CN102000542A - Method for preparing micro-mesoporous silicon oxide/montmorillonite nano composite material - Google Patents
Method for preparing micro-mesoporous silicon oxide/montmorillonite nano composite material Download PDFInfo
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Abstract
The invention discloses a method for preparing a micro-mesoporous silicon oxide/montmorillonite nano composite material. In the method, the nano composite material, which has the characteristics of microporous and mesoporous structures and high thermal stability, is prepared in a supercritical CO2 system by using a cetyl trimethyl ammonium bromide single cationic surfactant as a template agent and allowing ethyl orthosilicate to undergo an in-situ hydrolysis-polycondensation reaction between montmorillonite layers with the cationic surfactant micelle as a template. Compared with the conventional method for preparing the micro-mesoporous silicon oxide/montmorillonite nano composite material, the method has the advantages of reducing the use amount of the surfactant, making the synthesis process simple and convenient and operation simple, lowering cost and avoiding environmental pollution.
Description
Technical field
The invention belongs to molecular sieve and field of porous materials, be specifically related to a kind of little in order-mesopore silicon oxide/Nanometer Composite Material Of Montmorillonite And Its Preparation Method.
Background technology
Imvite is bentonitic main component, and it is extremely extensive to distribute in China, but mainly is to be applied to industry such as casting, metallurgy, drilling mud, feed addictive, papermaking and pottery.So adopting montmorillonite is a matrix, the exploitation high value-added product is applied to catalysis and the adsorbent field has broad prospects.The imvite of layer post is a kind of porous material of two-dimentional molecular sieve analog structure, shows wide application prospect in catalysis and adsorbing domain.But because its preparation method is by positive charge generation ion-exchange reactions between inorganic polycation or colloidal sol and cheating engaging layer, cause that its aperture is little, the pore size distribution broad, rod structure is wayward, heat endurance is not high.
1992, it is the ordered mesoporous molecular sieve (J.S.Beck of representative with MCM-41 that the Mobil oil company has successfully developed a class, J.C.Vartuli, W.J.Roth, et.al.J.Am.Chem.Soc.1992,114,10834-10843.), owing to adopted organic surface active agent as structure directing agent in the building-up process, make it have bigger specific area and regular adjustable pore passage structure, these results of study provide theoretical foundation for the controlled assembling of porous material.On this basis, (A.Galarneau such as Galarneau, A.Barodawalla, T.J.Pinnavaia, Nature 1995,374,529.) reported little-mesopore silicon oxide Nano composite material of montmorillonite (Porous clay heterostructures, synthesizing abbreviation PCHs), this method is initial raw clay with the fluorine hectorite, preparation process has comprised the template direction assembling of surfactant-inorganic precursor in interlayer, and the pore-size distribution of gained PCHs material is narrow, (but 1.4～2.5nm) modulations can be used for more macromolecular select shape acid catalyzed reaction and processing processing in the mesopore scope at the super large micropore in the aperture.This has opened up new road for the application of imvite.But, the subject matter that the method exists is to have adopted second kind of common mode plate agent neutral amine as the co-ordinative construction directed agents, because the alkalescence effect of neutral amine, during air dry, surperficial teos hydrolysis forms a certain proportion of amorphous Si O to the composite precursor of absorption ethyl orthosilicate in air
2, the purity of material is produced certain influence, and pore size distribution is not concentrated; Simultaneously, surfactant needs high-temperature roasting to remove the synthetic of porous material at last.Therefore, the adding of neutral amine surfactant has not only increased the complexity and the synthetic cost of material synthesis technique, has formed problem of environmental pollution to a great extent.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of green non-pollution, little-mesopore silicon oxide/Nano composite material of montmorillonite with low cost, simple to operate.
Solving the problems of the technologies described above the technical scheme that is adopted is made up of following step:
1, obtain solution
Imvite is scattered in the deionized water, stirs and to make it fully disperse swelling, be mixed with mass fraction and be 1%～5% montmorillonite suspension liquid; Softex kw is dissolved in the distilled water, and being mixed with amount of substance concentration is the softex kw aqueous solution of 0.5mol/L.
2, cation exchange reaction
Under stirring condition, with mass fraction is that 1%～5% montmorillonite suspension liquid is heated to 90 ℃, dripping amount of substance concentration with 1～2 droplet/second speed is the softex kw aqueous solution of 0.5mol/L, the dripping quantity that makes softex kw is 2 times of imvite cation exchange capacity, drip the back and continue reaction 12 hours, naturally be chilled to room temperature, 5000 rev/mins of centrifugations 5 minutes, product is washed till no Br with distilled water
-, air dry is 24 hours in the air, obtains the organo montmorillonite of quaternary cationics intercalation modifying.
