CN102824895A - 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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- CN102824895A CN102824895A CN201210319866XA CN201210319866A CN102824895A CN 102824895 A CN102824895 A CN 102824895A CN 201210319866X A CN201210319866X A CN 201210319866XA CN 201210319866 A CN201210319866 A CN 201210319866A CN 102824895 A CN102824895 A CN 102824895A
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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 the immobilized field of ionic liquid, relate to CO
2Capture and store (CO
2Capture and storage, CCS), flue gas SO
2Sour gas such as remove and capture the field.
Background technology
The acid gas trapping of tradition adopts the wet absorption technology, and chemical absorption method is a kind of selection comparatively commonly used.Its essence is to utilize acidly in alkaline absorbent and the flue gas to contact concurrent biochemical reaction, form unsettled salt; And salt under certain conditions, and reverse decomposition is discharged sour gas, makes the absorbability of absorbent obtain regeneration, thereby sour gas is separated from flue gas and enrichment, is convenient to utilize or seal up for safekeeping, makes absorbent be able to recycle simultaneously.Absorbent commonly used has alkanolamine solution, strong base solution, hot liquor kalii caustici, lime slurry etc.Wherein, be applied to CO
2It is alcamines that capture is paid close attention to maximum, for having the alkaline aqueous solution of hydroxyl and amido.Because MEA (MEA) molecular weight is little, it is strong to absorb the sour gas ability, is the main technology that is studied and uses.This technology subject matter is CO in the cyclic process
2Absorption efficiency is not high; Owing to reasons such as oxidation, thermal degradation, generation irreversible reaction and evaporations, cause the absorbent absorbability to descend; Rich CO
2Catabolite causes system's corrosion in the absorption liquid (abbreviation rich solution); The regeneration energy consumption is big; Initial investment and operating cost are higher etc.; Seriously reduced the economy of collecting carbonic anhydride.Be applied to SO in the flue gas
2The most ripe method that captures 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 product equally be liquid or sludge; More hard to manage, equipment corrosion is serious, and washing back flue gas needs heat again; Energy consumption is high, and floor space is big, and investment and operating cost are high.Problems such as system complex, equipment is huge, water consumption is big, one-time investment height.
Though and molecular sieve dry method absorbing process can overcome above-mentioned shortcoming, owing to mainly be to utilize 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 that captures is after flue gas desulfur device (post-FGD), and its typical flue-gas temperature is 45-55 ℃, is unfavorable for using separately molecular sieve to carry out dry method absorption.(Energy & Fuels 2007,21 3555-3559) has reported monoethanolamine (MEA) modification 13X molecular sieve and has been used for CO P.D.Jadhav etc.
2Absorption, MEA is loaded into the 13X duct through solution absorption.At 15vol%CO
2In, CO during 75 ℃ in this adsorbent
2Adsorbance is 10.1ml/g, but has only 8.1ml/g 50 ℃ the time.The little molecule MEA of this method is loaded into molecular sieve pore passage through simple absorption, certainly exists the problem that MEA runs off in the use, also has that MEA is volatile, the not high shortcoming of heat endurance simultaneously.
In recent years, as a kind of novel green solvent, ionic liquid (IL) does not almost have vapour pressure, thereby uses it for gas absorption separation and do not have the problem of polluting gas phase.In addition, utilize the characteristics of ionic liquid zwitterion Adjustable structure to develop functionalized ion liquid with specific function.Alkali ionic liquid is the one type of novel ion liquid that occurs recently; This type ionic liquid not only has the physico-chemical property of conventional ion liquid, and (vapour pressure, physics and chemical property are stable as almost not having, structure and performance are adjustable; Be fit to make to separate solvent or constitute reaction-separation coupling new system); And, therefore be expected to as one type of novel sour gas (CO because it presents alkalescence
2, SO
2, NO
x) selective absorber.Research about alkali ionic liquid absorption sour gas at present has a lot of reports; And show good sour gas absorption property; But because its process using single ionic liquid; Still belong to the Gas-Liquid Absorption process of wet method, thereby exist in the adsorption process liquid viscosity to uprush, shortcomings such as absorption, regenerative process method difficulty and regeneration technology flow process complicacy.Therefore, can and have both the novel process of the advantage that is easy to industrialization and regeneration of dry method, will have good application prospects and can be industry and remove sour gas another kind of approach is provided if can develop the high-absorbable that promptly has wet processing.
