CN102824895B - Mesoporous limited functionalized ionic liquid composite material and preparation method and application thereof - Google Patents
Mesoporous limited functionalized ionic liquid composite material and preparation method and application thereof Download PDFInfo
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- CN102824895B CN102824895B CN201210319866.XA CN201210319866A CN102824895B CN 102824895 B CN102824895 B CN 102824895B CN 201210319866 A CN201210319866 A CN 201210319866A CN 102824895 B CN102824895 B CN 102824895B
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Abstract
The invention discloses a mesoporous limited functionalized ionic liquid composite material and a preparation method and an application thereof. The method comprises the following steps of: synthesizing a functionalized siloxane ionic liquid precursor, and reacting a precursor A with a precursor B which are of equal molar weight at the temperature of 60-100 DEG C for 12-24 hours to obtain a functionalized siloxane ionic liquid, wherein the precursor A is organic trialkoxy silane R'Si(OR)3; mixing the functionalized siloxane ionic liquid, a mesoporous molecular sieve precursor and a template uniformly, and synthesizing a colloidal solution which contains a mesoporous limited functionalized ionic liquid composite material by adopting an in-situ sol-gel method; and performing suction filtration or centrifugal separation, and drying in vacuum. The composite material prepared with the method has a uniform mesoporous pore canal or a cage structure, so that the functionalized ionic liquid is heterogenized; and a quasi-liquid phase microenvironment is formed on the surface of a mesoporous material, so that the contact area between the ionic liquid and trapped gas can be increased, and the mass transfer capabilities in adsorption and desorption processed are increased.
Description
Technical field
The invention belongs to supported ionic liquids field, relate to CO
2trapping and storage (CO
2capture and storage, CCS), flue gas SO
2the sour gas trapping field such as remove.
Background technology
The acid gas trapping of tradition adopts wet absorption technology, and chemical absorption method is that the one of comparatively commonly using is selected.Its essence is and utilize alkaline absorbent to contact concurrent biochemical reaction with acid in flue gas, form unsettled salt; And salt is under certain conditions, inverse decomposition is discharged to sour gas, the absorbability of absorbent is regenerated, thereby sour gas is separated from flue gas and enrichment, be convenient to utilize or seal up for safekeeping, make absorbent be recycled simultaneously.Conventional absorbent has alkanolamine solution, strong base solution, hot liquor kalii caustici, lime slurry etc.Wherein, be applied to CO
2trap concerned maximum be alcamines, be the alkaline aqueous solution with hydroxyl and amido.Because MEA (MEA) molecular weight is little, absorb sour gas ability strong, be main technology studied and that use.This technology subject matter is CO in cyclic process
2absorption efficiency is not high; Due to reasons such as oxidation, thermal degradation, generation irreversible reaction and evaporations, cause absorbent absorbability to decline; Rich CO
2in absorption liquid (abbreviation rich solution), catabolite causes system corrosion; Regeneration energy consumption is large; Initial investment and operating cost are higher etc.; Seriously reduce the economy of collecting carbonic anhydride.Be applied to SO in flue gas
2the most ripe method of trapping is to utilize lime stone or lime slurry, and its principle is to utilize lime stone or lime slurry to absorb SO
2, generate calcium sulfite, separated calcium sulfite (CaSO
3) can abandon, also can be oxidized to calcium sulfate (CaSO
4), reclaim with gypsum form.Be the sulfur removal technology that at present technology is the most ripe in the world, operation conditions is the most stable, desulfuration efficiency reaches more than 90%, but its to have equally product be liquid or sludge, more difficult, equipment corrosion is serious, and after washing, flue gas needs heat again, energy consumption is high, and floor space is large, and investment and operating cost are high.The problems such as system complex, equipment is huge, water consumption is large, one-time investment is high.
And though molecular sieve Dry Adsorption technique can overcome above-mentioned shortcoming, because being mainly utilizes the physical absorption of molecular sieve to sour gas, the shortcoming such as reduction significantly so exist that adsorbance raises with adsorption temp, and carry out CO
2the best place of trapping is that its typical flue-gas temperature is 55 DEG C of 45 ?after flue gas desulfur device (post ?FGD), is unfavorable for using separately molecular sieve to carry out Dry Adsorption.P.D.Jadhav etc. (Energy & Fuels2007,21,3555 – 3559) have reported monoethanolamine (MEA) and have modified 13X molecular sieve for CO
2absorption, MEA is adsorbed and is loaded into 13X duct by solution.At 15vol%CO
2in, CO when 75 DEG C, this adsorbent
2adsorbance is 10.1ml/g, but only has 8.1ml/g 50 DEG C time.The little molecule MEA of the method is loaded into molecular sieve pore passage by simple absorption, certainly exists the problem that MEA runs off in use procedure, also has the shortcomings such as MEA is volatile, heat endurance is not high simultaneously.
