CN102489165B - Preparation method of ultrathin high network structural nanofiltration composite membrane - Google Patents
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- CN102489165B CN102489165B CN 201110385955 CN201110385955A CN102489165B CN 102489165 B CN102489165 B CN 102489165B CN 201110385955 CN201110385955 CN 201110385955 CN 201110385955 A CN201110385955 A CN 201110385955A CN 102489165 B CN102489165 B CN 102489165B
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- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001728 nano-filtration Methods 0.000 title abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001914 filtration Methods 0.000 claims abstract description 29
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 108
- BGQLKIRZQYRJPH-UHFFFAOYSA-N piperazine-1-carbaldehyde;hydrochloride Chemical class Cl.O=CN1CCNCC1 BGQLKIRZQYRJPH-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- IDAAIHKMEZKZQQ-UHFFFAOYSA-N formaldehyde piperazine-1-carbaldehyde Chemical compound C(=O)N1CCNCC1.C=O IDAAIHKMEZKZQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 15
- 230000004907 flux Effects 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 3
- VXPZSDUXKPVHJC-UHFFFAOYSA-N benzene-1,2,3-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1C(Cl)=O VXPZSDUXKPVHJC-UHFFFAOYSA-N 0.000 abstract 2
- ZYORFJZPPWUUCE-UHFFFAOYSA-N formaldehyde;piperazine Chemical compound O=C.C1CNCCN1 ZYORFJZPPWUUCE-UHFFFAOYSA-N 0.000 abstract 2
- MSQACBWWAIBWIC-UHFFFAOYSA-N hydron;piperazine;chloride Chemical compound Cl.C1CNCCN1 MSQACBWWAIBWIC-UHFFFAOYSA-N 0.000 abstract 2
- 230000014759 maintenance of location Effects 0.000 abstract 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- MSSDTZLYNMFTKN-UHFFFAOYSA-N 1-Piperazinecarboxaldehyde Chemical class O=CN1CCNCC1 MSSDTZLYNMFTKN-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 3
- 125000000879 imine group Chemical group 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- -1 salts ion Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229960002668 sodium chloride Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- MCPANHZWUBLTMU-UHFFFAOYSA-N chloro(trimethyl)silane hexane Chemical compound C[Si](Cl)(C)C.CCCCCC MCPANHZWUBLTMU-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IVXQBCUBSIPQGU-UHFFFAOYSA-N piperazine-1-carboxamide Chemical compound NC(=O)N1CCNCC1 IVXQBCUBSIPQGU-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method of an ultrathin high network structural nanofiltration composite membrane, comprising the following steps of: performing a reaction between benzenetricarbonyl trichloride and 1-formaldehyde piperazine with stirring at normal temperature, followed by filtering, solvent washing and drying to obtain trimesoyl piperazine formaldehyde, dissolving trimesoyl piperazine formaldehyde in anhydrous methanol, adding concentrated hydrochloric acid with stirring, filtering, washing, drying to obtain a trimesoyl piperazine hydrochloride monomer, and performing interfacial polymerization between trimesoyl piperazine hydrochloride monomer and benzenetricarbonyl trichloride to prepare the ultrathin high network structural nanofiltration composite membrane. The preparation method of the ultrathin high network structural nanofiltration composite membrane has advantages of simple technology and low cost. In comparison with a traditional polypiperazine-amide nanofiltration composite membrane, the nanofiltration composite membrane obtained by the adoption of the method has thinner cortex and higher crosslinking degree. In addition, its flux and retention rate are both raised.
Description
Technical field
The present invention relates to the NF membrane field, be specifically related to the synthetic of a kind of novel water monomer and with the preparation method of synthetic ultra-thin high network structure Nano filtering composite membrane.
Background technology
Nanofiltration can be traced back to the seventies in 20th century the earliest, is a kind of new membrane isolation technics between counter-infiltration and ultrafiltration.Compare counter-infiltration, nanofiltration can have higher flux under lower operating pressure, can hold back the organic matter that divalent salts ion and molecular weight are higher than the film molecular weight cut off efficiently, but lower to monovalent salt ion rejection.Because the own characteristic of nanofiltration, it is widely used in bitter desalination, micropollutants removal, water softening, wastewater treatment, dyestuff and the aspect such as holds back.