Ionic liquid is immobilized to be the frontier about ionic liquid research; Purpose is through immobilized on solid catalyst or inert solid ionic liquid, reaches raising system catalytic performance, reduces the ionic liquid consumption, is convenient to the purpose that product separates and catalyst utilizes again.Molecular sieve is a series of by TO
4The crystallized silicon aluminate porous material that tetrahedron (T=Si/Al) is formed, aspects such as it is applied in catalysis widely, adsorbs and separates, ion-exchange, medicament slow release.And silicon-based mesoporous molecular sieve wherein is as a kind of new-type functional material, because of its particular structure receives much concern.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 chemical modification, expand the hot issue that its range of application becomes mesoporous materials field research.Application study to mesopore molecular sieve is main with MCM-41 and modified product thereof mainly at present; Utilize the surface hydroxyl of some on the inwall of MCM-41 hole to make some material and siloxy reaction; Accomplishing the duct inner surface modifies or functionalization. and like surface silicon alkyl change surface polarity, introducing contains the organic compound of functional groups such as 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, the open and report of the immobilized patent with molecular sieve and application thereof of ionic liquid is arranged successively also wherein.
In enclose the meso-porous molecular sieve material that patent CN101773852A discloses load imidazoles acetate ionic liquid; It utilizes the aperture is the mesopore molecular sieve of 5～20nm; And the mesopore molecular sieve surface carried out silane-functionalized; The mesopore molecular sieve that again imidazoles acetate ionic liquid and finishing was carried out after hydride modified connects the skill reaction, thereby will be ionic liquid loaded surperficial with molecular sieve pore passage, and with this composite as catalyst applications in the preparing vinyl acetate using acetylene method process.
U.S.A encloses patent US7943543B1 and discloses the immobilized and MCM-41 type molecular screen membrane surface of mode of glyoxaline ion liquid being adopted infusion process coating load, is used for natural gas CO
2Remove.
Though the method for above-mentioned ionic liquid loadedization can be immobilized in the mesopore molecular sieve surface with ionic liquid; But shortcoming is to make ionic liquid to load on surface, the inner duct of molecular sieve uniformly; Uneven ionic liquid distributes also influences the inner pore passage structure of molecular sieve, influences mass transport process; Adopt the way of grafting, though there is chemical bonding on ionic liquid and molecular sieve pore passage surface, this process need carries out the preparatory functionalization of multistep to molecular sieve; Too much pre-treatment process has destruction to duct, molecular sieve inside, in addition; The preparation of employing dipping method then inevitably is difficult to guarantee ion liquid stability, makes in the subsequent applications process; Ionic liquid runs off easily, thereby influences the service life of composite.
For solving the immobilized defective in mesopore molecular sieve of above-mentioned ionic liquid; The present invention adopts the synthetic method of original position; Make functionalized ion liquid directly with the silicon source reaction of synthesis of molecular sieve, the direct limited functionalized ion liquid mesopore molecular sieve composite that synthesizes, this method has that step is few, ionic liquid is uniformly dispersed; Be difficult for running off stability and the excellent advantage of regenerability.
Summary of the invention
The objective of the invention is to overcome the defective that prior art exists, a kind of dry process is provided, absorb controlled with resolving, can adsorb mesoporous restricted function ionic liquid composite material of sour gas and preparation method thereof in higher flue-gas temperature scope.
The present invention also provides and uses mesoporous restricted function ionic liquid composite material at sour gas CO
2And SO
2The application of capture aspect.
The present invention hands over and utilizes the original position sol-gal process to functionalization silica alkane ionic liquid; The synthetic hybrid mesoporous silicon based composite material of functionalized ion liquid that contains of one-step method; Thereby synthesize limitedization of ionic liquid direct in-situ in the mesopore molecular sieve duct, make a kind of functionalized ion liquid mesopore molecular sieve composite that contains.This material is as a kind of Solid-state Chemistry adsorbent; Its except that the excellent absorption property that possesses dry method absorption and functionalized ion liquid etc. the advantage, can also under the higher temperatures condition, (typically the post-FGD flue-gas temperature is 45～55 ℃) rapidly and efficiently remove acidic gas in flue gas; The method can also be eliminated single use ionic liquid as adsorbent and intrinsic viscosity is uprushed, and absorption, desorption rate wait problem slowly.
