CN102728236B - Coordination polymer membrane material, preparation method for same and application of same in membrane separation - Google Patents
Coordination polymer membrane material, preparation method for same and application of same in membrane separation Download PDFInfo
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Abstract
The invention specifically relates to a coordination polymer membrane material, a preparation method for the same and application of the same in separation of mixed gas or chiral isomers, belonging to the field of membrane materials and separation technology thereof. The referred coordination polymer Ni2(L-asp)2bpy membrane material is a three-dimensional porous material which is formed by coordination between metallic nickel ions and L-aspartic acid (L-asp) and 4,4-bipyridine (bpy) and has a uniform pore channel size, wherein metallic nickel coordinates with oxygen atoms of L-aspartic acid to form a layer which is then propped up by a nitrogen atom coordination column in 4,4-bipyridine to form a three-dimensional skeleton structure. According to the invention, through selection of different carriers and carrier pretreatment methods, the coordination polymer membrane material is prepared by using an in situ or secondary growth method under different solvothermal conditions. Results show that the membrane material provided in the invention has a good separation effect on mixed gas or chiral isomers.
Description
Technical field
The invention belongs to membrane material and separation technology field thereof, be specifically related to a kind of Coordination Polymer membrane material, the application aspect mist or the separation of chirality isomer of preparation method and this membrane material.
Background technology
Coordination Polymer typically refers to the metallic organic framework crystalline material with periodic network structure that little molecule ligand and metal ion form by self assembling process.This class material both had been different from general organic polymer, the inorganic polymer that also is different from the Si-O class, it not only has the crystal structure similar to zeolite molecular sieve, and the expansion of the rational design by topological structure and organo-functional group can obtain duct and the hole of different size, there is the character such as unique light, electricity, magnetic simultaneously.As a kind of novel molecular functional material, it has crossed over a plurality of ambits such as inorganic chemistry, Coordinative Chemistry, organic chemistry, physical chemistry, supramolecular chemistry, materials chemistry, biochemistry, crystal engineering and topology.Therefore, synthetic, the structure of the design of Coordination Polymer in recent years and performance study develop rapidly and become one of study hotspot interdisciplinary.
Coordination polymer material is as a kind of novel inorganic porous material, and how its research method and research purpose mainly concentrate on by the design of organo-functional group and expand the breakthrough that realizes pore size.The design that people do one's utmost, synthetic and find new organic ligand, expectation obtains larger duct and void structure.Within nearly ten years, people have spent a large amount of energy and material resources to be devoted to the synthetic Coordination Polymer crystalline material with new construction of design, but the research for the Coordination Polymer membrane material is few, because this class material has regularly arranged pore passage structure as molecular screen material, the duct size, connectedness and controllability, and duct can be designed or modify to reach the variation of material character, for example can overcome the shortcoming of molecular sieve pore passage size restrictions, the duct radius of molecular sieve is between 0.4～2nm, and the duct of metal organic frame can reach greater or lesser scope.The duct of the coordination polymer material even the had generation breathing phenomenon that can stretch.Comprehensive above advantage, the Coordination Polymer membrane material has caused the interest of people's preparation and research.
Chiral chemistry was paid close attention in recent years always widely, this is to be as different as light from darkness because have the effect of two kinds of isomers in application of different chiral structures, for example, a kind of chiral configuration of this medicine of naproxen (NAP) is 28 times of another kind of Chiral anti-inflammatory drugs activity; A kind of enantiomer of dopamine, be used for treating parkinsonism, can act on nerve cell control and tremble, and its another kind of enantiomer is poisonous to nerve cell.Use the higher enantiomer of pharmaceutically active that following several advantage is arranged:
1. side effect still less;
2. patient can correspondingly take the medicine of few dosage;
3. can save and produce the waste that enantiomer that we do not wish to obtain brings;
4. " racemic production interchange originally " brings new business opportunity.
The film separation field past has some macromolecule member materials to be used to the separation of chirality isomer, but its preparation process more complicated, and macromolecule member material may with the compound reaction separated, limit its application.Although research widely of Coordination Polymer Membrane is for the separation of gas with various, for separating of the research of organic liquid or few.Particularly to the separation of chirality isomer.
