CN102188999A - Preparation method and application of ionic liquid functionalized Al-MCM-41 mesoporous material - Google Patents
Preparation method and application of ionic liquid functionalized Al-MCM-41 mesoporous material Download PDFInfo
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Abstract
The invention relates to a preparation method and application of an ionic liquid functionalized Al-MCM-41 mesoporous material. The preparation method comprises the following steps of: preparing a solution by taking CTAB (Cetyltrimethyl Ammonium Bromide) as a template agent, TEOS (Tetraethyl Orthosilicate) as a silicone source and aluminum nitrate or sodium metaaluminate as a precursor according to a molar ratio, and crystallizing, filtering, washing, drying and roasting the solution to obtain Al-MCM-41; obtaining Al-MCM-41-Cl through coupling; reacting the Al-MCM-41-Cl with N-methylimidazole, and carrying out cooling, suction filtering, washing and drying to obtain the ionic liquid functionalized mesoporous material Al-MCM-41-Im. The invention has the advantages that the method has simple process, and the ionic liquid functionalized Al-MCM-41 mesoporous material has ordered and uniformly distributed pore structure and acid-situ surface and can be used as a catalyst for a reaction between epoxypropane and carbon dioxide to produce propylene carbonate.
Description
Technical field
The present invention relates to a kind of preparation and application of Al-MCM-41 mesoporous material of ion liquid functionalization, belong to mesoporous material ion liquid functionalization technology.
Background technology
Mesoporous material has the high-sequential pore passage structure, the single distribution in aperture, and adjustable in 2-50nm, have good hydro-thermal and heat endurance, particle has the controlled profile of rule, bigger serface, therefore has wide application prospect, as bulky molecular catalysis, selection absorption, functional material etc.But,, limited its application greatly at catalytic field so catalytic activity is not high because itself lacks the activated centre.In order to improve the catalytic activity of mesoporous material, the mesoporous material modification becomes the main research topic that faces now.
The mesoporous material modification mainly contains skeleton and mixes and two kinds of method of modifying of surface chemical modification.The mesoporous material skeleton mixes and is meant that hetero atom enters in the mesoporous material skeleton through processes such as isomorphous replacements.Be directly to introduce metallic precursor in the process of synthesis of silica-base mesoporous material generally speaking, in-situ hydrolysis produces the metal species, replaces by the polymerization or the isomorphous to embed framework of molecular sieve.Many metal ions, be introduced in the mesoporous material skeleton as Mg, Al, Ti, changed the character in skeleton and duct, thereby improved the performance of mesoporous material at aspects such as skeleton stability, blemish, selection catalytic capability and ion-exchanges, for example in the meso pore silicon oxide material of adulterated al, the silicon of the aluminium substitution tetravalence of trivalent causes the unbalance of electric charge in the skeleton, produces the Bronsted acid center of some.But the modified mesoporous material that the skeleton doping method is synthetic, the content of heteroatoms in its skeleton is generally very low, so its catalytic activity is lower.
Surface chemical modification is by the silanol key on silica-based mesoporous material surface and active component Cheng Jian, and active sites is introduced duct or skeleton, mainly contains silane coupler method, direct grafting method and ionic adsorption exchange process etc.
The finishing of silane coupler method is by coprecipitation and back grafting active sites to be introduced duct or skeleton.Coprecipitation is to adopt once directly synthetic mode, in the silicon source of synthesize meso-porous material and surfactant solution, directly add the silane coupler that contains specific organic group, by hydrolysis, polycondensation, again remove surfactant after, organic group can be immobilized to hole wall.Because the architectural feature of silane coupler self causes it to be difficult for carrying out cross-linked polymeric with other tetrahedron silicon, the therefore synthetic mesoporous material degree of order is not high.And this method can only be applied to more stable organic group.For guaranteeing certain order, the introducing amount of organo-functional group also has certain restriction; Back grafting is promptly used the silicon hydroxyl reaction on silane coupler and mesoporous material surface, organic group is grafted in the mesopore orbit again.Generally be after heating in vacuum is removed the water of meso pore silicon oxide material physical absorption, in inert organic solvents and inert gas atmosphere, can obtain the mesoporous material of finishing then with the organo silane coupling agent back flow reaction.Utilize the back grafting, can synthesize structural behaviour mesoporous material preferably in advance, through behind the allograft reaction, mesoporous material still can keep the order structure.Therefore, on structurally ordered property, the synthetic mesoporous material of back grafting is better than the mesoporous material that coprecipitation obtains.