The object of the invention is realized through following technical scheme:
A kind of preparation method of mesoporous restricted function ionic liquid composite material comprises the steps:
(1) under nitrogen protection, the precursor A and the precursor B of equimolar amounts are reacted 12-24h down at 60～100 ℃, obtain functionalization silica alkane ionic liquid; Said 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 the following general formula:
R wherein
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 does
Functionalization group in the functionalization alkyl chain is one or more in amido, ehter bond, the hydramine;
The general formula of said precursor B is M-X; Wherein M is alkyl substituent or the alkyl substituent that has the functionalization group, and its carbon chain lengths is 1～4, and 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, the functionalization group is in amido, ehter bond, hydramine, guanidine class, acid amides, the nitrogen heterocyclic ring one or more in the said alkyl substituent that has a functionalization group;
(2) the functionalization silica alkane ionic liquid of step (1) gained and silicon source and masterplate agent is soluble in water and mix, through the original position sol-gal process, when selected template during for long alkane chain trimethyl ammonium cationic surfactant, adjusting the pH value is 4～6; When selected template was triblock polymer pluronic non-ionic surface active agent, adjusting to the pH value was 8～10; Next step synthesizes the colloidal solution that contains mesoporous restricted function ionic liquid composite material at acidity or alkali condition; 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 an element silicon sum in functionalization silica alkane ionic liquid and the silicon source; Said silicon source is one or more in ethyl orthosilicate, positive silicic acid propyl ester and the butyl silicate; Said masterplate agent is long alkane chain trimethyl ammonium cationic surfactant, two sections polymer non-ionic surface active agents or triblock polymer pluronic non-ionic surface active agent; Said long alkane chain trimethyl ammonium cationic surfactant is hexadecyltrimethylammonium chloride, DTAC, softex kw or NaOH; Said triblock polymer pluronic non-ionic surface active agent is PEO-PPOX-PEO triblock copolymer, and structural formula is EO
xPO
70EO
x, x=5～100 wherein;
(3) solution that step 2 gained is contained mesoporous restricted function ionic liquid composite material under 50～200 ℃ of conditions, ageing 2～120h under normal pressure or spontaneous press strip spare;
(4) step 3 gained solution suction filtration or centrifugation are obtained mesoporous restricted function ionic liquid composite material;
(5) the isolated mesoporous restricted function ionic liquid composite material of step 4 is removed presoma, the masterplate agent that has neither part nor lot in reaction through Suo Shi extraction or extraction, then it is carried out low-temperature vacuum drying, get composite.
Further, said functionalization silica alkane ionic liquid zwitterion is formed, and general structure is [(OR)
3SiR ' M]
+X
-
It is in water, methyl alcohol, ethanol, propyl alcohol and the butanols one or more that the described Suo Shi of step (5) extracts or extract employed solvent.
A kind of mesopore molecular sieve-functionalized ion liquid composite, this composite are by above-mentioned any method preparation.
The aperture of said mesopore molecular sieve-functionalized ion liquid composite is 1.5～30nm, and composite is configured as MCM-41, MCM-48, SBA-3, SBA-8, SBA-15 or SBA-16 mesopore molecular sieve structure.
Said mesopore molecular sieve-functionalized ion liquid composite is at sour gas CO
2Or SO
2The application that captures.
The present invention compared with prior art has following advantage:
(1) the prepared composite of the inventive method is owing to have the structural advantage of functionalized ion liquid and mesopore molecular sieve concurrently; Absorption can be brought into play the collaborative advantage function of 2 kinds of functional materials for sour gas, and its energy of adsorption to sour gas is realized preferable effect in higher flue-gas temperature scope.Dry process, absorption and resolving controlled
(2) the present invention is a 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 the framework of molecular sieve through chemical bond, and therefore the little losing issue that exists has also kept the high characteristics of ionic liquid heat endurance simultaneously, improves recycling performance.
(4) can increase the adsorbance of ionic liquid through structure and the quantity that produces the functional group of electrostatic interaction with sour gas on the regulation and control ionic liquid, thereby can effectively realize absorbing controlled with resolving sour gas.
Description of drawings
Fig. 1 is the infrared spectrum of embodiment 1Sample1MCM-41.
