CN102642846A - Preparation method of mesoporous material Ca-SBA-15 - Google Patents
Preparation method of mesoporous material Ca-SBA-15 Download PDFInfo
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Abstract
The invention relates to a preparation method of a mesoporous material, in particular to a preparation method of a mesoporous material Ca-SBA-15, and aims to solve the problems of complex operation, large energy consumption, difficult generation of a mesoporous structure, and easy Ca loss in a suction filtration process in the existing Ca-SBA-15 preparation process. The preparation method disclosed by the invention comprises the steps that: 1, a template agent P123, hydrochloric acid and anhydrous ethanol are mixed in proportion; 2, metal salt and a silicon source are added and stirred until liquid is fully volatilized to obtain solids; 3, the solids are ground, hydrothermal crystallization reaction, suction filtration and drying are carried out, and the mesoporous material Ca-SBA-15 is obtained after calcination. The preparation method of the mesoporous material Ca-SBA-15 disclosed by the invention not only ensures the mesoporous structure not to be damaged, but also alkaline earth metal Ca is introduced. The method for preparing the mesoporous material Ca-SBA-15 is easy to operate, the introduction volume of Ca is increased, and the energy consumption is less. The method disclosed by the invention is used in the fields of catalysis, adsorption and the like.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous material.
Background technology
Ca-SBA-15 be a kind of have high-specific surface area, big pore volume, good hydrothermal stability, mesoscopic structure controlled, have the porous material of acid-basicity simultaneously, it has a wide range of applications in fields such as catalysis, absorption.The synthetic of existing Ca-SBA-15 generally is through three kinds of compound methods: pickling process, microwave method and one kettle way.Wherein, microwave method and pickling process are wanted two step calcinings in the preparation process, cause caving in of pore structure easily, and complicated operation, power consumption are bigger; One kettle way exists Ca to be difficult for getting into mesoporous skeleton in synthetic, and the difficult problem that generates meso-hole structure and in suction filtration, washing process, be prone to cause the loss of Ca.
Summary of the invention
The objective of the invention is for solve existing Ca-SBA-15 prepare have complicated operation in the process, power consumption is big, meso-hole structure is difficult for generating and the suction filtration process in be prone to cause problem such as Ca loss, and the preparation method of a kind of mesoporous material Ca-SBA-15 is provided.
The preparation method of a kind of mesoporous material Ca-SBA-15 of the present invention carries out according to following steps:
One, the dissolving of template: take by weighing 7 ~ 10 parts template P123 by weight, 16 ~ 18 parts concentration is the hydrochloric acid of 0.32 ~ 1.6M and 72 ~ 77 parts absolute ethyl alcohol, under the speed of 600 ~ 800r/min, mixes, and gets mixed solution A;
Two, the adding in metal-salt and silicon source: the hydrochloric acid that with metal-salt dissolving and concentration is 0.32 ~ 1.6M is that the mixed of 6 ~ 55:55 is even by mass ratio, the first mixed liquid of metal-containing salt; The mixed solution A that the first mixed liquid and the step 1 of metal-containing salt obtained is the 1:6 mixed by volume, under the speed of 600 ~ 800r/min, stirs 1 ~ 2h then, mixing solutions B; Drip the silicon source with the speed of 20 ~ 40d/min again, the speed while dripping with 600 ~ 800r/min stirs, and volatilizees fully until the liquid of mixing solutions B, must solid;
Three, crystallization: with solid abrasive to 50 ~ 100 orders that step 2 obtains, put into reaction kettle, add water to still lining volumetrical 2/3 ~ 3/4, hydrothermal crystallizing 12 ~ 24h under 100 ℃ ~ 120 ℃ temperature; Take out reaction kettle, with the reaction solution in the reaction kettle be in vacuum tightness-condition of 0.09MPa under suction filtration, collect solid formation, with the solid formation of collecting dry 6 ~ 10h under 40 ~ 60 ℃ of conditions, calcine 6 ~ 8h at 450 ℃ ~ 550 ℃ then, promptly get mesoporous material Ca-SBA-15; Wherein, the volume ratio of the silicon source of step 2 and mixing solutions B is 1:5.