In above-mentioned mesoporous material modifying process, often have only a kind of active component to be introduced in the surface of mesoporous material, and form the mesoporous material of simple functionization.And in many application, often need the introducing of multiple functionalization group, have synergistic a plurality of activated centre in the formation of mesoporous silicon material surface, thereby make it have high catalytic activity.
The homogeneous catalyst that expoxy propane and carbon dioxide reaction generate propene carbonate mainly includes machine alkali, metal complex, ionic liquid etc., although homogeneous catalyst has advantages of high catalytic activity to this reaction, but, make the application of homogeneous catalyst be restricted because reaction back homogeneous catalyst separates the comparison difficulty with product.Compare with homogeneous catalyst, heterogeneous catalysis just can be separated from product by simple filtering, so develop the emphasis that this expoxy propane of heterogeneous catalysis catalysis efficiently and carbon dioxide reaction are this catalysts research.
Huang Kelin etc. are with bimetallic complexing solid-carrying type beaded catalyst system, its application process is that catalyst amount is the 0.1-0.5% of expoxy propane consumption, the mol ratio of expoxy propane and carbon dioxide is 1: 1.05-1.1, reaction temperature is 120-190 ℃, reaction pressure is 2.0-5.0MPa, and the reaction time is 2-3h
-1, the propene carbonate yield is 88%-98%.Referring to Huang Kelin, Yang Bo, Sun Guosong etc., the method for synthesizing ethylene carbonate and catalyst [P] .CN:101613339,2009.
The complex catalyst system that used catalyst such as Yang Caihong is made up of sylvite and active carbon, metal oxide or molecular sieve, consist of sylvite 10-20%, active carbon, metal oxide or molecular sieve 80-90%, its application process is that reaction temperature is 120-180 ℃, reaction pressure is 2.0-6.0MPa, and the reaction time is 0.5-2h
-1, the mol ratio of sylvite and expoxy propane and iodomethane is a sylvite: expoxy propane: iodomethane=0.003-0.01: 1: 0.02-0.03, and the expoxy propane conversion ratio can reach 99.4%, and the propene carbonate selectivity is 98.1%.Referring to Yang Caihong, Han Yizhuo, Luo Yuqin etc., a kind of catalyst of synthesizing acrylic ester and application thereof [P] .CN:1424141,2003.
Summary of the invention
The object of the present invention is to provide a kind of preparation and application of Al-MCM-41 mesoporous material of ion liquid functionalization.Described procedure is simple, and the mesoporous material of the ion liquid functionalization that makes is structurally ordered, and even aperture distribution has high activity to catalysis expoxy propane and carbon dioxide reaction generation propene carbonate.