Fig. 2 is the XRD figure of embodiment 1Sample1MCM-41.
Fig. 3 is the infrared spectrum of embodiment 3Sample1SBA-15.
Fig. 4 is the XRD figure of embodiment 3Sample1SBA-15.
The specific embodiment
For further understanding the present invention, below in conjunction with accompanying drawing and embodiment the present invention is described further, but embodiment of the present invention is limited to this for a short time.
The preparation method of a kind of mesopore molecular sieve-functionalized ion liquid composite, step is following:
(1) under nitrogen protection; The 1-of equimolar amounts (3-ethoxy silane propyl group)-4, the two hydrogen imidazoles of 5-and 2-bromine ethylamine hydrobromide stirring and refluxing 24h in ethanol evaporate solvent with the rotary evaporation instrument; Add benzinum (boiling range 30-60) layering then; Obtain lower floor's sample, the Rotary Evaporators evaporate to dryness promptly 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 following:
(2) under the room temperature, 1.0g CTAB is dissolved in (243g H in the aqueous solution of NaOH
2O and 0.28g NaOH), stir to clarify, add ethyl orthosilicate and 1.05g functionalization silica alkane ionic liquid 1-(3-ethoxy silane the propyl group)-3-ethylamine hydrobromide-4 of 4.5ml then slowly, the two hydrogen imidazolium bromides of 5-stir 2h in room temperature.
(3) step (2) products therefrom is transferred in the hydrothermal reaction kettle,, is placed on cool to room temperature in the air afterwards in 100 ℃ of following ageing 24h, with Buchner funnel filter, spend deionised water, drying at room temperature is spent the night and is obtained white powder afterwards.
(4) white powder with step (3) gained carries out demoulding processing, in the ethanol of the 150ml that is dissolved with 1g ammonium nitrate, stirs 30mins in 60 ℃ according to the 1.5g sample dispersion.Repeat aforesaid operations 3 times to remove template CTAB as far as possible, filter, obtain white powder behind 80 ℃ of dry 24h of vacuum, note is made Sample1MCM-41.
As shown in Figure 1, Sample1MCM-41 is carried out infrared (IR) characterization result show, the vibration peak of amido in the tangible functionalization silica alkane ionic liquid is arranged in the infrared spectrum of Sample1MCM-41, be specially 2840cm
-1And 2920cm
-1And the vibration 1631cm of the two keys of C=C above the imidazole ring
-1Characteristic peak, explain and contain the alkaline functional ionic liquid among the Sample1MCM-41.
As shown in Figure 2, Sample1MCM-41 is carried out small angle X-ray diffraction characterize its main diffraction maximum (100); And the weak diffraction maximum of (110) and (200) crystal face is also high-visible; Explain that Sample1MCM-41 is the 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 N
2Adsorption-desorption characterizes, and its specific area reaches 760m
2.g
-1, and its average pore size is 3.3nm, therefore pore diameter range obtains mesoporous limited alkaline functional ionic liquid composite material within mesoporous scope.
Breakthrough experiment is promptly in adsorption process, and adsorbed gas is through adsorption bed, and exit gas concentration reaches 5% o'clock of inlet gas concentration and is made as breakthrough point, reaches at 100% o'clock and is considered to adsorb saturated.From the time that begins to be adsorbed onto between the breakthrough point be time of break-through, be saturation time from beginning to be adsorbed onto the time of absorption between saturated, the adsorbance in the time of break-through is counted and is penetrated adsorbance.Through breakthrough experiment, at 15vol%CO
2In, in 45～55 ℃ of scopes, to CO
2Adsorbance be 6.32ml/g; At 8.08vol%SO
2In, in 45～55 ℃ of scopes, to SO
2Adsorbance be 12.53ml/g.
(1) preparation method of a kind of mesopore molecular sieve-functionalized ion liquid composite, step is following:
Under nitrogen protection; The 1-of equimolar amounts (3-ethoxy silane propyl group)-4, the two hydrogen imidazoles of 5-and 3-propantheline bromide hydrobromide stirring and refluxing 24h in ethanol evaporate solvent with the rotary evaporation instrument; Add benzinum (30～60) layering then; Obtain lower floor's sample, the Rotary Evaporators evaporate to dryness promptly 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 the room temperature, 1.0g CTAB is dissolved in (243g H in the aqueous solution of NaOH
2O and 0.28g NaOH), stir to clarify, add ethyl orthosilicate and 1.08g 1-(3-ethoxy silane the propyl group)-3-propylamine hydrobromate-4 of 4.5ml then slowly, the two hydrogen imidazolium bromides of 5-stir 2h in room temperature;
(3) step (2) products therefrom is transferred in the hydrothermal reaction kettle,, is placed on cool to room temperature in the air afterwards in 100 ℃ of following ageing 24h, with Buchner funnel filter, spend deionised water, drying at room temperature is spent the night and is obtained white powder afterwards.
