CN100556518C - Hydrophilic organic ceramic composite permeable vaporizing membrane and its production and application - Google Patents
Hydrophilic organic ceramic composite permeable vaporizing membrane and its production and application Download PDFInfo
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- CN100556518C CN100556518C CNB2007100417109A CN200710041710A CN100556518C CN 100556518 C CN100556518 C CN 100556518C CN B2007100417109 A CNB2007100417109 A CN B2007100417109A CN 200710041710 A CN200710041710 A CN 200710041710A CN 100556518 C CN100556518 C CN 100556518C
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- 239000012528 membrane Substances 0.000 title claims abstract description 56
- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 230000008016 vaporization Effects 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- -1 siloxanes Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001994 activation Methods 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 3
- 230000003466 anti-cipated effect Effects 0.000 claims 1
- 125000002081 peroxide group Chemical group 0.000 claims 1
- 230000037452 priming Effects 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 18
- 230000003204 osmotic effect Effects 0.000 abstract description 16
- 230000018044 dehydration Effects 0.000 abstract description 13
- 238000006297 dehydration reaction Methods 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 12
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000001764 infiltration Methods 0.000 abstract description 8
- 230000008595 infiltration Effects 0.000 abstract description 8
- 238000009834 vaporization Methods 0.000 abstract description 8
- 230000010148 water-pollination Effects 0.000 abstract description 7
- 150000007524 organic acids Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000002444 silanisation Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 description 32
- 230000000149 penetrating effect Effects 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 18
- 230000004907 flux Effects 0.000 description 13
- 229910000077 silane Inorganic materials 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052908 analcime Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- 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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Transplantation (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the diffusion barrier technical field, be specially the compound infiltration of a kind of hydrophilic organic ceramic and divide from film and its production and application.This diffusion barrier is carrier with the ceramic porous membrane, and hydrophilic polymer is an active layer.Porous ceramic film is through ethyl orthosilicate (TEOS) gas phase or liquid deposition, and silanization is handled and formed the hydrophily separating layer that is connected with chemical bond with the graft reaction of hydrophilic monomer in surface or surface holes on inorganic microporous barrier carrier.The organic ceramic composite separating film of making has stability height, good, the advantage of wide range of application of separating property.Be the efficient hydrophilic osmotic vaporisation separation membrane of a kind of selectivity height, good penetrability, applicable to dehydration, the purifying and concentrated of most of organic solvents and organic acid soln.
Description
Technical field
The invention belongs to the diffusion barrier technical field, being specifically related to a kind of is carrier with the micropore ceramics film, efficient hydrophilic organic ceramic composite permeable vaporizing membrane of surface grafting hydrophilic polymer and preparation method thereof and application in dehydration of organic solvent separates.
Background technology
The infiltration evaporation membrane separation technique is specifically designed to the separation of liquid mixture, is specially adapted to separating of the azeotropic mixture liquid mixture close with boiling point, has characteristics such as efficient, energy-conservation, pollution-free, is a kind of isolation technics that development potentiality is arranged very much.But up to now, this technology is in industrial application and unsatisfactory.Tracing it to its cause, mainly is because the permeation flux of film is little, production efficiency is low, equipment investment expense height, lacks competitiveness.
The separating effect of infiltration evaporation has confidential relation with the character of diffusion barrier.Concerning the hydrophily diffusion barrier, its basic demand is:
Under operating condition, film has sufficiently high mechanical strength and anti-solvent stability in processed aqueous organopolysiloxane;
Film has high as far as possible selectivity to component to be removed in the mixture (water), and promptly the content of water in the penetrating fluid that separated film removes should be high more good more;
Permeability of the membrane will be got well, and promptly the amount of the penetrating fluid that removes through diffusion barrier in the unit interval wants big, and the quantity of solvent that film was handled in the unit interval is big, the production efficiency height.
At present, commercial hydrophilic osmotic vaporization film mainly contains two kinds, and a kind of is to be the organic film of homogeneous that raw material is made with the hydrophily high polymer, and a kind of is to be the inoranic membrane of raw material with the molecular sieve.