The present invention is realized that by the following technical programs a kind of preparation method of Al-MCM-41 mesoporous material of ion liquid functionalization is characterized in that comprising following process:
(1) being the template agent with softex kw (CTAB), is the silicon source with ethyl orthosilicate (TEOS), with aluminum nitrate (Al (NO
3)
39H
2O) or sodium metaaluminate (NaAlO
2) be aluminium salt precursor, press softex kw and Si, Al and H
2The O mol ratio is 0.15: 1: 25～80: 120, earlier with softex kw, aluminum nitrate (Al (NO
3)
39H
2O) or sodium metaaluminate join in the deionized water, stirring adding ethylenediamine adjusting pH is 11, drip the ethyl orthosilicate stirring at room, place the water-bath heating at 100 ℃ of following hydrothermal crystallizing 72h again, more after filtering, washing, after the drying, in Muffle furnace, be warming up to 550 ℃,, obtain the mesoporous material Al-MCM-41 of skeleton adulterated al at 550 ℃ of following roasting 6h with 1 ℃/min speed;
(2) by every gram Al-MCM-41 with the 20mL toluene solvant, with the 3-r-chloropropyl trimethoxyl silane coupling agent of 1mL with 0.1mL triethylamine catalyst, step (1) is made Al-MCM-41 to join in the toluene, add the 3-r-chloropropyl trimethoxyl silane then, adding triethylamine again, is 110-115 ℃ of back flow reaction 48h in temperature, again through cooling, suction filtration, with toluene, ethanol water, deionized water and methanol solution washing, reach drying successively, obtain the Al-MCM-41-Cl mesoporous material;
(3) by every gram Al-MCM-41-Cl with the 20mL toluene solvant with 1mLN-methylimidazole organic cation, the Al-MCM-41-Cl that step (2) is made joins in the toluene, add the N-methylimidazole then, in temperature is 110-115 ℃ of back flow reaction 48h, through cooling, suction filtration is successively with toluene, ethanol water, deionized water and methanol solution washing again, reach drying, obtain the mesoporous material Al-MCM-41-Im of ion liquid functionalization.
The mesoporous material Al-MCM-41-Im of the ion liquid functionalization that makes with said method is for catalyst is applied to the reaction that expoxy propane and carbon dioxide reaction generate propene carbonate.
The invention has the advantages that, this method preparation process is simple, the mesoporous material Al-MCM-41-Im of prepared ion liquid functionalization, has pore passage structure orderly and that be evenly distributed, the surface has acidic site, and the reaction that expoxy propane and carbon dioxide reaction is generated propene carbonate has high catalytic activity.
Description of drawings
Fig. 1 is the high-resolution-ration transmission electric-lens photo of embodiment 2 prepared Al-MCM-41-Im (30).
Fig. 2 is embodiment 2 prepared Al-MCM-41-Im's (30)
27Al solid state nmr spectrogram.
Fig. 3 is embodiment 2 prepared Al-MCM-41-Cl's (30)
13C solid state nmr spectrogram.
Fig. 4 is embodiment 2 prepared Al-MCM-41-Im's (30)
13C solid state nmr spectrogram.
Fig. 5 is the NH of embodiment 2 prepared Al-MCM-41-Im (30) and MCM-41
3Temperature programmed desorption curve map, the wherein curve map of a:MCM-41; The curve map of b:Al-MCM-41-Im (30).
The specific embodiment
Further describe feature of the present invention below by example, but the present invention is not limited to following example.
Embodiment 1
0.213g aluminum nitrate and 2.4g softex kw are dissolved in the deionized water of 100mL (Si: the Al mol ratio is 80), add the 3mL ethylenediamine, fully stir under the room temperature, drip the 10mL ethyl orthosilicate, behind the room temperature vigorous stirring 4h, place 80 ℃ water-bath 1h, it is moved in the 100mL hydrothermal reaction kettle, at 100 ℃ of following hydrothermal crystallizing 72h, after filtration, the washing of 300mL deionized water, dry 8h under 100 ℃ is warming up to 550 ℃ with 1 ℃/min speed at last in Muffle furnace, at 550 ℃ of following roasting 6h, obtain the mesoporous material Al-MCM-41 (80) of skeleton adulterated al.
Get the Al-MCM-41 (80) of 5.0g preparation, add 100mL toluene, the 3-r-chloropropyl trimethoxyl silane that adds 5.0mL, the triethylamine that adds 0.5mL, in temperature is 112 ℃ of back flow reaction 48h, after reaction finishes, cool to room temperature, carry out vacuum filtration, and then successively use 100mL toluene, 100mL ethanol and water mixed solution (1: 1), the 500mL deionized water, the washing of 100mL methanol solution at last at 60 ℃ of following vacuum drying 8h, obtains the mesoporous material Al-MCM-41-Cl (80) of silane coupler modified skeleton adulterated al.