Summary of the invention
The purpose of this invention is to provide a kind of Coordination Polymer membrane material, its preparation method and utilize this Coordination Polymer membrane material to carry out the separation of mist or chirality isomer.
Related Coordination Polymer Ni
2(L-asp)
2the bpy membrane material is by metallic nickel ions and L-Aspartic acid (L-asp), 4, the three-dimensional apertures material with homogeneous duct size that 4-bipyridyl (bpy) coordination forms, the oxygen atom ligand of metallic nickel atom and L-Aspartic acid forms layer, again with 4,4-bipyridyl in the pillared three-dimensional framework structure that forms of nitrogen-atoms coordination.
The present invention, by selecting different carrier and carrier preprocess method, adopts the method for original position or diauxic growth to obtain the Coordination Polymer membrane material under different solvent heat conditions, and its step is as follows:
1, the pretreatment of carrier
A) the individual layer nickel screen (100～400 order) of 2～5 layers is pressed into to nickel screen pieces on the press of 10～200MPa, or the nickel powder of 10～20 microns of average grain diameters is pressed into to aperture on the press of 10～200MPa is less than the Ni-based micro-filtration diaphragm that 1 micron, porosity are 30～40%, thickness is 1～3mm;
B) Ni-based micro-filtration diaphragm, individual layer nickel screen or nickel screen pieces are put into to beaker, to adding deionized water that mass ratio is 1:0.01～0.1 and washing agent (industry or detergent for household use all can), ultrasonic 10～30 minutes in beaker; Put into beaker after Ni-based micro-filtration diaphragm, individual layer nickel screen or nickel screen pieces are taken out, add the ultrasonic processing of deionized water 10～15 minutes, outwell the liquid in beaker; Repeat deionized water ultrasound treatment step 2～5 times, put into 80～150 ℃ of baking ovens after taking-up dry 1～5 hour, thereby obtain cleaned Ni-based micro-filtration diaphragm, individual layer nickel screen or nickel screen pieces carrier;
2, growth:
Growth in situ: add L-asp, bpy, water and methyl alcohol that mass ratio is 1:0.1～10:0.1～10:1～100 in beaker, obtain reaction mother liquor after stirring evenly, again reaction mother liquor is transferred in stainless steel casing, teflon-lined reactor, cleaned Ni-based micro-filtration diaphragm or nickel screen pieces carrier level are immersed in reaction mother liquor, tighten the reaction kettle cover, then reactor is put into to 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards reactor being taken out, the last Coordination Polymer Ni grown that takes out from reactor
2(L-asp)
2the bpy film;
Or diauxic growth:
1) at first prepare Ni (L-asp) (H
2o)
2, by NiCO
3with L-asp, by the mass ratio of 1:0.5～2, be added to the water, heating is stirred to dissolve, and remain under 80～100 ℃ water is constantly evaporated, when having crystal to separate out, stop heating, naturally cool to after room temperature and put into refrigerator and keep crystal all being separated out in 5～20 hours under 0～5 ℃, filter and natural drying Ni (the L-asp) (H that obtains at room temperature
2o)
2;
2) then, add L-asp, bpy, water and methyl alcohol that mass ratio is 1:0.1～10:0.1～10:1～100 in beaker, obtain reaction mother liquor after stirring evenly, again reaction mother liquor is forwarded in stainless steel casing, teflon-lined reactor, cleaned individual layer nickel screen carrier level is immersed in reaction mother liquor, tighten the reaction kettle cover, then reactor is put into to 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards reactor being taken out, finally from reactor, taking out growth has Coordination Polymer Ni
2(L-asp)
2the individual layer nickel screen carrier of bpy crystal seed;
3) add again Ni (the L-asp) (H that mass ratio is 1:0.1～10:1～100:1～100 in beaker
2o)
2, bpy, water and methyl alcohol, obtain reaction mother liquor after stirring evenly, then reaction mother liquor be transferred in stainless steel casing, teflon-lined reactor, above-mentioned length is had well to Coordination Polymer Ni
2(L-asp)
2the individual layer nickel screen carrier of bpy crystal seed vertically immerses in reaction mother liquor, tighten the reaction kettle cover, then reactor is put into to 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, after afterwards reactor being taken out, be cooled to room temperature, the last good Coordination Polymer Ni of diauxic growth that takes out from reactor
2(L-asp)
2the bpy film.