3, the little-mesopore silicon oxide/Nano composite material of montmorillonite of preparation
Is 1: 2～30 to join in the autoclave organo montmorillonite and ethyl orthosilicate by mass ratio, opens attemperating unit and will be warming up to 80 ℃ in the autoclave, opens high pressure syringe pump, is pressed into CO with 20mL/ minute air inlet speed in autoclave
2Gas, make the autoclave internal pressure reach 10～30MPa, start agitating device, reacted 0.5～5 hour, stop to stir and heating, naturally be cooled to 30 ℃, open vent valve, slowly exit to pressure and be shown as 0MPa, open autoclave, reactant is moved in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, 550～600 ℃ of roastings are 5 hours in the Muffle furnace, be prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite, its interlamellar spacing is 1.8～3.5nm, and specific area is 500～800m
2/ g, pore volume are 0.31～0.70m
3/ g, average pore size is 2.5～3.12nm.
Preparation of the present invention is little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 in, best is to join in autoclave at 1: 20 organo montmorillonite and ethyl orthosilicate by mass ratio, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 20MPa, starts agitating device, reacts 1 hour.
The present invention is at supercritical CO
2In the system, with single cationic surfactant as the template agent, making ethyl orthosilicate is template at interlayer with the cationic surfactant micella, and in-situ hydrolysis-polycondensation reaction takes place, be prepared into have micropore and mesoporous double-pore structure characteristics, nano composite material that heat endurance is high.The present invention with existing little-mesopore silicon oxide/Nano composite material of montmorillonite preparation methods compares, and has that dosage of surfactant is few, simple synthetic method, easy operating, cost are low, the advantage of green non-pollution.
Description of drawings
Fig. 1 is the XRD figure of the little-mesopore silicon oxide/Nano composite material of montmorillonite of the embodiment of the invention 1 preparation.
Fig. 2 is the N of the little mesoporous little-mesopore silicon oxide/Nano composite material of montmorillonite of the embodiment of the invention 1 preparation
2-adsorption desorption isollaothermic chart.
Fig. 3 is the DFT graph of pore diameter distribution of the little mesoporous little-mesopore silicon oxide/Nano composite material of montmorillonite of the embodiment of the invention 1 preparation.
The specific embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
1, obtain solution
The 0.5g imvite is scattered in the deionized water, stirs and to make it fully disperse swelling, be mixed with mass fraction and be 2% montmorillonite suspension liquid 25g; The 0.4g softex kw is dissolved in the distilled water, and being mixed with amount of substance concentration is the softex kw aqueous solution 2.2mL of 0.5mol/L.
2, cation exchange reaction
Under stirring condition, with the 25g mass fraction is that 2% montmorillonite suspension liquid is heated to 90 ℃, dripping amount of substance concentration with 1～2 droplet/second speed is the softex kw aqueous solution 2.2mL of 0.5mol/L, the dripping quantity that makes softex kw is 2 times of imvite cation exchange capacity, drip the back and continue reaction 12 hours, naturally be chilled to room temperature, 5000 rev/mins of centrifugations 5 minutes, product is washed till no Br with distilled water
-, air dry is 24 hours in the air, obtains the organo montmorillonite of quaternary cationics intercalation modifying.
3, the little-mesopore silicon oxide/Nano composite material of montmorillonite of preparation
0.5g organo montmorillonite and 10g ethyl orthosilicate are joined in the autoclave that volume is 30mL, the mass ratio of organo montmorillonite and ethyl orthosilicate is 1: 20, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 20MPa, starts agitating device, reacted 1 hour, and stopped to stir and heating, be cooled to 30 ℃ naturally, open vent valve, slowly exit to pressure and be shown as 0MPa, open autoclave, reactant is moved in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, and 600 ℃ of roastings are 5 hours in the Muffle furnace, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Prepared little-mesopore silicon oxide/Nano composite material of montmorillonite adopts D/Max-3c type x-ray diffractometer and ASAP 2020 type physical adsorption appearances to characterize, and the results are shown in Figure 1～3.
As seen from Figure 1, the interlamellar spacing of prepared little-mesopore silicon oxide/Nano composite material of montmorillonite is increased to 3.2nm by the 1.2nm of natural montmorillonite, illustrates at supercritical CO
2Ethyl orthosilicate can form regular pore passage structure by effective hydrolysis-condensation in the system between cheating engaging layer.