The present invention has the following advantages:
The present invention provides a kind of novel preparation method for mesoporous material Ca-SBA-15 synthetic; I.e. " solvent evaporates self-assembly method "; So-called solvent evaporates self-assembly method is that mixing solutions is at room temperature stirred; Let solvent volatilize naturally, by means of the reactive force between molecule in the volatilization process and the molecule, the spontaneous self-assembly of molecule is a liquid crystal structure.
The present invention can introduce Ca when SBA-15 forms meso-hole structure.This method is compared with present method, has simple to operate, Ca and introduces advantages such as mesopore orbit, power consumption are few easily.
1, adopts the solvent evaporates self-assembly method directly to prepare mesoporous material Ca-SBA-15, both guaranteed that its meso-hole structure is not destroyed, introduced earth alkali metal Ca again, solved the problem of the loss of Ca, can be used for fields such as catalysis, absorption.
2, method of the present invention makes mesoporous material Ca-SBA-15, and is simple to operate, and the introducing amount of Ca improves, less energy intensive.
Description of drawings
Fig. 1 is the XRD spectra of the test 1 mesoporous material Ca-SBA-15 that makes;
Fig. 2 is the infrared spectrum of the test 1 mesoporous material Ca-SBA-15 that makes;
Fig. 3 is the XRD spectra of the test 2 mesoporous material Ca-SBA-15 that make;
Fig. 4 is the infrared spectrum of the test 2 mesoporous material Ca-SBA-15 that make;
Fig. 5 is the XRD spectra of the test 3 mesoporous material Ca-SBA-15 that make, and wherein, a is the little angle XRD spectra of SBA-15; B is original calcium silicon than the little angle XRD spectra that is 0.3 Ca-SBA-15;
Fig. 6 is the infrared spectrum of the test 3 mesoporous material Ca-SBA-15 that make, and wherein, a is the SBA-15 infrared spectrum; B is original reinforced calcium silicon than the infrared spectrum that is 0.3 Ca-SBA-15;
Fig. 7 is the N of the test 3 mesoporous material Ca-SBA-15 that make
2The adsorption-desorption graphic representation, wherein, curve 1 and 3 is respectively the desorption curve of SBA-15 and Ca-SBA-15, and curve 2 and 4 is respectively the adsorption curve of SBA-15 and Ca-SBA-15;
Fig. 8 is the pore size distribution curve figure of the test 3 mesoporous material Ca-SBA-15 that make, and wherein, a is the SBA-15 pore size distribution curve; B is the pore size distribution curve of Ca-SBA-15;
Fig. 9 schemes for the TEM of the mesoporous material Ca-SBA-15 that test 3 makes.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of a kind of mesoporous material Ca-SBA-15 carries out according to following steps:
One, the dissolving of template: take by weighing 7 ~ 10 parts template P123 by weight, 16 ~ 18 parts concentration is the hydrochloric acid of 0.32 ~ 1.6M and 72 ~ 77 parts absolute ethyl alcohol, under the speed of 600 ~ 800r/min, mixes, and gets mixed solution A;
Two, the adding in metal-salt and silicon source: the hydrochloric acid that with metal-salt dissolving and concentration is 0.32 ~ 1.6M is that the mixed of 6 ~ 55:55 is even by mass ratio, the first mixed liquid of metal-containing salt; The mixed solution A that the first mixed liquid and the step 1 of metal-containing salt obtained is the 1:6 mixed by volume, under the speed of 600 ~ 800r/min, stirs 1 ~ 2h then, mixing solutions B; Drip the silicon source with the speed of 20 ~ 40d/min again, the speed while dripping with 600 ~ 800r/min stirs, and volatilizees fully until the liquid of mixing solutions B, must solid;
Three, crystallization: with solid abrasive to 50 ~ 100 orders that step 2 obtains, put into reaction kettle, add water to still lining volumetrical 2/3 ~ 3/4, hydrothermal crystallizing 12 ~ 24h under 100 ℃ ~ 120 ℃ temperature; Take out reaction kettle, with the reaction solution in the reaction kettle be in vacuum tightness-condition of 0.09MPa under suction filtration, collect solid formation, with the solid formation of collecting dry 6 ~ 10h under 40 ~ 60 ℃ of conditions, calcine 6 ~ 8h at 450 ℃ ~ 550 ℃ then, promptly get mesoporous material Ca-SBA-15; Wherein, the volume ratio of the silicon source of step 2 and mixing solutions B is 1:5.
