CN107638870A - A kind of preparation method and application of ionic liquid and metal organic frame compound adsorbent - Google Patents
A kind of preparation method and application of ionic liquid and metal organic frame compound adsorbent Download PDFInfo
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Abstract
The invention discloses a kind of ionic liquid and metal organic frame compound adsorbent and its preparation method and application, using stable metal-organic framework material as carrier, using ionic liquid as active component, by the adsorption mode of action by inside the duct of different kinds of ions fluid load to metal-organic framework material, load capacity is 0.05~3.0mmol/g.The invention also discloses the preparation method of the adsorbent, prepare various metals organic framework materials MIL 101, UiO 66, HKUST 1 etc., metal-organic framework material is mixed with the alcoholic solution of ionic liquid again, loaded through suction-operated, obtains described adsorbent IL@MOF.Preparation technology is simple, mild condition, and the adsorbent being prepared can realize the high selectivity separation to alkene/alkynes mixed gas.
Description
Technical field
The present invention relates to the technical field of sorbing material and the energy, more particularly to a kind of ionic liquid to have machine frame with metal
The preparation method of frame compound adsorbent and its application in terms of alkene alkynes separation.
Background technology
Alkene is widely used in lubricating oil, plastics, polymer and other changes as one of most important chemical raw material
In the production of work material, wherein ethene is even more the title for having " mother of petrochemical industry ".Alkene is mainly by oil, natural at this stage
The hydrocarbon of gas and more carbon cracks to obtain, but pyrolysis product is complex, alkane often containing a variety of different carbon numbers,
Monoolefine, alkadienes, alkynes, diyne etc..Commercial Application generally requires the polymer grade olefin of high-purity again.It is such as poly- in production
During ethene, if there is micro acetylene residual to will result in catalyst activity reduction in ethene, acetylene content is more than 5ppm in ethene,
The Ziegler-Natta catalyst in ethylene polymerization will be made to be poisoned.Alkynes is as very important base in chemical industry
Plinth raw material, for manufacturing acrylate, synthetic rubber, synthetic fibers etc..The acetylene being wherein most widely used, due to tradition
Calcium carbide prepare that method power consumption is big, cost is high, pollution is heavy, gradually substituted by natural gas, coal, petroleum cracking, but pyrolysis product
Complicated component is, it is necessary to which further separating-purifying can just obtain being applied to industrial polymer grade acetylene.Alkene alkynes simultaneously
A certain degree of waste gas and pollution are often produced in its production and separation process, is got in environmental protection and green chemical industry concept
To get over by today of concern, how on the premise of the quality of production is not reduced, replaceable material or technique are found to subtract
Few pollution and infringement to environment, turn into researchers' focus of attention.
At present, the method for being commercially used for separating between acetylene and ethene is relatively fewer, mainly there is part hydrogenization method, solvent
Absorption process and absorption method etc..Part hydrogenization method needs to use noble metal catalyst, and production cost is high, and part ethene can be turned
Turning to ethane reduces olefin yield；Absorption process is big to the consumption of solvent, general to use volatile solvent, such as dimethyl methyl more
Acid amides, 1-METHYLPYRROLIDONE, ethyl acetate, acetone etc., it is big to environmental hazard, and operating pressure is high, and energy consumption is big.Therefore people
Need a kind of separation means more economically saved to carry out purifies and separates alkene alkynes in a hurry.Adsorption method of separation has operation letter
Just the features such as, energy consumption is small, cost is low, particularly there is good separating effect to ethene/acetylene.
The adsorbing separation of alkene alkynes is it is crucial that absorption of the selection with compared with high adsorption capacity and larger adsorptive selectivity
Agent.Conventional adsorbent includes activated carbon, silica gel, molecular sieve, aluminum oxide, resin etc..Yang etc. (Ind.Eng.Chem.Res.,
2000,39:3108) it have studied load NiCl2Separation, Lewis etc. of the porous zeolite to ethylene acetylene
(J.Am.Chem.Soc., 1950,72,1157.) reports the selective absorption of activated carbon and silica gel to ethylene acetylene, but imitates
Fruit is all bad, can not reach commercial Application level.
