CN103691400A - Functionalized ionic liquid hybrid mesoporous molecular sieve MCM-48 composite material and preparation method and application thereof - Google Patents
Functionalized ionic liquid hybrid mesoporous molecular sieve MCM-48 composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of functionalized ionic liquid immobilization, and discloses a functionalized ionic liquid hybrid mesoporous molecular sieve MCM-48 composite material and a preparation method and application thereof. The preparation method comprises the following steps: (1) uniformly mixing ethanol, deionized water and ammonium hydroxide, adding a template agent, and stirring until the template agent is completely dissolved; (2) preparing the functionalized ionic liquid by using two precursors, and mixing the functionalized ionic liquid with tetraethoxysilane; (3) dropwise adding the mixed solution obtained in the step (1) to generate a flocculent product, transferring the flocculent product in a polytetrafluoroethylene reaction still and carrying out hydrothermal crystallization; and (4) suction-filtering, chemically extracting filter residue, washing, drying in vacuum, activating to obtain the functionalized ionic liquid hybrid mesoporous molecular sieve MCM-48 composite material. The composite material prepared by the method disclosed by the invention combines the dual adsorption effect of the functionalized ionic liquid and MCM-48 on the post-FGD, and the good adsorption effect can be realized at low temperature.
Description
Technical field
The invention belongs to the immobilized field of functionalized ion liquid, be specifically related to hybrid mesoporous MCM-48 composite of a kind of functionalized ion liquid and preparation method thereof and application.
Background technology
Along with the development of Chemical Engineering Technology in recent years, ionic liquid is subject to the extensive attention of academia and business circles as a kind of novel " green solvent ".Meanwhile, by ionic liquid is carried out to functionalization, can give physical and chemical performance and function that ionic liquid is new.Due to the design of functionalized ion liquid, synthetic and application expansion rapidly, the ionic liquid in a large number with specific function is synthesized out, and in each application, is applied widely.Adopt the mode of physical absorption immobilized in organic polymer or inorganic material surface functionalized ion liquid, can realize simple separation, but synthetic stability of material is bad, catalytic activity is relatively lower, and reusability is also bad.Therefore, take into full account the feature of carrier and ionic liquid, further the hybrid material of the efficient and reusable solid-carrying type functionalized ion liquid of design and researchp has very important scientific meaning and using value.
Mesopore molecular sieve MCM-48 is as a member of M41S series mesopore molecular sieve, compare with the MCM-41 in straight hole road, the double helical form three-dimensional open-framework of MCM-48 has more superiority, and it is difficult for stopping up and having better transmission performance, thereby has more tempting application potential in fields such as adsorbing separation.And using functionalized ion liquid as organic component, by the immobilized functionalized ion liquid on the hole wall surface of molecular sieve of rear grafting, easily come off, and water resistant heat endurance neither be fine.Therefore adopt cohydrolysis-condensation methods that functionalized ion liquid is immobilized in mesopore molecular sieve MCM-48, this method can not only embed the structure of functionalized ion liquid in the hole wall of molecular sieve well, and the hydrothermally stable of the hybrid mesoporous silica-base material of functionalized ion liquid of making is also relatively good.This composite has possessed the Acidity of Aikalinity two-fold advantage of loose structure and the functionalized ion liquid of mesopore molecular sieve simultaneously, this material had both had the specific function of functionalized ion liquid, have again the advantages such as mesoporous carrier specific area is large, pore passage structure is regular, it is a new direction of the immobilized research of functionalized ion liquid.