Get the Al-MCM-41-Cl (80) of 5.0g preparation, adding the 100mL dry toluene, add the N-methylimidazole of 5mL, is 112 ℃ of back flow reaction 48h in temperature, after reaction finishes, cool to room temperature, vacuum filtration is successively used 350mL methyl alcohol then, the 300mL deionized water, 150mL methanol wash, finally prepd product obtain the mesoporous material Al-MCM-41-Im (80) of ion liquid functionalization at 50 ℃ of following vacuum drying 8h.
Embodiment 2
The preparation method only changes aluminium salt precursor body sodium metaaluminate (NaAlO with embodiment 1
2), promptly get 0.122g sodium metaaluminate (NaAlO
2) be dissolved in the deionized water of 100mL (Si: the Al mol ratio is 30) with the 2.4g softex kw, add the 4mL ethylenediamine, fully stir under the room temperature, drip the 10mL ethyl orthosilicate, behind the room temperature vigorous stirring 4h, place 80 ℃ water-bath 1h, it is moved in the 100mL hydrothermal reaction kettle, at 100 ℃ of following hydrothermal crystallizing 72h, after filtration, 300mL deionized water washing, at 100 ℃ of dry 8h down, in Muffle furnace, be warming up to 550 ℃ at last with 1 ℃/min speed, at 550 ℃ of following roasting 6h, obtain the mesoporous material Al-MCM-41 (30) of skeleton adulterated al.
Get the Al-MCM-41 (30) of 5.0g preparation, add 100mL toluene, the 3-r-chloropropyl trimethoxyl silane that adds 5.0mL, the triethylamine that adds 0.5mL, in temperature is 112 ℃ of back flow reaction 48h, after reaction finishes, cool to room temperature, carry out vacuum filtration, and then successively use 100mL toluene, 100mL ethanol and water mixed solution (1: 1), the 500mL deionized water, the washing of 100mL methanol solution at last at 60 ℃ of following vacuum drying 8h, obtains the mesoporous material Al-MCM-41-Cl (30) of silane coupler modified skeleton adulterated al.
Get the Al-MCM-41-Cl (30) of 5.0g preparation, adding the 100mL dry toluene, add the 5mLN-methylimidazole, is 112 ℃ of back flow reaction 48h in temperature, after reaction finishes, cool to room temperature, vacuum filtration is successively used 350mL methyl alcohol then, the 300mL deionized water, 150mL methanol wash, finally prepd product obtain the mesoporous material Al-MCM-41-Im (30) of ion liquid functionalization at 50 ℃ of following vacuum drying 8h.
Embodiment 3
Carry out in the stainless steel autoclave that is reflected at 50mL of expoxy propane and carbon dioxide reaction generation propene carbonate, adopt the electromagnetic agitation heating.Add the 5g expoxy propane in reactor, add the Al-MCM-41 mesoporous material catalyst of the prepared ion liquid functionalization of 0.4g, feed the carbon dioxide emptying then, close outlet valve, pressure is closed inlet valve after showing 3MPa.Stirring is warming up to 130 ℃ of reaction temperatures, and constant temperature is reaction 6h down.Reaction places ice-water bath 3h with reactor after finishing, and emits unreacted carbon dioxide then, and centrifugation goes out solid catalyst.
Product adopts gas chromatographic analysis: flame ionization ditector, nitrogen is carrier gas, 260 ℃ of vaporizer temperature, 260 ℃ of detector temperatures, sample size is 0.2 μ L, analysis condition is that initial column temperature is 40 ℃, and the heating rate with 30 ℃/min rises to 220 ℃ then, keeps 10min down at 220 ℃ at last.The result shows that the expoxy propane conversion ratio can reach 96%, and the propene carbonate selectivity can reach 99%.