3, the activation of membrane material:
By the Coordination Polymer Ni grown
2(L-asp)
2the bpy film is put into 100～200 ℃ of baking ovens 5～10 hours, takes out and naturally cools to room temperature, thereby obtain removing the good membrane material of activation of water and methyl alcohol guest molecule, and the duct size of resulting materials is
Coordination Polymer membrane material of the present invention can be widely used in mist (H
2/ CO
2, H
2/ CH
4, H
2/ N
2deng), the separation of chirality isomer (chiral diol isomer, chiral amino acid, chiral drug molecule).
The method of testing of separating chiral glycol isomer of the present invention is the fluid separation applications method of testing under the infiltration evaporation pattern, the surface of the film that the chiral diol isomer of different temperatures, pressure and composition is prepared in the present invention is flow through, another side will be collected in the receiving flask in cold-trap (77K) by the component vaporization of film by the method for decompression, the penetrating rate of Mass Calculation of effective area, acquisition time and collection sample by the film surface, the component obtained is carried out to gas chromatographic analysis and form evaluation, thus the separation factor of definite film.
Dependence test condition and the method that the present invention relates to:
Electron scanning micrograph: SEM is that to use is the JSM-6510A AnalyticalScanning Eletron Microscope of JEOL.
X-ray electronic diffraction spectrogram: XRD test is used is the LabX XRD-6000X-ray～Diffract Meter of SHIMAZU.Adopt the Cu launching site, scanning 2theta scope is 4～40 °.
Gas chromatographic analysis: Shimadzu GC2014; Column temperature: 30 ℃; Detector: TCD, mist consist of the volume ratio hydrogen of 1: 1 and carbon dioxide (or methane, nitrogen).
Liquid-phase chromatographic analysis: Shimadzu GC2014; Column temperature: 150; Chromatographic column: CP-Chirasil-Dex CB
The accompanying drawing explanation
The x-ray diffraction spectra of Fig. 1: embodiment 1 and embodiment 2 samples;
SEM (SEM) photo of Fig. 2: embodiment 1 sample;
SEM (SEM) photo of Fig. 3: embodiment 2 samples;
The mist separation factor curve of Fig. 4: embodiment 2 samples;
Fig. 5: the present invention is for the device schematic diagram of chirality isomer discrete testing;
(A) mother liquor, (B) He gas cylinder, (C) flow controller 1, and (D) flow controller 2, (E) temperature controller, (F) oil bath heater, (G) membrane module, (H) receiving flask, (I) cold-trap, (J) gas chromatograph, (K) Pressure gauge, (L) valve.
In Fig. 1: a standard x optical diffraction spectrogram that its crystal structure simulation (materials studio 4.0) goes out of serving as reasons, the x-ray diffraction spectra that b is the synthetic film of embodiment 1, c and d are respectively the x-ray diffraction spectra after the synthetic and activation of embodiment 2.To recently seeing, can find that the spectrogram peak position after synthetic and activation is consistent with the standard spectrogram of simulation, illustrate that membrane material has the microstructure identical with corresponding Coordination Polymer, and still keep original skeleton structure after removing guest molecule, do not cave in.
Fig. 2 is Coordination Polymer Membrane front and cross section electron scanning micrograph synthetic in embodiment 1.The full face that wherein a is the nickel screen pieces carrier, the film cross-section photograph that b is embodiment 1 preparation, c, d are respectively the scanned photograph under the positive different amplification of film of embodiment 1 preparation.We can obtain conclusion comprehensive a few width figure, and we have prepared the thick continuous Coordination Polymer Ni of large tracts of land in 20 microns left and right of one deck on the nickel screen pieces surface by growth in situ
2(L-asp)
2the bpy film.
Fig. 3 is ligand compound film front and cross section electron scanning micrograph synthetic in embodiment 2.Wherein a be after individual layer nickel screen carrier seeded growth full face, the film cross-section photograph that c is embodiment 2 preparation, b, d are respectively the scanned photograph under the positive different amplification of film of embodiment 2 preparations.We can obtain conclusion comprehensive a few width figure, and we have prepared the continuous Coordination Polymer Ni of one deck large tracts of land by the method for diauxic growth on individual layer nickel screen surface
2(L-asp)
2the bpy film.
