CN102728236A - 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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- CN102728236A CN102728236A CN2012101995408A CN201210199540A CN102728236A CN 102728236 A CN102728236 A CN 102728236A CN 2012101995408 A CN2012101995408 A CN 2012101995408A CN 201210199540 A CN201210199540 A CN 201210199540A CN 102728236 A CN102728236 A CN 102728236A
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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 Polymers membrane material, the application aspect mist or the separation of chirality isomer of preparation method and this membrane material.
Background technology
Coordination Polymers typically refers to the metallic organic framework crystalline material with periodic network structure that little molecule ligand and metal ion form through self assembling process.This type 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 with zeolite molecular sieve; And the expansion of design of the orientation through topological structure and organo-functional group can obtain the duct and the hole of different size, has the character such as light, electricity, magnetic of uniqueness 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, structure of the design of Coordination Polymers in recent years and performance study develop rapidly and become one of research focus interdisciplinary.
Coordination polymer material is as a kind of novel inorganic porous material, and how its research method and research purpose mainly concentrate on through the design of organo-functional group and expand the breakthrough that realizes the duct size.The design that people do one's utmost, synthetic and seek new organic ligand, expectation obtains bigger duct and void structure.People had spent a large amount of energy and material resources to be devoted to design synthetic Coordination Polymers crystalline material with new construction in nearly ten years; But the research for the Coordination Polymers membrane material is few; Because this type material has regularly arranged pore passage structure, duct size, connectedness and controllability as molecular screen material; And the duct can be designed or modify the variation that reaches 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.Even the duct of the coordination polymer material that the has generation breathing phenomenon that to stretch.Comprehensive above advantage, Coordination Polymers membrane material have caused the interest of people's preparation and research.
The chirality chemistry received in recent years widely always and paying close attention to; This is to be as different as light from darkness because have the effect of two kinds of isomers on using of different chiral structures; For example, a kind of chiral configuration of this medicine of naproxen (NAP) is active 28 times of another kind of chirality anti-inflammatory drug; A kind of enantiomer of dopamine is 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 kinds of advantages are arranged:
1. still less side effect;
2. patient can correspondingly take the medicine of few dosage;
3. can save and produce us and do not hope the waste that enantiomer brought that obtains;
4. " racemic product is originally changed " brought 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 react with isolated compound, limits its application.Although Coordination Polymer Membrane extensive studies is used for the separation of gas with various, the research that is used to separate organic liquid still is few.Particularly to the separation of chirality isomer.
Summary of the invention
The purpose of this invention is to provide a kind of Coordination Polymers membrane material, its preparation method and utilize this Coordination Polymers membrane material to carry out the separation of mist or chirality isomer.
Related Coordination Polymers 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 that 4-bipyridyl (bpy) coordination forms with homogeneous duct size; The oxygen atom ligand of metallic nickel atom and L-aspartic acid forms layer; Again with 4, the pillared three-dimensional framework structure that forms of the nitrogen-atoms coordination in the 4-bipyridyl.
The present invention adopts the method for original position or diauxic growth under different solvent thermal conditions, to obtain the Coordination Polymers membrane material through selecting different carrier and carrier preprocess method, and its step is following:
1, the preliminary treatment of carrier
A) 2～5 layers individual layer nickel screen (100～400 order) is pressed into the nickel screen sheet on the press of 10～200MPa, or with the nickel powder of 10～20 microns of average grain diameters on the press of 10～200MPa, be pressed into the aperture less than 1 micron, porosity be 30～40%, thickness is the Ni-based micro-filtration diaphragm of 1～3mm;