In recent years, as a kind of novel green solvent, ionic liquid (IL) is almost without vapour pressure, thereby uses it for gas absorption separation and do not have the problem of polluting gas phase.In addition, utilize the adjustable feature of ionic liquid zwitterion structure to develop the functionalized ion liquid with specific function.Alkali ionic liquid is the class novel ion liquid occurring recently, this class ionic liquid not only has the physico-chemical property of conventional ion liquid (as almost not having vapour pressure, physics and chemistry stable in properties, structure and performance adjustable, be applicable to making to separate solvent or form anti-Ying ?separation coupling new system), and because it presents alkalescence, be therefore expected to the sour gas (CO novel as a class
2, SO
2, NO
x) selective absorber.There are a lot of reports about the research of alkali ionic liquid absorption sour gas at present, and show good sour gas absorption property, but due to its process using single ionic liquid, still belong to the Gas-Liquid Absorption process of wet method, thereby exist liquid viscosity in adsorption process to uprush, the shortcomings such as absorption, regenerative process method difficulty and regeneration technology flow process complexity.Therefore,, if can develop the novel process that there is the high-absorbable energy of wet processing and have both the advantage that is easy to industrialization and regeneration of dry method, will there is good application prospect and can be industry and remove sour gas another kind of approach is provided.
Supported ionic liquids is the frontier about ionic liquid research, object be by ionic liquid supported on solid catalyst or inert solid, reach raising system catalytic performance, reduce ionic liquid consumption, be convenient to the object of product separation and catalyst recycle.Molecular sieve is a series of by TO
4the crystallized silicon aluminate porous material of tetrahedron (T=Si/Al) composition, its be widely used in catalysis, absorption and separate, the aspect such as ion-exchange, medicament slow release.And silicon-based mesoporous molecular sieve is wherein as a kind of novel functional material, because its unique structure receives much concern.The drawbacks limit such as the chemical reactivity of mesopore molecular sieve is not high, stability is lower its practical application.Mesopore molecular sieve is carried out to chemical modification, and expanding its range of application becomes the hot issue of mesoporous materials field research.At present to the application study of mesopore molecular sieve mainly taking MCM ?41 and modified product as main, utilize MCM ?on 41 hole inwalls the surface hydroxyl of some Cucumber is reacted with siloxy, completing duct inner surface modifies or functionalization. as surface silicon alkylization changes surface polarity, introduce the organic compound of functional groups such as containing mercaptan, amino etc.Because the mesopore molecular sieve of aminofunctional is with a wide range of applications in fields such as catalysis, environmental protection, biologies, wherein also there is successively the patent of supported ionic liquids and molecular sieve and application thereof to disclose and report.
Chinese patent CN101773852A discloses the meso-porous molecular sieve material of load imidazole acetate ionic liquid, it utilizes aperture is the mesopore molecular sieve of 5～20nm, and silane-functionalized is carried out in mesopore molecular sieve surface, the mesopore molecular sieve again imidazole acetate ionic liquid and finishing being carried out after hydride modified carries out graft reaction, thereby by ionic liquid loaded and molecular sieve pore passage surface, and be applied to preparing vinyl acetate using acetylene method process using this composite as catalyst.
US Patent No. 7943543B1 disclose by glyoxaline ion liquid adopt infusion process apply the mode of load immobilized with MCM ?41 type molecular screen membrane surfaces, for natural gas CO
2remove.
Though the method for above-mentioned ionic liquid loadedization can be by supported ionic liquids in mesopore molecular sieve surface, but shortcoming is to make ionic liquid to load on uniformly surface, the inner duct of molecular sieve, inhomogeneous ionic liquid distributes also affects the inner pore passage structure of molecular sieve, affects mass transport process; Adopt the way of grafting, although there is chemical bonding on ionic liquid and molecular sieve pore passage surface, but this process need carries out the pre-functionalization of multistep to molecular sieve, too much pretreatment process, has destruction to duct, molecular sieve inside, in addition, prepared by employing dipping method, be inevitably difficult to ensure the stability of ionic liquid, makes in subsequent applications process, ionic liquid easily runs off, thereby affects the service life of composite.