Claims (2)
1. the preparation method of the Al-MCM-41 mesoporous material of an ion liquid functionalization is characterized in that comprising following process:
(1) being the template agent with the softex kw, is the silicon source with the ethyl orthosilicate, is aluminium salt precursor with aluminum nitrate or sodium metaaluminate, presses softex kw and Si, Al and H
2The O mol ratio is 0.15: 1: 25～80: 120, earlier softex kw, aluminum nitrate or sodium metaaluminate are joined in the deionized water, stirring adding ethylenediamine adjusting pH is 11, drips the ethyl orthosilicate stirring at room, places the water-bath heating at 100 ℃ of following hydrothermal crystallizing 72h again, again after filtering, washing after the drying, is warming up to 550 ℃ with 1 ℃/min speed in Muffle furnace, at 550 ℃ of following roasting 6h, obtain the mesoporous material Al-MCM-41 of skeleton adulterated al;
(2) by every gram Al-MCM-41 with the 20mL toluene solvant, with the 3-r-chloropropyl trimethoxyl silane coupling agent of 1mL with 0.1mL triethylamine catalyst, step (1) is made Al-MCM-41 to join in the toluene, add the 3-r-chloropropyl trimethoxyl silane then, adding triethylamine again, is 110-115 ℃ of back flow reaction 48h in temperature, again through cooling, suction filtration, with toluene, ethanol water, deionized water and methanol solution washing, reach drying successively, obtain mesoporous material Al-MCM-41-Cl;
(3) by every gram Al-MCM-41-Cl with the 20mL toluene solvant, with 1mLN-methylimidazole organic cation, the Al-MCM-41-Cl that step (2) is made joins in the toluene, add the N-methylimidazole then, in temperature is 110-115 ℃ of back flow reaction 48h, through cooling, suction filtration is successively with toluene, ethanol water, deionized water and methanol solution washing again, reach drying, obtain the mesoporous material Al-MCM-41-Im of ion liquid functionalization.
2. the application of the mesoporous material Al-MCM-41-Im of an ion liquid functionalization that makes by the described method of claim 1 is applied to the reaction that expoxy propane and carbon dioxide reaction generate propene carbonate as catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055937A (en) * | 2012-12-18 | 2013-04-24 | 常州大学 | Preparation method of immobilized ionic liquid used for ester exchange reaction |
| CN104624242A (en) * | 2015-02-05 | 2015-05-20 | 江南大学 | Synthetic biodiesel acidic ionic liquid immobilized catalyst and preparation method thereof |
| CN108191810A (en) * | 2017-12-28 | 2018-06-22 | 东莞理工学院 | Application of the metastructure MCM-48 silicates as catalyst |
| CN109746047A (en) * | 2018-12-28 | 2019-05-14 | 浙江理工大学 | A kind of preparation and application of difunctional triphase-transfer catalyst |
| CN110075915A (en) * | 2019-04-23 | 2019-08-02 | 南京工业大学 | Double-acid immobilized ionic liquid catalyst and preparation method thereof |
| CN116062733A (en) * | 2023-03-08 | 2023-05-05 | 中国石油大学(华东) | Method for preparing ordered mesoporous carbon in one step |
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| CN101318949A (en) * | 2008-07-23 | 2008-12-10 | 中国科学院过程工程研究所 | Process for synthesizing cyclic carbonate with catalysis of solid carried ion liquid catalyst |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055937A (en) * | 2012-12-18 | 2013-04-24 | 常州大学 | Preparation method of immobilized ionic liquid used for ester exchange reaction |
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| CN108191810A (en) * | 2017-12-28 | 2018-06-22 | 东莞理工学院 | Application of the metastructure MCM-48 silicates as catalyst |
| CN109746047A (en) * | 2018-12-28 | 2019-05-14 | 浙江理工大学 | A kind of preparation and application of difunctional triphase-transfer catalyst |
| CN109746047B (en) * | 2018-12-28 | 2021-08-31 | 浙江理工大学 | Preparation and application of bifunctional three-phase transfer catalyst |
| CN110075915A (en) * | 2019-04-23 | 2019-08-02 | 南京工业大学 | Double-acid immobilized ionic liquid catalyst and preparation method thereof |
| CN116062733A (en) * | 2023-03-08 | 2023-05-05 | 中国石油大学(华东) | Method for preparing ordered mesoporous carbon in one step |
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