Along with industrial expansion, atmosphere pollution is day by day serious, wherein how to eliminate flue gas CO
2and SO
2deng sour gas, cause the concern of countries in the world, Japan, the U.S. and Germany have carried out a large amount of research work removing aspect sour gas, have developed several different methods perhaps.These methods can be classified as two large classes, abandon method and absorption method.Abandon in method, for example, occupy the limestone-based process of critical role, although method is simple, it produces a large amount of waste residues, waste liquid, causes secondary pollution.In absorption method, wherein a kind of important method is that charcoal absorption removes sour gas, and this method is simple, and does not produce secondary pollution, but its investment cost is high.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide the preparation method of the hybrid mesoporous MCM-48 composite of a kind of functionalized ion liquid, the inventive method combines sol-gel law technology and the hybrid material absorption process technology of functionalized ion liquid and mesoporous material, and experimentation operation is relatively simple, trapping sour gas effect is better;
The hybrid mesoporous MCM-48 composite of functionalized ion liquid that provides above-mentioned preparation method to obtain is provided, the hybrid mesoporous MCM-48 composite of this functionalized ion liquid has not only retained alkali ionic liquid and the original function of mesoporous material, and the synergy of the two can strengthen the absorption function of hybrid material to sour gas;
A further object of the present invention is to provide the above-mentioned functions hybridization of ionic liquid mesopore molecular sieve MCM-48 application of composite.
Object of the present invention is achieved through the following technical solutions:
A preparation method for the hybrid mesoporous MCM-48 composite of functionalized ion liquid, comprises the steps:
(1) be incorporated at 70～90 ℃ stirring and refluxing 20～48 hours by the precursor B of 0.01mol precursor A and 0.01mol is mixed, obtain functionalized ion liquid;
The general formula of wherein said precursor A is R ' (CH
2)
nsi (OEt)
3or R ' (CH
2)
nsi (OMt)
3, wherein R ' is Cl
-, Br
-, I
-,
in a kind of, the integer that n is 0～4; Described precursor B is with the alkane of functionalization group or nitrogen azole compounds, its with functionalization group, be one or more in halogen, amido, sulfydryl, imidazoles, pyridine, pyrazoles, described alkane carbon chain lengths is 2～4;
(2) 50mL absolute ethyl alcohol, 120mL deionized water are added to 12mL ammoniacal liquor after mixing, then add 2.6g template that it is dissolved completely, obtain reaction solution;
(3) functionalized ion liquid and the ethyl orthosilicate of getting in proportion step (1) gained mix in solvent, obtain mixed liquor; Wherein, in described mixed liquor, total molar content of element silicon is 0.016mol;
(4) mixed liquor of step (3) is added dropwise to by constant pressure funnel in the reaction solution of step (2), stirring at room reaction 1～3 hour, obtains cotton-shaped product;
(5) the described cotton-shaped product of step (4) is proceeded in polytetrafluoroethylene reactor, at 80 ℃～120 ℃, hydrothermal crystallizing is 2 days, obtains solid product; Solid product is through cold filtration, and distilled water washing, obtains composite crude product after drying at room temperature;
(6) the described composite crude product of step (5) is carried out to vacuum aging;
(7) the aging products therefrom of step (6) vacuum is dispersed in the extractant of 0.08～0.15mol/L, at 50～70 ℃, constant temperature return stirring is 0.5～1.5 hour, after suction filtration, get filter residue and repeat 2～3 times with abundant removed template method and unreacted raw material, obtain composite extraction product;
(8) composite extraction product described in step (7) is dispersed in 100mL weakly alkaline solution, 60 ℃ of constant temperature return stirrings 1 hour, then 80～100 ℃ of vacuum drying 12～24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
Wherein, the general structure of the described functionalized ion liquid of step (1) be [RR ' (CH
2)
nsi (OEt)
3]
+x
-or [RR ' (CH
2)
nsi (OMt)
3]
+x
-.
Preferably, the described template of step (2) is softex kw (CTAB).
Preferably, the mole that the described ratio of step (3) is functionalized ion liquid: the mole=1:19～3:7 of ethyl orthosilicate;
Preferably, the described solvent of step (3) is a kind of in water, methyl alcohol, ethanol or chloroform;
Preferably, described in step (7), extractant is HCl/ alcohol mixed solution, NH
4a kind of in Cl/ alcohol mixed solution or HCl/ water mixed solution;
Preferably, the NaHCO that the described alkalescent solvent of step (8) is 0.1mol/L
3the aqueous solution or NH
3h
2o.
