DK145526B - PROCEDURE FOR THE PREPARATION OF A MEMBRANE FOR REVERSE OSMOSES AND ITS APPLICATION FOR SALTING OF SALT WATER - Google Patents
PROCEDURE FOR THE PREPARATION OF A MEMBRANE FOR REVERSE OSMOSES AND ITS APPLICATION FOR SALTING OF SALT WATER Download PDFInfo
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- DK145526B DK145526B DK510573AA DK510573A DK145526B DK 145526 B DK145526 B DK 145526B DK 510573A A DK510573A A DK 510573AA DK 510573 A DK510573 A DK 510573A DK 145526 B DK145526 B DK 145526B
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- Prior art keywords
- pei
- film
- membrane
- solution
- polysulfone
- Prior art date
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- 239000012528 membrane Substances 0.000 title description 27
- 238000000034 method Methods 0.000 title description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 16
- 150000003839 salts Chemical class 0.000 title description 4
- 238000002360 preparation method Methods 0.000 title description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 42
- 239000000243 solution Substances 0.000 description 25
- 239000003431 cross linking reagent Substances 0.000 description 19
- 229920002492 poly(sulfone) Polymers 0.000 description 16
- 238000001223 reverse osmosis Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 208000029422 Hypernatremia Diseases 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010952 in-situ formation Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- -1 cyanurohloride Chemical compound 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
- B01D71/601—Polyethylenimine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Description
1 KSQt I1 KSQt I
dø) DANMARK \ξ£/die) DENMARK \ ξ £ /
(12) FREMLÆGGELSESSKRIFT od 145526 B(12) PUBLICATION OF 145526 B
DIREKTORATET FOR PATENT-OG VAREMÆRKEVÆSENETPATENT AND TRADEMARKET DIRECTORATE
(21) Ansøgning nr. 5)05/73 (51) Int.CI.® B 01 D 13/OA(21) Application No. 5) 05/73 (51) Int.CI.® B 01 D 13 / OA
(22) Indleveringsdag 18. 8ep. 1973 C 08 J 5/18 (24) Løbedag 18. S ep. 1973 (41) Aim. tilgængelig 20. mar. 197^+ (44) Fremlagt 6. dec. 1982 (86) International ansøgning nr. - (86) International indleveringsdag (85) Videreførelsesdag - (62) Stamansøgning nr. -(22) Filing Day 18. 8ep. 1973 C 08 J 5/18 (24) Race day 18. S ep. 1973 (41) Aim. available Mar 20 197 ^ + (44) Presented Dec. 6; 1982 (86) International application # - (86) International filing day (85) Continuation day - (62) Master application no -
(30) Prioritet 19. sep. 1972, 287592* US(30) Priority Sep 19 1972, 287592 * US
(71) Ansøger NORTH STAR RESEARCH AND DEVELOPMENT INSTITUTE, Minnea= polis, US.(71) Applicant NORTH STAR RESEARCH AND DEVELOPMENT INSTITUTE, Minnea = police, US.
(72) Opfinder John Edward _Cadotte, US.(72) Inventor John Edward _Cadotte, US.
(74) Fuldmægtig Ingeniørfirmaet Budde, Schou & Co.(74) Associate Engineering Company Budde, Schou & Co.
(54) Fremgangsmåde til fremstilling af en membran til omvendt osmose samt dens anvendelse til afsaltning af saltvand.(54) Process for preparing a reverse osmosis membrane and its use in desalination of saline.
Inden for området for rensning af saltvand har man vist en betydelig interesse for omvendt osmose. Ved denne proces påføres et tryk, der er højere end det osmotiske tryk i saltvandsfødeopløsningen, på den opløsning, der er adskilt fra renset vand ved q en semipermeabel membran. Derved bevirkes, at rent vand diffunde- £> rer gennem membranen, medens saltmolekylerne eller andre urenhederIn the area of saline purification, considerable interest in reverse osmosis has been shown. In this process, a pressure higher than the osmotic pressure in the saline feed solution is applied to the solution separated from purified water by q a semipermeable membrane. This causes pure water to diffuse through the membrane while the salt molecules or other impurities
'M'M
^ holdes tilbage af membranen.^ is held back by the diaphragm.