The Coordination Polymer membrane material that Fig. 4 is embodiment 2 preparations carries out two component mist discrete testing results.Can find that from figure the separating effect that film separated the mist of hydrogen and carbon dioxide is best, separation factor can reach 8～9, and the separation factor of the mist that the mist that film forms hydrogen and methane and film form hydrogen and nitrogen also can reach 5～6.Simultaneously, separating effect is along with the time keeps stable.
Separation factor alpha=(w
a p/ w
b p)/(w
a f/ w
b f)
In above formula, w
a p, w
b prepresentative sees through a of film, the amount of b component, w respectively
a f, w
b frepresent respectively a in material liquid, the amount of b component.
Fig. 5 is the device schematic diagram for chirality isomer discrete testing.This device, for homemade, is made by stainless steel material, and each several part title and connected mode are as shown in the figure.Under the drive and flow controller (C) control (D) of the different chiral diol isomer mixing mother liquors (A) that form through pipeline liquid injecting device helium in helium tank (B), heater (F) through temperature controller (E) temperature control, enter the one side of membrane module (G), and control the pressure in whole pipeline by valve (L), the force value registration is shown by Pressure gauge (K), the another side of membrane module (G) connects the receiving flask (H) in cold-trap (I), the isolated component of collection membrane under the condition vacuumized, the collection sample obtained the most at last carries out gas-chromatography (J) and analyzes wherein each constituent content.The temperature of heater (F) is 25 ° of C～200 ° C, film prepared by the present invention is fixed in the middle of membrane module (in separation for placing the fixedly parts of film), mix the one side circulation of mother liquor (A) film in membrane module, the another side of film vacuumizes, to collect in cold-trap through the isolated component of film, the temperature of cold-trap is 77K.
Preferred forms
Embodiment 1:
The pretreatment of step 1, carrier:
3 layer of 180 order nickel screen (Xinxiang, Henan 504 factories) is pressed into to nickel screen pieces with 20MPa on hydraulic press, will press afterwards nickel screen pieces put into the 50ml beaker, add wherein 20ml deionized water and 0.1g washing agent (vertical white washing agent), ultrasonic 30 minutes; Then put into the 50ml beaker after nickel screen pieces being taken out, add deionized water 30ml, the liquid that ultrasonic processing is outwelled in beaker in 15 minutes; Repeat deionized water ultrasonic cleaning step 5 time; Put into 100 ℃ of baking ovens dry 5 hours after finally nickel screen pieces being taken out, thereby obtain cleaned nickel screen pieces carrier.
Add the L-asp of 0.1g and the bpy of 0.058g in the 20ml beaker, and add 0.1ml water and 1ml methyl alcohol, obtain reaction mother liquor after stirring evenly, again reaction mother liquor is proceeded in stainless steel casing, teflon-lined reactor, cleaned nickel screen pieces carrier level is put into to reaction mother liquor, after tightening the reaction kettle cover, put into 150 ℃ of baking ovens and carry out growth in situ 2 days, afterwards reactor is taken out and is cooled to room temperature, take out the Coordination Polymer Ni grown
2(L-asp)
2the bpy film.
The activation of step 3, membrane material:
By the Ni grown
2(L-asp)
2the bpy film is put into 150 ℃ of baking ovens 10 hours, then takes out and to naturally cool to room temperature, obtains removing the good membrane material of activation of guest molecule.
Step 4, sign:
The membrane material activated is carried out to the test of powder X ray diffracting spectrum, SEM sign and chirality isomer discrete testing, that separates is respectively R (S)-2-methyl-2,4-pentanediol or R (S)-1, the 3-succinic acid, the 2-methyl-2 that the RS isomer is mixed, 4-pentanediol or 1,3-succinic acid enter respectively the one side of film under the drive of flow controller, and another side vacuumizes and collect the component that sees through the film surface under 77K liquid nitrogen condition by mechanical pump.Separating resulting is in Table 1.
Show that at high temperature (150～200 ℃) separating effect is better, during former because low temperature, Ni
2(L-asp)
2the chirality duct of bpy is little to the selective absorption of two kinds of chiral diol isomers, and along with temperature raises, the glycol molecules of S configuration is more stable in duct, hinder passing through of R configuration glycol molecules simultaneously, so it is more that S type configuration molecule is crossed, separating effect rises.