Commercial hydrophilic polymer film such as composite membrane of polyvinyl alcohol, though very excellent separation selectivity is arranged, permeability of the membrane is poor.Cause equipment investment expense and production cost all very high, restricted the infiltration evaporation isolation technics in industrial extensive use.And polymer film is the meeting swelling in processed solution, and film strength, separating property and service life are descended, and the application of film is very limited.
With the hydrophilic inorganic film that molecular sieve is made, have that selectivity is good, good penetrability and a high advantage of stability, be a kind of infiltration vaporization separation film of high comprehensive performance.But, the preparation process complexity of this film, the specification requirement height, yield rate is low.Because the preparation cost height of film is difficult to promote equally.
The organic-abio compound permeation vaporisation film is subjected to people's attention in recent years.This class film combines the high and inoranic membrane mechanical strength height of organic film selectivity, the characteristics that chemical stability is good, and also preparation cost is low, has potential application prospect.The preparation of hybrid organic-inorganic film has a lot of methods, and the inorganic particulate that has commonly used mixes in polymer film, and polymer is in inorganic porous membrane surface-coated film forming, and polymer is filled film forming etc. in inorganic porous membrane.Wherein the organic-inorganic film for preparing with the method for free yl graft polymerization on the inorganic porous ceramic film of Y.Cohen invention makes organic active layer combine with ceramic membrane surface by covalent bond, (US 6 to have improved the stability of organic separating layer, 440309B1,2002).It is the breakthrough in the organic and inorganic film preparation.This invention in the aperture less than
The surface contains monomer such as grafting vinylacetate and vinyl pyrrolidone on the ceramic membrane of activity hydroxy, and the composite membrane of making is mainly used in and removes volatile organic solvent from sewage.
The present invention is on the basis of foregoing invention, improves from the several aspects of preparation method, grafted monomers and application, makes this diffusion barrier be applicable to the osmotic, evaporating and dewatering of organic solvent, and has quite good performance.At first, the present invention relaxes the requirement in the aperture of inorganic ceramic membrane, can be as big as 10 μ m.The present invention forms the active coating of hydroxyl in the inoranic membrane surface holes by the method for ethyl orthosilicate (TEOS) low temperature vapor deposition or liquid phase deposition on the throne, further organic graft reaction mainly is to carry out in the surface holes of inorganic ceramic membrane, and formation has the separating layer of centrifugation.Therefore in fact the present invention can be regarded as surface grafting and the organic and inorganic composite membrane that combines and form is filled in the hole, with the preparation method of above-mentioned organic-inorganic film very big difference is arranged.At last, grafting of the present invention all be the water-soluble monomer of strong polarity, the diffusion barrier of formation is mainly used in the dehydration of organic solvent, except alcohols dehydration, also can be used for the stronger organic acid of corrosivity and separates.
Summary of the invention
The object of the present invention is to provide a kind of separation selectivity height, good penetrability, excellent in stability, hydrophilic osmotic vaporisation separation membrane that cost of manufacture is low and preparation method thereof and the application in dehydration of organic solvent.
The hydrophilic osmotic vaporisation separation membrane that the present invention proposes is to be base material with the porous ceramic film, by the free-radical chemistry grafting method, forms the hydrophilic polymer separating layer that connects with chemical bond on its surface.This hydrophily organic and inorganic composite membrane is applicable to the dehydration of organic solvent, has the separation selectivity height, permeability and the high characteristics of stability.
Being applicable to that porous ceramic film of the present invention is a kind of inorganic porous material, can be that flat sheet membrane also can be a tubular membrane.Its average pore size is between 0.5 μ m～10 μ m.The present invention does not have special requirement to the composition of inorganic ceramic membrane, as long as in use can be by water or organic solvent dissolution or extraction.Aluminium oxide (Al
2O
3), zirconia (ZrO
2), silica (SiO
2), titanium dioxide (TiO
2), silicate, cordierite etc. may be used to the preparation of porous ceramic film.
This class hydrophily that the present invention proposes is organic-and the preparation process of ceramic composite permeable vaporizing membrane comprises three steps, the first step is the chemical vapour deposition (CVD) of ethyl orthosilicate or hydrolysis on the throne deposition, second step to be surface activation process, and the 3rd step was the graft reaction of hydrophilic polymer monomer.
