CN109174008A - The adsorbent and the preparation method and application thereof of solid-loaded ionic-liquid in metal organic framework - Google Patents
The adsorbent and the preparation method and application thereof of solid-loaded ionic-liquid in metal organic framework Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The present invention provides a kind of adsorbent and its preparation method and application of solid-loaded ionic-liquid in metal organic framework, the adsorbent is immobilized acidic ion liquid inside the duct of metallic framework material, wherein, the metallic framework material is MIL-53 (Cr), and acidic ion liquid is [Bmim] [PF6].It will be in 1- butyl -3- methylimidazole hexafluorophosphate ionic liquid supported to the cavity of MIL-53 (Cr) by the post-synthesis of chemical anchoring, MIL-53 (Cr)@[Bmim] [PF6] adsorbent after solid-loaded ionic-liquid is as acid centre, it plays a role to weakly alkaline thiophene, composite structure will be made more stable inside the duct ionic liquid supported to MIL-53 (Cr), it is larger to overcome ionic liquid viscosity, it is difficult to the disadvantages of recycling, realize increasing substantially for absorption desulfurization amount, and there is good reusability.
Description
Technical field
The present invention relates to a kind of adsorbent and the preparation method and application thereof, more particularly to one kind are solid in metal organic framework
Adsorbent of borne ionic liquid and the preparation method and application thereof.
Background technique
Metal-organic framework materials, English name Metal-organic frameworks, abbreviation MOFs are a kind of new
The porous material of type, crystal structure have regular octahedron type, cubic type etc..MOFs has porosity, large specific surface area, skeleton
The advantages that scale is variable and can make chemical modification, structure-rich according to target call, in adsorption seperation of gas, catalysis
The fields such as agent, magnetic material and optical material have huge potential using value.Specific to absorption desulfuration field, although MOFs
Adsorbing and removing research of the material for aromatic series sulphur compound in fuel oil is started late.But the huge specific surface area of MOFs material,
The adjustability of hole is big and high porosity, structure rich and exposed metallic atom the advantages that, make it in absorption desulfurization side
The application in face gets more and more people's extensive concerning.In 2008, when Rodriguez et al. assesses the adsorption capacity of MOFs material, hair
Existing MOFs material adsorption capacity compared with the NaY zeolite of benchmark more preferable (Rodriguez.J A, Liu P, Takahashi Y, et
al.Desulfurization of thiophene on Au/TiC(001):Au-C interactions and charge
polarization[J].Am.Chem.Soc.2009,131:8595-8602.).Contain many places gold in the structure of MIL-53 (Cr)
Belong to position, provides efficient adsorption site for adsorbing and removing aromatic series sulphur compound, improve adsorptive selectivity.
Ionic liquid at room temperature (rILs) is the organic salt with low melting point and extremely low vapour pressure.In general, rIL is by organic miaow
Azoles cation and inorganic anion composition.So far, due to its unique physicochemical properties, rILs has been widely recognized as
The substitution solvent of various organic syntheses, and received more and more attention due to its various catalysis is reacted.In spite of these advantages,
Ionic liquid hinders its industrial application there is also the disadvantages of at high cost, viscosity is high, and purifying products are difficult, recycling.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide a kind of immobilized ionic liquid at room temperature of metal-organic framework materials
Compound adsorbent, second is designed to provide the preparation method of the adsorbent, and third is designed to provide the adsorbent de-
Application in sulphur absorption.
Technical solution: a kind of adsorbent of the solid-loaded ionic-liquid in metal organic framework, the adsorbent are metal bone
Immobilized acidic ion liquid inside the duct of frame material, wherein the metallic framework material is MIL-53 (Cr), acidic ionic liquid
Body is [Bmim] [PF6]。
Wherein, above-mentioned acidic ion liquid [Bmim] [PF6] be represented by 1- butyl -3- methylimidazole hexafluorophosphate from
Sub- liquid.