Table 1: different separation temperatures (℃) under separation factor
| Separation temperature (℃) | 25 | 100 | 200 |
| 2-methyl-2, the 4-pentanediol | 1.19 | 1.20 | 1.41 |
| 1,3-succinic acid | 1.71 | 1.83 | 2.61 |
The pretreatment of step 1, carrier:
Individual layer nickel screen (180 orders, Xinxiang, Henan 504 factories) is put into to the 50ml beaker, add 20ml deionized water and washing agent, ultrasonic 30 minutes.Put into the 50ml beaker after taking out, add deionized water 30ml, the liquid that ultrasonic processing is outwelled in beaker in 15 minutes, repeat deionized water ultrasonic cleaning step 5 time.Put into 100 ℃ of baking ovens after taking-up dry 5 hours, obtain cleaned individual layer nickel screen carrier.
Add the L-asp of 0.1g and the bpy of 0.058g in the 20ml beaker, and add 0.1ml water and 1ml methyl alcohol, after stirring evenly, proceed in stainless steel casing, teflon-lined reactor, the individual layer nickel screen carrier level that previous step is handled well is put into reaction mother liquor, after tightening kettle cover, put into 150 ℃ of baking ovens and carry out growth in situ 2 days, be cooled to room temperature after taking-up, take out the coordination polymerization Ni grown
2(L-asp)
2the carrier of bpy crystal seed.Step 3, Ni (L-asp) (H
2o)
2preparation:
NiCO
3with L-asp, by the mass ratio of 1: 0.92, be added to the water, heating is stirred to dissolve, and remain under 100 ℃ water is constantly evaporated, when having crystal to separate out, stop heating, and naturally cool to after room temperature and put into refrigerator and keep crystal all being separated out in 10 hours under 5 ℃, filter and natural drying Ni (the L-asp) (H that obtains at room temperature
2o)
2.
Step 4, diauxic growth:
Add Ni (the L-asp) (H that mass ratio is 0.219g in the 20ml beaker
2o)
2, 0.078g bpy, 6ml water and 6ml methyl alcohol, after stirring evenly, proceed in stainless steel casing teflon-lined reactor, there is to coordination polymerization Ni on synthetic before surface
2(L-asp)
2the nickel screen carrier of bpy crystal seed is vertically put into reaction mother liquor, after tightening kettle cover, puts into 150 ℃ of baking ovens and carries out growth in situ 2 days, is cooled to room temperature after taking-up, takes out the good Coordination Polymer Ni of diauxic growth
2(L-asp)
2the bpy film.
The activation of step 5, membrane material:
Synthetic membrane material is put into to 150 ℃ of baking ovens 10 hours, then take out and to naturally cool to room temperature, obtain removing the membrane material that guest molecule activates.
Step 6, sign:
It is carried out to the test of powder X ray diffracting spectrum, SEM sign and mist discrete testing, that adopt is Wicke-Kallenbach Technique device (Angew.Chem.Int.Ed.2006,45,7053-7056), two kinds of gas and carrier gas Ar enter membrane module from gas cylinder under the control of mass flow controller, and gas outlet end is by the pressure reduction at counterbalance valve controlling diaphragm two ends.The gas seen through enters gas-chromatography by the carrier gas purging and checks that various gas contents are to determine separating effect, and test result as shown in Figure 4.Its mean value is as shown in table 2:
Table 2: different separation factor and the H that mix gas composition
2transmitance
Transmitance is the number of moles of gas that unit interval elementary membrane area was thrown.
Result shows with respect to other two kinds of gases, H
2to CO
2separating effect best, can reach 8.7, higher than the Knudsen diffusion theoretical value, illustrate that this film can be used for H
2with other gases, separate.Simultaneously, the transmitance of hydrogen is also very high, can reach 10
-6the order of magnitude, have good using value.
Embodiment 3
Step 4, diauxic growth:
Add Ni (the L-asp) (H that mass ratio is 0.219g in the 20ml beaker
2o)
2, 0.156g bpy, 6ml water and 6ml methyl alcohol, after stirring evenly, proceed in stainless steel casing teflon-lined reactor, there is to coordination polymerization Ni on synthetic before surface
2(L-asp)
2the nickel screen carrier of bpy crystal seed is vertically put into reaction mother liquor, after tightening kettle cover, puts into 150 ℃ of baking ovens and carries out growth in situ 2 days, is cooled to room temperature after taking-up, takes out the good Coordination Polymer Ni of diauxic growth
2(L-asp)
2the bpy film.