This embodiment has the following advantages:
This embodiment is that mesoporous material Ca-SBA-15 synthetic provides a kind of novel preparation method; I.e. " solvent evaporates self-assembly method "; So-called solvent evaporates self-assembly method is that mixing solutions is at room temperature stirred, and lets solvent volatilize naturally, by means of the reactive force between molecule in the volatilization process and the molecule; The spontaneous self-assembly of molecule is a liquid crystal structure
This embodiment can be introduced Ca when SBA-15 forms meso-hole structure.This method is compared with present method, has simple to operate, Ca and introduces advantages such as mesopore orbit, power consumption are few easily.
1, adopts the solvent evaporates self-assembly method directly to prepare mesoporous material Ca-SBA-15, both guaranteed that its meso-hole structure is not destroyed, introduced earth alkali metal Ca again, solved the problem of the loss of Ca, can be used for fields such as catalysis, absorption.
2, the method for this embodiment makes mesoporous material Ca-SBA-15, and is simple to operate, and the introducing amount of Ca improves, less energy intensive.
Embodiment two: what this embodiment and embodiment one were different is: the described hydrochloric acid of step 1 is 0.8 ~ 1.0M.Other is identical with embodiment one.
Embodiment three: what this embodiment and embodiment one to two were different is: the described metal-salt of step 2 is nitrocalcite or calcium chloride.Other is identical with embodiment one to two.
Embodiment four: what this embodiment was different with one of embodiment one to three is: the described silicon of step 2 source is a tetraethoxy.Other is identical with one of embodiment one to three.
Embodiment five: what this embodiment was different with one of embodiment one to four is: the hydrothermal crystallizing under 110 ℃ of temperature described in the step 3.Other is identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to five is: described in the step 3 the hydrothermal crystallizing time at 16 ~ 20h.Other is identical with one of embodiment one to five.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: described in the step 3 500 ℃ ~ 550 ℃ the calcining 6 ~ 8h.Other is identical with one of embodiment one to six.
Through following verification experimental verification effect of the present invention:
Test 1
The preparation method of a kind of mesoporous material Ca-SBA-15 of this test carries out according to following steps:
One, the dissolving of template: the polyoxyethylene-poly-oxypropylene polyoxyethylene (template P123) that takes by weighing 2g; Add the hydrochloric acid of the 1.6M of 4mL, add the 15mL absolute ethyl alcohol simultaneously, under the speed of 600r/min, carry out magnetic agitation under the room temperature; Treat that P123 dissolves fully, promptly get mixing solutions;
Two, the adding of metal-salt: the Ca (NO that takes by weighing 0.48g
3)
24H
2O after mixing with the 1.6M HCl of 4mL, joins in the mixing solutions that step 1 obtains; Under the speed of 600r/min, stir 2h; Drip the tetraethoxy (TEOS) of 4.5mL with the speed of 20 ~ 40d/min, continue speed with 600r/min and be stirred to liquid and volatilize fully, solid;
Three, crystallization:, be loaded in the reaction kettle the solid grinding powder with mortar, add the deionized water of 15mL; Behind hydrothermal crystallizing 24h under 100 ℃ of temperature, take out reaction kettle, with the mixing solutions after the crystallization be in vacuum tightness-condition of 0.09MPa under suction filtration; Collect solid formation; With the solid formation of collecting dry 6h under 60 ℃, at 550 ℃ of calcining 6h, promptly get mesoporous material Ca-SBA-15 then.
Characterize as follows testing the 1 mesoporous material Ca-SBA-15 that makes:
1) the XRD diffraction characterizes
Adopt X-ray diffractometer that institute's synthetic material is characterized.The result is as shown in Figure 1, and Fig. 1 has shown the little angle XRD spectra of the Ca-SBA-15 that the original reinforced calcium silicon ratio of employing solvent evaporates self-assembly method synthetic is 0.1 (mol ratio), can be known by Fig. 1; Mesoporous material is 1.1 ° at 2 θ; A tangible broad peak appears, this corresponding two-dimentional hexagonal hole road (100) crystal face, but (110) (200) crystal face diffraction peak disappears; This is because after introducing calcium, due to the meso-hole structure degree of order reduces.