Wherein, the reaction temperature that the described vacuum of step (6) is aging is 120～160 ℃, and the reaction time is 20～30 hours.
Preferably, in above-mentioned preparation method, described each material molar ratio in step (2) and (3) is: absolute ethyl alcohol: deionized water: ammoniacal liquor: template: the silicon content=0.86:6.667:0.312:0.007:0.016 of mixed liquor.
The hybrid mesoporous MCM-48 composite of functionalized ion liquid that a kind of above-mentioned preparation method prepares.
The application of above-mentioned functions hybridization of ionic liquid mesopore molecular sieve MCM-48 composite in absorbing acid gases.Preferably, described sour gas is CO
2or SO
2.
Principle of the present invention:
The present invention carries out by sol-gel process functionalized ion liquid the hydridization of ionic liquid and synthesizes in mesopore molecular sieve MCM-48, thereby ionic liquid is directly immobilized in the hole wall of molecular sieve MCMC-48, make a kind of micropore and mesoporous functionalized ion liquid hydridization MCM-48 composite of being rich in, as a kind of Solid-state Chemistry adsorbent, except possessing the advantage of Dry Adsorption, can also under higher temperatures condition, rapidly and efficiently remove the sour gas in flue gas.
The present invention has following advantage and effect with respect to prior art:
(1) the hybrid mesoporous MCM-48 composite of the prepared functionalized ion liquid of the inventive method is owing to having functionalized ion liquid and the porous material synergy for sour gas absorption, and it is to SO
2energy of adsorption within the scope of typical post-FGD flue-gas temperature, realizing good effect.
(2) the present invention is dry process, does not have liquid flux, can overcome the shortcoming of traditional handicraft, has reduced the energy consumption of hot regeneration simultaneously.
(3) immobilized functionalized ion liquid formation chemical bond is fixed on MCM-48 skeleton, therefore do not have losing issue, transportation and the high feature of functionalized ion liquid heat endurance that the cubic structure that has simultaneously retained MCM-48 is convenient to gas recycle performance to improve.
(4) by changing difference in functionality group and the group number of functionalized ion liquid, can reach adjusting to sour gas adsorbance, can realize the controllable adsorption of gas and desorption simultaneously.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum (XRD figure) of embodiment 1 product ILS@MCM-48 and MCM-48 molecular sieve.
Fig. 2 is the infrared spectrum (IR figure) of embodiment 1 product ILS@MCM-48 and MCM-48 molecular sieve.
Fig. 3 is the adsorption-desorption isothermal curve figure (BET figure) of embodiment 1 product ILS@MCM-48 and MCM-48 molecular sieve.
Fig. 4 is the breakthrough curve figure of embodiment 1 product ILS@MCM-48 and MCM-48 molecular sieve.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) by the N-[3-of equimolar amounts (three ethoxy silylation) propyl group]-4, the two hydrogen imidazoles (0.01mol, 2.74g) of 5-and 3-propantheline bromide hydrobromide (0.01mol, 2.19g) join in 10mL ethanol, and stirring and refluxing is 24 hours at 80 ℃.At 80 ℃, rotary evaporation is removed ethanol, and last product is removed unreacted presoma with pentane washing, and room temperature vacuum drying, obtains functionalized ion liquid.The synthesis technique of functionalized ion liquid is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially.By the mol ratio of 1:9, get after 0.8g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 3.05g TEOS, stirring at room 2 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 110 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 24 hours of (3) gained composite crude product vacuum at 150 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1mol/L HCl/ ethanol, 60 ℃ of constant temperature return stirrings 1 hour, after suction filtration, get filter residue and repeat 2 times with abundant removed template method CTAB, finally at 100 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NaHCO of 100ml0.1mol/L
3in the aqueous solution, 60 ℃ of constant temperature return stirring 1h, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite, are denoted as ILs@MCM-48.