JT) Effektiviteten af omvendt osmose-processen er i stor ud- ^ strækning afhængig af membranen, og talrige typer membraner og fremgangsmåder til deres fremstilling er blevet beskrevet i den jijjjjj kendte teknik. Disse membraner støbes sædvanligvis ud fra en opløs ning omfattende membranmaterialet og et opløsningsmiddel med eller 145526 2 uden yderligere opløsningskomponenter, såsom vand, kvældningsmidler osv. Membranerne kan anvendes ved omvendt osmose-processen i form af en fri film, eller mere almindeligt, som en film aflejret på et porøst bæremateriale. Disse kendte membraner har imidlertid sædvanligvis været behæftet med sådanne mangler som sammenpresning og kemisk og biologisk nedbrydning, hvilket resulterer i en for kort effektiv levetid og en for lav strømning eller salttilbageholdelse, hvilket resulterer i ineffektiv drift.JT) The efficiency of the reverse osmosis process is highly dependent on the membrane, and numerous types of membranes and methods for their preparation have been described in the prior art. These membranes are usually cast from a solution comprising the membrane material and a solvent with or without additional solvents such as water, swelling agents, etc. The membranes can be used in the reverse osmosis process in the form of a free film, or more commonly, as a film. deposited on a porous support material. However, these known membranes have usually suffered from such deficiencies as compression and chemical and biological degradation, resulting in too short a useful life and too low flow or salt retention resulting in inefficient operation.
I overensstemmelse med den foreliggende opfindelse har det nu vist sig, at membraner til omvendt osmose, der har fortrinlige strømnings- og salttilbageholdelsesegenskaber samt er fri for sammentrængning eller nedbrydning, kan fremstilles ved reaktion af en polyethyleniminfilm med et tværbindingsmiddel, der har funktionelle grupper, der reagerer med amingrupper i polyethyleniminet.In accordance with the present invention, it has now been found that reverse osmosis membranes which have excellent flow and salt retention properties and are free of contraction or degradation can be prepared by reacting a polyethyleneimine film with a crosslinking agent having functional groups having reacts with amine groups in the polyethyleneimine.
Fra FR-patentskrift nr. 2.088.598 kendes en fremgangsmåde, ved hvilken en filmdannende polymer tværbindes over på en porøs bærer. Det er essentielt ved denne fremgangsmåde, at den filmdannende polymer og tværbindingsmidlet bringes i kontakt i tør, gasformig tilstand, sandsynligvis fordi den kendte fremgangsmåde har til formål at fremstille en membran omfattende to lag med forskellig tværbindingsgrad. Denne fremgangsmåde har den ulempe, at den fordrer tid- og arbejdskrævende tørrings- og fordampningstrin, før kontakten mellem polymer og tværbindingsmiddel kan etableres.FR-A-2,088,598 discloses a method in which a film-forming polymer is cross-linked onto a porous support. It is essential in this process that the film-forming polymer and crosslinking agent be contacted in a dry, gaseous state, probably because the known process aims to prepare a membrane comprising two layers of different degree of crosslinking. This process has the disadvantage that it requires time and labor-intensive drying and evaporation steps before the polymer-crosslinking agent can be established.
Dette undgås ved fremgangsmåden ifølge opfindelsen, som er ejendommelig ved, at (1) en porøs bærer overtrækkes med en poly-.ethyleniminfilm, (2) produktet fra trin (1) bringes i kontakt med en 0,1-5,0 vægtprocents opløsning af et polyfunktionelt tværbindingsmiddel i et flydende opløsningsmiddel, og (3) produktet fra trin (2) varmehærdes ved en temperatur på ca. 90 til 130°C i ca. 5 til 30 minutter.This is avoided by the process of the invention, which is characterized in that (1) a porous support is coated with a polyethyleneimine film, (2) the product of step (1) is contacted with a 0.1-5.0% by weight solution of a polyfunctional cross-linking agent in a liquid solvent, and (3) the product of step (2) is heat-cured at a temperature of approx. 90 to 130 ° C for approx. 5 to 30 minutes.
Opfindelsen angår ligeledes en fremgangsmåde til afsalt-ning af saltvand ved omvendt osmose og af den i krav 8's indledning angivne art, hvilken fremgangsmåde er ejendommelig ved det i den kendtegnende del af krav 8 angivne.The invention also relates to a method for desalinating saline by reverse osmosis and of the nature specified in the preamble of claim 8, which is characterized by the method of claim 8.
145526 3145526 3
Polyethylenimin, nedenfor betegnet PEI, fremstilles ved polymerisation af ethylenimin og er tidligere blevet anvendt kommercielt på en mangfoldighed af måder, f.eks. som adhæsiver, flokkuleringsmidler, ionbytterharpikser, komplekseringsmidler og absorbenter. Det er en stærkt forgrenet polyamin med amlnonitro-gener i et forhold mellem primær, sekundær og tertiær på ca. 1:2:1.JPolyethyleneimine, hereinafter referred to as PEI, is produced by polymerization of ethyleneimine and has previously been used commercially in a variety of ways, e.g. such as adhesives, flocculants, ion exchange resins, complexing agents and absorbents. It is a highly branched polyamine with aminonitro genes in a ratio of primary, secondary and tertiary to approx. 1: 2: 1.J
V ,V,
Den er tilgængelig i en lang række molekylvægte på fra ca. 600 til 100.000, der alle er opløselige i vand, idet de giver opløs- i- ninger med et let uklart udseende.It is available in a wide range of molecular weights from approx. 600 to 100,000, all of which are soluble in water, providing solutions with a slightly unclear appearance.