The activation of step 5, membrane material:
Synthetic membrane material is put into to 150 ℃ of baking ovens 10 hours, then take out and to naturally cool to room temperature, obtain removing the membrane material that guest molecule activates.
Step 6, sign:
It is carried out to the test of powder X ray diffracting spectrum, SEM and characterize and the mist discrete testing, two kinds of gas and carrier gas Ar enter membrane module from gas cylinder under the control of mass flow controller, and gas outlet end is by the pressure reduction at counterbalance valve controlling diaphragm two ends.The gas seen through enters gas-chromatography by the carrier gas purging and checks that various gas contents are to determine separating effect, and test result is as shown in table 3:
Table 3: different separation factor and the H that mix gas composition
2transmitance
| H 2/CO 2 | H 2/CH 4 | H 2/N 2 | |
| Separation factor | 7.2 | 5.3 | 4.2 |
| H 2Transmitance | 1.77×10 -6 | 1.76×10 -6 | 1.82×10 -6 |
Result shows to add the more bpy of vast scale, the Quality Down of film, and separation factor reduces, and transmitance rises.
Embodiment 4
Step 4, diauxic growth:
Add Ni (the L-asp) (H that mass ratio is 0.219g in the 20ml beaker
2o)
2, 0.312g bpy, 6ml water and 6ml methyl alcohol, after stirring evenly, proceed in stainless steel casing teflon-lined reactor, there is to coordination polymerization Ni on synthetic before surface
2(L-asp)
2the nickel screen carrier of bpy crystal seed is vertically put into reaction mother liquor, after tightening kettle cover, puts into 150 ℃ of baking ovens and carries out growth in situ 2 days, is cooled to room temperature after taking-up, takes out the good Coordination Polymer Ni of diauxic growth
2(L-asp)
2the bpy film.
The activation of step 5, membrane material:
Synthetic membrane material is put into to 150 ℃ of baking ovens 10 hours, then take out and to naturally cool to room temperature, obtain removing the membrane material that guest molecule activates.
Step 6, sign:
It is carried out to the test of powder X ray diffracting spectrum, SEM and characterize and the mist discrete testing, two kinds of gas and carrier gas Ar enter membrane module from gas cylinder under the control of mass flow controller, and gas outlet end is by the pressure reduction at counterbalance valve controlling diaphragm two ends.The gas seen through enters gas-chromatography by the carrier gas purging and checks that various gas contents are to determine separating effect, and test result is as shown in table 4:
Table 4: different separation factor and the H that mix gas composition
2transmitance
| H 2/CO 2 | H 2/CH 4 | H 2/N 2 | |
| Separation factor | 6.4 | 4.8 | 3.2 |
| H 2Transmitance | 2.01×10 -6 | 1.97×10 -6 | 2.14×10 -6 |
Conclusion shows further to improve the ratio of bpy in synthetic system, and the quality of film is poorer, and separating effect only is better than the Knudsen diffusion theoretical value reluctantly, but flow has increased nearly one times.
Embodiment 5:
The pretreatment of step 1, carrier:
Ni-based micro-filtration diaphragm (2mm is thick) is put into to the 50ml beaker, add wherein 20ml deionized water and 0.1g washing agent (vertical white washing agent), ultrasonic 30 minutes; Then put into the 50ml beaker after Ni-based micro-filtration diaphragm being taken out, add deionized water 30ml, the liquid that ultrasonic processing is outwelled in beaker in 15 minutes; Repeat deionized water ultrasonic cleaning step 5 time; Put into 100 ℃ of baking ovens dry 5 hours after finally Ni-based micro-filtration diaphragm being taken out, thereby obtain cleaned Ni-based micro-filtration diaphragm carrier.