Chemical vapor deposition processes carries out in autoclave.Porous ceramic film in being the inorganic acid aqueous solution of 0.1M～1M, concentration is soaked 0.5h～2h in advance.Place autoclave then, add ethyl orthosilicate, its consumption is 5%～10% of a solution volume.The temperature of chemical vapour deposition (CVD) is usually between 160 ℃～200 ℃.Sedimentation time is 2h～20h.Deposition is taken out porous ceramic film after finishing from autoclave, in the high-temperature electronic stove, handle 1h～10h at 500 ℃～600 ℃.
Hydrolysis deposition process on the throne is that porous ceramic film is immersed in ethyl orthosilicate-ethanolic solution, and the mass concentration of ethyl orthosilicate in solution is 1%～10%, and soak time is 0.1h～10h.After deposition finishes, with the film handled in the high-temperature electronic stove, at 500 ℃～600 ℃ processing 1h～10h.
In the present invention, the activation processing on porous ceramic film surface is to carry out under the boiling point of high boiling organic solvent, and used solvent is toluene, dimethylbenzene, ethyl acetate etc., and the processing time is more than 0.5 hour.Used activator is siloxanes, acid anhydrides or the chloride compounds that contains unsaturated bond, as silicone couplet (methacryloxy) propyl trimethoxy silicane (KH570), VTES (KH-151), vinyltrimethoxy silane (KH-171), vinyl three ('beta '-methoxy ethyoxyl) silane (KH-172) and maleic anhydride etc.The mass concentration of activator in solution between 1%～20%,
In the present invention, the graft reaction of hydrophilic monomer carries out in the aqueous solution.Be applicable to that hydrophily grafted monomers of the present invention is that some contain hydroxyl (OH), amido (NH
2), amide groups (CONH
2) or sulfonic group (SO
3H) olefinic monomer is as acrylic acid, methacrylic acid, acrylamide, vinyl pyrrolidone, vinylpyridine, styrene sulfonic acid or vinyl imidazole etc.
The mass concentration of monomer in the aqueous solution is generally between 1%～10%.The initator that is suitable for is water soluble starter commonly used, mainly contains peroxide initiator (as persulfate, ammonium persulfate etc.) or redox initiator (as persulfate-sulphite etc.).Its consumption is below 2% of monomer mass.It is fixed that the temperature of graft reaction should be come according to used initator, and generally between-50 ℃～100 ℃, the reaction time is 0.5h～20h.
The organic and inorganic composite membrane that the present invention makes is a kind of hydrophilic osmotic vaporisation separation membrane of function admirable, is applicable to dehydration, the purifying and concentrated of most of organic solvents.The solvent that is suitable for has alcohols: as methyl alcohol, ethanol, isopropyl alcohol, butanols etc., ethers: as ether, oxolane etc., ketone: as butanone, cyclohexanone etc., the ester class: as ethyl acetate, acrylate, methacrylate and hydroxy-ethyl acrylate etc., acids: as acetate, acrylic acid etc.; Other solvents: as pyridine, acetonitrile, acrylonitrile etc., acids: as acetic acid, acrylic acid etc.Wherein, grafted polyacrylamide, the organic and inorganic composite membrane of polyvinyl imidazol and polyvinylpyridine etc. is specially adapted to the dehydration of organic acid solvent.
The dewatering of the diffusion barrier that the present invention makes can be measured in small-sized infiltration evaporation pond.The volume of osmotic cell is 100mL, and diameter is 5cm, is made by stainless steel material.Magnetic stirrer, heater and thermostat are housed in the osmotic cell.The outlet of osmotic cell links to each other with vavuum pump with cold-trap.In osmotic cell, add 50mL solution during operation.The vacuum of system is 150Pa, and probe temperature is 30 ℃.Penetrating fluid is collected with cold-trap, regularly switches.With gas chromatography determination solution (c
0) and penetrating fluid (c ') in water content; Measure the weight (W) of penetrating fluid with weight method, and calculate penetrating fluid flux J, be i.e. the weight of the penetrating fluid that removes of the film that is per hour amassed by unit plane.Computing formula is as follows:
Wherein, W is the weight of the penetrating fluid collected in the cold-trap, and A is a membrane area, and t is the time interval of sampling.The weight percentage c ' of the selectivity water of diffusion barrier in penetrating fluid (%) represents.