Metal-organic framework material is because it has high specific surface area and pore volume, and aperture is adjustable, hole inner structure
The features such as can modifying, it is widely used in gas separation field.Xiang etc. (Angew.Chem.Int.Edit., 2010,
49:4615) [M is utilized2(DHTP)]] (M=Co2+,Mn2+,Mg2+,Zn2+；DHTP=2,5- dihydric para-phthalic acids) absorption second
Alkynes, 230cm is reached3/ mL acetylene reserves.Meanwhile Xiang etc. (Nat.Commun., 2011,2:204) also synthesized porous
Enantiomter hybrid metal organic framework materials (M ' MOFs), it is found that its adsorbance to acetylene is higher than ethene, and have
Certain acetylene/ethylene separation effect.Although metal-organic framework material adsorbance is higher, generally existing hydrothermal stability
Difference, the shortcoming such as gas-selectively is low.
Ionic liquid is in room temperature or what is be in a liquid state close under room temperature condition have yin, yang completely as a kind of novel dissolvent
From molecular salt, there is extremely low volatility and good heat endurance, be widely used in chemical reaction, extraction point
From fields such as, electrochemistry.In terms of gas absorption separation, ionic liquid is also of considerable interest.Lee etc.
(Phys.Chem.Chem.Phys.,2010,12:1812) it have studied [DMIM] [MeHPO3] to the selectivity of ethene/acetylene, hair
Its existing selectivity is 5 times of DMF.Although ionic liquid has the good potentiality of absorption and separation ethylene acetylene, and should for industry
For, absorptive capacity is also to be related to the important parameter of absorbent dosage and process economy benefit, existing design synthesis from
Sub- liquid is also smaller to the absorptive capacity of acetylene, limits the commercial Application of ionic liquid.Ionic liquid is applied to ethene simultaneously
Acetylene absorption separates, and it is big inevitably to run into ionic liquid dosage, the problems such as desorption and regeneration high energy consumption；And ionic liquid sticks
Degree is big, greatly reduces its absorption efficiency.
The content of the invention
The present invention provides a kind of ionic liquid and metal organic frame compound adsorbent and its preparation method and application, will be few
The ionic liquid of amount and the metal-organic framework material of hydrothermally stable are organically combined, and giving full play to ionic liquid and metal has
Synergy between machine frame, the high selectivity separation to alkene/alkynes mixed gas is realized, and preparation method is simple, bar
Part is gentle.
A kind of ionic liquid and metal organic frame compound adsorbent, using the stable metal-organic framework material of water as load
Body, with least one of ionic liquid [Bmim] [X], [Dmim] [X] and [BMPyrr] [Y] for active component, the activity
Component pass through with inside the adsorption used load of metal organic frame to carrier duct, with pure metal-organic framework material
On the basis of gross mass, the load capacity of active component is 0.05mmol/g~3.0mmol/g.
The present invention both remains metal-organic framework material successfully by ionic liquid loaded in metal-organic framework material
The characteristics of high to acetylene adsorbance, simultaneously because ionic liquid designability is strong, the architectural feature of specific gas molecule can be directed to,
The zwitterion structure of preferred ion liquid, and the functional group for being favorably improved separating property is further introduced into, structure is provided
There is the ionic liquid of particular separation selectivity.Therefore can be multiple according to ionic liquid species and the difference of load capacity, controllable adjustment
Selectivity of the adsorbent to ethylene acetylene is closed, to meet that different industrial requirements provides diversified selection.
Preferably, metal-organic framework material includes but is not limited to MIL-101, MIL-100, UiO-66, UiO-67,
At least one of HKUST-1 and ZIF-8.All have raw material cheap and easy to get, prepare it is simple and convenient, the features such as Stability Analysis of Structures, together
When with good hydrothermal stability, can adapt to different industrial environments.Metal-organic framework material of the present invention
It can be obtained by approach purchased in market or be prepared with reference to existing literature.
In ionic liquid [Bmim] [X], [Dmim] [X] and [BMPyrr] [Y] of the present invention, [Bmim] refers to 1- fourths
Base -3- methylimidazole salts, [Dmim] refer to 1,3- methylimidazole salt, and [BMPyrr] refers to 1- butyl -1- methylpyrroles
Alkane salt；[X] [Y] [Z] each means alternative.