(4) step (3) gained white powder being carried out the demoulding handles; According to the 1.5g sample dispersion in the ethanol of the 150ml that is dissolved with 1g ammonium nitrate; Stir 30min. in 60 ℃ and repeat aforesaid operations 3 times to remove template CTAB as far as possible; Filter, obtain product behind 80 ℃ of dry 24h of vacuum, note is made Sample2MCM-41;
Characterizing method with instance 1 is consistent, and material is characterized, and explains that the material that obtains is the hybrid mesoporous silica-base material of alkali ionic liquid.Through the breakthrough curve experiment, at 15vol%CO
2In, in 45～55 ℃ of scopes, to CO
2Adsorbance be 12.73ml/g; At 8.08vol%SO
2In (all the other are He), in 45～55 ℃ of scopes, to SO
2Adsorbance be 16.57ml/g.
The preparation method of a kind of mesopore molecular sieve-functionalized ion liquid composite, step is following:
(1) under protection of nitrogen gas with the methylimidazole of equimolar amounts and 3-chloropropyl triethoxysilane in 95 ℃ of following stirring and refluxing 24h; Afterwards with the methyl alcohol dissolving of trying one's best few; Use ethyl acetate extraction then; Obtain lower floor's sample, the Rotary Evaporators evaporate to dryness promptly obtains siloxanes ionic liquid 1-(3-ethyoxyl silicon propyl group)-3-methylimidazole chloride;
(2) under the room temperature, 1.0g CTAB is dissolved in (243g H in the aqueous solution of NaOH
2O and 0.28g NaOH), stir to clarify, add ethyl orthosilicate and 0.71g 1-(3-ethyoxyl silicon the propyl group)-3-methylimidazole chloride of 4.5ml then slowly, in room temperature, stir 2h.
(3) step (2) products therefrom is transferred in the hydrothermal reaction kettle,, is placed on cool to room temperature in the air afterwards in 100 ℃ of following ageing 24h, with Buchner funnel filter, spend deionised water, drying at room temperature is spent the night and is obtained white powder afterwards.
(4) step (3) gained white powder being carried out the demoulding handles; According to the 1.5g sample dispersion in the ethanol of the 150ml that is dissolved with 1g ammonium nitrate; Stir 30min. in 60 ℃ and repeat aforesaid operations 3 times to remove template CTAB as far as possible; Filter, obtain product behind 80 ℃ of dry 24h of vacuum, note is made Sample3MCM-41;
Characterizing method with instance 1 is consistent, and material is characterized.
As shown in Figure 3, Sample1SBA-15 is carried out infrared (IR) characterization result show, the vibration peak of amido in the weak functionalization silica alkane ionic liquid is arranged in the infrared spectrum of Sample1SBA-15, be specially 2840cm
-1And the vibration 1620cm of the two keys of C=C above the imidazole ring
-1Characteristic peak and two key chattering 1450cm of C=N above the imidazole ring
-1Characteristic peak, explain and contain the alkaline functional ionic liquid among the Sample1SBA-15.
As shown in Figure 4; Sample1SBA-15 is carried out small angle X-ray diffraction characterize, its main diffraction maximum (100), and the weak diffraction maximum of (110) and (200) crystal face is also high-visible; Explain that Sample1MCM-41 is the MCM-41 molecular sieve; Its degree of internal order is higher, is the close heap type of six sides structure, therefore obtains mesoporous limited alkaline functional ionic liquid composite material.
Through the breakthrough curve experiment, at 15vol%CO
2In (all the other are He), in 45～55 ℃ of scopes, to CO
2Adsorbance be 6.41ml/g; At 8.08vol%SO
2In (all the other are He), in 45～55 ℃ of scopes, to SO
2Adsorbance be 10.03ml/g.