B) Ni-based micro-filtration diaphragm, individual layer nickel screen or nickel screen sheet are put into beaker, in beaker, add mass ratio and be deionized water and the washing agent (industry or detergent for household use all can) of 1:0.01～0.1, ultrasonic 10～30 minutes; With putting into beaker after Ni-based micro-filtration diaphragm, individual layer nickel screen or the taking-up of nickel screen sheet, added the deionized water sonicated 10～15 minutes, outwell the liquid in the beaker; Repeat deionized water ultrasound treatment step 2～5 times, put into 80～150 ℃ of baking ovens after the taking-up dry 1～5 hour, thereby obtain cleaned Ni-based micro-filtration diaphragm, individual layer nickel screen or nickel screen sheet carrier;
2, growth:
Growth in situ: in beaker, adding mass ratio is L-asp, bpy, water and the methyl alcohol of 1:0.1～10:0.1～10:1～100; Obtain reaction mother liquor after stirring; Again reaction mother liquor is transferred in stainless steel casing, the teflon-lined agitated reactor; Cleaned Ni-based micro-filtration diaphragm or nickel screen sheet carrier level are immersed in the reaction mother liquor, tighten the reaction kettle cover, then agitated reactor is put into 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day; Be cooled to room temperature after afterwards agitated reactor being taken out, from agitated reactor, take out the good Coordination Polymers Ni of growth at last
2(L-asp)
2The bpy film;
Or diauxic growth:
1) at first prepares Ni (L-asp) (H
2O)
2, with NiCO
3Be added to the water by the mass ratio of 1:0.5～2 with L-asp; Heated and stirred makes dissolving; And remain under 80～100 ℃ water is constantly evaporated, when crystal to be had is separated out, stop heating; Naturally cool to and put into refrigerator after the room temperature and keep down crystal all being separated out in 5～20 hours, filter and air dry at room temperature obtains Ni (L-asp) (H at 0～5 ℃
2O)
2
2) then; In beaker, adding mass ratio is L-asp, bpy, water and the methyl alcohol of 1:0.1～10:0.1～10:1～100; Obtain reaction mother liquor after stirring, again reaction mother liquor is forwarded in stainless steel casing, the teflon-lined agitated reactor, cleaned individual layer nickel screen carrier level is immersed in the reaction mother liquor; Tighten the reaction kettle cover; Then agitated reactor is put into 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards agitated reactor being taken out, from agitated reactor, taking out growth at last has Coordination Polymers Ni
2(L-asp)
2The individual layer nickel screen carrier of bpy crystal seed;
3) in beaker, adding mass ratio again is Ni (the L-asp) (H of 1:0.1～10:1～100:1～100
2O)
2, bpy, water and methyl alcohol, obtain reaction mother liquor after stirring, again reaction mother liquor is transferred in stainless steel casing, the teflon-lined agitated reactor, above-mentioned length is had Coordination Polymers Ni well
2(L-asp)
2The individual layer nickel screen carrier of bpy crystal seed vertically immerses in the reaction mother liquor; Tighten the reaction kettle cover; Then agitated reactor is put into 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards agitated reactor being taken out, from agitated reactor, take out the good Coordination Polymers Ni of diauxic growth at last
2(L-asp)
2The bpy film.
3, the activation of membrane material:
The Coordination Polymers Ni that growth is good
2(L-asp)
2The bpy film was put into 100～200 ℃ of baking ovens 5～10 hours, took out and naturally cooled to room temperature, thereby obtain removing the good membrane material of activation of water and methyl alcohol guest molecule, and the duct size of gained material does
Coordination Polymers 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 chiral diol isomer of different temperatures, pressure and composition is in the surface current mistake of the prepared film of the present invention; Another side will be collected in the receiving flask in the cold-trap (77K) through the component vaporization of film through the method for decompression; The penetrating rate of Mass Calculation through surperficial effective area, acquisition time and collection sample of film; The component that obtains is carried out gas chromatographic analysis form evaluation, thus the separation factor of definite film.
Dependence test condition and the method that the present invention relates to:
That electron scanning micrograph: SEM is to use is the JSM-6510A AnalyticalScanning Eletron Microscope of JEOL.
That X-ray electronic diffraction spectrogram: XRD test is used is LabX XRD-6000X-ray～Diffract Meter of SHIMAZU.Adopt the Cu launching site, scanning 2theta scope is 4～40 °.
Gas chromatographic analysis: Tianjin, island GC2014; Column temperature: 30 ℃; Detector: TCD, mist consist of 1: 1 hydrogen of volume ratio and carbon dioxide (or methane, nitrogen).
Liquid-phase chromatographic analysis: Tianjin, island GC2014; Column temperature: 150; Chromatographic column: CP-Chirasil-Dex CB
Description of drawings
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 used for the device sketch map 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.