Preferably, [X] in described [Bmim] [X] and [Dmim] [X] is [MeHPO3],[Me2PO4],[OAc],
[MeSO4],[Tf2N],[BF4],[TFA],[EtHPO3] in one or more；[Y] in [BMPyrr] [Y] is
[BuHPO3],[OAc],[Tf2N], [TFA], the one or more in [DCA].The present invention uses ionic liquid to pass through city
Purchase is obtained or synthesized with reference to existing literature.
It is further preferred that the ionic liquid is：[Bmim] [X], wherein [X] is [OAc]；Or [Dmim] [X], wherein
[X] is [Me2PO4]；Or [BMPyrr] [Y], wherein [Y] is [BuHPO3]。
It is further preferred that when ionic liquid is [Bmim] [X], wherein when [X] is [OAc], the metal has machine frame
Frame material is MIL-101 or UiO-66；When ionic liquid is [Dmim] [X], wherein [X] is [Me2PO4] when, the metal is organic
Frame material is MIL-100 or HKUST-1；When ionic liquid is [BMPyrr] [Y], wherein [Y] is [BuHPO3] when, the gold
Category organic framework materials are ZIF-8.
Further preferably, the load capacity of the active component is 0.05mmol/g~1.0mmol/g；Still more preferably it is
0.5mmol/g~1.0mmol/g.
Most preferably, compound adsorbent is [Bmim] [OAc]@MIL-101, [Dmim] [Me2PO4]@MIL-100 or
[Dmim][Me2PO4]@HKUST-1, the wherein load capacity of active component is 1.0mmol/g.
The present invention also provides the preparation method of a kind of ionic liquid and metal organic frame compound adsorbent, as previously described
Compound adsorbent is preferably prepared using this method, is comprised the following steps：
Ion liquid dissolving is obtained into ionic liquid solution in solvent, is then sufficiently mixed with metal-organic framework material,
Ionic liquid enters inside metal organic frame duct, most afterwards through filtering, drying process obtains ionic liquid and metal machine frame
Frame compound adsorbent；The ionic liquid is [Bmim] [X], [Dmim] [X] and [BMPyrr] [Y]；The metal organic frame
Material is the stable metal-organic framework material of water.
The solvent is methanol and ethanol.
Preferably, the mass concentration of ionic liquid solution intermediate ion liquid is 10~1000mg/mL.
Preferably, dissolution time of the ionic liquid in alcohol solvent is 0.5~2h, speed of agitator is 500~1000 turns/
Minute.
The mixing time can allow ionic liquid to be substantially dissolved in ethanol, avoid ionic liquid from dissolving in ethanol not
Uniformly, situation about subsequently loading is influenceed.
Preferably, when ionic liquid solution mixes with metal-organic framework material, metal-organic framework material and ionic liquid
The mass ratio of body is 1:0.5~25.Or on the basis of the gross mass of metal-organic framework material pure in finished catalyst, it is living
Property component load capacity matched for 0.05mmol/g~3.0mmol/g.Further, with the load capacity of the active component
Matched for 0.05mmol/g~1.0mmol/g.
Ionic liquid loaded amount is too low, and it is too low to improve selective effect；Load capacity is too high, and ionic liquid can block metal
The duct of organic framework materials, cause specific surface area and pore volume significantly to decline, directly affect adsorption capacity and gas diffusion effect
Rate.Therefore preferably after metal-organic framework material and ionic liquid mass ratio be 1:0.5~25.
Preferably, ionic liquid solution and metal-organic framework material incorporation time are 12~24h；Dry temperature is 50
~200 DEG C, the dry time is 12~24h.
Mixing time is unsuitable too short.Ionic liquid has larger molecular volume, is spread in carrier duct
Drag effects are, it is necessary to the regular hour, therefore mixing time is set to 12~24h.Stir speed (S.S.) can directly affect ionic liquid and enter
Enter the efficiency in duct, therefore stir speed (S.S.) is set to 500~1000 revs/min.Fully after diffusion, then through filtering, at vacuum drying
Reason.
Drying temperature and drying time are moderate.Temperature is too low, the time is too short, and alcohol solvent evaporation is slow, is easily trapped in
In duct；Temperature is too high, overlong time can influence the stability of ionic liquid and metal-organic framework material, causes its structure quilt
Destroy.Therefore the temperature dried is 50~200 DEG C, and the dry time is 12~24h.