The preparation method of a kind of mesopore molecular sieve-functionalized ion liquid composite, step is following:
(1) under nitrogen protection; The 1-of equimolar amounts (3-ethoxy silane propyl group)-4, the two hydrogen imidazoles of 5-and 3-propantheline bromide hydrobromide stirring and refluxing 24h in ethanol evaporate solvent with the rotary evaporation instrument; Add benzinum (30～60) layering then; Obtain lower floor's sample, the Rotary Evaporators evaporate to dryness promptly 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 125g 1.9mol/L stirs, be heated 40 ℃ afterwards, and add 8.22ml TEOS, hydrolysis 3h.
(3) add 2.02g functionalization silica alkane ionic liquid 1-(3-ethoxy silane propyl group)-3-propylamine hydrobromate-4 then, the two hydrogen imidazolium bromides of 5-stir 20h down at 40 ℃.
(4) it is changed over to have in the spontaneous pressure agitated reactor that overlaps in the polytetrafluoroethylene (PTFE) in 100 ℃ of down aging 120h.Filter, drying at room temperature is spent the night, and extracts 24h with ethanol Suo Shi at last, behind 80 ℃ of dry 24h of vacuum, promptly obtains the hybrid mesoporous silica-base material of alkali ionic liquid, and note is made Sample1SBA-15;
Sample1SBA-15 characterizes to material, records through breakthrough experiment simultaneously, and Sample1SBA-15 is at 15vol% (all the other are He) CO
2In, in 45～55 ℃ of scopes, to CO
2Adsorbance be 13.89ml/g; At 8.08vol%SO
2In, in 45～55 ℃ of scopes, to SO
2Adsorbance be 24.37ml/g.
The preparation method of a kind of mesopore molecular sieve-functionalized ion liquid composite, step is following:
(1) under nitrogen protection; The 1-of equimolar amounts (3-ethoxy silane propyl group)-4, the two hydrogen imidazoles of 5-and 2-bromine ethylamine hydrobromide stirring and refluxing 24h in ethanol evaporate solvent with the rotary evaporation instrument; Add benzinum (30～60) layering then; Obtain lower floor's sample, the Rotary Evaporators evaporate to dryness promptly 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 125g 1.9mol/L stirs, be heated 40 ℃ afterwards, and add 8.22ml TEOS, hydrolysis 3h.
(3) add 1.96g functionalization silica alkane ionic liquid 1-(3-ethoxy silane propyl group)-3-ethylamine hydrobromide-4 then, the two hydrogen imidazolium bromides of 5-stir 20h down at 40 ℃.
(4) it is changed over to have in the spontaneous pressure agitated reactor that overlaps in the polytetrafluoroethylene (PTFE) in 100 ℃ of down aging 24h.Filter, drying at room temperature is spent the night, and extracts 24h with ethanol Suo Shi at last, behind 80 ℃ of dry 24h of vacuum, promptly obtains the hybrid mesoporous silica-base material of alkali ionic liquid, and note is made Sample2SBA-15.
Through the breakthrough curve experiment, at 15vol%CO
2In (all the other are He), in the 45-55 ℃ of scope, to CO
2Adsorbance be 14.28ml/g; At 8.08vol%SO
2In (all the other are He), in the 45-55 ℃ of scope, to SO
2Adsorbance be 29.37ml/g.
Embodiment 6
The preparation method of a kind of mesopore molecular sieve-functionalized ion liquid composite, step is following:
(1) under protection of nitrogen gas with the 3-r-chloropropyl trimethoxyl silane of the methylimidazole of equimolar amounts and equimolar amounts in 95 ℃ of following stirring and refluxing 24h; Afterwards with the methyl alcohol dissolving of trying one's best few; Use ethyl acetate extraction then; Obtain lower floor's sample, the Rotary Evaporators evaporate to dryness promptly 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 125g 1.9mol/L stirs, be heated 40 ℃ afterwards, and add 8.22ml TEOS, hydrolysis 3h;
(3) add 1.15g siloxanes ionic liquid 1-(3-ethyoxyl silicon propyl group)-3-methylimidazole chloride then, stir 20h down at 40 ℃;
(4) it is changed over to have in the spontaneous pressure agitated reactor that overlaps in the polytetrafluoroethylene (PTFE) in 100 ℃ of down aging 24h.Filter, drying at room temperature is spent the night, and extracts 24h with ethanol Suo Shi at last, and behind 80 ℃ of dry 24h of vacuum, note is made Sample3SBA-15.