Compare with present commercial organic polymer films or inoranic membrane, main feature of the present invention is,
1, the mechanical strength of film and chemical stability height.The organic and inorganic composite membrane of the present invention's preparation is grafted on hydrophily organic monomer molecule on the porous ceramic film by chemical bond.Organic active layer stable very good can not dissolve in boiling water and organic acid.
2, the selectivity of film and permeability are all very good.The dehydration that the film that makes is used for organic solvent has good selectivity and permeability, is a kind of hydrophilic osmotic vaporisation separation membrane of excellent performance.
3, the adaptability of film is good.The present invention can change the separating property of active separating layer by changing the character and the structure of chemical graft monomer.Therefore, be applicable to the separation of aqueous solutions of organic solvent of different nature.
4, the preparation method of film is simple, cost of manufacture is cheap.
The specific embodiment
Embodiment 1:
The micropore ceramics film that present embodiment uses, its main material is Al
2O
3The about 3mm of the thickness of microporous barrier, effective area are 1cm
2The average pore size on this microporous barrier top layer is about 0.5 μ m.
With the sulfuric acid treatment 1h of this micropore ceramics film with 0.2M, place the 100mL autoclave then, add the 2mL ethyl orthosilicate, 2h is handled in the sealing back in 180 ℃ of baking ovens, handle 1h then in 550 ℃ of electric furnaces.The pure water flux of film after the processing under 150Pa vacuum is 540L/m
2H.
Above-mentioned micropore ceramics film is placed the three-neck flask that spherical condensation tube is housed, add 20mL toluene and 1g (methacryloxy) propyl trimethoxy silicane, added hot reflux 5 hours.After the cooling, film is taken out, wash to remove unreacted silane coupler with toluene.
Micropore ceramics film through silane treatment places the 100mL there-necked flask, adds 8% acrylamide aqueous solution 50mL, potassium peroxydisulfate 0.06g.Under nitrogen protection, 80 ℃ were reacted 1 hour.Reaction finishes back hot deionized water washing three times.Place 120 ℃ of baking ovens to dry then.
Polyacrylamide/microporous ceramic composite membrane of making is installed in the osmotic cell, and adding 50mL concentration is 95% ethanol water.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.It is 99.7% that experiment records the content of water in penetrating fluid, and the penetrating fluid flux is 0.64kg/m
2H.This film is used for 90% isopropanol dehydration, and recording the content of water in penetrating fluid is 99.8%, and the penetrating fluid flux is 0.95kg/m
2H.This film is used for the dehydration of 95% acrylic acid, and recording the content of water in penetrating fluid is 99.5%, and the penetrating fluid flux is 0.76kg/m
2H.
Embodiment 2:
The analcime microporous layers of the about 10 μ m of composite thickness prepares microporous ceramic composite membrane on the micropore cordierite carrier.The thickness of composite membrane is about 3mm, and area is 1cm
2The about 1 μ m of the average pore size of microporous barrier.
With the sulfuric acid treatment 1h of above-mentioned ceramic membrane with 0.2M, place the 100mL autoclave then, add the 4mL ethyl orthosilicate, 2h is handled in the sealing back in 180 ℃ of baking ovens, handle 1h then in 550 ℃ of electric furnaces.The pure water flux of film after the processing under 150Pa vacuum is 350L/m
2H.
Above-mentioned ceramic membrane is placed the three-neck flask that spherical condensation tube is housed, add 25mL toluene and 5g (methacryloxy) propyl trimethoxy silicane then.Added hot reflux 3 hours.After the cooling, microporous barrier is taken out, use toluene, ethanol, water that the surface washing of film is clean successively, to remove unreacted silane.
Micro-pore zeolite composite membrane through silane treatment places the 100mL there-necked flask, adds 10% acrylic acid aqueous solution 50mL, potassium peroxydisulfate 0.05g.Under nitrogen protection, 100 ℃ were reacted 0.5 hour.Reaction finishes back hot deionized water washing three times.Place 120 ℃ of baking ovens to dry then.
Polyacrylic acid/analcime composite membrane of making is installed in the osmotic cell, and adding 50mL concentration is 95% ethanol water.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.It is 99.8% that experiment records the content of water in penetrating fluid, and the penetrating fluid flux is 0.79kg/m
2H.
