprises and being mixed by spherical mesoporous sepiolite complex carrier, phosphoric acid and the water described in claim 1,2 or 10, and the mixture obtained is carried out spraying dry.
13. phosphoric acid loaded catalyst according to claim 11 application in the esterification reaction.
The preparation method of 14. 1 kinds of ethyl acetate, the method comprises: in the presence of a catalyst and under the condition of esterification, is contacted by acetic acid, obtain ethyl acetate with ethanol, it is characterized in that, described catalyst is phosphoric acid loaded catalyst according to claim 11.
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