Preferably, the preparation method of above-mentioned metal-organic framework materials MIL-53 (Cr) is described in Serre, C.；
Millange, F.；Thouvenot,C.；Nogues,M.；Marsolier,G.；Louer,D.；Ferey,G.,Very large
breathing effect in the first nanoporous chromium(III)-based solids:MIL-53or
Cr-III(OH)center dot{O2C-C6H4-CO2}center dot{HO2C-C6H4-CO2H}(x)center dot
H2Oy.Journal of the American Chemical Society 2002,124(45),13519；Above-mentioned acid ion
Liquid [Bmim] [PF6] preparation method of 1- butyl -3- methylimidazole hexafluorophosphate is described in Jiang, Y.；Xia,H.；
Yu,J.；Chen,G.；Liu,H., Hydrophobic ionic liquids-assisted polymer recovery
during penicillin extraction in aqueous two-phase system.Chemical Engineering
Journal 2009,147(1),22-26。
Preferably, above-mentioned MIL-53 (Cr) by following methods but is not limited to be made using following methods: 20gCr (NO3)3·
9H2The H of O, 16.62g2BDC measures 252ml deionized water, mixes closed stirring 1h, and 8 drop hydrofluoric acid are added dropwise, are stirred for 1h,
Enter 500ml ptfe autoclave, reacts 72h at 220 DEG C.It after crystallization, is cooled to room temperature, vacuum pump filters, and uses
Deionization is washed four times, then is washed twice with DMF, is filtered, and by sample, 2h is dried at 100 DEG C.The pure sample grinding-in that will be obtained
It saves.
Preferably, above-mentioned 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid [Bmim] [PF6] by following methods but
It is not limited to be made using following methods: weighing 21.10gN- methylimidazole in 500ml three-necked flask, under nitrogen protection, 70
DEG C oil bath is simultaneously stirred, and 34.25g bromobutane is slowly added dropwise with constant pressure funnel, back flow reaction 30h generates [Bmim] Br.It will
[Bmim] Br is dried under vacuum to constant weight at 70 DEG C, obtains intermediate [Bmim] Br after purification.36.81g KPF is weighed again6, molten
In distilled water.Then 42.21g [Bmim] Br is weighed in single-necked flask, and KPF is slowly added dropwise with constant pressure funnel6Solution,
Stirring at normal temperature 10h.Lower layer's light yellow clear thick liquid is taken, is repeatedly washed with distilled water, [Bmim] after purification is obtained
[PF6], it is dried under vacuum to constant weight in 70 DEG C, obtains required final product.
Preferably, above-mentioned immobilized acidic ion liquid [Bmim] [PF6] mass percent that accounts for the adsorbent is
8~40%；Remaining part is metal organic framework MIL-53 (Cr).
Preferably, immobilized acidic ion liquid [Bmim] [PF6] mass percent be 8~12%.It chooses best
The range of mass ratio, so that the absorption desulfurization amount of the composite material is maximum.
The preparation method of the adsorbent of the solid-loaded ionic-liquid in metal organic framework, comprising the following steps:
(1) by [Bmim] [PF6] it is dissolved in CH2Cl2Obtain CH2Cl2@[Bmim][PF6] solution；In proportion by MIL-53 (Cr)
Solution is added and obtains mixed system, mixed system is reacted in a heated condition after stirring and obtains reactant；
(2) reactant is cooling, stir to get solid sample, solid sample is dry, obtain described in the organic bone of metal
The adsorbent of solid-loaded ionic-liquid in frame.
Preferably, by [Bmim] [PF described in step (1)6] it is dissolved in CH2Cl2For sealing dissolution.
Preferably, above-mentioned by [Bmim] [PF6] it is dissolved in CH2Cl2For every gram of [Bmim] [PF6] it is dissolved in the CH of 0.2L or more2Cl2
Solution；It is advisable so that ionic liquid to be completely dissolved.
Preferably, above-mentioned sealing is dissolved as ultrasonic dissolution 30 minutes, and sealing is in order to avoid CH2Cl2It volatilizees as solvent,
Ultrasound is to obtain at normal temperature and disperse more uniform CH2Cl2@[Bmim][PF6] solution.
Preferably, above-mentioned ultrasound is primary every 15min ultrasound, every time ultrasound ten minutes, in total ultrasound three times,
Preferably, stirring described in step (1) is to be stirred by ultrasonic to uniformly mixed.