Molekylvægten af PEI er ikke en kritisk faktor’ved fremgangsmåden ifølge opfindelsen, selv om de optimale værdier kan variere i afhængighed af forskellige faktorer, såsom typen af bærer, naturen af saltvandsfødeopløsningen, den ønskede salttilbageholdelse og den ønskede strømning. Sædvanligvis er en molekylvægt på fra ca. 600 til 100.000 hensigtsmæssig, idet en molekylvægt på fra ca. 12.000 til 100.000 sædvanligvis foretrækkes.The molecular weight of PEI is not a critical factor in the process of the invention, although the optimal values may vary depending on various factors such as the type of carrier, the nature of the saline feed solution, the desired salt retention and the desired flow. Usually, a molecular weight of from about 600 to 100,000 is appropriate, with a molecular weight of from approx. 12,000 to 100,000 are usually preferred.
En film af PEI fremstilles sædvanligvis ud fra en opløsning af den polymere i vand. Denne opløsning fremstilles lettest ved gradvis fortynding af PEI med vand, indtil den ønskede koncentra- ,v tion er nået. Blandingen fortsættes, indtil der er opnået en ensartet, uklart udseende opløsning, og dernæst filtreres opløsningen fortrinsvis. Den optimale koncentration af PEI i den vandige opløsning er afhængig af molekylvægten af PEI. Koncentrationen af PEI kan ligge mellem 0,033 og 2,7 vægtprocent, idet en koncentration på fra 0,33 til 1,0 vægtprocent sædvanligvis foretrækkes.A film of PEI is usually prepared from a solution of the polymer in water. This solution is most readily prepared by gradually diluting PEI with water until the desired concentration is reached. The mixing is continued until a uniform, vague-looking solution is obtained, and then the solution is preferably filtered. The optimal concentration of PEI in the aqueous solution is dependent on the molecular weight of PEI. The concentration of PEI can range from 0.033 to 2.7% by weight, with a concentration of from 0.33 to 1.0% by weight being usually preferred.
PEI-Filmen kan være fremstillet ved en hvilken som helst kendt fremgangsmåde, f.eks. udhældning af den vandige opløsning af PEI på en bærer, neddypning eller nedsænkning af bæreren i opløsningen osv. Almindeligvis gennemføres dannelsen af filmen imidlertid mest hensigtsmæssigt og effektivt ved, at bæreren simpelt hen anbringes i PEI-opløsningen i et tidsrum, der er tilstrækkeligt til at muliggøre adsorption af en film af opløsningen på bæreren. Almindeligvis er kontakttidsrummet ikke kritisk, og tidsrum på fra nogle få sekunder til 24 timer har alle vist sig at frembringe gode membraner.The PEI film can be made by any known method, e.g. pouring the aqueous solution of PEI onto a support, immersing or immersing the support in the solution, etc. Generally, however, the formation of the film is most conveniently and effectively accomplished by simply placing the support in the PEI solution for a period sufficient to enable adsorption of a film of the solution onto the support. Generally, the contact time is not critical and periods of from a few seconds to 24 hours have all been shown to produce good membranes.
4 145526 Bæreren kan være af en hvilken som helst af de typer, der anvendes konventionelt ved omvendt osmose-processer. Disse indbefatter porøst glas, sintrede metaller, keramik og organiske polymere materialer, såsom celluloseestere, styren, vinylbutyral og polysulfon. En polysulfonfilm har vist sig at være et særlig effektivt bæremateriale for de her omhandlede membraner. Fremstillingen af disse bærerfilm er beskrevet i Office of Saline Water Research and' Development Progress Report No. 359, oktober 1968. Den består i det væsentlige af udhældning af en opløsning af polysulfon i dimethylformamid (DMF) på en glasplade efterfulgt af nedsænkning i en 2 vægtprocents vandig DMF-opløsning til gelatinering af filmen.The carrier may be any of the types conventionally used in reverse osmosis processes. These include porous glass, sintered metals, ceramics and organic polymeric materials such as cellulose esters, styrene, vinyl butyral and polysulfone. A polysulfone film has been found to be a particularly effective carrier for the membranes herein. The preparation of these carrier films is described in the Office of Saline Water Research and 'Development Progress Report No. 359, October 1968. It consists essentially of pouring a solution of polysulfone in dimethylformamide (DMF) onto a glass plate followed by immersion in a 2% by weight aqueous DMF solution to gelatinize the film.