The present invention also provides a kind of ionic liquid being prepared such as the preparation method and the compound suction of metal organic frame
Attached dose.
The adsorbent that the present invention is prepared has higher selectivity to the equilibrium separation of ethene/acetylene gas mixture,
The requirement in practical application can still be met to the adsorbance of ethene, acetylene simultaneously.
Therefore, the present invention also provides a kind of ionic liquid as described in metal organic frame compound adsorbent in ethene/second
Application in the Selective Separation of alkynes mixed gas.
Application of the described adsorbent in ethene/acetylene gas mixture separation；The use condition of adsorbent：Temperature is 0
~30 DEG C, pressure is 0~100kPa.
Preferably, by taking metal-organic framework material MIL-101 and ionic liquid [Bmim] [OAc] as an example, at [Bmim]
[OAc] ethanol solution concentration is 110mg/mL, and MIL-101 and [Bmim] [OAc] mass ratio are 1:In the case of 4, the present invention
The adsorbent being prepared is adapted to the separation of ethene/acetylene gas mixture.Under 298K, 100kPa, it is maintained to
More than 2mmol/g acetylene adsorbance, and acetylene/ethylene selectivity more than 5.5.
Described adsorbent need to only be heated to 100~150 DEG C under vacuum conditions after use or after adsorption saturation, protect
Hold 6~12 hours and regeneration can be achieved.
Compared with prior art, the invention has the advantages that：
For the present invention using metal-organic framework material as adsorbing agent carrier, ionic liquid is active component, passes through adsorption
Effect by ionic liquid loaded to inside the duct of metal-organic framework material, in reservation metal-organic framework material to gas height
While adsorbance feature, its selectivity to ethene/acetylene is improved, and ionic liquid dosage is few.Used in the present invention
Carrier has higher hydrothermal stability and acid-proof alkaline, can adapt to different operating environment and use condition, and should
Adsorbent regenerating easily and recycling, efficient separation selectivity is still kept after regeneration.The ionic liquid and metal are organic
Framework compound adsorbent is an ethene/acetylene separation material with high industrial applications prospect.
Brief description of the drawings
Fig. 1 is [Bmim] [OAc]@MIL-101 prepared in the MIL-101 and embodiment 3 prepared in embodiment 1 XRD
Phenogram.
Fig. 2 is the adsorbent [Bmim] prepared in the MIL-101 and embodiment 2, embodiment 3 prepared in embodiment 1
[OAc]@MIL-101 BET figures.
Fig. 3 is the adsorption isotherm of adsorbent [Bmim] [OAc] the@MIL-101 separating ethenes/acetylene prepared in embodiment 2
Line, temperature 298K, 0~100kPa of pressure.
Fig. 4 is the adsorption isotherm of adsorbent [Bmim] [OAc] the@MIL-101 separating ethenes/acetylene prepared in embodiment 2
Line, temperature 273K, 0~100kPa of pressure.
Fig. 5 is MIL-101 points of adsorbent [Bmim] [OAc]@prepared in the MIL-101 and embodiment 2 prepared in example 1
From the Selective Separation coefficient curve of ethene/acetylene, temperature 298K.
Embodiment
The following examples will be further described to the present invention, but the complete not limited to this of present disclosure.
Embodiment 1
MIL-101 can be prepared by the literature method of existing disclosed report, be specially：By the water chromic nitrates of 4.00g nine,
1.64g terephthalic acid (TPA)s, 125 μ L hydrofluoric acid and 70mL water are added in 100mL reactors, ultrasonic 3h.Reacted at 220 DEG C
8h, you can obtain unpurified MIL-101 crystal.Unpurified MIL-101 is handled into 5h with hot water at 80 DEG C successively after cooling,
3h is handled at 60 DEG C with hot ethanol, 10h is handled at 60 DEG C with ammonium fluoride, finally with hot water supersound washing 5 times, it is therefore an objective to be
Remove the terephthalic acid (TPA) part remained in duct.Product after purification is dried in vacuo 12h at 80 DEG C and 150 DEG C respectively
And 5h, you can obtain MIL-101 after purification, product is green solid powder.Specific surface area is 3000m2/ g, pore volume are
1.5cm3/g(P/P0=0.95).Unless stated otherwise, following instance is the MIL-101 synthesized using the method.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment calculates C with IAST2H2/C2H4(1:1) divide
It is 2.8 from selectivity.