Preferably, above-mentioned ultrasonic agitation is closed stirring 2h, then primary every 30min ultrasound, each ultrasound 30min, always
Total ultrasound is three times.
Preferably, the operation of above-mentioned all " ultrasounds " can use existing ultrasonic cleaning device, such as ultrasonic cleaning machine.
Further, reaction is 24~48h of reaction at 95~105 DEG C under heating condition described in step (1).
Preferably, above-mentioned reaction carries out in ptfe autoclave liner.
Preferably, it is cooled to be cooled to room temperature described in step (2), i.e., 20~25 DEG C.
Preferably, stirring described in step (2) is opening, stirs at 45~50 DEG C of oil bath, can accelerate CH2Cl2Wave
Hair, to CH in system2Cl2Until being evaporated completely.
Further, dry to be dried in vacuo 4~6h at 80~100 DEG C described in step (2), vacuum drying heating makes
Obtain the CH in mixture2Cl2It completely removes.
Preferably, it is sealed after the adsorbent of solid-loaded ionic-liquid in metal organic framework described in obtaining.
Application of the adsorbent of the above-mentioned solid-loaded ionic-liquid in metal organic framework in desulfurization absorption.
After metal organic framework solid-loaded ionic-liquid, based on interacting between ionic liquid and alkalescent substance thiophene,
Ionic liquid is the advantageous adsorption site of thiophene, to realize that desulfurization is adsorbed.
Preferably, in application of the adsorbent of the above-mentioned solid-loaded ionic-liquid in metal organic framework in desulfurization is adsorbed,
The adsorbent of the solid-loaded ionic-liquid in metal organic framework is the adsorbent recycled.
Further, above-mentioned recycling are as follows: organic in metal to what is isolated with nitrogen at 200~220 DEG C of heating
The adsorbent of solid-loaded ionic-liquid carries out 4~6h of purging in skeleton.
Preferably, it is above-mentioned be heated to be placed in stainless steel heater, temperature is excessively high or can then destroy adsorbent more than 220 DEG C
Structure.
The utility model has the advantages that the present invention is by the post-synthesis of chemical anchoring by 1- butyl -3- methylimidazole hexafluorophosphate
In ionic liquid supported to the cavity of MIL-53 (Cr), the new adsorbent prepared can have the Common advantages of the two, this hair
MIL-53 (Cr)@[Bmim] [PF6] adsorbent after bright middle solid-loaded ionic-liquid plays weakly alkaline thiophene as acid centre
To certain effect, composite structure will be made more stable inside the duct ionic liquid supported to MIL-53 (Cr), overcome
Ionic liquid viscosity is larger, it is difficult to which the disadvantages of recycling realizes increasing substantially for absorption desulfurization amount, and has good
Reusability.
Detailed description of the invention
Fig. 1 is MIL-53 (Cr) and 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid different quality in embodiment 7
The compound XRD spectra of ratio；From top to bottom it is followed successively by 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid mass percent
It is 40%, 30%, 10% and 0%；
Fig. 2 is MIL-53 (Cr) and 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid different quality in embodiment 7
The compound FT-IR spectrogram of ratio；From top to bottom it is followed successively by 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid quality percentage
Than being 40%, 30%, 10%, 100% and 0%；
Fig. 3 is MIL-53 (Cr) and 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid different quality in embodiment 7
The N of the compound of ratio2Absorption figure；From top to bottom it is followed successively by 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid quality hundred
Divide than being 0%, 10%, 30% and 40%.
Specific embodiment:
It is described further below for technical solution of the present invention.
Embodiment 1
The preparation of metal organic framework
Weigh 20gCr (NO3)3·9H2The H of O, 16.62g2BDC measures 252ml deionized water, mixes closed stirring 1h,
8 drop hydrofluoric acid are added dropwise, is stirred for 1h, pours into 500ml ptfe autoclave, react 72h at 220 DEG C.It is cooled to room temperature
Afterwards, it filters, washs, vacuum drying.MIL-53 (Cr) sample is made.