As seen from Figure 2, prepared little-mesopore silicon oxide/Nano composite material of montmorillonite sharply increases in the adsorbance of low-pressure area, explanation has formed certain microcellular structure between cheating engaging layer, be that the increase of 0.3～0.45 adsorbance has reflected and formed certain meso-hole structure between cheating engaging layer at relative pressure.The pore-size distribution that be can be clearly seen that prepared little-mesopore silicon oxide Nano composite material of montmorillonite by Fig. 3 mainly concentrates on 1.2nm and 2.7nm, respectively in ultramicropore and little mesoporous scope.
In the obtain solution step 1 of present embodiment, the 0.5g imvite is scattered in the deionized water, stir and to make it fully disperse swelling, be mixed with mass fraction and be 5% montmorillonite suspension liquid 10g, other steps of this step are identical with embodiment 1.In cation exchange reaction step 2, under stirring condition, with the 10g mass fraction is that 5% montmorillonite suspension liquid is heated to 90 ℃, dripping amount of substance concentration with 1～2 droplet/second speed is the softex kw aqueous solution 2.2mL of 0.5mol/L, the dripping quantity that makes softex kw is 2 times of imvite cation exchange capacity, and other steps of this step are identical with embodiment 1.In the little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 of preparation, 0.5g organo montmorillonite and 1.0g ethyl orthosilicate are joined in the autoclave that volume is 30mL, the mass ratio of organo montmorillonite and ethyl orthosilicate is 1: 2, and other steps of this step are identical with embodiment 1.Be prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Embodiment 3
In the obtain solution step 1 of present embodiment, the 0.5g imvite is scattered in the deionized water, stir and to make it fully disperse swelling, be mixed with mass fraction and be 1% montmorillonite suspension liquid 50g, other steps of this step are identical with embodiment 1.In cation exchange reaction step 2, under stirring condition, with the 50g mass fraction is that 1% montmorillonite suspension liquid is heated to 90 ℃, dripping amount of substance concentration with 1～2 droplet/second speed is the softex kw aqueous solution 2.2mL of 0.5mol/L, the dripping quantity that makes softex kw is 2 times of imvite cation exchange capacity, and other steps of this step are identical with embodiment 1.In the little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 of preparation, 0.5g organo montmorillonite and 15.0g ethyl orthosilicate are joined in the autoclave that volume is 30mL, the mass ratio of organo montmorillonite and ethyl orthosilicate is 1: 30, and other steps of this step are identical with embodiment 1.Be prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Embodiment 4
Preparation at present embodiment is little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 in, 0.5g organo montmorillonite and 7.5g ethyl orthosilicate are joined in the autoclave that volume is 30mL, the mass ratio of organo montmorillonite and ethyl orthosilicate is to join in autoclave at 1: 15, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 10MPa, starts agitating device, reacts 3 hours, and other steps of this step are identical with embodiment 1.Other steps are identical with embodiment 1, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Embodiment 5
In the little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 of preparation, 0.5g organo montmorillonite and 12.5g ethyl orthosilicate are joined in the autoclave that volume is 30mL, the mass ratio of organo montmorillonite and ethyl orthosilicate is to join in autoclave at 1: 25, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 25MPa, starts agitating device, reacts 1 hour.Other steps of this step are identical with embodiment 1.Other steps are identical with embodiment 1, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Preparation at embodiment 1～5 is little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 in, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 10MPa, starts agitating device, reacts 5 hours, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Embodiment 7
Preparation at embodiment 1～5 is little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 in, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 30MPa, starts agitating device, reacts 0.5 hour, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Preparation at embodiment 1～5 is little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 in, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 20MPa, starts agitating device, reacts 3 hours, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Embodiment 9
Preparation at embodiment 1～8 is little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 in, mixture is moved in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, 550 ℃ of roastings are 5 hours in the Muffle furnace, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Preparation at embodiment 1～8 is little-mesopore silicon oxide/Nano composite material of montmorillonite step 3 in, mixture is moved in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, 580 ℃ of roastings are 5 hours in the Muffle furnace, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
In order to determine optimised process step of the present invention, the inventor has carried out a large amount of laboratory research experiments, and various experiment situations are as follows:
Laboratory apparatus: ASAP 2020 type physical adsorption appearances are produced by U.S. Merck ﹠ Co., Inc; D/Max-3c type x-ray diffractometer is produced by Japan company of science.
1, the ethyl orthosilicate consumption is to the influence of product structure
Raw material that obtain solution, cation exchange reaction are used and proportioning thereof and processing step are identical with embodiment 1.