Among Fig. 1: a standard x optical diffraction spectrogram that its crystal structure simulation (materials studio 4.0) goes out of serving as reasons, b be the x-ray diffraction spectra of the synthetic film of embodiment 1, and c and d are respectively embodiment 2 and synthesize the x-ray diffraction spectra that reaches after the activation.To recently seeing, can find that the spectrogram peak position after synthetic and the activation is consistent with the standard spectrogram of simulation, explain that membrane material has the microstructure identical with corresponding Coordination Polymers, and still keep original skeleton structure behind the removal guest molecule, do not cave in.
Fig. 2 is Coordination Polymer Membrane front and a cross section electron scanning micrograph synthetic among the embodiment 1.Wherein a is the full face of nickel screen sheet carrier, and b is the film cross-section photograph of embodiment 1 preparation, and 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 of cloth figure, and we have prepared the thick continuous Coordination Polymers Ni of large tracts of land in 20 microns left and right sides of one deck on nickel screen sheet surface through growth in situ
2(L-asp)
2The bpy film.
Fig. 3 is ligand compound film front and a cross section electron scanning micrograph synthetic among the embodiment 2.Wherein a be behind the individual layer nickel screen carrier seeded growth full face, c is the film cross-section photograph of 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 of cloth figure, our method through diauxic growth in individual layer nickel screen surface preparation the continuous Coordination Polymers Ni of one deck large tracts of land
2(L-asp)
2The bpy film.
Fig. 4 carries out two component mist discrete testing results for the Coordination Polymers membrane material of embodiment 2 preparations.Can find that from figure film is best to the separating effect that the mist of hydrogen and carbon dioxide separates; Separation factor can reach 8～9, and mist that film is formed hydrogen and methane and film also can reach 5～6 to the separation factor of the hydrogen and the mist of nitrogen composition.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 the following formula, w
a p, w
b pRepresentative sees through a of film, the amount of b component, w respectively
a f, w
b fRepresent a in the material liquid respectively, the amount of b component.
Fig. 5 is the device sketch map that is used for chirality isomer discrete testing.This device is processed by stainless steel material for homemade, 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 of forming (A) through airtight pipeline helium in helium tank (B); Heater (F) through temperature controller (E) temperature control; Get into the one side of membrane module (G); And through the pressure in the whole pipeline of valve (L) control, the force value registration is shown that by Pressure gauge (K) another side of membrane module (G) connects the receiving flask (H) in the cold-trap (I); The isolated component of collection membrane under the condition that vacuumizes, the collection sample that obtains are the most at last carried out gas-chromatography (J) and are analyzed wherein each constituent content.The temperature of heater (F) is 25 ° of C～200 ° C; The film of the present invention's preparation is fixed in the middle of the membrane module (being used to place the fixedly parts of film in the separation); Mix the one side circulation of mother liquor (A) film in membrane module; The another side of film vacuumizes, and will collect in the cold-trap through the isolated component of film, and the temperature of cold-trap is 77K.
Preferred forms
Embodiment 1:
The preliminary treatment of step 1, carrier:
3 layer of 180 order nickel screen (Xinxiang, Henan 504 factories) is pressed into the nickel screen sheet with 20MPa on hydraulic press, will press afterwards the nickel screen sheet put into the 50ml beaker, to wherein adding 20ml deionized water and 0.1g washing agent (upright white washing agent), ultrasonic 30 minutes; Put into the 50ml beaker after then the nickel screen sheet being taken out, add deionized water 30ml, the liquid that sonicated was outwelled in the beaker in 15 minutes; Repeat deionized water ultrasonic cleaning step 5 time; Put into 100 ℃ of baking ovens dry 5 hours after at last the nickel screen sheet being taken out, thereby obtain cleaned nickel screen sheet carrier.
In the 20ml beaker, add the L-asp of 0.1g and the bpy of 0.058g, and add 0.1ml water and 1ml methyl alcohol, obtain reaction mother liquor after stirring; Again reaction mother liquor is changed in stainless steel casing, the teflon-lined agitated reactor; Cleaned nickel screen sheet carrier level is put into reaction mother liquor, tighten the reaction kettle cover after, put into 150 ℃ of baking ovens and carried out growth in situ 2 days; Afterwards agitated reactor is taken out and be cooled to room temperature, take out the good Coordination Polymers Ni of growth
2(L-asp)
2The bpy film.
The activation of step 3, membrane material:
The Ni that growth is good
2(L-asp)
2The bpy film was put into 150 ℃ of baking ovens 10 hours, took out and naturally cooled to room temperature, obtained removing the good membrane material of activation of guest molecule.