2) infrared spectrum characterization
Adopt IR that institute's synthetic material is carried out IR Characterization.The result is as shown in Figure 2, and Fig. 2 has shown that the original reinforced calcium silicon ratio of use solvent evaporates self-assembly method synthetic is the infrared spectrum of the Ca-SBA-15 of 0.1 (mol ratio), can be known by Fig. 2, at 3454cm
-1The broad peak at place is the OH key stretching vibration absorption peak of Ca-SBA-15,1635cm
-1The absorption peak at place is the flexural vibration absorption peak of the OH of its physical absorption water, 1065cm
-1The absorption peak at place is its Si-O key chattering absorption peak, at 1497cm
-1And 1431cm
-1Two absorption peaks appear in the place, are attributable to CO
3 2-Symmetry stretching vibration absorption peak, this explanation nitrocalcite in the incinerating process, adsorbed airborne CO
2Generated a certain amount of CO
3 2-, the CO of generation
3 2-With the calcium effect, calcium links to each other with silicon through chemical bond, and forms the four-coordination structure.This explains that we have introduced Ca with the solvent evaporates self-assembly method in meso-hole structure, prepared the Ca-SBA-15 with meso-hole structure.
Hence one can see that, and the Ca-SBA-15 with meso-hole structure is successfully prepared in this test.
The mesoporous material Ca-SBA-15 that this test makes has easy formation meso-hole structure, introduces the advantage of calcium metal easily.
Test 2
The preparation method of a kind of mesoporous material Ca-SBA-15 of this test carries out according to following steps:
One, the dissolving of template: the polyoxyethylene-poly-oxypropylene polyoxyethylene (template P123) that takes by weighing 2g; Add the 1.6M HCl of 4mL, add the 15mL absolute ethyl alcohol simultaneously, under the speed of 600r/min, carry out magnetic agitation under the room temperature; Treat that P123 dissolves fully, promptly get mixing solutions;
Two, the adding of metal-salt: the Ca (NO that takes by weighing 2.40g
3)
24H
2O after mixing with the 1.6M HCl of 4mL, joins in the mixing solutions that step 1 obtains; Under the speed of 600r/min, stir 2h; Drip the tetraethoxy (TEOS) of 4.5mL with the speed of 20 ~ 40d/min, continue speed with 600r/min and be stirred to liquid and volatilize fully, solid;
Three, crystallization:, be loaded in the reaction kettle the solid grinding powder with mortar, add the deionized water of 15mL; Behind hydrothermal crystallizing 24h under 100 ℃ of temperature, take out reaction kettle, with the mixing solutions after the crystallization be in vacuum tightness-condition of 0.09MPa under suction filtration; Collect solid formation; With the solid formation of collecting dry 6h under 60 ℃, at 550 ℃ of calcining 6h, promptly get mesoporous material Ca-SBA-15 then.
Characterize as follows testing the 2 mesoporous material Ca-SBA-15 that make:
1) the XRD diffraction characterizes
Adopt X-ray diffractometer that institute's synthetic material is characterized.The result is as shown in Figure 3, and Fig. 3 has shown the little angle XRD spectra of the Ca-SBA-15 that the original reinforced calcium silicon ratio of employing solvent evaporates self-assembly method synthetic is 0.2 (mol ratio), can be known by Fig. 3; Mesoporous material is 1.2 ° at 2 θ; A tangible broad peak appears, this corresponding two-dimentional hexagonal hole road (100) crystal face, but (110) (200) crystal face diffraction peak disappears; This is because after introducing calcium, due to the meso-hole structure degree of order reduces.