NF membrane generally can be passed through method preparations such as phase inversion, submergence coating, plasma polymerization, interfacial polymerization.Wherein, interfacial polymerization is because easy, the processed film of its preparation technology is wide with the function monomer range of choice, flux becomes method the most commonly used at present than advantages such as height.
Monomeric species selected when interfacial polymerization prepares Nano filtering composite membrane plays conclusive effect to structure of composite membrane and performance.Usually, commercial with pyromellitic trimethylsilyl chloride or its mixture and piperazine or its mixture respectively as oil, the interfacial polymerization of water monomer, the ultra-thin cortex of deposition one deck obtains the polypiperazine-amide nanofiltration composite membrane on the ultrafiltration counterdie.The NTR-7250 of the NF-40 of FilmTec company, Nitto Denko company, the UTC-20 of Tory company and UTC-60 are comparatively classical poly-piperazine amide commercial membranes.
High flux is the development trend of NF membrane always, then is a difficult problem that needs solution at present but how not lose rejection when improving flux.It has been generally acknowledged that the degree of cross linking of high network structure can increase the rejection of film, reduce film thickness and then can improve flux.Therefore, if can obtain suitable monomers, make it in interfacial polymerization process, reduce thickness when forming high network cross-linked structure, then be expected to prepare all good Nano filtering composite membranes of flux and rejection.
Summary of the invention
To achieve these goals, the invention provides the benzene three formyl piperazine hydrochlorides of the novel water function monomer that a kind of preparation has branched structure-all, and with prepare the method for ultra-thin high network structure Nano filtering composite membrane with the pyromellitic trimethylsilyl chloride interfacial polymerization.It is thinner and the degree of cross linking is higher that its cortex of the Nano filtering composite membrane that the inventive method prepares is compared the cortex of traditional polypiperazine-amide nanofiltration composite membrane, and flux and rejection all are improved.
A kind of preparation method of ultra-thin high network structure Nano filtering composite membrane, comprise the equal benzene three formyl piperazine hydrochlorides of the novel water function monomer of preparation, and prepare ultra-thin high network structure Nano filtering composite membrane with this monomer and pyromellitic trimethylsilyl chloride interfacial polymerization, concrete steps are as follows:
(1) with pyromellitic trimethylsilyl chloride and 1-formaldehyde piperazine with mol ratio 1: (3-5), stirring reaction under the normal temperature, the preferred 24-30h of mixing time, question response filters after finishing, filter cake solvent wash 3-5 time obtains equal benzene three formyl piperazine formaldehyde after super-dry, described solvent is preferred with the chloroform; Equal benzene three formyl piperazine formaldehyde are dissolved in the absolute methanol (purity is greater than 99.8%), the concentrated hydrochloric acid that adds 1/4th to 1/3rd absolute methanol volumes stirs 5-7h, filters, filter cake washs 3-5 time with absolute methanol, and drying obtains equal benzene three formyl piperazine hydrochlorides.
(2) the equal benzene three formyl piperazine hydrochlorides that step (1) obtained are mixed with the equal benzene three formyl piperazine hydrochloride aqueous solution, getting the quality bulk concentration is the equal benzene three formyl piperazine hydrochloride aqueous solution of 0.3-2.3%, regulate between the pH to 9-13 the preferred NaOH of described acid absorbent or triethylamine with acid absorbent; Counterdie is immersed in 5-15min in the above-mentioned equal benzene three formyl piperazine hydrochloride aqueous solution, again film surface excessive solution is outwelled, treat film surface moisture natural air drying 5-10min, film is immersed in the pyromellitic trimethylsilyl chloride solution that mass concentration is 0.02-0.18%, interfacial polymerization 40-100s obtains the nascent state composite membrane.Described solvent is for dissolving the solvent that pyromellitic trimethylsilyl chloride does not dissolve each other with water, preferred n-hexane, cyclohexane, Isopar (synthesising different structure alkane solvents) or heptane.Behind 40-70 ℃ of heat treatment 15-25min, pure water rinsing 2-3 time obtains Nano filtering composite membrane with the nascent state composite membrane, and placing the quality volumetric concentration is the aqueous solution of sodium bisulfite preservation of 1-2%.