Step 4, sign:
The good membrane material of activation is carried out 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)-1,3-succinic acid; 2-methyl-2 with the mixing of RS isomer; 4-pentanediol or 1,3-succinic acid get into the one side of film respectively under the drive of flow controller, another side vacuumizes through mechanical pump and under 77K liquid nitrogen condition, collects the component that sees through the film surface.Separating resulting is seen 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 the 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, the 3-succinic acid | 1.71 | 1.83 | 2.61 |
The preliminary treatment of step 1, carrier:
(180 orders, Xinxiang, Henan 504 factories) put into the 50ml beaker with the individual layer nickel screen, 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 sonicated was outwelled in the beaker in 15 minutes repeats deionized water ultrasonic cleaning step 5 time.Put into 100 ℃ of baking ovens after the taking-up dry 5 hours, and obtained cleaned individual layer nickel screen carrier.
In the 20ml beaker, add the L-asp of 0.1g and the bpy of 0.058g; And add 0.1ml water and 1ml methyl alcohol, and change over to after stirring in stainless steel casing, the teflon-lined agitated reactor, the individual layer nickel screen carrier level that a last step is handled well is put into reaction mother liquor; After tightening kettle cover; Put into 150 ℃ of baking ovens and carried out growth in situ 2 days, be cooled to room temperature after the taking-up, take out long good coordination polymerization Ni
2(L-asp)
2The carrier of bpy crystal seed.Step 3, Ni (L-asp) (H
2O)
2Preparation:
NiCO
3Be added to the water by 1: 0.92 mass ratio with L-asp; Heated and stirred makes dissolving; And remain under 100 ℃ water is constantly evaporated, when crystal to be had is separated out, stop heating; And naturally cool to and put into refrigerator after the room temperature and keep down crystal all being separated out in 10 hours at 5 ℃, filter and air dry at room temperature obtains Ni (L-asp) (H
2O)
2
Step 4, diauxic growth:
In the 20ml beaker, adding mass ratio is Ni (the L-asp) (H of 0.219g
2O)
2, 0.078g bpy, 6ml water and 6ml methyl alcohol, after stirring, change in the stainless steel casing teflon-lined agitated reactor, with before synthetic surface coordination polymerization Ni is arranged
2(L-asp)
2The nickel screen carrier of bpy crystal seed is vertically put into reaction mother liquor, tighten kettle cover after, put into 150 ℃ of baking ovens and carried out growth in situ 2 days, be cooled to room temperature after the taking-up, take out the good Coordination Polymers Ni of diauxic growth
2(L-asp)
2The bpy film.
The activation of step 5, membrane material:
Synthetic good membrane material is put into 150 ℃ of baking ovens 10 hours, take out again and naturally cool to room temperature, obtain removing the good membrane material of guest molecule activation.
Step 6, sign:
It is carried out 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 get into 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 that sees through is purged by carrier gas and gets into gas-chromatography inspection all gases content to confirm separating effect, and test result is 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.
The result shows with respect to other two kinds of gases, H
2To CO
2Separating effect best, can reach 8.7, be higher than and exert gloomy diffusion theory value, explain that this film can be used for H
2Separate with other gases.Simultaneously, the transmitance of hydrogen is also very high, can reach 10
-6The order of magnitude has good using value.
Embodiment 3
Step 4, diauxic growth:
In the 20ml beaker, adding mass ratio is Ni (the L-asp) (H of 0.219g
2O)
2, 0.156g bpy, 6ml water and 6ml methyl alcohol, after stirring, change in the stainless steel casing teflon-lined agitated reactor, with before synthetic surface coordination polymerization Ni is arranged
2(L-asp)
2The nickel screen carrier of bpy crystal seed is vertically put into reaction mother liquor, tighten kettle cover after, put into 150 ℃ of baking ovens and carried out growth in situ 2 days, be cooled to room temperature after the taking-up, take out the good Coordination Polymers Ni of diauxic growth
2(L-asp)
2The bpy film.
The activation of step 5, membrane material:
Synthetic good membrane material is put into 150 ℃ of baking ovens 10 hours, take out again and naturally cool to room temperature, obtain removing the good membrane material of guest molecule activation.