For solving the defect of above-mentioned supported ionic liquids in mesopore molecular sieve, the present invention adopts the synthetic method of original position, functionalized ion liquid is directly reacted with the silicon source of synthesis of molecular sieve, the directly limited functionalized ion liquid mesoporous molecular sieve composite material that synthesizes, the method has that step is few, ionic liquid is uniformly dispersed, be difficult for running off, the advantage of stability and regenerability excellence.
Summary of the invention
The object of the invention is to overcome the defect that prior art exists, a kind of dry process is provided, absorb and resolving controlled, can be in mesoporous restricted function ionic liquid composite material of higher flue-gas temperature scope absorbing acid gases and preparation method thereof.
The present invention also provides the mesoporous restricted function ionic liquid composite material of application at sour gas CO
2and SO
2the application of trapping aspect.
The present invention utilizes in-situ sol-gel functionalization silica alkane ionic liquid, the synthetic hybrid mesoporous silicon based composite material of functionalized ion liquid that contains of one-step method, thereby limitedization of ionic liquid direct in-situ is synthesized in mesopore molecular sieve duct, make one and contain functionalized ion liquid mesoporous molecular sieve composite material.This material is as a kind of Solid-state Chemistry adsorbent, its except possess Dry Adsorption and functionalized ion liquid excellent absorption property etc. advantage, can also be under higher temperatures condition (typical post ?FGD flue-gas temperature be 45～55 DEG C) rapidly and efficiently remove the sour gas in flue gas; The method can also be eliminated single use ionic liquid as adsorbent and the problem such as intrinsic viscosity is uprushed, and adsorption and desorption speed is slow.
Object of the present invention is achieved through the following technical solutions:
A preparation method for mesoporous restricted function ionic liquid composite material, comprises the steps:
(1) under nitrogen protection, the precursor A of equimolar amounts is reacted at 60～100 DEG C to 12 ?24h with precursor B, obtain functionalization silica alkane ionic liquid; Described precursor A is organotrialkoxysilane R ' Si (OR)
3, wherein R is methyl or ethyl, R ' is one or more the functionalized ion liquid building stone in following general formula:
Wherein R
1, R
2, R
3, R
4, R
5identical or different is hydrogen atom or functionalization alkyl chain; [PR1,2,3,4] are quaternary phosphonium cations, and structure is
functionalization group in functionalization alkyl chain is one or more in amido, ehter bond, hydramine;
The general formula of described precursor B be M ?X; Wherein M is alkyl substituent or the alkyl substituent with functionalization group, and its carbon chain lengths is that 1～4, X is Cl
?, Br
?, I
?, [BF
4]
?, [PF
6]
?, [AlCl
4]
?, [Al
2cl
7]
?, [CF
3cOO]
?, [CF
3sO
3]
?, [C
nh
2n+1cOO]
?, [Tf
2n]
?, [AA]
?, lactate or citrate; Wherein, described is one or more in amido, ehter bond, hydramine, guanidine class, acid amides, nitrogen heterocyclic ring with functionalization group in the alkyl substituent of functionalization group;
(2), by soluble in water and mix to the functionalization silica alkane ionic liquid of step (1) gained and silicon source and template, by in-situ sol-gel, when selected template is during for long alkane chain trimethyl ammonium cationic surfactant, adjustment pH value is 4～6; In the time that selected template is triblock polymer pluronic non-ionic surface active agent, adjusting to pH value is 8～10; At acidity or alkali condition, next step synthesizes the colloidal solution that contains mesoporous restricted function ionic liquid composite material; Wherein the mol ratio in functionalization silica alkane ionic liquid and silicon source is 1/10 ?1/2:1; The mol ratio of water and element silicon is 200～800:1; The mol ratio of element silicon and template is 8～60:1; Element silicon is element silicon sum in functionalization silica alkane ionic liquid and silicon source; Described silicon source is one or more in ethyl orthosilicate, positive silicic acid propyl ester and butyl silicate; Described template is long alkane chain trimethyl ammonium cationic surfactant, two sections of polymer non-ionic surface active agents or triblock polymer pluronic non-ionic surface active agent; Described long alkane chain trimethyl ammonium cationic surfactant is hexadecyltrimethylammonium chloride, DTAC or softex kw; Described triblock polymer pluronic non-ionic surface active agent be Ju Huan Yang Yi Wan ?Ju Huan Yang Bing Wan ?PEO triblock copolymer, structural formula is EO
xpO
70eO
x, wherein x=5～100;
(3) solution that step (2) gained is contained to mesoporous restricted function ionic liquid composite material under 50～200 DEG C of conditions, ageing 2～120h under normal pressure or spontaneous press strip part;
(4) step (3) gained solution suction filtration or centrifugation are obtained to mesoporous restricted function ionic liquid composite material;
(5) the isolated mesoporous restricted function ionic liquid composite material of step (4) is extracted or extracted by Soxhlet remove the presoma, the template that have neither part nor lot in reaction, then it is carried out to low-temperature vacuum drying, obtain composite.