The preferred polysulfones of described counterdie, polyacrylonitrile or polyether sulfone counterdie.
In the preparation process of the present invention, the reaction of the imine group of the acid chloride groups of pyromellitic trimethylsilyl chloride and 1-formaldehyde piperazine generates amido link, forms intermediate product.Under concentrated hydrochloric acid and the effect of methyl alcohol mixed solution, obtain equal benzene three formyl piperazine hydrochlorides after sloughing formoxyl.Concrete course of reaction is as follows:
The present invention has designed the equal benzene three formyl piperazines of a kind of synthesizing new water monomer and has prepared the method for polypiperazine-amide nanofiltration composite membrane, the Nano filtering composite membrane that adopts this preparation method to make, show under the Electronic Speculum that its skin thickness only is about 100nm, less than the skin thickness (about 200nm) of the polypiperazine-amide nanofiltration composite membrane for preparing with piperazine and pyromellitic trimethylsilyl chloride.Through two kinds of films of test to magnesium sulfate and two kinds of salting liquids of sodium chloride solution with the separating property of PEG 200 this non-charged small organic molecule solution, confirm that pyromellitic trimethylsilyl chloride/all flux and the rejection of benzene three formyl piperazine Nano filtering composite membranes have all had significant raising than traditional pyromellitic trimethylsilyl chloride/piperazine Nano filtering composite membrane.Preparation method of the present invention is that the scope of widening the material of preparing selection has played positive role.
Description of drawings
The FTIR collection of illustrative plates of the equal benzene three formyl piperazine hydrochlorides of the water function monomer with branched structure that Fig. 1 synthesizes for the present invention.
Fig. 2 is for the equal benzene three formyl piperazine hydrochlorides of the water function monomer with branched structure synthetic in the embodiment of the invention 1
1H NMR collection of illustrative plates.
Fig. 3 is the section SEM figure of the prepared Nano filtering composite membrane of the embodiment of the invention 1.
Fig. 4 is that the embodiment of the invention 14 prepared Nano filtering composite membrane section SEM scheme.
The specific embodiment:
Embodiment 1
With pyromellitic trimethylsilyl chloride and 1-formaldehyde piperazine with mol ratio 1: 4, stirring reaction 24h under the normal temperature.Question response filters after finishing, filter cake washs 3 times with chloroform, after super-dry, obtain equal benzene three formyl piperazine formaldehyde, and be dissolved in the absolute methanol, the concentrated hydrochloric acid (quality volumetric concentration 38%) that adds 1/4th absolute methanol volumes stirs 6h, filters, filter cake washs 3 times with absolute methanol, and drying obtains equal benzene three formyl piperazine hydrochlorides.
It is 1.3% the equal benzene three formyl piperazine hydrochloride aqueous solution (NaOH is regulated pH to 11) 10min that the polysulfones counterdie is immersed in the quality volumetric concentration, remove the unnecessary aqueous solution in polysulfones counterdie surface, treat film surface moisture natural air drying 5min, immerse the quality volumetric concentration and be the hexane solution interfacial polymerization 60s of 0.1% pyromellitic trimethylsilyl chloride, the nascent state composite membrane that obtains.The nascent state composite membrane in 50 ℃ of heat treatment 20min, after the clear rinsing of pure water, is obtained Nano filtering composite membrane.
Under 25 ℃, 0.6MPa, magnesium sulfate and the sodium-chloride water solution with 2000ppm is the desalting performance of feed liquid test Nano filtering composite membrane respectively.
Rejection and flux are two important parameters estimating reverse osmosis composite membrane, and rejection R is defined as: under certain operating condition, 1 deducts the mass concentration (C of solute in the penetrating fluid
p) with feeding liquid in the mass concentration (C of solute
f) ratio, multiply by 100.