Step 6, sign:
To its carry out powder X ray diffracting spectrum test, SEM characterizes and the mist discrete testing, from gas cylinder entering membrane module, gas outlet end is by the pressure reduction at counterbalance valve controlling diaphragm two ends under the control of mass flow controller for two kinds of gas and carrier gas Ar.The gas that sees through is purged by carrier gas and gets into gas-chromatography inspection all gases content to confirm 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 |
The result shows and adds the more bpy of vast scale, and the quality of film descends, and separation factor reduces, and transmitance rises.
Embodiment 4
Step 4, diauxic growth:
In the 20ml beaker, adding mass ratio is Ni (the L-asp) (H of 0.219g
2O)
2, 0.312g bpy, 6ml water and 6ml methyl alcohol, after stirring, change in the stainless steel casing teflon-lined agitated reactor, with before synthetic surface coordination polymerization Ni is arranged
2(L-asp)
2The nickel screen carrier of bpy crystal seed is vertically put into reaction mother liquor, tighten kettle cover after, put into 150 ℃ of baking ovens and carried out growth in situ 2 days, be cooled to room temperature after the taking-up, take out the good Coordination Polymers Ni of diauxic growth
2(L-asp)
2The bpy film.
The activation of step 5, membrane material:
Synthetic good membrane material is put into 150 ℃ of baking ovens 10 hours, take out again and naturally cool to room temperature, obtain removing the good membrane material of guest molecule activation.
Step 6, sign:
To its carry out powder X ray diffracting spectrum test, SEM characterizes and the mist discrete testing, from gas cylinder entering membrane module, gas outlet end is by the pressure reduction at counterbalance valve controlling diaphragm two ends under the control of mass flow controller for two kinds of gas and carrier gas Ar.The gas that sees through is purged by carrier gas and gets into gas-chromatography inspection all gases content to confirm 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 the ratio of bpy in the further raising synthetic system, and the quality of film is poorer, and separating effect only is better than reluctantly exerts gloomy diffusion theory value, but flow has increased nearly one times.
Embodiment 5:
The preliminary treatment of step 1, carrier:
Ni-based micro-filtration diaphragm (2mm is thick) is put into the 50ml beaker, to wherein adding 20ml deionized water and 0.1g washing agent (upright white washing agent), ultrasonic 30 minutes; Put into the 50ml beaker after then Ni-based micro-filtration diaphragm being taken out, add deionized water 30ml, the liquid that sonicated was outwelled in the beaker in 15 minutes; Repeat deionized water ultrasonic cleaning step 5 time; Put into 100 ℃ of baking ovens dry 5 hours after at last Ni-based micro-filtration diaphragm being taken out, thereby obtain cleaned Ni-based micro-filtration diaphragm carrier.
In the 20ml beaker, add the L-asp of 0.1g and the bpy of 0.058g, and add 0.1ml water and 1ml methyl alcohol, obtain reaction mother liquor after stirring; Again reaction mother liquor is changed in stainless steel casing, the teflon-lined agitated reactor; Cleaned Ni-based micro-filtration diaphragm carrier level is put into reaction mother liquor, tighten the reaction kettle cover after, put into 150 ℃ of baking ovens and carried out growth in situ 2 days; Afterwards agitated reactor is taken out and be cooled to room temperature, take out the good Coordination Polymers Ni of growth
2(L-asp)
2The bpy film.
The activation of step 3, membrane material:
The Ni that growth is good
2(L-asp)
2The bpy film was put into 150 ℃ of baking ovens 10 hours, took out and naturally cooled to room temperature, obtained removing the good membrane material of activation of guest molecule.
Step 4, sign:
The good membrane material of activation is carried out 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)-1,3-succinic acid; 2-methyl-2 with the mixing of RS isomer; 4-pentanediol or 1,3-succinic acid get into the one side of film respectively under the drive of flow controller, another side vacuumizes through mechanical pump and under 77K liquid nitrogen condition, collects the component that sees through the film surface.Separating resulting is seen table 5.
Conclusion is that separating effect is better under the high temperature, and is 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, the 3-succinic acid | 1.66 | 1.72 | 2.59 | - |
Claims (7)
1. Coordination Polymer Membrane Ni
2(L-asp)
2The bpy material; It is characterized in that: be the three-dimensional apertures material that forms by metallic nickel ions and L-asp, bpy coordination with homogeneous duct size; The oxygen atom ligand of metallic nickel and L-asp forms layer, again with bpy in the pillared three-dimensional framework structure that forms of nitrogen-atoms coordination.