Den side af polysulfonfilmen, der er udsat for luften under udhæld-ningen, kaldes "forsiden" og indeholder særdeles små porer, for det meste under 100 ångstrOm i diameter. Filmens "bagside", der er i kontakt med glaspladen, har meget grove porer. PEI-Overtrækket skal påføres forsiden af polysulfonbærerfilmen til opnåelse af effektive resultater ved afsaltning under anvendelse af omvendt osmose.The side of the polysulfone film exposed to the air during the pour is called the "front" and contains very small pores, usually less than 100 angstroms in diameter. The film's "back" in contact with the glass plate has very coarse pores. The PEI coating should be applied to the front of the polysulfone carrier film to achieve effective desalination results using reverse osmosis.
Den her omhandlede membran til omvendt osmose fremstilles dernæst ved reaktion af PEI-filmen med tværbindingsreagenset. Dette reagens udgøres af en difuktionel eller trifunktionel organisk forbindelse, dvs. en forbindelse indeholdende to eller tre funktionelle grupper, der er i stand til at reagere med amingrupper i PEI. Chlorid-og isocyanat-funktionelle grupper har vist sig særlig effektive til tværbinding af PEI. Andre konventionelle, tværbindingsfunktionelle grupper, såsom anhydrid, epoxy og definer, der er aktiverede ved hjælp af polære substituentgrupper, er imidlertid også egnede.The reverse osmosis membrane of the present invention is then prepared by reaction of the PEI film with the crosslinking reagent. This reagent is a difunctional or trifunctional organic compound, i.e. a compound containing two or three functional groups capable of reacting with amine groups in PEI. Chloride and isocyanate functional groups have been found to be particularly effective for cross-linking PEI. However, other conventional cross-linking functional groups such as anhydride, epoxy and defines activated by polar substituent groups are also suitable.
Tværbindingsreagenset er fortrinsvis en aromatisk eller hete-rocyclisk forbindelse, da sådanne reagenser har vist sig at tilvejebringe overlegne omvendt osmose-egenskaber, især modstandsevne mod sammentrængning. Selv om forklaringen på disse reagensers overlegenhed ikke kendes med sikkerhed, menes det, at deres cycliske brogrupper, der sammenbinder PEI-strukturen, bibringer membranen større stivhed, således at den udviser bedre modstandsevne mod sammenpresning.Preferably, the crosslinking reagent is an aromatic or heterocyclic compound, as such reagents have been found to provide superior reverse osmosis properties, especially contraction resistance. Although the explanation for the superiority of these reagents is not known with certainty, it is believed that their cyclic bridging groups linking the PEI structure impart greater stiffness to the membrane so that it exhibits better resistance to compression.
5 1455265 145526
Overlegenheden af de chlorid- og isoeyanat-funktionelle grupper og de aromatiske og heterocyeliske bindingsgrupper er illustreret i nedenstående eksempler. Som vist i eksemplernes data har fire forbindelser, dvs. tolylen-2,4-diisocyanat, cyanurohlorid, terephthaloylehlorid og diphenyletherdisulfonylchlorid, vist sig særdeles effektive ved omvendt osmose-processer. Reaktion af disse forbindelser med PEI frembringer polyamid- og polyurinstofbindinger i PEI-strukturen. Andre egnede tværbindingsreagenser indbefat- ' ter isophthaloyldichlorid, trimelLithanhydridsyrechlorid og méta-benzendisulfonylchlorid.The superiority of the chloride and isoeyanate functional groups and the aromatic and heterocylic bonding groups is illustrated in the examples below. As shown in the examples data, four compounds have, i. tolylene-2,4-diisocyanate, cyanurohloride, terephthaloyl chloride and diphenyl ether disulfonyl chloride have been shown to be particularly effective in reverse osmosis processes. Reaction of these compounds with PEI produces polyamide and polyurea bonds in the PEI structure. Other suitable cross-linking reagents include isophthaloyl dichloride, trimelithanhydride acid chloride and meta-benzenedisulfonyl chloride.
Reaktionen af PEI-filmen med tværbindingsreagenset gennemføres hensigtsmæssigt ved nedsænkning af filmen i en opløsningsmiddelopløsning af reagenset. Opløsningsmidlet må hverken opløse PEI eller bærematerialet. Carbonhydridopløsningsmidler, såsom n-hexan, heptan, octan eller cyclohexan, er sædvanligvis mest anvendelige i praksis. Den optimale koneentrAtion af tværbindings-reagenset i opløsningsmidlet kan variere betydeligt i afhængighed af det specifikke reagens, opløsningsmiddel, bærer osv. og den bestemmes bedst eksperimentelt. Koncentrationer på fra ca. 0,1 til 5,0 vægtprocent er imidlertid almindeligvis tilfredsstillende.The reaction of the PEI film with the crosslinking reagent is conveniently carried out by immersing the film in a solvent solution of the reagent. The solvent must not dissolve PEI or the carrier material. Hydrocarbon solvents such as n-hexane, heptane, octane or cyclohexane are usually most useful in practice. The optimal concentration of the crosslinking reagent in the solvent can vary considerably depending on the specific reagent, solvent, carrier, etc. and is best determined experimentally. Concentrations of approx. However, 0.1 to 5.0 weight percent is generally satisfactory.