Embodiment 3:
Present embodiment uses macropore ceramic membrane (φ 36mm * 2.5mm, average pore size: 2～3 μ m).This ceramic membrane is at first handled 50min with the TEOS vapour deposition process at 180 ℃, and the consumption of TEOS is 5mL.Handling the film of gained calcined 5 hours in 500 ℃ of electric furnaces.Pure water infiltration capacity under the 150Pa vacuum is 760L/m
2H.
Above-mentioned ceramic membrane is placed the three-neck flask that spherical condensation tube is housed, add 50mL toluene and 5g (methacryloxy) propyl trimethoxy silicane then and added hot reflux 4 hours.After the cooling, microporous barrier is taken out, with toluene, the surface washing of film is clean, to remove unreacted silane coupler.
Macropore ceramic membrane composite membrane through silane treatment places the 100mL there-necked flask, adds 8% acrylic acid aqueous solution 50mL, potassium peroxydisulfate 0.03g.Under nitrogen protection, 80 ℃ were reacted 5 hours.Reaction finishes back hot deionized water washing three times.Then, place 120 ℃ of baking ovens to dry.
Polyacrylic acid/ceramic composite membrane of making is placed osmotic cell, and adding 50mL concentration is 95% ethanol water.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.It is 99.3% that the result records the content of water in penetrating fluid, and the penetrating fluid flux is 1.36kg/m
2H.Film is used for the dehydration of 10% isopropyl alcohol, and recording the content of water in penetrating fluid is 99.8%, and the penetrating fluid flux is 0.97kg/m
2H.
Embodiment 4:
Present embodiment uses macropore ceramic membrane (φ 36mm * 2.5mm, average pore size: 2～3 μ m).This ceramic membrane is in 10% the TEOS solution with concentration at first, handles 48h by liquid phase deposition at 60 ℃.Handling the film of gained calcined 3 hours in 500 ℃ of electric furnaces.Pure water infiltration capacity under the 150Pa vacuum is 360L/m
2H.
This film is placed the three-neck flask that spherical condensation tube is housed, add 50mL toluene and 5g (methacryloxy) propyl trimethoxy silicane then and added hot reflux 4 hours.After the cooling, microporous barrier is taken out, with toluene, the surface washing of film is clean, to remove unreacted silane coupler.
Macropore ceramic membrane composite membrane through silane treatment places the 100mL there-necked flask, adds 8% acrylic acid aqueous solution 50mL, potassium peroxydisulfate 0.03g.Under nitrogen protection, 80 ℃ were reacted 1 hour.Reaction finishes back hot deionized water washing three times.Then, place 120 ℃ of baking ovens to dry.
Polyacrylic acid/ceramic composite membrane of making is placed osmotic cell, and adding 50mL concentration is 95% ethanol water.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.It is 98.5% that the result records the content of water in penetrating fluid, and the penetrating fluid flux is 0.55kg/m
2H.
Embodiment 5:
The film of making is handled in embodiment 4 usefulness TEOS liquid depositions placed the three-neck flask that spherical condensation tube is housed, add 50mL toluene and 3g (methacryloxy) propyl trimethoxy silicane then and added hot reflux 5 hours.After the cooling, microporous barrier is taken out, with toluene, the surface washing of film is clean, to remove unreacted silane coupler.
Macropore ceramic membrane composite membrane through silane treatment places the 100mL there-necked flask, the DMF solution 50mL of the vinyl imidazole of adding 8%, AIBN0.03g.Under nitrogen protection, 80 ℃ were reacted 1 hour.Reaction finishes back hot deionized water washing three times.Then, place 120 ℃ of baking ovens to dry.
Polyacrylic acid/ceramic composite membrane of making is placed osmotic cell, and adding 50mL concentration is 90% acetic acid aqueous solution.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.It is 99.7% that the result records the content of water in penetrating fluid, and the penetrating fluid flux is 0.42kg/m
2H.This film is used for 95% acrylic acid dehydration, and the result records, and the content of water in penetrating fluid is 99.8%, and the penetrating fluid flux is 0.37kg/m
2H.