2. the described a kind of Coordination Polymers preparation method of film material of claim 1, its step is following:
(1) preliminary treatment of carrier:
A) 2～5 layers, 100～400 purpose individual layer nickel screens are pressed into the nickel screen sheet on the press of 10～200MPa, or with the nickel powder of 10～20 microns of average grain diameters on the press of 10～200MPa, be pressed into the aperture less than 1 micron, porosity be 30～40%, thickness is the Ni-based micro-filtration diaphragm of 1～3mm;
B) Ni-based micro-filtration diaphragm or nickel screen sheet are put into beaker, in beaker, adding mass ratio is the deionized water and the washing agent of 1:0.01～0.1, ultrasonic 10～30 minutes; With putting into beaker after Ni-based micro-filtration diaphragm or the taking-up of nickel screen sheet, add the deionized water sonicated 10～15 minutes then, outwell the liquid in the beaker; Repeat deionized water ultrasound treatment step 2～5 times, put into 80～150 ℃ of baking ovens after the taking-up dry 1～5 hour, thereby obtain cleaned Ni-based micro-filtration diaphragm or nickel screen sheet carrier;
(2) growth:
In beaker, adding mass ratio is L-asp, bpy, water and the methyl alcohol of 1:0.1～10:0.1～10:1～100; Obtain reaction mother liquor after stirring; Again reaction mother liquor is transferred in stainless steel casing, the teflon-lined agitated reactor; Cleaned Ni-based micro-filtration diaphragm or nickel screen sheet carrier level are put into reaction mother liquor, tighten the reaction kettle cover, then agitated reactor is put into 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day; Be cooled to room temperature after afterwards agitated reactor being taken out, from agitated reactor, take out the good Coordination Polymer Membrane Ni of growth at last
2(L-asp)
2Bpy;
(3) activation of membrane material:
The Coordination Polymer Membrane Ni that growth is good
2(L-asp)
2Bpy put into 100～200 ℃ of baking ovens 5～10 hours, took out and naturally cooled to room temperature, thereby obtain removing the good membrane material of activation of water and methyl alcohol guest molecule.
3. the described a kind of Coordination Polymers preparation method of film material of claim 1, its step is following:
(1) preliminary treatment of carrier
The individual layer nickel screen is put into beaker, in beaker, add the deionized water and the washing agent of mass ratio 1:0.01～0.1, ultrasonic 10～30 minutes; Put into beaker after then the individual layer nickel screen being taken out, added the deionized water sonicated 10～15 minutes, outwell the liquid in the 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 with NiCO
3Be added to the water by the mass ratio of 1:0.5～2 with L-asp; Heated and stirred makes dissolving; And remain under 80～100 ℃ water is constantly evaporated, when crystal to be had is separated out, stop heating; And naturally cool to and put into refrigerator after the room temperature and remain on 0～5 ℃ and crystal was all separated out in 5～20 hours down, filter and air dry at room temperature obtains Ni (L-asp) (H
2O)
2
Then; In beaker, adding mass ratio is L-asp, bpy, water and the methyl alcohol of 1:0.1～10:0.1～10:1～100; Obtain reaction mother liquor after stirring, again reaction mother liquor is forwarded in stainless steel casing, the teflon-lined agitated reactor, cleaned individual layer nickel screen carrier level is put into reaction mother liquor; Tighten the reaction kettle cover; Then agitated reactor is put into 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards agitated reactor being taken out, from agitated reactor, taking out to grow at last has Coordination Polymers Ni
2(L-asp)
2The individual layer nickel screen carrier of bpy crystal seed;
In beaker, adding mass ratio again is Ni (the L-asp) (H of 1:0.1～10:1～100:1～100
2O)
2, bpy, water and methyl alcohol, obtain reaction mother liquor after stirring, again reaction mother liquor is transferred in stainless steel casing, the teflon-lined agitated reactor, above-mentioned length is had Coordination Polymers Ni well
2(L-asp)
2The individual layer nickel screen carrier of bpy crystal seed is vertically put into reaction mother liquor; Tighten the reaction kettle cover; Then agitated reactor is put into 100～200 ℃ of baking ovens and carried out growth in situ 1～5 day, be cooled to room temperature after afterwards agitated reactor being taken out, from agitated reactor, take out the good Coordination Polymers Ni of diauxic growth at last
2(L-asp)
2The bpy film;
(3) activation of membrane material:
The Coordination Polymers Ni that growth is good
2(L-asp)
2The bpy film was put into 100～200 ℃ of baking ovens 5～10 hours, took out and naturally cooled to room temperature, thereby obtain removing the good membrane material of activation of water and methyl alcohol guest molecule.