Carrying out sour gas SO
2adsorption experiment in, when the additional proportion of ionic liquid is 10% left and right to SO
2there is maximum adsorption effect, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 30.00ml/g.
The functionalized ion liquid hydridization MCM-48 composite ILS@MCM-48 of embodiment 1 preparation is carried out to phenetic analysis with the MCM-48 without hydridization:
Functionalized ion liquid hydridization MCM-48 composite ILS@MCM-48 to embodiment 1 preparation carries out small angle X-ray diffraction sign, curve map as shown in Figure 1, result shows that gained composite has the crystalline structure similar to MCM-48 molecular sieve, and the functionalized ion liquid hydridization MCM-48 composite of preparation contains stable and orderly pore passage structure.
The functionalized ion liquid hydridization MCM-48 composite ILS@MCM-48 of embodiment 1 preparation is carried out to infrared (IR) to be characterized, curve map as shown in Figure 2, result shows that described functionalized ion liquid hydridization MCM-48 composite not only has the characteristic peak of MCM-48 molecular sieve, and at 2900cm
-1, 1700cm
-1and 1450cm
-1place all has ionic liquid characteristic peak to occur, functions ionic liquid successfully accesses in the skeleton of molecular sieve.
Functionalized ion liquid hydridization MCM-48 composite ILS@MCM-48 to embodiment 1 preparation carries out N
2adsorption-desorption characterizes, isothermal curve figure as shown in Figure 3, result shows that gained functionalized ion liquid hydridization MCM-48 composite has obvious mesoporous material hysteresis loop, shows still to retain the pore size in its loose structure and mesoporous scope after composite access function ionic liquid.
Functionalized ion liquid hydridization MCM-48 composite ILs@MCM-48 to embodiment 1 preparation carries out penetration test, result as shown in Figure 4, result shows that described functionalized ion liquid hydridization MCM-48 composite has better adsorption and desorption effect to sour gas with respect to pure MCM-48 molecular sieve, shows that the access of functionalization group in ionic liquid can realize the better absorption of composite.
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) by the N-(3-butyl triethoxysilane of equimolar amounts)-imidazoles (0.01mol, 2.44g) and 2-iodine ethamine hydriodate (0.01mol, 2.99g) join in 10mL ethanol, and stirring and refluxing is 48 hours at 70 ℃.At 80 ℃, rotary evaporation is removed ethanol, and last product is removed unreacted presoma with pentane washing, and room temperature vacuum drying, obtains functionalized ion liquid.The synthesis technique of functionalized ion liquid is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially.By the mol ratio of 1:19, get after 0.44g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 3.23g TEOS, stirring at room 3 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 80 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 30 hours of (3) gained composite crude product vacuum at 120 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1mol/L NH
4in Cl/ ethanol, 50 ℃ of constant temperature return stirrings 1.5 hours, get filter residue and repeat 2 times with abundant removed template method CTAB after suction filtration, and finally at 80 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NH of 100ml0.1mol/L
3h
2in the O aqueous solution, 60 ℃ of constant temperature return stirrings 1 hour, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
With example 1, carry out relevant characterization, carrying out sour gas SO
2adsorption experiment in, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 12.51ml/g.
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) by the 2-(2-pyridine radicals of equimolar amounts) ethyl trimethoxy silylation (0.01mol, 2.27g) and 2-chloroethyl amine hydrogen salt hydrochlorate (0.01mol, 1.16g) join in 10mL ethanol, and stirring and refluxing is 20 hours at 90 ℃.At 80 ℃, rotary evaporation is removed ethanol, and last product is removed unreacted presoma with pentane washing, and room temperature vacuum drying, obtains functionalized ion liquid.The synthesis technique of functionalized ion liquid is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially.By the mol ratio of 3:17, get after 0.84g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 2.89g TEOS, stirring at room 3 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 120 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 20 hours of (3) gained composite crude product vacuum at 160 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1M HCl/ water, 70 ℃ of constant temperature return stirrings 0.5 hour, after suction filtration, get filter residue and repeat 3 times with abundant removed template method CTAB, finally at 100 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NaHCO of 100ml0.1mol/L
3in the aqueous solution, 60 ℃ of constant temperature return stirrings 1 hour, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
Carrying out sour gas SO
2adsorption experiment in, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 15.43ml/g.