Further, described functionalization silica alkane ionic liquid zwitterion composition, general structure is [(OR)
3siR ' M]
﹢x
?.
The described solvent that Soxhlet is extracted or extraction is used of step (5) is one or more in water, methyl alcohol, ethanol, propyl alcohol and butanols.
A kind of Jie Kong Fen Shai ?functionalized ion liquid composite, this composite is to be prepared by above-mentioned any one method.
It is 1.5～30nm that the aperture of son sieve ?functionalized ion liquid composite is divided in the hole of giving an account of, and composite is configured as MCM ?41, MCM ?48, SBA ?3, SBA ?8, SBA ?15 or SBA ?16 mesopore molecular sieve structures.
The hole of giving an account of divides son sieve ?functionalized ion liquid composite at sour gas CO
2or SO
2the application of trapping.
The present invention compared with prior art tool has the following advantages:
(1) the prepared composite of the inventive method is owing to having the structural advantage of functionalized ion liquid and mesopore molecular sieve concurrently, for sour gas, absorption can be brought into play the collaborative advantage function of 2 kinds of functional materials, and it realizes preferably effect within the scope of higher flue-gas temperature to the energy of adsorption of sour gas.Dry process, absorption and resolving controlled
(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) functionalized ion liquid of institute's load is fixed on framework of molecular sieve by chemical bond, does not therefore have losing issue, has also retained the high feature of ionic liquid heat endurance simultaneously, improves and recycles performance.
(4) can increase the adsorbance of ionic liquid to sour gas by structure and the quantity of functional group that produces electrostatic interaction with sour gas on regulation and control ionic liquid, absorb and resolving controlled thereby can effectively realize.
Brief description of the drawings
Fig. 1 be embodiment 1Sample1MCM ?41 infrared spectrum.
Fig. 2 be embodiment 1Sample1MCM ?41 XRD figure.
Fig. 3 is the infrared spectrum of embodiment 3Sample1SBA-15.
Fig. 4 be embodiment 3Sample1SBA ?15 XRD figure.
Detailed description of the invention
For further understanding the present invention, below in conjunction with drawings and Examples, the invention will be further described, but embodiment of the present invention is not limited to this.
Jie Kong Fen Shai ?the preparation method of functionalized ion liquid composite, step is as follows:
(1) under nitrogen protection, the 1-(3-ethoxy silane propyl group)-4 of equimolar amounts, the two hydrogen imidazoles of 5-and 2-bromine ethylamine hydrobromide stirring and refluxing 24h in ethanol, solvent is evaporated with rotary evaporation instrument, then add benzinum (boiling range 30-60) layering, obtain lower floor's sample, Rotary Evaporators evaporate to dryness obtains functionalization silica alkane ionic liquid 1-(3-ethoxy silane propyl group)-3-ethylamine hydrobromide-4, the two hydrogen imidazolium bromides of 5-; Functionalization silica alkane ionic liquid 1-(3-ethoxy silane propyl group)-3-ethylamine hydrobromide-4, the reaction equation of the two hydrogen imidazolium bromides of V5-is as follows:
(2), under room temperature, 1.0g CTAB is dissolved in to (243g H in the aqueous solution of NaOH
2o and 0.28g NaOH), stir to clarify, then the ethyl orthosilicate and the two hydrogen imidazolium bromides of 1.05g functionalization silica alkane ionic liquid 1 ?(3 ?ethoxy silane propyl group) ?3 ?second amine hydrogen bromine acid salt ?4,5 ? that add slowly 4.5ml stir 2h in room temperature.
(3) step (2) products therefrom is transferred in hydrothermal reaction kettle, ageing 24h at 100 DEG C, is placed on cool to room temperature in air afterwards, with Buchner funnel filter, with deionized water washing, drying at room temperature is spent the night and is obtained white powder afterwards.