Take by weighing the 0.5g organo montmorillonite, respectively by the mass ratio of organo montmorillonite and ethyl orthosilicate be took by weighing 1,5,7.5,10,12.5 in 1: 2,1: 10,1: 15,1: 20,1: 25,1: 30, the 15g ethyl orthosilicate, join in the 30mL autoclave, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas, making the autoclave internal pressure is 20MPa, starts agitating device, reacted 1 hour, and stopped to stir and heating, be cooled to 30 ℃ naturally, open vent valve, slowly exit to pressure and be shown as 0MPa, open autoclave, reactant is poured in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, and 600 ℃ of roastings are 5 hours in the Muffle furnace, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Prepared little-mesopore silicon oxide/Nano composite material of montmorillonite adopts physical adsorption appearance and x-ray diffractometer to characterize, and the results are shown in Table 1.
Table 1 ethyl orthosilicate consumption is to the influence of product structure
By table 1 as seen, the mass ratio of organo montmorillonite and ethyl orthosilicate is 1: 2～30 o'clock, increase along with the ethyl orthosilicate consumption, the interlamellar spacing of prepared little-mesopore silicon oxide/Nano composite material of montmorillonite and pore volume change little, and specific area is and increases trend gradually, after the mass ratio of organic imvite and ethyl orthosilicate surpassed 1: 20, the specific area increase seldom.It is 1: 2～30 that the present invention selects the mass ratio of organo montmorillonite and ethyl orthosilicate, and the best is 1: 20.
2, reaction pressure is to the influence of product structure
Raw material that obtain solution, cation exchange reaction are used and proportioning thereof and processing step are identical with embodiment 1.
Take by weighing 0.5g organo montmorillonite and 10g ethyl orthosilicate, join in the 30mL autoclave, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas is 7.5,10,15,20,25 at autoclave pressure respectively, during 30MPa, starts agitating device, reacted 1 hour, and stopped to stir and heating, be cooled to 30 ℃ naturally, open vent valve, slowly exit to pressure and be shown as 0MPa, open autoclave, reactant is poured in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, and 600 ℃ of roastings are 5 hours in the Muffle furnace, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Prepared little-mesopore silicon oxide/Nano composite material of montmorillonite adopts physical adsorption appearance and x-ray diffractometer to characterize, and the results are shown in Table 2.
Table 2 reaction pressure is to the influence of product structure
| Pressure (MPa) | Interlamellar spacing (nm) | Specific area (m 2·g -1) | Pore volume (cm 3·g -1) | Average pore size (nm) |
| ?7.5 | 1.7 | 325.6 | 0.23 | 7.50 |
| ?10 | 3.0 | 625.36 | 0.41 | 3.51 |
| ?15 | 3.1 | 700.02 | 0.49 | 3.21 |
| ?20 | 3.2 | 775.93 | 0.54 | 2.81 |
| ?25 | 3.2 | 725.6 | 0.52 | 2.83 |
| ?30 | 3.1 | 700.30 | 0.49 | 2.85 |
By table 2 as seen, when reaction pressure was 7.5MPa, the interlamellar spacing of little-mesopore silicon oxide/Nano composite material of montmorillonite, specific area and pore volume were all less, and average pore size is bigger, illustrated that this condition is unfavorable for that ethyl orthosilicate diffuses between cheating engaging layer; When reaction pressure was 10～30Mpa, along with the increase of reaction pressure, interlamellar spacing, specific area and pore volume were elder generation and increase the trend that afterwards reduces, and average pore size reduces gradually.Choice reaction pressure of the present invention is 10～30MPa, and the best is 20MPa.
3, the reaction time is to the influence of product structure
Raw material that obtain solution, cation exchange reaction are used and proportioning thereof and processing step are identical with embodiment 1.
Take by weighing 0.5g organo montmorillonite and 10g ethyl orthosilicate, join in the 30mL autoclave, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas, making autoclave pressure is 20MPa, starts agitating device, reacted respectively 0.5,1,3,5 hour, and stopped to stir and heating, be cooled to 30 ℃ naturally, open vent valve, slowly exit to pressure and be shown as 0MPa, open autoclave, reactant is poured in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, and 600 ℃ of roastings are 5 hours in the Muffle furnace, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
Prepared little-mesopore silicon oxide/Nano composite material of montmorillonite adopts physical adsorption appearance and x-ray diffractometer to characterize, and the results are shown in Table 3.