Embodiment 2
Adsorbent [Bmim] [OAc]@MIL-101 preparation：Accurately 0.5500g [Bmim] [OAc] stirring and dissolving is weighed to exist
In the ethanol of 5mL chromatographically pures, thoroughly dissolved in ethanol through stirring [Bmim] [OAc] in half an hour.Again in above-mentioned solution
The MIL-101 of 150mg after purification are added, persistently stir 24h.Green solid powder is obtained through filtering, is dried in vacuo at 80 DEG C
12h, you can obtain [Bmim] [OAc]@MIL-101 that load capacity is 1.0mmol/g.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment is 2.0mmol/g to the adsorbance of acetylene,
Adsorbance to ethene is 0.84mmol/g, and IAST calculates C2H2/C2H4(1:1) separation selectivity is 6.7；In 273K, 100kPa
Under, the adsorbance to acetylene is 3.0mmol/g, and the adsorbance to ethene is 1.5mmol/g, and IAST calculates C2H2/C2H4(1:1)
Separation selectivity is 7.9.
Embodiment 3
Adsorbent [Bmim] [OAc]@MIL-101 preparation：Accurately 0.0500g [Bmim] [OAc] stirring and dissolving is weighed to exist
In the ethanol of 5mL chromatographically pures, thoroughly dissolved in ethanol through stirring [Bmim] [OAc] in half an hour.Again in above-mentioned solution
The MIL-101 of 150mg after purification are added, persistently stir 24h.Green solid powder is obtained through filtering, is dried in vacuo at 80 DEG C
12h, you can obtain [Bmim] [OAc]@MIL-101 that load capacity is 0.1mmol/g.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment is 2.5mmol/g to the adsorbance of acetylene,
Adsorbance to ethene is 1.3mmol/g, and IAST calculates C2H2/C2H4(1:1) separation selectivity is 3.2；In 273K, 100kPa
Under, the adsorbance to acetylene is 4.1mmol/g, and the adsorbance to ethene is 2.3mmol/g, and IAST calculates C2H2/C2H4(1:1)
Separation selectivity is 3.7.
Fig. 1 is [Bmim] [OAc]@MIL-101 prepared in the MIL-101 and embodiment 3 prepared in embodiment 1 XRD
Phenogram.For MIL-101 after supported ion liquid, XRD peak shape illustrates metal-organic framework materials with being consistent originally
Structure load before and after do not change；Peak position is integrally slightly offset to the right, this also demonstrate ionic liquid load into
Inside MIL-101.
Fig. 2 is the adsorbent [Bmim] prepared in the MIL-101 and embodiment 2, embodiment 3 prepared in embodiment 1
[OAc]@MIL-101 BET figures.After load, the specific surface area of material is from 3198m2/ g drops to 2092m2(0.1mmol/g is born/g
Carrying capacity) and 645m2/ g (1.0mmol/g load capacity), also demonstrates the duct that ionic liquid has successfully loaded to MIL-101
It is interior.
Fig. 3 is the adsorption isotherm of adsorbent [Bmim] [OAc] the@MIL-101 separating ethenes/acetylene prepared in embodiment 2
Line, temperature 298K, 0~100kPa of pressure.In 100kPa, the adsorbance of acetylene reaches 2.0mmol/g, and the adsorbance of ethene is only
For 0.84mmol/g.IAST calculates C2H2/C2H4(1:1) separation selectivity is 6.7.
Fig. 4 is the adsorption isotherm of adsorbent [Bmim] [OAc] the@MIL-101 separating ethenes/acetylene prepared in embodiment 2
Line, temperature 273K, 0~100kPa of pressure.In 100kPa, the adsorbance of acetylene reaches 3.0mmol/g, and the adsorbance of ethene is only
For 1.5mmol/g.IAST calculates C2H2/C2H4(1:1) separation selectivity is 7.9.