(4) white powder of step (3) gained is carried out to demoulding processing, in the ethanol of 150ml that is dissolved with 1g ammonium nitrate, stir 30min in 60 DEG C according to 1.5g sample dispersion.Repeat aforesaid operations 3 times to remove template CTAB as far as possible, filter, after 80 DEG C of dry 24h of vacuum, obtain white powder, be denoted as Sample1MCM ?41.
As shown in Figure 1, Sample1MCM-41 is carried out to infrared (IR) characterization result and show, in the infrared spectrum of Sample1MCM-41, have the vibration peak of amido in obvious functionalization silica alkane ionic liquid, be specially 2840cm
-1and 2920cm
-1and the vibration 1631cm of the two keys of C=C above imidazole ring
-1characteristic peak, illustrate and in Sample1MCM-41, contain basic functionalized ionic liquid.
As shown in Figure 2, Sample1MCM-41 is carried out to small angle X-ray diffraction sign, its main diffraction maximum (100), and the weak diffraction maximum of (110) and (200) crystal face is also high-visible, illustrate that Sample1MCM-41 is MCM-41 molecular sieve, its degree of internal order is higher, is the close heap type of six sides structure.
Sample1MCM-41 is carried out to N
2adsorption-desorption characterizes, and its specific area reaches 760m
2g
-1, and its average pore size is 3.3nm, pore diameter range, within mesoporous scope, therefore obtains mesoporous limited basic functionalized ionic liquid composite.
Breakthrough experiment is in adsorption process, and adsorbed gas is by adsorption bed, exit gas concentration reach inlet gas concentration 5% time be made as breakthrough point, while reaching 100%, be considered to adsorb saturated.From the time that starts to be adsorbed onto between breakthrough point be time of break-through, be saturation time from starting to be adsorbed onto the time of absorption between saturated, the adsorbance in time of break-through is counted and is penetrated adsorbance.By breakthrough experiment, at 15vol%CO
2in, within the scope of 45～55 DEG C, to CO
2adsorbance be 6.32ml/g; At 8.08vol%SO
2in, within the scope of 45～55 DEG C, to SO
2adsorbance be 12.53ml/g.
(1) Jie Kong Fen Shai ?the preparation method of functionalized ion liquid composite, step is as follows:
Under nitrogen protection, the 1-(3-ethoxy silane propyl group)-4 of equimolar amounts, the two hydrogen imidazoles of 5-and 3-propantheline bromide hydrobromide stirring and refluxing 24h in ethanol, solvent is evaporated with rotary evaporation instrument, then add benzinum (30～60) layering, obtain lower floor's sample, Rotary Evaporators evaporate to dryness obtains functionalization silica alkane ionic liquid 1-(3-ethoxy silane propyl group)-3-propylamine hydrobromate-4, the two hydrogen imidazolium bromides of 5-;
(2), under room temperature, 1.0g CTAB is dissolved in to (243g H in the aqueous solution of NaOH
2o and 0.28g NaOH), stir to clarify, then add slowly ethyl orthosilicate and 1.08g1-(3-ethoxy silane propyl group)-3-propylamine hydrobromate-4 of 4.5ml, the two hydrogen imidazolium bromides of 5-stir 2h in room temperature;
(3) step (2) products therefrom is transferred in hydrothermal reaction kettle, ageing 24h at 100 DEG C, is placed on cool to room temperature in air afterwards, with Buchner funnel filter, with deionized water washing, drying at room temperature is spent the night and is obtained white powder afterwards.
(4) step (3) gained white powder is carried out to demoulding processing, according to 1.5g sample dispersion in the ethanol of 150ml that is dissolved with 1g ammonium nitrate, stir 30min. in 60 DEG C and repeat aforesaid operations 3 times to remove template CTAB as far as possible, filter, after 80 DEG C of dry 24h of vacuum, obtain product, be denoted as Sample2MCM-41;
Characterizing method with example 1 is consistent, and material is characterized, and illustrates that the material obtaining is the hybrid mesoporous silica-base material of alkali ionic liquid.Test by breakthrough curve, at 15vol%CO
2in, within the scope of 45～55 DEG C, to CO
2adsorbance be 12.73ml/g; At 8.08vol%SO
2in (all the other are He), within the scope of 45～55 DEG C, to SO
2adsorbance be 16.57ml/g.