The preparation of acidic ion liquid
21.10gN- methylimidazole is weighed in 500mL three-necked flask, under nitrogen protection, 70 DEG C of oil baths are simultaneously stirred, and are used
34.25g bromobutane is slowly added dropwise in constant pressure funnel, and back flow reaction 30h generates [Bmim] Br.[Bmim] Br is true at 70 DEG C
Sky is dry to constant weight, obtains intermediate [Bmim] Br after purification.36.81gKPF is weighed again6, it is dissolved in distilled water.Then claim
It takes 42.21g [Bmim] Br in single-necked flask, KPF is slowly added dropwise with constant pressure funnel6Solution, stirring at normal temperature 10h.It removes
Layer light yellow clear thick liquid, is repeatedly washed with distilled water, obtains final product [Bmim] [PF after purification6], in 70 DEG C
It is dried under vacuum to constant weight, obtains 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid, i.e. acidic ion liquid [Bmim]
[PF6]。
The preparation of metal-organic framework materials solid-loaded ionic-liquid adsorbent
Weigh above-mentioned 0.08g [Bmim] [PF being prepared6] it is dissolved in 25ml CH2Cl2And it seals ultrasound and is obtained after 30 minutes
To CH2Cl2@[Bmim][PF6] solution.0.92g MIL-53 (Cr) addition solution is obtained into mixed system, will be mixed after stirring ultrasound
Zoarium system is transferred to polytetrafluoroethyllining lining and reacts for 24 hours at 95 DEG C.It is cooled to room temperature, is stirred in 45 DEG C of lower open mouths of oil bath, to
CH in system2Cl2Completely until volatilization.Obtained sample is finally dried in vacuo 4h at 80 DEG C.Obtain metal organic framework material
Expect solid-loaded ionic-liquid adsorbent, i.e. MIL-53 (Cr)@[Bmim] [PF6] adsorbent.
It weighs 0.035g adsorbent to be placed in the conical flask of 25mL, the simulation oil for being separately added into the 5mL of 100~600ppm is molten
Liquid under normal temperature and pressure, samples and uses gas chromatographic analysis sulfur content, the sulfur content before and after measurement absorption after shaking 20h.Adsorbance
For 12.7mg sulphur/g adsorbent.
Embodiment 2
The preparation of MIL-53 (Cr) is the same as embodiment 1.
[Bmim][PF6] preparation with embodiment 1.
Weigh 0.2g [Bmim] [PF6] it is dissolved in 25ml CH2Cl2And it seals ultrasound and obtains CH after 30 minutes2Cl2@[Bmim]
[PF6] solution.0.8gMIL-53 (Cr) addition solution is obtained into mixed system, mixed system is transferred to poly- four after stirring is ultrasonic
Vinyl fluoride liner reacts 48h at 105 DEG C.It is cooled to room temperature, in 50 DEG C of lower open mouth stirrings of oil bath, to CH in system2Cl2Completely
Until volatilization.Obtained sample is finally dried in vacuo 6h at 100 DEG C.Obtain MIL-53 (Cr)@[Bmim] [PF6] absorption
Agent.
Using embodiment 1 method gas chromatographic analysis sulfur content, adsorbance is 11.7mg sulphur/g adsorbent.
Embodiment 3
The preparation of MIL-53 (Cr) is the same as embodiment 1.
[Bmim][PF6] preparation with embodiment 1.
Weigh 0.4g [Bmim] [PF6] it is dissolved in 25ml CH2Cl2And it seals ultrasound and obtains CH after 30 minutes2Cl2@[Bmim]
[PF6] solution.0.6gMIL-53 (Cr) addition solution is obtained into mixed system, mixed system is transferred to poly- four after stirring is ultrasonic
Vinyl fluoride liner reacts 36h at 100 DEG C.It is cooled to room temperature, in 48 DEG C of lower open mouth stirrings of oil bath, to CH in system2Cl2Completely
Until volatilization.Obtained sample is finally dried in vacuo 5h at 90 DEG C.Obtain MIL-53 (Cr)@[Bmim] [PF6] absorption
Agent.
Using embodiment 1 method gas chromatographic analysis sulfur content, adsorbance is 11.4mg sulphur/g adsorbent.