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) equimolar 3-pyridine triethoxysilane (0.01mol, 2.41g) and 4-neoprene amine hydrogen salt hydrochlorate (0.01mol, 1.44g) are joined in 10mL ethanol, stirring and refluxing is 36 hours at 85 ℃.At 80 ℃, rotary evaporation is removed ethanol, and last product is removed unreacted presoma with pentane washing, and room temperature vacuum drying, obtains functionalized ion liquid.Its synthesis technique is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially, by the mol ratio of 1:4, get after 1.26g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 2.72g TEOS, stirring at room 2 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 100 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 25 hours of (3) gained composite crude product vacuum at 130 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1M HCl/ ethanol, 60 ℃ of constant temperature return stirrings 1 hour, after suction filtration, get filter residue and repeat 2 times with abundant removed template method CTAB, finally at 90 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NaHCO of 100ml0.1mol/L
3in the aqueous solution, 60 ℃ of constant temperature return stirrings 1 hour, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
Functionalized ion liquid hydridization MCM-48 composite is carried out to relevant characterization, in breakthrough curve experiment, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 16.22ml/g.
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) equimolar chloromethyl trimethoxy silane (0.01mol, 1.71g) and 3-aminopyridine (0.01mol, 0.94g) are joined in 10mL ethanol, stirring and refluxing is 24 hours at 80 ℃, and cool to room temperature obtains thick liquid.At 80 ℃, rotary evaporation is removed ethanol, and last product is removed unreacted presoma with pentane washing, and room temperature vacuum drying, obtains functionalized ion liquid.Its synthesis technique is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially.By the mol ratio of 1:3, get after 1.08g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 2.55g TEOS, stirring at room 2 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 90 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 24 hours of (3) gained composite crude product vacuum at 150 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1M HCl/ ethanol, 60 ℃ of constant temperature return stirrings 1 hour, after suction filtration, get filter residue and repeat 2 times with abundant removed template method CTAB, finally at 100 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NaHCO of 100ml0.1mol/L
3in the aqueous solution, 60 ℃ of constant temperature return stirrings 1 hour, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
Functionalized ion liquid hydridization MCM-48 composite is carried out to relevant characterization, in breakthrough curve experiment, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 14.17ml/g.
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) equimolar 2-bromoethyl trimethoxy silane (0.01mol, 2.29g) and 3-iodine pyridine (0.01mol, 2.05g) are joined in 10mL ethanol, stirring and refluxing is 24 hours at 80 ℃.At 80 ℃, rotary evaporation is removed ethanol, and last product is removed unreacted presoma with pentane washing, and room temperature vacuum drying, obtains functionalized ion liquid.Its synthesis technique is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially.By the mol ratio of 3:7, get after 2.12g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 2.38g TEOS, stirring at room 2 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 110 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 24 hours of (3) gained composite crude product vacuum at 150 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1M HCl/ ethanol, 60 ℃ of constant temperature return stirrings 1 hour, after suction filtration, get filter residue and repeat 3 times with abundant removed template method CTAB, finally at 100 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NaHCO of 100ml0.1mol/L
3in the aqueous solution, 60 ℃ of constant temperature return stirrings 1 hour, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
Functionalized ion liquid hydridization MCM-48 composite is carried out to relevant characterization, in breakthrough curve experiment, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 18.92ml/g.