4. the application of the described a kind of Coordination Polymers membrane material of claim 1 aspect the mist separation.
5. the application of a kind of Coordination Polymers membrane material as claimed in claim 4 aspect the mist separation is characterized in that: mist is the mist that the mist formed of mist, hydrogen and methane that hydrogen and carbon dioxide are formed or hydrogen and nitrogen are formed.
6. the application of the described a kind of Coordination Polymers membrane material of claim 1 aspect the separation of chirality isomer.
7. the application of a kind of Coordination Polymers membrane material as claimed in claim 6 aspect the separation of chirality isomer is characterized in that: be used for separating chiral glycol, chiral amino acid or chiral drug molecule.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012494A (en) * | 2012-12-14 | 2013-04-03 | 中国科学院青岛生物能源与过程研究所 | Phosphonate metal organic frame compound, preparation method and application |
| CN103816812A (en) * | 2014-02-24 | 2014-05-28 | 中国石油大学(华东) | Coordination polymer film material and its application in carbon dioxide separation |
| CN105771697A (en) * | 2016-03-29 | 2016-07-20 | 中国石油大学(华东) | Coordination polymer membrane material modified by hydrophobic polymer coating as well as preparation method and application of coordination polymer membrane material |
| CN105854651A (en) * | 2016-04-06 | 2016-08-17 | 中国石油大学(华东) | High-permeability mixed matrix membrane as well as preparation method and application thereof |
| CN105977483A (en) * | 2016-05-17 | 2016-09-28 | 中国石油大学(华东) | Carbon-based nanocomposite material for electrode |
| CN111151145A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Super-hydrophobic separation membrane and preparation method and application thereof |
| CN114602331A (en) * | 2020-12-07 | 2022-06-10 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100075123A1 (en) * | 2008-04-08 | 2010-03-25 | University of Illinois - Office of Technology Management | Water repellent metal-organic frameworks, process for making and uses regarding same |
| CN101890305A (en) * | 2010-04-01 | 2010-11-24 | 大连理工大学 | Method for preparing metallic organic frame films |
-
2012
- 2012-06-15 CN CN 201210199540 patent/CN102728236B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100075123A1 (en) * | 2008-04-08 | 2010-03-25 | University of Illinois - Office of Technology Management | Water repellent metal-organic frameworks, process for making and uses regarding same |
| CN101890305A (en) * | 2010-04-01 | 2010-11-24 | 大连理工大学 | Method for preparing metallic organic frame films |
Non-Patent Citations (1)
| Title |
|---|
| RUIGE CAO: "Organic-Inorganic Hybrids Constructed of Anderson-Type Polyoxoanions and Oxalato-Bridged Dinuclear Copper Complexes", 《INORGANIC CHEMISTRY》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012494A (en) * | 2012-12-14 | 2013-04-03 | 中国科学院青岛生物能源与过程研究所 | Phosphonate metal organic frame compound, preparation method and application |
| CN103816812A (en) * | 2014-02-24 | 2014-05-28 | 中国石油大学(华东) | Coordination polymer film material and its application in carbon dioxide separation |
| 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 |
| CN105771697A (en) * | 2016-03-29 | 2016-07-20 | 中国石油大学(华东) | Coordination polymer membrane material modified by hydrophobic polymer coating as well as preparation method and application of coordination polymer membrane material |
| CN105854651A (en) * | 2016-04-06 | 2016-08-17 | 中国石油大学(华东) | High-permeability mixed matrix membrane as well as preparation method and application thereof |
| 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 |
| CN111151145A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Super-hydrophobic separation membrane and preparation method and application thereof |
| CN114602331A (en) * | 2020-12-07 | 2022-06-10 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite membrane |
| CN114602331B (en) * | 2020-12-07 | 2023-11-17 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite film |
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