Embodiment 4
The adsorbent of solid-loaded ionic-liquid in metal organic framework in Example 1 after the completion of adsorption reaction, is adding
Purging 4h is carried out to the adsorbent isolated with nitrogen at 200 DEG C of heat.Contained using 1 method gas chromatographic analysis sulphur of embodiment
Amount, adsorbance are 11.5 sulphur/g adsorbent.
Embodiment 5
The adsorbent of solid-loaded ionic-liquid in metal organic framework in Example 1 after the completion of adsorption reaction, is adding
Purging 6h is carried out to the adsorbent isolated with nitrogen at 220 DEG C of heat.Contained using 1 method gas chromatographic analysis sulphur of embodiment
Amount, adsorbance are 11.7mg sulphur/g adsorbent.
Embodiment 6
The adsorbent of solid-loaded ionic-liquid in metal organic framework in Example 1 after the completion of adsorption reaction, is adding
Purging 5h is carried out to the adsorbent isolated with nitrogen at 210 DEG C of heat.Contained using 1 method gas chromatographic analysis sulphur of embodiment
Amount, adsorbance are 11.6mg sulphur/g adsorbent.
Embodiment 7
7 groups of parallel tests are designed, MIL-53 (Cr)@[Bmim] of the ionic liquid of immobilized different quality content is designed
[PF6] composite material, remaining raw material and experimental procedure are same as Example 1 with condition, obtain in metal organic framework
The absorption property comparison of the adsorbent of solid-loaded ionic-liquid is as shown in the table.
In above-mentioned test group, 0% indicates to be used only MIL-53 (Cr) as adsorbent.Comparative composite and pure MIL-
The absorption property of 53 (Cr), the composite material after solid-loaded ionic-liquid are all better than pure MIL-53 (Cr).This is because in simulation oil
When contacting with adsorbent, the ionic liquid in composite material duct has stronger active force to thiophene, in addition immobilized ionic liquid
Adsorbent after body plays a role to weakly alkaline thiophene as acid centre, to improve its absorption property.When from
When sub- content liquid increases, adsorbance declines instead, illustrates that ionic liquid is not The more the better, and ionic liquid content excessively then can
Duct is blocked, hinders simulation oil to enter inside duct, to reduce absorption desulfurization amount.MIL-53 (Cr)@[Bmim] in summary
[PF6] composite property it is best when, the mass content of immobilized alkali ionic liquid is 8%~12%, more preferably, best solid
Carry alkali ionic liquid mass content be 10%.
At the same time, as shown in Figure 1, after MIL-53 (Cr) solid-loaded ionic-liquid, no change has taken place for characteristic peak positions, Gu
It carrying two characteristic peaks of the material of front and back near 10 ° and still maintains origin-location, the characteristic peak near 18 ° is also kept, and 28 °
There are still it is possible thereby to illustrate that MIL-53 (Cr) crystal structure does not become after solid-loaded ionic-liquid for neighbouring characteristic peak
Change, still maintain original crystal form, illustrates that ionic liquid does not destroy the structure of MIL53 (Cr), but enter inside duct.
As shown in Figure 2, MIL-53 (Cr)@[Bmim] [PF6] other than containing MIL-53 (Cr) characteristic peak itself, also
847cm-1The P-N characteristic peak at place, 1170cm-1The C=N characteristic peak at place, these characteristic peaks illustrate MIL-53 (Cr)@[Bmim]
[PF6] contain [Bmim] [PF in adsorbent6] molecule.
From the figure 3, it may be seen that nitrogen adsorption capacity is reduced with the increase of supported quantity.Illustrate that MIL-53 (Cr) is immobilized at high temperature
After ionic liquid, ionic liquid enters inside duct, is dispersed in duct, and accounts for certain space, and pore volume is with immobilized
The increase of amount and reduce.
Claims (10)
1. a kind of adsorbent of the solid-loaded ionic-liquid in metal organic framework, it is characterised in that: the adsorbent is in metal
Immobilized acidic ion liquid inside framework material duct, wherein the metallic framework material is MIL-53 (Cr), acid ion
Liquid is [Bmim] [PF6]。
2. according to claim 1 in metal organic framework solid-loaded ionic-liquid adsorbent, it is characterised in that: the acid
Property ionic liquid [Bmim] [PF6] account for adsorbent mass percent be 8~40%.