2) infrared spectrum characterization
Adopt IR that institute's synthetic material is carried out IR Characterization.The result is as shown in Figure 4, and Fig. 4 has shown that the original reinforced calcium silicon ratio of use solvent evaporates self-assembly method synthetic is the infrared spectrum of the Ca-SBA-15 of 0.2 (mol ratio), can be known by Fig. 4, at 3436cm
-1The broad peak at place is the OH key stretching vibration absorption peak of Ca-SBA-15,1635cm
-1The absorption peak at place is the flexural vibration absorption peak of the OH of its physical absorption water, 1065cm
-1The absorption peak at place is its Si-O key chattering absorption peak, at 1503cm
-1And 1425cm
-1Two absorption peaks appear in the place, are attributable to CO
3 2-Symmetry stretching vibration absorption peak, this explanation nitrocalcite in the incinerating process, adsorbed airborne CO
2Generated a certain amount of CO
3 2-, the CO of generation
3 2-With the calcium effect, calcium links to each other with silicon through chemical bond, and forms the four-coordination structure.This explains that we have introduced Ca with the solvent evaporates self-assembly method in meso-hole structure, prepared the Ca-SBA-15 with meso-hole structure.
Hence one can see that, and the Ca-SBA-15 with meso-hole structure is successfully prepared in this test.
The mesoporous material Ca-SBA-15 that this test makes has easy formation meso-hole structure, introduces the advantage of calcium metal easily.
Test 3
The preparation method of a kind of mesoporous material Ca-SBA-15 of this test carries out according to following steps:
One, the dissolving of template: the polyoxyethylene-poly-oxypropylene polyoxyethylene (template P123) that takes by weighing 2g; Add the 1.6M HCl of 4mL, add the 15mL absolute ethyl alcohol simultaneously, under the speed of 600r/min, carry out magnetic agitation under the room temperature; Treat that P123 dissolves fully, promptly get mixing solutions;
Two, the adding of metal-salt: the Ca (NO that takes by weighing 1.44g
3)
24H
2O after mixing with the 1.6M HCl of 4mL, joins in the mixing solutions that step 1 obtains; Under the speed of 600r/min, stir 2h; Drip the tetraethoxy (TEOS) of 4.5mL with the speed of 20 ~ 40d/min, continue speed with 600r/min and be stirred to liquid and volatilize fully, solid;
Three, crystallization:, be loaded in the reaction kettle the solid grinding powder with mortar, add the deionized water of 15mL; Behind hydrothermal crystallizing 24h under 100 ℃ of temperature, take out reaction kettle, with the mixing solutions after the crystallization be in vacuum tightness-condition of 0.09MPa under suction filtration; Collect solid formation; The solid formation of collecting at 40 ~ 60 ℃ of down dry 6 ~ 10h, at 550 ℃ of calcining 6h, is promptly got mesoporous material Ca-SBA-15 then.
The mesoporous material Ca-SBA-15 that this test makes has easy formation meso-hole structure, introduces the advantage of calcium metal easily.
Characterize as follows testing the 3 mesoporous material Ca-SBA-15 that make:
1) the XRD diffraction characterizes
Adopt X-ray diffractometer that institute's synthetic material is characterized.The result is as shown in Figure 5; Fig. 5 has shown the little angle XRD spectra of the Ca-SBA-15 that employing solvent evaporates self-assembly method synthetic mesoporous material SBA-15 and original reinforced calcium silicon ratio are 0.3 (mol ratio); Can know by Fig. 5; (100) (110) (200) crystal face diffraction peak of mesoporous material SBA-15 is apparent in view, appears at 1.12 °, 1.98 ° and 2.27 ° respectively and locates.After introducing calcium, (100) crystal face diffraction peak is still apparent in view, appears at 1.23 ° and locates, and just peak intensity descends than pure SBA-15, and this explanation is after introducing calcium, and meso-hole structure keeps but the degree of order reduces.In addition, (100) crystal face diffraction peak squints to big angular direction, and this is because the introducing of calcium causes the mesoporous material aperture to diminish and causes.