En forhøjet temperatur på fra ca. 90 til 150°C, fortrinsvis ca. 110-115°C, er sædvanligvis nødvendig til fuldstændiggørelse af tværbindingsreaktionen. Reaktionen kan gennemføres til fuldstændiggørelse i opløsningsmiddelopløsningen (éttrinsreaktion), i hvilket tilfælde opløsningsmiddelopløsningen opvarmes til den nødvendige temperatur. Ellers kan PÉI-filmen fjernes efter et kort tidsrum, f.eks. fra ca. 10 sekunder til 10 minutter, og anbringes i en ovn ved den nødvendige temperatur til fuldstændiggørelse af reaktionen (totrinsreaktion). Den optimale reaktionstid kan også variere med de ovenfor omtalte variable, men et tidsrum på fra ca. 5 til 5° minutter er sædvanligvis tilfredsstillende.An elevated temperature of from approx. 90 to 150 ° C, preferably approx. 110-115 ° C, is usually required to complete the crosslinking reaction. The reaction can be carried out to complete in the solvent solution (one step reaction), in which case the solvent solution is heated to the required temperature. Otherwise, the PÉI film can be removed after a short period of time, e.g. from approx. 10 seconds to 10 minutes, and place in an oven at the temperature required to complete the reaction (two-step reaction). The optimum reaction time can also vary with the variables mentioned above, but a time period of approx. 5 to 5 ° minutes is usually satisfactory.
Tørring af PEI-filmen til fjernelse af frit vand forud for reaktionen med tværbindingsmidlet er nødvendig, hvis tværbindingsmidlet let hydrolyseres af vand. Lufttørring er sædvanligvis til 145526 6 fredsstillende, men påføring af varme, såsom med strålegasvarmere eller infrarøde lamper, kan anvendes til aceelerering af tørringen. Tørringen kan imidlertid udelades, hvis tværbindingsreagenset er af en type, der ikke hydrolyseres let af vand. Der er f.eks. opnået særdeles gode resultater (jvf. eksemplerne) ved omsætning af PEI med lav molekylvægt (molekylvægt 12.000) på en polysulfonbærer-film med tolylendiisocyanat uden anvendelse af et tørringstrin.Drying of the PEI film to remove free water prior to the reaction with the crosslinking agent is necessary if the crosslinking agent is easily hydrolyzed by water. Air drying is usually pacific, but application of heat, such as with radiant gas heaters or infrared lamps, can be used to accelerate drying. However, the drying can be omitted if the crosslinking reagent is of a type that is not easily hydrolyzed by water. There are e.g. obtained very good results (cf. the examples) by reacting low molecular weight PEI (molecular weight 12,000) on a polysulfone carrier film with tolylene diisocyanate without using a drying step.
Når en PEI-overtrukket polysulfonbærer tørres, påføres varme på bagsiden af polysulfonfilmen, således at vanddamp undslipper gennem de grove porer i filmens bagside og derfor ikke forstyrrer PEI-laget på filmens forside.When a PEI-coated polysulfone support is dried, heat is applied to the back of the polysulfone film so that water vapor escapes through the rough pores in the back of the film and therefore does not interfere with the PEI layer on the front of the film.
Optimale resultater, hvad angår både hensigtsmæssighed og omvendt osmose-egenskaber af slutmembranerne, opnås sædvanligvis ved hjæLp af in situ-dannelse af membran®. på bæreren. Ved denne fremgangsmåde adsorberes PEI-filmen indledningsvis på bærematerialet ved, at bæreren bringes i kontakt med en vandig opløsning af PEI som beskrevet ovenfor. Eftersom PEI er en kationisk polyelek-trolyt, der let adsorberes på porøse materialer, er det særlig egnet til in situ-dannelse af membraner på porøse bærematerialer.Optimal results, in terms of both expediency and reverse osmosis properties of the end membranes, are usually achieved by using in situ membrane® formation. on the carrier. In this process, the PEI film is initially adsorbed onto the support material by contacting the support with an aqueous solution of PEI as described above. Since PEI is a cationic polyelectrolyte that is readily adsorbed on porous materials, it is particularly suitable for in situ formation of membranes on porous substrates.