Fig. 5 is adsorbent [Bmim] [OAc] the@MIL-101 prepared in the MIL-101 and embodiment 2 prepared in embodiment 1
The Selective Separation coefficient curve of separating ethene/acetylene, temperature 298K.MIL-101 selectivity is 2.8~3.1；[Bmim]
[OAc]@MIL-101 selectivity is 6.7~11.
Embodiment 4
UiO-66 can be prepared by the literature method of existing disclosed report, be specially：By 0.24g zirconium chlorides, 0.171g
Terephthalic acid (TPA), 20mL N, N '-dimethyl formamide and 2.1mL glacial acetic acid are added in 100mL reactors, and ultrasonic agitation is equal
It is even.24h is reacted at 120 DEG C, you can obtains unpurified UiO-66.After cooling by above-mentioned synthesis do not purify UiO-66 according to
Secondary to use N, N '-dimethyl formamide, methanol difference exchange of solvent 3 times and 6 times, purpose remains to remove in duct respectively
The higher boiling N that unreacted part and removing remain after exchanging, N '-dimethyl formamide solvent.Product after exchange of solvent pass through from
The heart, 12h is dried in vacuo at 80 DEG C, you can the UiO-66 purified.Specific surface area is 1035m2/ g, pore volume 0.57cm3/g
(P/P0=0.95).Unless stated otherwise, following instance is the UiO-66 synthesized using the method.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment calculates C with IAST2H2/C2H4(1:1) divide
It is 1.2 from selectivity.
Embodiment 5
Adsorbent [Bmim] [OAc]@UiO-66 preparation：Accurately 0.0827g [Bmim] [OAc] stirring and dissolving is weighed to exist
In the ethanol of 5mL chromatographically pures, thoroughly dissolved in ethanol through stirring [Bmim] [OAc] in half an hour.Again in above-mentioned solution
The UiO-66 of 200mg after purification are added, persistently stir 24h.White solid powder is obtained through filtering, 12h is dried in vacuo at 80 DEG C,
It can obtain [Bmim] [OAc] UiO-66 that load capacity is 0.05mmol/g.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment is 1.48mmol/ to the adsorbance of acetylene
G, the adsorbance to ethene are 0.82mmol/g, and IAST calculates C2H2/C2H4(1:1) separation selectivity is 3.1；In 273K,
Under 100kPa, the adsorbance to acetylene is 2.51mmol/g, and the adsorbance to ethene is 1.33mmol/g, and IAST calculates C2H2/
C2H4(1:1) separation selectivity is 4.1.
Embodiment 6
Adsorbent [Bmim] [OAc]@UiO-66 preparation：Accurately 1.6530g [Bmim] [OAc] stirring and dissolving is weighed to exist
In the ethanol of 5mL chromatographically pures, thoroughly dissolved in ethanol through stirring [Bmim] [OAc] in half an hour.Again in above-mentioned solution
The UiO-66 of 200mg after purification are added, persistently stir 24h.White solid powder is obtained through filtering, 12h is dried in vacuo at 80 DEG C,
It can obtain [Bmim] [OAc] UiO-66 that load capacity is 0.76mmol/g.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment is 0.40mmol/ to the adsorbance of acetylene
G, the adsorbance to ethene are 0.13mmol/g, and IAST calculates C2H2/C2H4(1:1) separation selectivity is 6.1.
Embodiment 7
MIL-100 can be prepared by the literature method of existing disclosed report, be specially：By 1,3,5- equal benzene tricarbonic acid, iron
Powder, hydrofluoric acid, concentrated nitric acid and water are with 0.67:1.0:2.0:0.6:277 mixed in molar ratio is uniform.12h is reacted at 150 DEG C.
Then product is filtered to obtain the solid of light orange, and is washed with water repeatedly.Purification phase, 5h is persistently first boiled with boiling water, then
With boiling Ethanol Treatment 3h untill no foreign pigment.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment calculates C with IAST2H2/C2H4(1:1) divide
It is 2.5 from selectivity.