Through the breakthrough curve experiment, at 15vol%CO
2In (all the other are He), in 45～55 ℃ of scopes, to CO
2Adsorbance be 4.17ml/g; At 8.08vol%SO
2In (all the other are He), in 45～55 ℃ of scopes, to SO
2Adsorbance be 13.78ml/g.
Claims (6)
1. the preparation method of a mesoporous restricted function ionic liquid composite material is characterized in that, comprises the steps:
(1) under nitrogen protection, the precursor A and the precursor B of equimolar amounts are reacted 12-24h down at 60～100 ℃, obtain functionalization silica alkane ionic liquid; Said 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 the following general formula:
R wherein
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 does
Functionalization group in the functionalization alkyl chain is one or more in amido, ehter bond, the hydramine;
The general formula of said precursor B is M-X; Wherein M is alkyl substituent or the alkyl substituent that has the functionalization group, and its carbon chain lengths is 1～4, and X is Cl
-, Br
-, I
-, [BF
4]
-, [PF
6]
-, [AlCl
4]
-, [Al
2Cl
7]
-, [CF
3COO]
-, [CF
3SO
3]
-, [CnH
2n+1COO]
-, [Tf
2N]
-, [AA]
-, lactate or citrate; Wherein, the functionalization group is in amido, ehter bond, hydramine, guanidine class, acid amides, the nitrogen heterocyclic ring one or more in the said alkyl substituent that has a functionalization group;
(2) the functionalization silica alkane ionic liquid of step (1) gained and silicon source and masterplate agent is soluble in water and mix, through the original position sol-gal process, when selected template during for long alkane chain trimethyl ammonium cationic surfactant, adjusting the pH value is 4～6; When selected template was triblock polymer pluronic non-ionic surface active agent, adjusting to the pH value was 8～10; Next step synthesizes the colloidal solution that contains mesoporous restricted function ionic liquid composite material at acidity or alkali condition; 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 an element silicon sum in functionalization silica alkane ionic liquid and the silicon source; Said silicon source is one or more in ethyl orthosilicate, positive silicic acid propyl ester and the butyl silicate; Said masterplate agent is long alkane chain trimethyl ammonium cationic surfactant, two sections polymer non-ionic surface active agents or triblock polymer pluronic non-ionic surface active agent; Said long alkane chain trimethyl ammonium cationic surfactant is hexadecyltrimethylammonium chloride, DTAC, softex kw or NaOH; Said triblock polymer pluronic non-ionic surface active agent is PEO-PPOX-PEO triblock copolymer, and structural formula is EO
xPO
70EO
x, x=5～100 wherein;
(3) solution that step 2 gained is contained mesoporous restricted function ionic liquid composite material under 50～200 ℃ of conditions, ageing 2～120h under normal pressure or spontaneous press strip spare;
(4) step 3 gained solution suction filtration or centrifugation are obtained mesoporous restricted function ionic liquid composite material;
(5) the isolated mesoporous restricted function ionic liquid composite material of step 4 is removed presoma, the masterplate agent that has neither part nor lot in reaction through Suo Shi extraction or extraction, then it is carried out low-temperature vacuum drying, get composite.
2. preparation method according to claim 1 is characterized in that, said functionalization silica alkane ionic liquid zwitterion is formed, and general structure is [(OR)
3SiR ' M]
+X
-
3. preparation method according to claim 1 is characterized in that: it is in water, methyl alcohol, ethanol, propyl alcohol and the butanols one or more that the described Suo Shi of step (5) extracts or extract employed solvent.
4. mesopore molecular sieve-functionalized ion liquid composite is characterized in that, this composite is by any method preparation of claim 1～3.
5. according to the said mesopore molecular sieve of claim 4-functionalized ion liquid composite; It is characterized in that: the aperture of said mesopore molecular sieve-functionalized ion liquid composite is 1.5～30nm, and composite is configured as MCM-41, MCM-48, SBA-3, SBA-8, SBA-15 or SBA-16 mesopore molecular sieve structure.
6. the said mesopore molecular sieve of claim 4-functionalized ion liquid composite is at sour gas CO
2Or SO
2The application that captures.
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