2) infrared spectrum characterization
Adopt IR that institute's synthetic material is carried out IR Characterization.The result is as shown in Figure 6, and Fig. 6 has shown the infrared spectrum that uses solvent evaporates self-assembly method synthetic SBA-15 and original reinforced calcium silicon than being 0.3 Ca-SBA-15, can be known by Fig. 6, at 3436cm
-1The broad peak at place is the OH key stretching vibration absorption peak of Ca-SBA-15,1629cm
-1The absorption peak at place is the flexural vibration absorption peak of the OH of its physical absorption water, 1083cm
-1The absorption peak at place is its Si-O key chattering absorption peak.Introduce after the calcium, the peak position that goes out of above-mentioned three absorption peaks is respectively 3442cm
-1, 1641cm
-1, 1053cm
-1, peak shape remains unchanged.Simultaneously, introduce calcium afterwards at 1497cm
-1And 1431cm
-1Two absorption peaks appear in the place, are attributable to CO
3 2-Symmetry stretching vibration absorption peak, this explanation nitrocalcite in the incinerating process, adsorbed airborne CO
2Generated a certain amount of CO
3 2-, the CO of generation
3 2-With the calcium effect, calcium links to each other with silicon through chemical bond, and forms the four-coordination structure.This explains that we have introduced Ca with the solvent evaporates self-assembly method in meso-hole structure, prepared the Ca-SBA-15 with meso-hole structure.
3) adsorption/desorption characterizes
Adopt N
2Absorption/desorption appearance characterizes institute's synthetic material.The adsorption curve result is as shown in Figure 7, and Fig. 7 has shown the N with solvent evaporates self-assembly method synthetic SBA-15 and Ca-SBA-15
2The adsorption/desorption curve can be found out by Fig. 7, and synthetic SBA-15 of institute and Ca-SBA-15 demonstrate typical IV type adsorption curve, is the characteristic adsorption curve of meso-hole structure, introduces after the calcium, and pore volume diminishes, by 1.231cm
3/ g reduces to 0.556cm
3/ g.
4) pore size distribution characterizes
Adopt N
2Absorption/desorption appearance characterizes institute's synthetic material.The pore size distribution curve result is as shown in Figure 8, and Fig. 8 has shown with the pore size distribution curve of solvent evaporates self-assembly method synthetic SBA-15 and Ca-SBA-15, can have been found out by Fig. 8; There are the pore passage structure of single-size in synthetic SBA-15 of institute and Ca-SBA-15; After introducing Ca, mesoporous aperture descends to some extent, reduces to 4.39nm by 7.12nm; Consistent with XRD result, the introducing of Ca causes mesoporous aperture to diminish.
5) transmission electron microscope characterizes
Adopt transmission electron microscope to characterize testing the 3 mesoporous material Ca-SBA-15 that make, the result is as shown in Figure 9.Can find out that by Fig. 9 Ca is introduced among the mesoporous framework structure, form the mesoporous material that metal Ca supports.
Simultaneously, adopt one kettle way, " solvent evaporates self-assembly method " synthetic Ca-SBA-15 of pickling process and test 3 adopts the ICP plasma emission spectroscopy that the introducing amount of calcium is characterized, and the result is as shown in table 1.
Three kinds of compound methods of table 1 are to the influence of the introducing amount of calcium
| Compound method | The Ca/Si mol ratio of original adding | Ca/Si mol ratio in the product |
| One kettle way | 0.2 | 0.048 |
| Pickling process | 0.2 | 0.152 |
| The solvent evaporates self-assembly method | 0.2 | 0.195 |
Can know by table 1, adopt the solvent evaporates self-assembly method more to be prone to be incorporated into metal Ca in the mesoporous framework.
In sum, successfully prepared and had the mesoporous material Ca-SBA-15 that alkaline earth metals calcium supports.
In addition, the catalytic performance of testing the 3 mesoporous material Ca-SBA-15 that make is detected:
Concrete steps are following: will test the 3 mesoporous material Ca-SBA-15 and the ZnBr that make
2Press 1:1 (mol ratio) and mix, as catalyzer, the cycloaddition reaction of catalysis phenyl ring oxidative ethane and carbonic acid gas under 150 ℃ of temperature.
The result shows that the transformation efficiency of phenyl ring oxidative ethane is 93%, and the productive rate of phenyl ring shape carbonic ether is 72%.Explain that the mesoporous material Ca-SBA-15 that test 3 makes has good catalysis carbonic acid gas and the phenyl ring oxidative ethane transforms the synthesizing carbonate ester performance.