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) by equimolar 3-iodine propyl-triethoxysilicane (0.01mol, 3.32g) with 4-amino-pyrazol (0.01mol, 0.83g) join in 10mL ethanol, at 80 ℃, stirring and refluxing reaction is 24 hours, reacted rear dry with three final vacuums of pentane (50ml) washing, 80 ℃ of rotary evaporations and drying under reduced pressure obtain functionalized ion liquid.Its synthesis technique is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially.By the mol ratio of 1:9, get after 0.68g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 3.05g TEOS, stirring at room 2 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 110 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 24 hours of (3) gained composite crude product vacuum at 150 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1M HCl/ ethanol, 60 ℃ of constant temperature return stirrings 1 hour, after suction filtration, get filter residue and repeat 2 times with abundant removed template method CTAB, finally at 100 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NaHCO of 100ml0.1mol/L
3in the aqueous solution, 60 ℃ of constant temperature return stirrings 1 hour, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
Functionalized ion liquid hydridization MCM-48 composite is carried out to relevant characterization, in breakthrough curve experiment, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 22.43ml/g.
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) by equimolar 3-chloropropyl triethoxysilane (0.01mol, 2.41g) with 2-mercaptopyridine (0.01mol, 1.11g) join in 10mL ethanol, at 80 ℃, stirring and refluxing reaction is 24 hours, cooling rear with pentane (50ml), wash three times after at 80 ℃ rotary evaporation vacuum drying obtain functionalized ion liquid.Its synthesis technique is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially.By the mol ratio of 1:9, get after 0.57g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 3.05g TEOS, stirring at room 2 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 110 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 24 hours of (3) gained composite crude product vacuum at 150 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1M HCl/ ethanol, 60 ℃ of constant temperature return stirrings 1 hour, after suction filtration, get filter residue and repeat 2 times with abundant removed template method CTAB, finally at 100 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NaHCO of 100ml0.1mol/L
3in the aqueous solution, 60 ℃ of constant temperature return stirrings 1 hour, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
Functionalized ion liquid hydridization MCM-48 composite is carried out to relevant characterization, in breakthrough curve experiment, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 16.10ml/g.
Embodiment 9
A preparation method for functionalized ion liquid hydridization MCM-48 composite, step is as follows:
(1) by equimolar 4-chlorobutyl triethoxysilane (0.01mol, 2.55g) with 2-aminooimidazole (0.01mol, 0.83g) join in 10mL ethanol, at 80 ℃, stirring and refluxing reaction is 24 hours, cool to room temperature obtains brown thick liquid, with after pentane (50ml) washing three times at 80 ℃ rotary evaporation vacuum drying obtain functionalized ion liquid.Its synthesis technique is as follows:
(2) 2.6g CTAB is dissolved in to the ethanol by 50ml, 12ml ammoniacal liquor, the mixed liquor that 120ml distilled water forms, stirring at room is until solid dissolves completely and liquid level bubble disappears substantially.By the mol ratio of 1:9, get after 0.55g functionalized ion liquid dissolves with 5mL methyl alcohol and mix and be added dropwise to said mixture with 3.05g TEOS, stirring at room 2 hours, generates cotton-shaped product.
(3) the cotton-shaped product of (2) gained is proceeded in polytetrafluoroethylene reactor, at 110 ℃, hydrothermal crystallizing is 2 days, obtains solid product.Solid product is through cold filtration, and distilled water washing, obtains faint yellow composite crude product after drying at room temperature.
(4) by aging 24 hours of (3) gained composite crude product vacuum at 150 ℃, prevent that product structure from caving in.
(5) the composite crude product after (4) are aging carries out the processing of chemical removal template: get the flaxen composite crude product of 0.6g powder and be dispersed in 100ml0.1M HCl/ ethanol, 60 ℃ of constant temperature return stirrings 1 hour, after suction filtration, get filter residue and repeat 2 times with abundant removed template method CTAB, finally at 100 ℃, vacuum drying obtains composite extraction product.