Jie Kong Fen Shai ?the preparation method of functionalized ion liquid composite, step is as follows:
(1) under the protection of nitrogen by the methylimidazole of equimolar amounts and 3-chloropropyl triethoxysilane stirring and refluxing 24h at 95 DEG C, dissolve with the methyl alcohol of trying one's best few afterwards, then be extracted with ethyl acetate, obtain lower floor's sample, Rotary Evaporators evaporate to dryness obtains siloxanes ionic liquid 1-(3-ethyoxyl silicon propyl group)-3-methylimidazole chloride;
(2), under room temperature, 1.0g CTAB is dissolved in to (243g H in the aqueous solution of NaOH
2o and 0.28g NaOH), stir to clarify, then add slowly ethyl orthosilicate and 0.71g1-(3-ethyoxyl silicon the propyl group)-3-methylimidazole chloride of 4.5ml, in room temperature, stir 2h.
(3) step (2) products therefrom is transferred in hydrothermal reaction kettle, ageing 24h at 100 DEG C, is placed on cool to room temperature in air afterwards, with Buchner funnel filter, with deionized water washing, drying at room temperature is spent the night and is obtained white powder afterwards.
(4) step (3) gained white powder is carried out to demoulding processing, according to 1.5g sample dispersion in the ethanol of 150ml that is dissolved with 1g ammonium nitrate, stir 30min. in 60 DEG C and repeat aforesaid operations 3 times to remove template CTAB as far as possible, filter, after 80 DEG C of dry 24h of vacuum, obtain product, be denoted as Sample3MCM-41;
Characterizing method with example 1 is consistent, and material is characterized.
As shown in Figure 3, Sample1SBA-15 is carried out to infrared (IR) characterization result and show, in the infrared spectrum of Sample1SBA-15, have the vibration peak of amido in weak functionalization silica alkane ionic liquid, be specially 2840cm
-1and the vibration 1620cm of the two keys of C=C above imidazole ring
-1characteristic peak and two key chattering 1450cm of C=N above imidazole ring
-1characteristic peak, illustrate and in Sample1SBA-15, contain basic functionalized ionic liquid.
As shown in Figure 4, Sample1SBA-15 is carried out to small angle X-ray diffraction sign, its main diffraction maximum (100), and the weak diffraction maximum of (110) and (200) crystal face is also high-visible, illustrate that Sample1MCM-41 is MCM-41 molecular sieve, its degree of internal order is higher, is the close heap type of six sides structure, therefore obtains mesoporous limited basic functionalized ionic liquid composite.
Test by breakthrough curve, at 15vol%CO
2in (all the other are He), within the scope of 45～55 DEG C, to CO
2adsorbance be 6.41ml/g; At 8.08vol%SO
2in (all the other are He), within the scope of 45～55 DEG C, to SO
2adsorbance be 10.03ml/g.
Jie Kong Fen Shai ?the preparation method of functionalized ion liquid composite, step is as follows:
(1) under nitrogen protection, the 1-(3-ethoxy silane propyl group)-4 of equimolar amounts, the two hydrogen imidazoles of 5-and 3-propantheline bromide hydrobromide stirring and refluxing 24h in ethanol, solvent is evaporated with rotary evaporation instrument, then add benzinum (30～60) layering, obtain lower floor's sample, Rotary Evaporators evaporate to dryness obtains functionalization silica alkane ionic liquid 1-(3-ethoxy silane propyl group)-3-propylamine hydrobromate-4, the two hydrogen imidazolium bromides of 5-;
(2) 4.0g P123 is dissolved in the solution of HCl of 125g1.9mol/L and stirs, be heated afterwards 40 DEG C, and add 8.22ml TEOS, hydrolysis 3h.
(3) then add the two hydrogen imidazolium bromides of 2.02g functionalization silica alkane ionic liquid 1 ?(3 ?ethoxy silane propyl group) ?3 ?propylamine hydrogen bromine acid salt ?4,5 ?, at 40 DEG C, stir 20h.
(4) proceeded to in the spontaneous pressure reactor of polytetrafluoroethylene (PTFE) inner sleeve at 100 DEG C aging 120h.Filter, drying at room temperature is spent the night, and finally extracts 24h by ethanol Soxhlet, after 80 DEG C of dry 24h of vacuum, obtains the hybrid mesoporous silica-base material of alkali ionic liquid, be denoted as Sample1SBA ?15;
To material Sample1SBA ?15 characterize, record by breakthrough experiment simultaneously, Sample1SBA ?15 at 15vol%(, all the other are He) CO
2in, within the scope of 45～55 DEG C, to CO
2adsorbance be 13.89ml/g; At 8.08vol%SO
2in, within the scope of 45～55 DEG C, to SO
2adsorbance be 24.37ml/g.