Embodiment 8
Adsorbent [Dmim] [Me2PO4]@MIL-100 preparation：Accurately weigh 0.6164g [Dmim] [Me2PO4] stirring it is molten
Solution is in the ethanol of 5mL chromatographically pures, through stirring [Dmim] [Me in half an hour2PO4] thoroughly dissolve in ethanol.Again above-mentioned
The MIL-100 of 150mg after purification are added in solution, persistently stir 24h.Solid powder is obtained through filtering, is dried in vacuo at 80 DEG C
12h, you can obtain [Dmim] [Me that load capacity is 1.0mmol/g2PO4]@MIL-100。
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment is 1.80mmol/ to the adsorbance of acetylene
G, the adsorbance to ethene are 0.71mmol/g, and IAST calculates C2H2/C2H4(1:1) separation selectivity is 5.0.
Embodiment 9
HKUST-1 can be prepared by the literature method of existing disclosed report, be specially：The equal benzene tricarbonic acids of 12mg 1,3,5-
DMF/H is dissolved into 35mg copper nitrates2In O (2mL/0.5mL) solution, with the tetrafluoro boron of the 1mL drop 48% of disposable dropper drop 2
Acid solution, reaction 24h obtains blue colored crystal at 65 DEG C.Purification phase：The crystal of synthesis is exchanged 3 to 4 times with DMF solvent,
Exchanged 8 times with acetone solvent again.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment calculates C with IAST2H2/C2H4(1:1) divide
It is 1.5 from selectivity.
Embodiment 10
Adsorbent [Dmim] [Me2PO4]@HKUST-1 preparation：Accurately weigh 0.6164g [Dmim] [Me2PO4] stirring it is molten
Solution is in the ethanol of 5mL chromatographically pures, through stirring [Dmim] [Me in half an hour2PO4] thoroughly dissolve in ethanol.Again above-mentioned
The HKUST-1 of 150mg after purification are added in solution, persistently stir 24h.Solid powder is obtained through filtering, is dried in vacuo at 80 DEG C
12h, you can obtain [Dmim] [Me that load capacity is 1.0mmol/g2PO4]@HKUST-1。
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment is 4.1mmol/g to the adsorbance of acetylene,
Adsorbance to ethene is 1.9mmol/g, and IAST calculates C2H2/C2H4(1:1) separation selectivity is 4.5.
Embodiment 11
ZIF-8 can be prepared by the literature method of existing disclosed report, be specially：0.47g zinc nitrate hexahydrates are dissolved in
The in the mixed solvent of 10mL methanol and 10mL water, 1.0g 2-methylimidazoles are dissolved in 10mL methanol.Two kinds of solution mix
2h.White solid powder is obtained by centrifugation, is washed with water 2 times, is washed 1 time with methanol successively.
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment calculates C with IAST2H2/C2H4(1:1) divide
It is 1.5 from selectivity.
Embodiment 12
Adsorbent [BMPyrr] [BuHPO3]@ZIF-8 preparation：Accurately weigh 0.3875g [BMPyrr] [BuHPO3] stirring
It is dissolved in the ethanol of 5mL chromatographically pures, through stirring [BMPyrr] [BuHPO in half an hour3] thoroughly dissolve in ethanol.Exist again
The ZIF-8 of 150mg after purification are added in above-mentioned solution, persistently stir 24h.Solid powder is obtained through filtering, vacuum is done at 80 DEG C
Dry 12h, you can obtain [BMPyrr] [BuHPO that load capacity is 0.05mmol/g3]@ZIF-8。
After tested, under 298K, 100kPa, adsorbent manufactured in the present embodiment is 1.0mmol/g to the adsorbance of acetylene,
Adsorbance to ethene is 0.53mmol/g, and IAST calculates C2H2/C2H4(1:1) separation selectivity is 3.8.
The specific implementation case of patent of the present invention is the foregoing is only, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art in the field of the invention, all cover in the special of the present invention by the change or modification made
Among sharp scope.
Claims (10)
1. a kind of ionic liquid and metal organic frame compound adsorbent, it is characterised in that with the metal organic frame that water is stable
Material is carrier, with least one of ionic liquid [Bmim] [X], [Dmim] [X] and [BMPyrr] [Y] for active component,
The active component through adsorption used load to carrier duct inside, using the gross mass of pure metal-organic framework material as
Benchmark, the load capacity of active component is 0.05mmol/g~3.0mmol/g.
2. ionic liquid and metal organic frame compound adsorbent according to claim 1, it is characterised in that metal has machine frame
Frame material is MIL-101, MIL-100, UiO-66, UiO-67, at least one of HKUST-1 and ZIF-8.