Claims (7)
1. the preparation method of a mesoporous material Ca-SBA-15 is characterized in that the preparation method of mesoporous material Ca-SBA-15 carries out according to following steps:
One, the dissolving of template: take by weighing 7 ~ 10 parts template P123 by weight, 16 ~ 18 parts concentration is the hydrochloric acid of 0.32 ~ 1.6M and 72 ~ 77 parts absolute ethyl alcohol, under the speed of 600 ~ 800r/min, mixes, and gets mixed solution A;
Two, the adding in metal-salt and silicon source: the hydrochloric acid that with metal-salt and concentration is 0.32 ~ 1.6M is that the mixed of 6 ~ 55:55 is even by mass ratio, the first mixed liquid of metal-containing salt; The mixed solution A that the first mixed liquid and the step 1 of metal-containing salt obtained is the 1:6 mixed by volume, under the speed of 600 ~ 800r/min, stirs 1 ~ 2h then, mixing solutions B; Drip the silicon source with the speed of 20 ~ 40d/min again, the speed while dripping with 600 ~ 800r/min stirs, and volatilizees fully until the liquid of mixing solutions B, must solid;
Three, crystallization: with solid abrasive to 50 ~ 100 orders that step 2 obtains, put into reaction kettle, add water to still lining volumetrical 2/3 ~ 3/4, hydrothermal crystallizing 12 ~ 24h under 100 ℃ ~ 120 ℃ temperature; Take out reaction kettle, with the reaction solution in the reaction kettle be in vacuum tightness-condition of 0.09MPa under suction filtration, collect solid formation, with the solid formation of collecting dry 6 ~ 10h under 40 ~ 60 ℃ of conditions, calcine 6 ~ 8h at 450 ℃ ~ 550 ℃ then, promptly get mesoporous material Ca-SBA-15; Wherein, the volume ratio of the silicon source of step 2 and mixing solutions B is 1:5.
2. the preparation method of a kind of mesoporous material Ca-SBA-15 according to claim 1 is characterized in that the described concentration of hydrochloric acid of step 1 is 0.8 ~ 1.0M.
3. the preparation method of a kind of mesoporous material Ca-SBA-15 according to claim 1 is characterized in that the described metal-salt of step 2 is nitrocalcite or calcium chloride.
4. the preparation method of a kind of mesoporous material Ca-SBA-15 according to claim 1 is characterized in that the described silicon of step 2 source is a tetraethoxy.
5. the preparation method of a kind of mesoporous material Ca-SBA-15 according to claim 1 is characterized in that the hydrothermal crystallizing under 110 ℃ of temperature described in the step 3.
6. the preparation method of a kind of mesoporous material Ca-SBA-15 according to claim 1 is characterized in that the hydrothermal crystallizing time described in the step 3 is at 16 ~ 20h.
7. the preparation method of a kind of mesoporous material Ca-SBA-15 according to claim 1, it is characterized in that described in the step 3 500 ℃ ~ 550 ℃ the calcining 6 ~ 8h.
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| CN101289358A (en) * | 2008-05-23 | 2008-10-22 | 浙江工业大学 | Method for synthesizing linear alkylbenzene |
| CN102442683A (en) * | 2011-09-27 | 2012-05-09 | 华东理工大学 | Solvent volatilization method for preparing titanium-containing zeolite with multilevel porous channels |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356265A (en) * | 2001-08-20 | 2002-07-03 | 复旦大学 | Process for preparing shape-controllable big-pore mesoporous molecular sieve |
| CN101153051A (en) * | 2007-09-06 | 2008-04-02 | 复旦大学 | Ordered mesoporous material with ultra-large bore diameter and method of producing the same |
| CN101289358A (en) * | 2008-05-23 | 2008-10-22 | 浙江工业大学 | Method for synthesizing linear alkylbenzene |
| CN102442683A (en) * | 2011-09-27 | 2012-05-09 | 华东理工大学 | Solvent volatilization method for preparing titanium-containing zeolite with multilevel porous channels |
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Application publication date: 20120822 |