Det adsorberede PEI omsættes derpå med tværbindingsreagenset, som beskrevet ovenfor, hvilket resulterer i in situ-dannelsen af membranen på bæreren. PEI er igen enestående effektivt i dets høje grad af reaktivitet med tværbindingsreagenserne samt i dets ovennævnte fremragende evne til at blive absorberet.The adsorbed PEI is then reacted with the crosslinking reagent as described above, resulting in the in situ formation of the membrane on the support. PEI is again outstandingly effective in its high degree of reactivity with the crosslinking reagents as well as in its above-mentioned excellent ability to be absorbed.
De her omhandlede membraner, der fremkommer ved reaktionen af amingrupperne i PEI med tværbindingsreagenserne, ligger sædvanligvis i området fra ca. 1000 til 10.000 Ångstr'dm i tykkelse, er uopløselige i vand eller opløsningsmidler, når de er dannet in situ, og kan sædvanligvis ikke fjernes mekanisk fra bæreren.The membranes of this invention, which result from the reaction of the amine groups in PEI with the crosslinking reagents, are usually in the range of from ca. 1000 to 10,000 Angstroms in thickness, are insoluble in water or solvents when formed in situ, and usually cannot be mechanically removed from the support.
Poiysulfonbærerfilm af den ovenfor omtalte type har vist sig særlig effektive til in situ-dannelsen af de her omhandlede membraner på grund af deres høje modstandsevne mod sammentrykning, ringe porestørrelse (på forsiden af polysulfonfilmen) og modstandsevne mod virkningerne af tørring.Polysulfone carrier films of the type mentioned above have been found to be particularly effective for the in situ formation of the membranes herein because of their high compressive resistance, poor pore size (on the front of the polysulfone film) and resistance to the effects of drying.
Nedenstående eksempler tjener til en mere specifik illustrering af den foreliggende opfindelse.The following examples serve to illustrate the present invention more specifically.
Eksempel 1-6 I disse eksempler er bæreren en polysulfonfilm, der er frem- 7 145526 stillet på den ovenfor beskrevne måde, har en tykkelse på fra 0,028 til 0,051 mm og udgøres af et polysulfon med en molekylvægt på fra 20.000 til 40.000.Examples 1-6 In these examples, the carrier is a polysulfone film prepared in the manner described above, has a thickness of from 0.028 to 0.051 mm and is a polysulfone having a molecular weight of from 20,000 to 40,000.
Et PEI-overtræk påføres forsiden af polysulfonfilmen ved nedenstående trin: 1. En 0,33 - 1 vægtprocents opløsning af PEI med en molekylvægt på 12.000 fremstilles ved gradvis fortynding af PEI med vand, indtil den ønskede koncentration er opnået. Blandingen fortsættes, indtil der er opnået en ensartet uklårt udseende opløsning, og opløsningen filtreres.A PEI coating is applied to the front of the polysulfone film by the following steps: 1. A 0.33 - 1 wt% solution of PEI having a molecular weight of 12,000 is prepared by gradually diluting PEI with water until the desired concentration is reached. The mixture is continued until a uniformly cloudy appearance solution is obtained and the solution is filtered.
2. Polysulfonbærerfilmen lægges i stadig våd tilstand med forsiden nedad på overfladen af PEI-opløsningen i et tidsrum på 1 minut.2. Place the polysulfone carrier film in still wet condition face down on the surface of the PEI solution for a period of 1 minute.
3. Bærerfilmen løftes op fra PEI-opløsningen og fastspændes i lodret stilling for at lufttørre i et tidsrum på 10 minutter til reduktion af vandindholdet til ca. 0,2#.3. The carrier film is lifted from the PEI solution and clamped vertically to air dry for a period of 10 minutes to reduce the water content to approx. 0.2 #.
Den PEI-overtrukne polysulfonbærerfilm nedsænkes dernæst i en opløsning af tværbindingsreagenset i n-heptan, idet opløsningen holdes ved en temperatur på 90°C. Reaktionen fortsættes i et tidsrum på 10 minutter, hvorefter det fremkomne sammensatte materiale af membran og bærer fjernes fra reaktionsmediet, vaskes med heptan og lufttørres ved 25°C i et tidsrum på 30 minutter.The PEI-coated polysulfone carrier film is then immersed in a solution of the crosslinking reagent in n-heptane, keeping the solution at a temperature of 90 ° C. The reaction is continued for a period of 10 minutes, after which the resulting composite material of membrane and support is removed from the reaction medium, washed with heptane and air dried at 25 ° C for a period of 30 minutes.
Det afprøves derpå i en forsøgscelle til omvendt osmose under nedenstående forsøgsbetingelser: pIt is then tested in a reverse osmosis test cell under the following test conditions: p
Tryk: 105 kg/cm overtrykPressure: 105 kg / cm overpressure
Strømningshastighed: 1 liter/minut Fødemateriale: 3>5# NaClFlow rate: 1 liter / minute Feeding material: 3> 5 # NaCl
Temperatur: 25°CTemperature: 25 ° C
Forsøgsvarighed: 20-24 timer.Trial duration: 20-24 hours.