Water flux is defined as: under certain operating condition, see through the volume of the water of elementary membrane area in the unit interval, its unit is l/m
2H.
The operating condition that the test of rejection and flux is adopted in the embodiment of the invention is: magnesium sulfate solution and sodium-chloride water solution, and mass concentration is 2000ppm; PEG 200 aqueous solution, mass concentration are 1000ppm.Operating pressure is 0.6MPa, and operating temperature is 25 ℃.
The support membrane that uses in the embodiment of the invention derives from State Oceanic Administration, Hangzhou Water Treatment Technology Research and Development Center as the porous polysulphone super-filter membrane.
Test result is:
Infrared and the nuclear-magnetism that the equal benzene three formyl piperazine hydrochlorides that adopt embodiment 1 preparation method to make obtain after tested characterizes collection of illustrative plates (as shown in Figure 2) and shows, among the FTIR, and 1760cm
-1The absworption peak that acyl chlorides do not occur, and at 1621cm
-1The C=O stretching vibration characteristic absorption peak of teritary amide has appearred in the place, shows that the imines on the piperazine ring reacts generation teritary amide key with the acid chloride groups of pyromellitic trimethylsilyl chloride.1550cm
-1For equal benzene three formyl piperazine hydrochlorides-NH
2+-flexural vibrations absworption peak proves that imine group and HCl have formed hydrochloride.3200-2400cm
-1Complicated multiplet in the zone is-NH
2+-stretching vibration absorption band causes, and confirms the formation of product equally.
Equal benzene three formyl piperazine hydrochlorides
1H NMR (solvent: D
2O; Frequency: 400MHz) collection of illustrative plates as shown in Figure 3.δ 7.63 is the chemical shift of H-1; δ 3.87～3.49 is the methylene H-2 chemical shift near carbonyl; δ 3.49～3.17 is the methylene H-3 chemical shift away from carbonyl, has overlapping between H-3 and the H-2 peak.In addition, because strong hygroscopicity and the D of equal benzene three formyl piperazine hydrochlorides
2Contain in the O solvent not by the deuterium H in generation
2O causes occurring bigger water peak.
Embodiment 2-5 adopts the quality volumetric concentration of pyromellitic trimethylsilyl chloride hexane solution to be respectively 0.02%, 0.06%, 0.14%, 0.18%, and other condition is all identical with embodiment 1.Test result is:
Embodiment 6-9 adopts equal benzene three formyl piperazine hydrochloride aqueous solution quality volumetric concentrations to be respectively 0.3%, 0.8%, 1.8%, 2.3%, and other condition is all identical with example 1.Test result is:
The equal benzene three formyl piperazine hydrochloride aqueous solution pH that embodiment 10-13 adopts are adjusted to 9.0,10.0,12.0,13.0 respectively with NaOH, and other condition is all identical with example 1.Test result is:
It is the water function monomer that embodiment 14 adopts piperazine, and its aqueous solution quality volumetric concentration is 0.26%, identical with equal benzene three formyl piperazine hydrochloride solution among the embodiment 1 with the imine group molar concentration that guarantees can react in the aqueous phase solution, is 0.06mol/l.Other conditions are all identical with embodiment 1.Test result is:
Embodiment 15-16 is that 1.3% the equal benzene three formyl piperazine hydrochloride aqueous solution and quality volumetric concentration are that 0.26% the piperazine aqueous solution is that water prepares Nano filtering composite membrane with the quality volumetric concentration respectively, and other condition is with embodiment 1.Under 25 ℃, 0.6MPa, be feed liquid with the PEG 200 of 1000ppm, test it to the cutoff performance of small organic molecule.Test result is:
Embodiment 1 with 14 and 15 with 16 comparison shows that under the condition that keeps the monomer molar concentration to equate, pyromellitic trimethylsilyl chloride/equal benzene three formyl piperazine Nano filtering composite membranes all are higher than pyromellitic trimethylsilyl chloride/piperazine Nano filtering composite membrane to the cutoff performance of salt ion and non-charged small organic molecule.This is that the cortex of formation is finer and close owing to all influences of benzene three formyl piperazine monomer branched structures.Simultaneously, the former flux also is higher than the latter, then is because thinner cortex causes due to resistance to mass tranfer reduces.