Add the L-asp of 0.1g and the bpy of 0.058g in the 20ml beaker, and add 0.1ml water and 1ml methyl alcohol, obtain reaction mother liquor after stirring evenly, again reaction mother liquor is proceeded in stainless steel casing, teflon-lined reactor, cleaned Ni-based micro-filtration diaphragm carrier level is put into to reaction mother liquor, after tightening the reaction kettle cover, put into 150 ℃ of baking ovens and carry out growth in situ 2 days, afterwards reactor is taken out and is cooled to room temperature, take out the Coordination Polymer Ni grown
2(L-asp)
2the bpy film.
The activation of step 3, membrane material:
By the Ni grown
2(L-asp)
2the bpy film is put into 150 ℃ of baking ovens 10 hours, then takes out and to naturally cool to room temperature, obtains removing the good membrane material of activation of guest molecule.
Step 4, sign:
The membrane material activated is carried out to the test of powder X ray diffracting spectrum, SEM sign and chirality isomer discrete testing, that separates is respectively R (S)-2-methyl-2,4-pentanediol or R (S)-1, the 3-succinic acid, the 2-methyl-2 that the RS isomer is mixed, 4-pentanediol or 1,3-succinic acid enter respectively the one side of film under the drive of flow controller, and another side vacuumizes and collect the component that sees through the film surface under 77K liquid nitrogen condition by mechanical pump.Separating resulting is in Table 5.
Conclusion is that under high temperature, separating effect is better, consistent with embodiment 1.
Table 5: different separation temperatures (℃) under separation factor
| Separation temperature (℃) | 25 | 100 | 150 | 200 |
| 2-methyl-2, the 4-pentanediol | 1.10 | 1.16 | 1.37 | 1.44 |
| 1,3-succinic acid | 1.66 | 1.72 | 2.59 | - |
Claims (7)
1. a Coordination Polymer Membrane Ni
2(L-asp)
24,4-bipyridyl material, it is characterized in that: be by metallic nickel ions and L-asp, 4, the three-dimensional apertures material with homogeneous duct size that the coordination of 4-bipyridyl forms, the oxygen atom ligand of metallic nickel and L-asp forms layer, again with 4,4-bipyridyl in the pillared three-dimensional framework structure that forms of nitrogen-atoms coordination.
2. the preparation method of a kind of Coordination Polymer membrane material claimed in claim 1, its step is as follows:
(1) pretreatment of carrier:
A) 2～5 layers, 100～400 purpose individual layer nickel screens are pressed into to nickel screen pieces on the press of 10～200MPa, or the nickel powder of 10～20 microns of average grain diameters is pressed into to aperture on the press of 10～200MPa is less than the Ni-based micro-filtration diaphragm that 1 micron, porosity are 30～40%, thickness is 1～3mm;
B) Ni-based micro-filtration diaphragm or nickel screen pieces are put into to beaker, add deionized water and the washing agent that mass ratio is 1:0.01～0.1 in beaker, ultrasonic 10～30 minutes; Then by after Ni-based micro-filtration diaphragm or nickel screen pieces taking-up, putting into beaker, add the ultrasonic processing of deionized water 10～15 minutes, outwell the liquid in beaker; Repeat deionized water ultrasound treatment step 2～5 times, put into 80～150 ℃ of baking ovens after taking-up dry 1～5 hour, thereby obtain cleaned Ni-based micro-filtration diaphragm or nickel screen pieces carrier;
(2) growth:
Add the L-asp, 4 that mass ratio is 1:0.1～10:0.1～10:1～100 in beaker, 4-bipyridyl, water and methyl alcohol, obtain reaction mother liquor after stirring evenly, again reaction mother liquor is transferred in stainless steel casing, teflon-lined reactor, cleaned Ni-based micro-filtration diaphragm or nickel screen pieces carrier level are put into to reaction mother liquor, tighten the reaction kettle cover, then reactor is put into to 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards reactor being taken out, the last Coordination Polymer Membrane Ni grown that takes out from reactor
2(L-asp)
24,4-bipyridyl;
(3) activation of membrane material:
By the Coordination Polymer Membrane Ni grown
2(L-asp)
24,4-bipyridyl is put into 100～200 ℃ of baking ovens 5～10 hours, takes out and naturally cools to room temperature, thereby obtain removing the good membrane material of activation of water and methyl alcohol guest molecule.