3. according to claim 1 in metal organic framework solid-loaded ionic-liquid adsorbent, it is characterised in that: the acid
Property ionic liquid [Bmim] [PF6] account for adsorbent mass percent be 8~12%.
4. it is a kind of based on described in claim 1 in metal organic framework the adsorbent of solid-loaded ionic-liquid preparation method,
It is characterized in that, comprising the following steps:
(1) by [Bmim] [PF6] it is dissolved in CH2Cl2Obtain CH2Cl2@[Bmim][PF6] solution；MIL-53 (Cr) addition solution is obtained
To mixed system, mixed system is reacted in a heated condition after stirring and obtains reactant；
(2) reactant is cooling, stir to get solid sample, solid sample is dry, obtain described in metal organic framework
The adsorbent of solid-loaded ionic-liquid.
5. according to claim 4 in metal organic framework the adsorbent of solid-loaded ionic-liquid preparation method, feature
It is: by [Bmim] [PF described in step (1)6] it is dissolved in CH2Cl2For every gram of [Bmim] [PF6] it is dissolved in the CH of 0.2L or more2Cl2
Solution.
6. according to claim 4 in metal organic framework the adsorbent of solid-loaded ionic-liquid preparation method, feature
Be: reaction is 24~48h of reaction at 95~105 DEG C under heating condition described in step (1).
7. according to claim 4 in metal organic framework the adsorbent of solid-loaded ionic-liquid preparation method, feature
It is: dry for 4~6h of vacuum drying at 80~100 DEG C described in step (2).
8. application of the adsorbent of solid-loaded ionic-liquid in desulfurization absorption in metal organic framework described in claim 1.
9. according to claim 8 in metal organic framework solid-loaded ionic-liquid adsorbent desulfurization absorption in answering
With, it is characterised in that: the adsorbent of the solid-loaded ionic-liquid in metal organic framework is the adsorbent recycled.
10. according to claim 9 in metal organic framework solid-loaded ionic-liquid adsorbent desulfurization absorption in answering
With, which is characterized in that the recycling are as follows: the adsorbent isolated is purged with nitrogen at 200~220 DEG C of heating
4~6h.
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| CN110496608A (en) * | 2019-08-13 | 2019-11-26 | 辽宁大学 | A kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101 and its preparation method and application |
| CN110918124A (en) * | 2019-12-12 | 2020-03-27 | 福建师范大学福清分校 | Preparation method and application of iron-based MOFs immobilized ionic liquid |
| CN111111786A (en) * | 2020-01-14 | 2020-05-08 | 西安工业大学 | MOFs supported fuel oil desulfurization catalyst, and preparation method and application thereof |
| CN111617705A (en) * | 2019-02-28 | 2020-09-04 | 华中科技大学 | Metal organic framework/graphene aerogel composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475158A (en) * | 2014-12-05 | 2015-04-01 | 长春工业大学 | Composite material of metal nano particles and microporous coordination polymer and preparation method thereof |
-
2018
- 2018-08-28 CN CN201810986739.2A patent/CN109174008A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475158A (en) * | 2014-12-05 | 2015-04-01 | 长春工业大学 | Composite material of metal nano particles and microporous coordination polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 靳洁: "MOFs复合物吸附脱硫研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617705A (en) * | 2019-02-28 | 2020-09-04 | 华中科技大学 | Metal organic framework/graphene aerogel composite material and preparation method thereof |
| CN110496608A (en) * | 2019-08-13 | 2019-11-26 | 辽宁大学 | A kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101 and its preparation method and application |
| CN110918124A (en) * | 2019-12-12 | 2020-03-27 | 福建师范大学福清分校 | Preparation method and application of iron-based MOFs immobilized ionic liquid |
| CN111111786A (en) * | 2020-01-14 | 2020-05-08 | 西安工业大学 | MOFs supported fuel oil desulfurization catalyst, and preparation method and application thereof |
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