3. ionic liquid and metal organic frame compound adsorbent according to claim 1, it is characterised in that [Bmim]
[X] in [X] and [Dmim] [X] is [MeHPO3],[Me2PO4],[OAc],[MeSO4],[Tf2N],[BF4],[TFA],
[EtHPO3] in one or more；[Y] in [BMPyrr] [Y] is [BuHPO3],[OAc],[Tf2N],[TFA],
One or more in [DCA].
4. the preparation method of a kind of ionic liquid and metal organic frame compound adsorbent, it is characterised in that comprise the following steps：
Ion liquid dissolving is obtained into ionic liquid solution in solvent, is then sufficiently mixed with metal-organic framework material, ionic liquid
Into inside metal organic frame duct, most ionic liquid and the compound suction of metal organic frame are obtained through suction filtration, drying process afterwards
Attached dose；The ionic liquid is [Bmim] [X], [Dmim] [X] and [BMPyrr] [Y]；The metal-organic framework material is water
Stable metal-organic framework material.
5. preparation method according to claim 4, it is characterised in that described solvent is methanol or ethanol.
6. preparation method according to claim 4, it is characterised in that ionic liquid solution mixes with metal-organic framework material
When, the mass ratio of metal-organic framework material and ionic liquid is 1:0.5~25.
7. preparation method according to claim 4, it is characterised in that the mass concentration of ionic liquid solution intermediate ion liquid is
10~1000mg/mL.
8. preparation method according to claim 4, it is characterised in that ionic liquid solution mixes with metal-organic framework material
Time is 12~24h；Dry temperature is 50~200 DEG C, and the dry time is 12~24h.
9. the ionic liquid and metal that a kind of preparation method as described in claim 4~8 any claim is prepared are organic
Framework compound adsorbent.
10. a kind of ionic liquid as described in claim 1 or 9 mixes with metal organic frame compound adsorbent in ethene/acetylene
Application in the Selective Separation of gas.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108404871A (en) * | 2018-04-20 | 2018-08-17 | 万玉梅 | A kind of preparation method of high adsorption metal-organic framework materials |
| CN109365003A (en) * | 2018-10-25 | 2019-02-22 | 大连理工大学 | A kind of magnetic ionic liquids immobilized AlCl_3 catalyst and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6339182B1 (en) * | 2000-06-20 | 2002-01-15 | Chevron U.S.A. Inc. | Separation of olefins from paraffins using ionic liquid solutions |
| CN104722284A (en) * | 2013-12-18 | 2015-06-24 | 中国科学院大连化学物理研究所 | Microporous material loaded ion liquid composite material or film, and preparation thereof |
| CN105688993A (en) * | 2016-03-04 | 2016-06-22 | 河北科技大学 | Load type polymeric acidic ionic liquid catalyst and preparation method and application thereof |
| CN105709692A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Copper based metal organic skeleton material and preparation method thereof |
-
2016
- 2016-07-22 CN CN201610591542.XA patent/CN107638870B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6339182B1 (en) * | 2000-06-20 | 2002-01-15 | Chevron U.S.A. Inc. | Separation of olefins from paraffins using ionic liquid solutions |
| CN104722284A (en) * | 2013-12-18 | 2015-06-24 | 中国科学院大连化学物理研究所 | Microporous material loaded ion liquid composite material or film, and preparation thereof |
| CN105709692A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Copper based metal organic skeleton material and preparation method thereof |
| CN105688993A (en) * | 2016-03-04 | 2016-06-22 | 河北科技大学 | Load type polymeric acidic ionic liquid catalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| JELLIARKO PALGUNADI ET AL.: "Ionic liquids for acetylene and ethylene separation: Material selection and solubility investigation", 《CHEMICAL ENGINEERING AND PROCESSING：PROCESS INTENSIFICATION》 * |
| NAZMUL ABEDIN KHAN ET AL.: "Ionic Liquids Supported on Metal-Organic Frameworks：Remarkable Adsorbents for Adsorptive Desulfurization", 《CHEMISTRY A EUROPEAN JOURNAL》 * |
| TONG-LIANG HU ET AL.: "Microporous metal–organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures", 《NATURE COMMUNICATIONS》 * |
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