PEI-Koncentrationerne i den vandige oplosning, de anvendte tværbindingsreagenser og koncentrationerne af tværbindingsreagenset i opløsningsmidlet er angivet i tabel I. Resultaterne, dvs. strømning (mængde produktvand, der passerer gennem membranen) udtrykt i liter pr. cm membran pr. dag og salttilbageholdelse udtrykt som den procentdel af det totale salt. i fødematerialet, der holdes tilbage af membranen, er også anført i denne tabel.The PEI concentrations in the aqueous solution, the crosslinking reagents used and the concentrations of the crosslinking reagent in the solvent are given in Table I. The results, i.e. flow (amount of product water passing through the membrane) expressed in liters per liter. cm per membrane day and salt retention expressed as the percentage of total salt. the feedstock retained by the membrane is also listed in this table.
8 1455268 145526
Tabel ITable I
Tværbindings- PEI-koncen- reagenskon- strdmninø· Salttil-Tværbindings- tration, centration, υ φ bageholdelse,Cross-linking PEI Concentration Reagent Control · Salt-to-Crosslinking, Centering, υ φ Retention,
Eks. reagens*_vægtprocent vægtprocent liter/cm^/dae %_ 1 TDI 0,55 1,0 0,0252 99,8 2 TDI 1,0 1,0 0,0232 99,82 5 TDI 1,0 0,1 0,0664 99,8 4 TPC 0,55 1,0 0,0517 97,0 5 dpesc 0,55 1,0 0,0216 99,2 6 CG 1,0 1,0 0,044 99,1 x TPC: terephthaloylchlorid TDI: tolylen-2,4-diisocyanat CC: cyanurchlorid DPESC: diphenyletherdisulfonylchloridEx. reagent * weight percent weight percent liter / cm 2 / day% 1 TDI 0.55 1.0 0.0252 99.8 2 TDI 1.0 1.0 0.0232 99.82 5 TDI 1.0 0.1 0, 0664 99.8 4 TPC 0.55 1.0 0.0517 97.0 5 dpesc 0.55 1.0 0.0216 99.2 6 CG 1.0 1.0 0.044 99.1 x TPC: terephthaloyl chloride TDI: tolylene-2,4-diisocyanate CC: cyanuric chloride DPESC: diphenyl ether disulfonyl chloride
Eksempel 7-11 I disse eksempler gennemføres reaktionen med tværbindingsreagenset uden forudgående tørring af bæreren. Bæreren er den poly-sulfonfilm, der anvendes i eksempel 1-6.Examples 7-11 In these examples, the reaction is carried out with the crosslinking reagent without prior drying of the support. The carrier is the polysulfone film used in Examples 1-6.
Bærerfilmen bringes i kontakt med en 0,66 vægtprocents vandig opløsning af PEI med molekylvægt på 12.000. Filmen fjernes og holdes i lodret stilling for at tillade, at overskud af PEI-op-løsning løber af, i et tidsrum på ca. 1 minut. Den våde film lægges på en flad bakke og dækkes med en opløsning af TDI i hexan ved stuetemperatur i et tidsrum på 5 minutter.The carrier film is contacted with a 0.66% by weight aqueous solution of 12,000 molecular weight PEI. The film is removed and held in a vertical position to allow excess PEI solution to run off, for a period of approx. 1 minute. The wet film is placed on a flat tray and covered with a solution of TDI in hexane at room temperature for a period of 5 minutes.
Filmen fjernes derpå, væden får lov at løbe af, og filmen hærdes i en ovn i 10 minutter ved en temperatur på oa. 115°C. Tykkelsen af det fremkomne PEI-overtræk på forsiden af bærerfilmen er 6000 Ångstrbm.The film is then removed, the moisture is allowed to run off, and the film is cured in an oven for 10 minutes at a temperature of oa. 115 ° C. The thickness of the resulting PEI coating on the front of the carrier film is 6000 Angstrbm.
Den afprøves derpå i en forsøgscelle til omvendt osmose under nedenstående betingelser:It is then tested in a reverse osmosis test cell under the following conditions:
OISLAND
Tryk: 105 kg/cm overtrykPressure: 105 kg / cm overpressure
Strømningshastighed: 1,5 liter/minut Fødemateriale: 5,5$ NaClFlow rate: 1.5 liters / minute Feeding Material: 5.5 $ NaCl
Temperatur: 25°CTemperature: 25 ° C
Forsøgsvarighed: 20-24 timer.Trial duration: 20-24 hours.
TDI-koncentrationerne og resultaterne er angivet i tabel II.The TDI concentrations and results are given in Table II.