Claims (6)
1. the preparation method of a ultra-thin high network structure Nano filtering composite membrane is characterized in that, may further comprise the steps:
(1) the equal benzene three formyl piperazine hydrochlorides of preparation: pyromellitic trimethylsilyl chloride is mixed with mol ratio 1:3～1:5 with 1-formaldehyde piperazine, filter behind the stirring reaction under the normal temperature, filter cake obtains equal benzene three formyl piperazine formaldehyde after with solvent wash, drying, equal benzene three formyl piperazine formaldehyde are dissolved in purity greater than in 99.8% the absolute methanol, the concentrated hydrochloric acid that adds 1/4th to 1/3rd absolute methanol volumes, stir, filter, filter cake obtains equal benzene three formyl piperazine hydrochlorides with absolute methanol washing, drying;
(2) the ultra-thin high network structure Nano filtering composite membrane of preparation: get the equal benzene three formyl piperazine hydrochlorides that step (1) obtains and be mixed with the equal benzene three formyl piperazine hydrochloride aqueous solution that the quality volumetric concentration is 0.3-2.3%, add the pH to 9-13 that acid absorbent is regulated the equal benzene three formyl piperazine hydrochloride aqueous solution; Counterdie is immersed in 5-15min in the above-mentioned equal benzene three formyl piperazine hydrochloride aqueous solution, described counterdie is polysulfones, polyacrylonitrile or polyether sulfone, again film surface excessive solution is outwelled, treat film surface moisture natural air drying, again film is immersed in the pyromellitic trimethylsilyl chloride solution that mass concentration is 0.02-0.18%, interfacial polymerization 40-100s obtains the nascent state composite membrane; With the nascent state composite membrane after heat treatment, the pure water rinsing obtains Nano filtering composite membrane for several times.
2. the preparation method of ultra-thin high network structure Nano filtering composite membrane as claimed in claim 1, it is characterized in that: the solvent described in the step (1) is chloroform.
3. the preparation method of ultra-thin high network structure Nano filtering composite membrane as claimed in claim 1, it is characterized in that: the stirring reaction time is 24-30h under the normal temperature described in the step (1), solvent wash 3-5 time of described filter cake, mixing time behind the adding concentrated hydrochloric acid is 5-7h, filters the filter cake that obtains afterwards and washs 3-5 time with absolute methanol.
4. the preparation method of ultra-thin high network structure Nano filtering composite membrane as claimed in claim 1, it is characterized in that: the acid absorbent described in the step (2) is NaOH or triethylamine.
5. the preparation method of ultra-thin high network structure Nano filtering composite membrane as claimed in claim 1, it is characterized in that: the solvent in the pyromellitic trimethylsilyl chloride solution described in the step (2) is n-hexane, cyclohexane, heptane or synthesising different structure alkane solvents.
6. the preparation method of ultra-thin high network structure Nano filtering composite membrane as claimed in claim 1, it is characterized in that: the Immersion time of the counterdie described in the step (2) in the equal benzene three formyl piperazine hydrochloride aqueous solution is 5-15min, the described natural air drying time is 5-10min, and the described interfacial polymerization time is 40-100s; Described heat treatment is: behind 40-70 ℃ of heat treatment 15-25min, and pure water rinsing 2-3 time.
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| US5922203A (en) * | 1997-10-07 | 1999-07-13 | Hydranautics | Amine monomers and their use in preparing interfacially synthesized membranes for reverse osmosis and nanofiltration |
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| Title |
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| 新型耐高温聚酰胺复合纳滤膜的制备及性能研究;武春瑞等;《功能材料》;20071231;第38卷(第12期);2025-2027，2031 * |
| 武春瑞等.新型耐高温聚酰胺复合纳滤膜的制备及性能研究.《功能材料》.2007,第38卷(第12期),2025-2027，2031. |
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