(6) products obtained therefrom in (5) is dispersed in to the NaHCO of 100ml0.1mol/L
3in the aqueous solution, 60 ℃ of constant temperature return stirrings 1 hour, then, with distilled water washing and 80 ℃ of vacuum drying 24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
Functionalized ion liquid hydridization MCM-48 composite is carried out to relevant characterization, in breakthrough curve experiment, at 8.10vol%SO
2in, within the scope of 45-55 ℃, to SO
2adsorbance be 26.45ml/g.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. a preparation method for the hybrid mesoporous MCM-48 composite of functionalized ion liquid, is characterized in that comprising the steps:
(1) be incorporated at 70～90 ℃ stirring and refluxing 20～48 hours by the precursor B of 0.01mol precursor A and 0.01mol is mixed, obtain functionalized ion liquid;
The general formula of wherein said precursor A is R ' (CH
2)
nsi (OEt)
3or R ' (CH
2)
nsi (OMt)
3, wherein R ' is Cl
-, Br
-, I
-,
in a kind of, the integer that n is 0～4; Described precursor B is with the alkane of functionalization group or nitrogen azole compounds, its with functionalization group, be one or more in halogen, amido, sulfydryl, imidazoles, pyridine, pyrazoles, the carbon chain lengths of described alkane is 2～4;
(2) 50mL absolute ethyl alcohol, 120mL deionized water are added to 12mL ammoniacal liquor after mixing, then add 2.6g template that it is dissolved completely, obtain reaction solution;
(3) functionalized ion liquid and the ethyl orthosilicate of getting in proportion step (1) gained mix in solvent, obtain mixed liquor; Wherein, in described mixed liquor, total molar content of element silicon is 0.016mol;
(4) mixed liquor of step (3) is added dropwise to by constant pressure funnel in the reaction solution of step (2), stirring at room reaction 1～3 hour, obtains cotton-shaped product;
(5) the described cotton-shaped product of step (4) is proceeded in polytetrafluoroethylene reactor, at 80 ℃～120 ℃, hydrothermal crystallizing is 2 days, obtains solid product; Solid product is through cold filtration, and distilled water washing, obtains composite crude product after drying at room temperature;
(6) the described composite crude product of step (5) is carried out to vacuum aging;
(7) the aging products therefrom of step (6) vacuum is dispersed in the extractant of 0.08～0.15mol/L, at 50～70 ℃, constant temperature return stirring is 0.5～1.5 hour, after suction filtration, get filter residue and repeat 2～3 times with abundant removed template method and unreacted raw material, obtain composite extraction product;
(8) composite extraction product described in step (7) is dispersed in 100mL weakly alkaline solution, 60 ℃ of constant temperature return stirrings 1 hour, then 80～100 ℃ of vacuum drying 12～24 hours, obtain functionalized ion liquid hydridization MCM-48 composite.
2. preparation method according to claim 1, is characterized in that: the described template of step (2) is softex kw.
3. preparation method according to claim 1, is characterized in that: the mole that the described ratio of step (3) is functionalized ion liquid: the mole=1:19～3:7 of ethyl orthosilicate.
4. preparation method according to claim 1, is characterized in that: the described solvent of step (3) is a kind of in water, methyl alcohol, ethanol or chloroform; Described in step (7), extractant is HCl/ alcohol mixed solution, NH
4a kind of in Cl/ alcohol mixed solution or HCl/ water mixed solution; The NaHCO that the described alkalescent solvent of step (8) is 0.1mol/L
3the aqueous solution or NH
3h
2o.
5. preparation method according to claim 1, is characterized in that: the reaction temperature that the described vacuum of step (6) is aging is 120～160 ℃, and the reaction time is 20～30 hours.
6. the hybrid mesoporous MCM-48 composite of the functionalized ion liquid preparing according to the preparation method described in claim 1～5 any one.
7. the application of the hybrid mesoporous MCM-48 composite of functionalized ion liquid according to claim 6 in absorbing acid gases.
8. application according to claim 7, is characterized in that: described sour gas is CO
2or SO
2.
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