9 1Λ 5 5 2 69 1Λ 5 5 2 6
Tabel IITable II
TDI-Koncentrationer, Strømning, Salttllbage-TDI Concentrations, Flow, Salt Baking
Eksempel vægtprocent___ liter/crrr/dag hol del se, % 7 0,01 0,179 84,50 8 0,1 0,096>- 98,51 9 0,5 0,0751 99,55 10 1,0 0,0550 99,80 11 2,0 0,0175 99,89Example weight percent ___ liter / crrr / day hol part se,% 7 0.01 0.179 84.50 8 0.1 0.096> - 98.51 9 0.5 0.0751 99.55 10 1.0 0.0550 99.80 11 2.0 0.0175 99.89
Yderligere forsøg med omvendt osmose pied forskellige membraner, der er fremstillet ved fremgangsmåden ifølge opfindelsen, har vist, at der ikke forekommer fald 1 strømningen ved 200 timers drift, hvilket angiver en høj grad af modstandsevne mod sammentrykning.Further reverse osmosis experiments on various membranes prepared by the method of the invention have shown that no decrease in flow occurs at 200 hours of operation, indicating a high degree of compression resistance.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US28759272A | 1972-09-19 | 1972-09-19 | |
US28759272 | 1972-09-19 |
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DK510573A DK145526C (en) | 1972-09-19 | 1973-09-18 | PROCEDURE FOR THE PREPARATION OF A MEMBRANE FOR REVERSE OSMOSES AND ITS APPLICATION FOR SALTING OF SALT WATER |
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JP (1) | JPS5824447B2 (en) |
AU (1) | AU475380B2 (en) |
CA (1) | CA1030711A (en) |
DE (1) | DE2346659C2 (en) |
DK (1) | DK145526C (en) |
FR (1) | FR2200030B1 (en) |
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FR2293960A2 (en) * | 1974-12-10 | 1976-07-09 | Rhone Poulenc Ind | Semi-permeable composite membranes for eg reverse osmosis - comprising polyelectrolyte skin contg sulphonic acid and quat ammonium gps and anisotropic membrane |
US4226673A (en) * | 1976-03-15 | 1980-10-07 | Champion International Corporation | Color removal from paper and pulp mill aqueous effluents |
JPS52127481A (en) * | 1976-04-19 | 1977-10-26 | Uop Inc | Complex semipermeable membrane and the manufacture |
US4125462A (en) * | 1977-08-30 | 1978-11-14 | Rohm And Haas Company | Coated membranes |
JPS5443882A (en) * | 1977-09-14 | 1979-04-06 | Nippon Zeon Co Ltd | Preparation of semipermeable membrane |
US4259183A (en) * | 1978-11-07 | 1981-03-31 | Midwest Research Institute | Reverse osmosis membrane |
US4337154A (en) * | 1979-04-04 | 1982-06-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Crosslinked composite semipermeable membrane |
JPS55134607A (en) * | 1979-04-06 | 1980-10-20 | Nippon Shokubai Kagaku Kogyo Co Ltd | Semipermeable composite membrane with excellent performance and preparation thereof |
IL70415A (en) * | 1982-12-27 | 1987-07-31 | Aligena Ag | Semipermeable encapsulated membranes,their manufacture and their use |
JPS6028803A (en) * | 1983-07-26 | 1985-02-14 | Agency Of Ind Science & Technol | Selective permeable membrane and its manufacture |
JPS60105854U (en) * | 1983-12-23 | 1985-07-19 | 本田技研工業株式会社 | vaporizer float valve |
US4761234A (en) * | 1985-08-05 | 1988-08-02 | Toray Industries, Inc. | Interfacially synthesized reverse osmosis membrane |
JPH07178327A (en) * | 1993-11-12 | 1995-07-18 | Nitto Denko Corp | Composite semipermeable membrane and its production |
WO2011097403A1 (en) | 2010-02-04 | 2011-08-11 | Dxv Water Technologies, Llc | Water treatment systems and methods |
JP5823761B2 (en) * | 2011-07-26 | 2015-11-25 | ダイセン・メンブレン・システムズ株式会社 | NF membrane and manufacturing method thereof |
US10513446B2 (en) | 2014-10-10 | 2019-12-24 | EcoDesal, LLC | Depth exposed membrane for water extraction |
CN112973460B (en) * | 2021-03-15 | 2022-07-08 | 中国石油大学(北京) | Crosslinked covalent organic framework desalting membrane and preparation method and application thereof |
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GB1441014A (en) | 1976-06-30 |
CA1030711A (en) | 1978-05-09 |
AU6034773A (en) | 1975-03-20 |
DE2346659C2 (en) | 1981-09-24 |
IL43201A0 (en) | 1973-11-28 |
IL43201A (en) | 1976-11-30 |
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