Jie Kong Fen Shai ?the preparation method of functionalized ion liquid composite, step is as follows:
(1) under nitrogen protection, the 1-(3-ethoxy silane propyl group)-4 of equimolar amounts, the two hydrogen imidazoles of 5-and 2-bromine ethylamine hydrobromide stirring and refluxing 24h in ethanol, solvent is evaporated with rotary evaporation instrument, then add benzinum (30～60) layering, obtain lower floor's sample, Rotary Evaporators evaporate to dryness obtains functionalization silica alkane ionic liquid 1-(3-ethoxy silane propyl group)-3-ethylamine hydrobromide-4, the two hydrogen imidazolium bromides of 5-;
(2) 4.0g P123 is dissolved in the solution of HCl of 125g1.9mol/L and stirs, be heated afterwards 40 DEG C, and add 8.22ml TEOS, hydrolysis 3h.
(3) then add the two hydrogen imidazolium bromides of 1.96g functionalization silica alkane ionic liquid 1 ?(3 ?ethoxy silane propyl group) ?3 ?second amine hydrogen bromine acid salt ?4,5 ?, at 40 DEG C, stir 20h.
(4) proceeded to in the spontaneous pressure reactor of polytetrafluoroethylene (PTFE) inner sleeve at 100 DEG C aging 24h.Filter, drying at room temperature is spent the night, and finally extracts 24h by ethanol Soxhlet, after 80 DEG C of dry 24h of vacuum, obtains the hybrid mesoporous silica-base material of alkali ionic liquid, be denoted as Sample2SBA ?15.
Test by breakthrough curve, at 15vol%CO
2in (all the other are He), within the scope of 45-55 DEG C, to CO
2adsorbance be 14.28ml/g; At 8.08vol%SO
2in (all the other are He), within the scope of 45-55 DEG C, to SO
2adsorbance be 29.37ml/g.
Jie Kong Fen Shai ?the preparation method of functionalized ion liquid composite, step is as follows:
(1) under the protection of nitrogen by the 3-r-chloropropyl trimethoxyl silane of the methylimidazole of equimolar amounts and equimolar amounts stirring and refluxing 24h at 95 DEG C, dissolve with the methyl alcohol of trying one's best few afterwards, then be extracted with ethyl acetate, obtain lower floor's sample, Rotary Evaporators evaporate to dryness obtains siloxanes ionic liquid 1-(3-ethyoxyl silicon propyl group)-3-methylimidazole chloride;
(2) 4.0g P123 is dissolved in the solution of HCl of 125g1.9mol/L and stirs, be heated afterwards 40 DEG C, and add 8.22ml TEOS, hydrolysis 3h;
(3) then add 1.15g siloxanes ionic liquid 1 ?(3 ?ethyoxyl silicon propyl group) ?3 ?methylimidazole chloride, at 40 DEG C, stir 20h;
(4) proceeded to in the spontaneous pressure reactor of polytetrafluoroethylene (PTFE) inner sleeve at 100 DEG C aging 24h.Filter, drying at room temperature is spent the night, and finally extracts 24h by ethanol Soxhlet, after 80 DEG C of dry 24h of vacuum, be denoted as Sample3SBA ?15.
Test by breakthrough curve, at 15vol%CO
2in (all the other are He), within the scope of 45～55 DEG C, to CO
2adsorbance be 4.17ml/g; At 8.08vol%SO
2in (all the other are He), within the scope of 45～55 DEG C, to SO
2adsorbance be 13.78ml/g.