Table 3 reaction time is to the influence of product structure
| Time (hour) | Interlamellar spacing (nm) | Specific area (m 2·g -1) | Pore volume (cm 3·g -1) | Average pore size (nm) |
| 0.5 | 2.90 | 540.6 | 0.38 | 4.11 |
| 1 | 3.2 | 775.93 | 0.54 | 2.81 |
| 3 | 3.1 | 710.26 | 0.46 | 3.52 |
| 5 | 3.2 | 689.25 | 0.40 | 3.79 |
By table 3 as seen, reaction time is when being 0.5～5 hour, prepared little-mesopore silicon oxide/Nano composite material of montmorillonite interlamellar spacing is all bigger, reaction time is during greater than 1 hour, interlamellar spacing is over time very little, but specific area and pore volume reduce gradually, and the choice reaction time of the present invention is 0.5～5 hour, and the best is 1 hour.
Claims (3)
1. the preparation method of little-mesopore silicon oxide/Nano composite material of montmorillonite is characterized in that being made up of following step:
(1) obtain solution
Imvite is scattered in the deionized water, stirs and to make it fully disperse swelling, be mixed with mass fraction and be 1%～5% montmorillonite suspension liquid; Softex kw is dissolved in the distilled water, and being mixed with amount of substance concentration is the softex kw aqueous solution of 0.5mol/L;
(2) cation exchange reaction
Under stirring condition, with mass fraction is that 1%～5% montmorillonite suspension liquid is heated to 90 ℃, dripping amount of substance concentration with 1～2 droplet/second speed is the softex kw aqueous solution of 0.5mol/L, the dripping quantity that makes softex kw is 2 times of imvite cation exchange capacity, drip the back and continue reaction 12 hours, naturally be chilled to room temperature, 5000 rev/mins of centrifugations 5 minutes, product is washed till no Br with distilled water
-, air dry is 24 hours in the air, obtains the organo montmorillonite of quaternary cationics intercalation modifying;
(3) little-mesopore silicon oxide/Nano composite material of montmorillonite of preparation
Is 1: 2～30 to join in the autoclave organo montmorillonite and ethyl orthosilicate by mass ratio, opens attemperating unit and will be warming up to 80 ℃ in the autoclave, opens high pressure syringe pump, is pressed into CO with 20mL/ minute air inlet speed in autoclave
2Gas makes the autoclave internal pressure reach 10～30MPa, starts agitating device, reacted 0.5～5 hour, and stopped to stir and heating, be cooled to 30 ℃ naturally, open vent valve, slowly exit to pressure and be shown as 0MPa, open autoclave, reactant is moved in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, and 550～600 ℃ of roastings are 5 hours in the Muffle furnace, are prepared into little-mesopore silicon oxide/Nano composite material of montmorillonite.
2. according to claim 1 little-preparation method of mesopore silicon oxide/Nano composite material of montmorillonite, it is characterized in that: in preparation little-mesopore silicon oxide/Nano composite material of montmorillonite step (3), is 1: 15～25 to join in the autoclave organo montmorillonite and ethyl orthosilicate by mass ratio, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 10～25MPa, starts agitating device, reacted 1～3 hour, stop to stir and heating, be cooled to 30 ℃ naturally, open vent valve, slowly exit to pressure and be shown as 0MPa, open autoclave, reactant is moved in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, and 550～600 ℃ of roastings are 5 hours in the Muffle furnace.
3. according to claim 1 little-preparation method of mesopore silicon oxide/Nano composite material of montmorillonite, it is characterized in that: in preparation little-mesopore silicon oxide/Nano composite material of montmorillonite step (3), is to join in autoclave at 1: 20 organo montmorillonite and ethyl orthosilicate by mass ratio, open attemperating unit and will be warming up to 80 ℃ in the autoclave, open high pressure syringe pump, in autoclave, be pressed into CO with 20mL/ minute air inlet speed
2Gas makes the autoclave internal pressure reach 20MPa, starts agitating device, reacted 1 hour, stop to stir and heating, be cooled to 30 ℃ naturally, open vent valve, slowly exit to pressure and be shown as 0MPa, open autoclave, reactant is moved in the centrifuge tube, 5000 rev/mins of centrifugations 5 minutes, air dry is 24 hours in the air, and 600 ℃ of roastings are 5 hours in the Muffle furnace.
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| CN115364843A (en) * | 2022-07-13 | 2022-11-22 | 河南科技学院 | Sm-Ti-MMT catalyst for synthesizing methyl phenyl carbonate and preparation method and application thereof |
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| CN103623825B (en) * | 2013-11-28 | 2015-12-09 | 中国华电集团科学技术研究总院有限公司 | Micro--mesoporous pillared montmorillonite carries Co catalysts and its preparation method and application |
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| CN115364843A (en) * | 2022-07-13 | 2022-11-22 | 河南科技学院 | Sm-Ti-MMT catalyst for synthesizing methyl phenyl carbonate and preparation method and application thereof |
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