3. the preparation method of a kind of Coordination Polymer membrane material claimed in claim 1, its step is as follows:
(1) pretreatment of carrier
The individual layer nickel screen is put into to beaker, to the deionized water and the washing agent that add mass ratio 1:0.01～0.1 in beaker, ultrasonic 10～30 minutes; Then put into beaker after the individual layer nickel screen being taken out, add the ultrasonic processing of deionized water 10～15 minutes, outwell the liquid in beaker; Repeat deionized water ultrasound treatment step 2～5 times, put into 80～150 ℃ of baking ovens dry 1～5 hour after then the individual layer nickel screen being taken out, thereby obtain cleaned individual layer nickel screen carrier;
(2) growth
Before this by NiCO
3with L-asp, by the mass ratio of 1:0.5～2, be added to the water, heating is stirred to dissolve, and remain under 80～100 ℃ water is constantly evaporated, when having crystal to separate out, stop heating, and naturally cool to after room temperature and put into refrigerator and remain under 0～5 ℃ 5～20 hours crystal is all separated out, filter and natural drying Ni (the L-asp) (H that obtains at room temperature
2o)
2;
Then, add the L-asp, 4 that mass ratio is 1:0.1～10:0.1～10:1～100 in beaker, 4-bipyridyl, water and methyl alcohol, obtain reaction mother liquor after stirring evenly, again reaction mother liquor is forwarded in stainless steel casing, teflon-lined reactor, cleaned individual layer nickel screen carrier level is put into to reaction mother liquor, tighten the reaction kettle cover, then reactor is put into to 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards reactor being taken out, finally from reactor, taking out to grow has Coordination Polymer Ni
2(L-asp)
2the individual layer nickel screen carrier of 4,4-bipyridyl crystal seed;
Add again Ni (the L-asp) (H that mass ratio is 1:0.1～10:1～100:1～100 in beaker
2o)
2, 4,4-bipyridyl, water and methyl alcohol, obtain reaction mother liquor after stirring evenly, then reaction mother liquor is transferred in stainless steel casing, teflon-lined reactor, and above-mentioned length is had well to Coordination Polymer Ni
2(L-asp)
24, the individual layer nickel screen carrier of 4-bipyridyl crystal seed is vertically put into reaction mother liquor, tighten the reaction kettle cover, then reactor is put into to 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards reactor being taken out, the last good Coordination Polymer Ni of diauxic growth that takes out from reactor
2(L-asp)
24,4-bipyridyl film;
(3) activation of membrane material:
By the Coordination Polymer Ni grown
2(L-asp)
24,4-bipyridyl film is put into 100～200 ℃ of baking ovens 5～10 hours, takes out and naturally cools to room temperature, thereby obtain removing the good membrane material of activation of water and methyl alcohol guest molecule.
4. the application of a kind of Coordination Polymer membrane material claimed in claim 1 aspect the mist separation.
5. the application of a kind of Coordination Polymer membrane material as claimed in claim 4 aspect the mist separation is characterized in that: the mist that the mist that mist, hydrogen and the methane that mist is hydrogen and carbon dioxide composition forms or hydrogen and nitrogen form.
6. the application of a kind of Coordination Polymer membrane material claimed in claim 1 aspect the separation of chirality isomer.
7. the application of a kind of Coordination Polymer membrane material as claimed in claim 6 aspect the separation of chirality isomer, is characterized in that: for separating of chiral diol, chiral amino acid or chiral drug molecule.
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| CN103816812B (en) * | 2014-02-24 | 2015-10-14 | 中国石油大学(华东) | Coordination polymer membrane material and the application in carbon dioxide separation thereof |
| CN105771697B (en) * | 2016-03-29 | 2018-02-09 | 中国石油大学(华东) | The coordination polymer membrane material of hydrophobic polymeric coating modification, preparation method and applications |
| CN105854651B (en) * | 2016-04-06 | 2018-06-29 | 中国石油大学(华东) | A kind of high permeability mixed substrate membrane containing nano-grade molecular sieve and its preparation method and application |
| CN105977483A (en) * | 2016-05-17 | 2016-09-28 | 中国石油大学(华东) | Carbon-based nanocomposite material for electrode |
| CN111151145B (en) * | 2018-11-08 | 2022-04-05 | 中国石油化工股份有限公司 | Super-hydrophobic separation membrane and preparation method and application thereof |
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