Claims (6)
1. a preparation method for mesoporous restricted function ionic liquid composite material, is characterized in that, comprises the steps:
(1) under nitrogen protection, the precursor A of equimolar amounts is reacted at 60～100 DEG C to 12 ?24h with precursor B, obtain functionalization silica alkane ionic liquid; Described precursor A is organotrialkoxysilane R ' Si (OR)
3, wherein R is methyl or ethyl, R ' is one or more the functionalized ion liquid building stone in following general formula:
Wherein R
1, R
2, R
3, R
4, R
5identical or different is hydrogen atom or functionalization alkyl chain; [PR1,2,3,4] are quaternary phosphonium cations, and structure is
functionalization group in functionalization alkyl chain is one or more in amido, ehter bond, hydramine;
The general formula of described precursor B be M ?X; Wherein M is alkyl substituent or the alkyl substituent with functionalization group, and its carbon chain lengths is that 1～4, X is Cl
?, Br
?, I
?, [BF
4]
?, [PF
6]
?, [AlCl
4]
?, [Al
2cl
7]
?, [CF
3cOO]
?, [CF
3sO
3]
?, [C
nh
2n+1cOO]
?, [Tf
2n]
?, [AA]
?, lactate or citrate; Wherein, described is one or more in amido, ehter bond, hydramine, guanidine class, acid amides, nitrogen heterocyclic ring with functionalization group in the alkyl substituent of functionalization group;
(2), by soluble in water and mix to the functionalization silica alkane ionic liquid of step (1) gained and silicon source and template, by in-situ sol-gel, when selected template is during for long alkane chain trimethyl ammonium cationic surfactant, adjustment pH value is 4～6; In the time that selected template is triblock polymer pluronic non-ionic surface active agent, adjusting to pH value is 8～10; At acidity or alkali condition, next step synthesizes the colloidal solution that contains mesoporous restricted function ionic liquid composite material; Wherein the mol ratio in functionalization silica alkane ionic liquid and silicon source is 1/10 ?1/2:1; The mol ratio of water and element silicon is 200～800:1; The mol ratio of element silicon and template is 8～60:1; Element silicon is element silicon sum in functionalization silica alkane ionic liquid and silicon source; Described silicon source is one or more in ethyl orthosilicate, positive silicic acid propyl ester and butyl silicate; Described template is long alkane chain trimethyl ammonium cationic surfactant or triblock polymer pluronic non-ionic surface active agent; Described long alkane chain trimethyl ammonium cationic surfactant is hexadecyltrimethylammonium chloride, DTAC or softex kw; Described triblock polymer pluronic non-ionic surface active agent be Ju Huan Yang Yi Wan ?Ju Huan Yang Bing Wan ?PEO triblock copolymer, structural formula is EO
xpO
70eO
x, wherein x=5～100;
(3) solution that step (2) gained is contained to mesoporous restricted function ionic liquid composite material under 50～200 DEG C of conditions, ageing 2～120h under normal pressure or spontaneous press strip part;
(4) step (3) gained solution suction filtration or centrifugation are obtained to mesoporous restricted function ionic liquid composite material;
(5) the isolated mesoporous restricted function ionic liquid composite material of step (4) is extracted or extracted by Soxhlet remove the presoma, the template that have neither part nor lot in reaction, then it is carried out to low-temperature vacuum drying, obtain composite.
2. preparation method according to claim 1, is characterized in that, described functionalization silica alkane ionic liquid is made up of zwitterion, and general structure is [(OR)
3siR ' M]
﹢x
?.
3. preparation method according to claim 1, is characterized in that: the described solvent that Soxhlet is extracted or extraction is used of step (5) is one or more in water, methyl alcohol, ethanol, propyl alcohol and butanols.
4. a mesoporous restricted function ionic liquid composite material, is characterized in that, this composite is made by preparation method described in claim 1～3 any one.
5. mesoporous restricted function ionic liquid composite material according to claim 4, it is characterized in that: the aperture of described mesoporous restricted function ionic liquid composite material is 1.5～30nm, composite be configured as MCM ?41, MCM ?48, SBA ?3, SBA ?8, SBA ?15 or SBA ?16 mesopore molecular sieve structures.
Described in claim 4 mesoporous restricted function ionic liquid composite material at sour gas CO
2or SO
2the application of trapping.
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| CN103706330B (en) * | 2013-12-20 | 2015-10-28 | 华南理工大学 | A kind of two siloxanes hybridization of ionic liquid mesoporous molecular sieve SBA-15 composite and preparation method thereof and application |
| CN103691400B (en) * | 2013-12-20 | 2015-09-16 | 华南理工大学 | Hybrid mesoporous MCM-48 composite of functionalized ion liquid and preparation method thereof and application |
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| CN112340749B (en) * | 2019-08-06 | 2023-10-13 | 中国石油化工股份有限公司 | Preparation method and application of organic functional group functionalized MCM molecular sieve |
| CN113651913B (en) * | 2021-09-10 | 2022-10-28 | 浙江巨化股份有限公司氟聚厂 | Preparation method of high-strength polytetrafluoroethylene resin |
| CN115849391A (en) * | 2022-12-20 | 2023-03-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of hydrophobic silica aerogel material |
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