Claims (1)
1, a kind of preparation method of hydrophilic organic ceramic composite permeable vaporizing membrane, it is characterized in that comprising three steps, the first step is the chemical vapour deposition (CVD) of ethyl orthosilicate or hydrolysis on the throne deposition, second step to be surface activation process, and the 3rd step was the graft reaction of hydrophilic polymer monomer;
Described chemical vapour deposition (CVD) is carried out in autoclave, porous ceramic film in being the inorganic acid aqueous solution of 0.1M～1M, concentration is soaked 0.5h～2h in advance, place autoclave then, add ethyl orthosilicate, its consumption is 5%～10% of an inorganic aqueous solution volume, the temperature of chemical vapour deposition (CVD) is 160 ℃～200 ℃, and sedimentation time is 2h～20h; Deposition places the high-temperature electronic stove with porous ceramic film after finishing, and handles 1h～10h at 500 ℃～600 ℃; Described porous ceramic film is that the aperture is 0.5 μ m～10 μ m porous film materials, and its main component is aluminium oxide, zirconia, silica, titanium dioxide, silicate or cordierite;
The process of described hydrolysis deposition on the throne is that the porous ceramic film that acid was anticipated is immersed in ethyl orthosilicate-ethanolic solution, and the mass concentration of ethyl orthosilicate in solution is 1%～20%, and soak time is 0.1h～72h; After deposition finishes, with the film handled in the high-temperature electronic stove, at 500 ℃～600 ℃ processing 1h～10h;
The used activator of described surface activation process is siloxanes, acid anhydrides or the chloride compounds that contains unsaturated bond, priming reaction carries out under the boiling point of high boiling organic solvent, used solvent is toluene, dimethylbenzene or ethyl acetate, the mass concentration of activator in solution is 1%～20%, and the processing time is more than 0.5 hour;
Described hydrophilic polymer monomer is to contain hydroxyl, amido, amide groups or sulfonic olefinic monomer, the graft reaction of hydrophilic monomer is to carry out in water, monomer mass concentration is 1%～10%, used initator is peroxide initiator or redox initiator, and its consumption is below 2% of monomer mass; The temperature of graft reaction is-50 ℃～100 ℃, and the reaction time is 0.5h～20h, and grafting hydrophilic polymer monomer forms the hydrophilic polymer separating layer that connects with chemical bond in film surface or surface holes.
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| US8657123B2 (en) * | 2008-09-12 | 2014-02-25 | Toray Industries, Inc. | Composite semipermeable membrane and manufacturing method therefor |
| EP2650044A4 (en) * | 2010-12-07 | 2015-09-16 | Toray Industries | Composite semipermeable membrane and method for producing same |
| CN102569700B (en) * | 2011-12-23 | 2014-01-08 | 深圳市星源材质科技股份有限公司 | Ceramic coating membrane and preparation method thereof |
| CN102698612B (en) * | 2012-05-21 | 2014-02-26 | 北京工业大学 | Automatic device and method for preparing prior-alcohol-permeable composite membrane |
| CN103482999B (en) * | 2013-09-29 | 2015-12-23 | 汪金荣 | A kind of Thief zone porous ceramic film and preparation method thereof |
| CN105960273A (en) * | 2013-10-30 | 2016-09-21 | 分子过滤有限公司 | Separation of organic compounds from liquid |
| CN104857861B (en) * | 2015-04-24 | 2017-06-06 | 南京工业大学 | A kind of preparation method of the ceramic composite membrane for anionic dye desalination |
| CN104959043B (en) * | 2015-06-25 | 2018-07-03 | 北京天恒盛通科技发展有限公司 | Organic liquid separate mesh membrane preparation method and purposes based on infiltration sex differernce |
| KR20180104708A (en) * | 2016-02-02 | 2018-09-21 | 유니버시티 오브 워싱턴 | Ceramic selective film |
| CN108014654B (en) * | 2017-12-15 | 2023-08-18 | 南京工业大学 | Molecular sieve membrane modification method for dehydration separation of strong polar solvent |
| CN108479435A (en) * | 2018-04-16 | 2018-09-04 | 哈尔滨工业大学 | A kind of preparation method of ceramic base polyvinyl acetate composite membrane |
| CN108654401A (en) * | 2018-05-29 | 2018-10-16 | 安徽工业大学 | The surface supersonic modifying processing method of coal-based carbon film |
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