CN103882536B - Hollow fiber for adsorption or filtration and method for producing the same - Google Patents
Hollow fiber for adsorption or filtration and method for producing the same Download PDFInfo
- Publication number
- CN103882536B CN103882536B CN201310184692.5A CN201310184692A CN103882536B CN 103882536 B CN103882536 B CN 103882536B CN 201310184692 A CN201310184692 A CN 201310184692A CN 103882536 B CN103882536 B CN 103882536B
- Authority
- CN
- China
- Prior art keywords
- doughnut
- weight
- spinning liquid
- liquid
- spinneret
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000001914 filtration Methods 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 title abstract description 27
- 239000012510 hollow fiber Substances 0.000 title abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000000835 fiber Substances 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims abstract 3
- 235000012489 doughnuts Nutrition 0.000 claims description 130
- 239000007788 liquid Substances 0.000 claims description 107
- 238000009987 spinning Methods 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 57
- 239000003463 adsorbent Substances 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 20
- 239000010457 zeolite Substances 0.000 claims description 20
- 238000005452 bending Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 13
- -1 polydimethylsiloxane Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 8
- 229910000278 bentonite Inorganic materials 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 8
- 230000035699 permeability Effects 0.000 claims description 8
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000010427 ball clay Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical group O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000391 magnesium silicate Substances 0.000 claims description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 5
- 239000012621 metal-organic framework Substances 0.000 claims description 5
- 229920012287 polyphenylene sulfone Polymers 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229910010252 TiO3 Inorganic materials 0.000 claims description 4
- 235000012241 calcium silicate Nutrition 0.000 claims description 4
- 239000005355 lead glass Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 239000005368 silicate glass Substances 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 229920000954 Polyglycolide Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910052586 apatite Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 239000004633 polyglycolic acid Substances 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 235000019794 sodium silicate Nutrition 0.000 claims description 3
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000004760 aramid Substances 0.000 claims 1
- 229920003235 aromatic polyamide Polymers 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229920001610 polycaprolactone Polymers 0.000 claims 1
- 239000004632 polycaprolactone Substances 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229940092782 bentonite Drugs 0.000 description 6
- 210000005239 tubule Anatomy 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000491 Polyphenylsulfone Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010458 rotten stone Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- FZTLLUYFWAOGGB-UHFFFAOYSA-N 1,4-dioxane dioxane Chemical compound C1COCCO1.C1COCCO1 FZTLLUYFWAOGGB-UHFFFAOYSA-N 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JHXCINJSAAFBDH-UHFFFAOYSA-N [Ca].O[Si](O)(O)O Chemical compound [Ca].O[Si](O)(O)O JHXCINJSAAFBDH-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000281 calcium bentonite Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 238000013148 permeation assay Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000000433 stratum disjunctum Anatomy 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
A hollow fiber for adsorption or filtration. The hollow fiber comprises a tubular matrix having a first end and a second end, and a fiber core extending through the tubular matrix and at the first endAnd a meandering channel extending between the second ends. The tubular substrate is porous and has a thickness of 10 to 20000m2/m3Has a thickness of 0.05 to 9.95mm, an outer diameter of 0.1 to 10mm and a length of 10 to 90% of the length of the meandering channel. The present disclosure also provides a method of making such a hollow fiber.
Description
Technical field
The disclosure about doughnut and preparation method thereof, especially spiral doughnut and preparation method thereof.
Background technology
Typically utilize molecular sieve or use the zeolite in packed bed system or honeycomb structure system to carry out little Molecular Adsorption.
Packed bed system has high adsorption capacity.Can regenerate after system reaches its complete adsorbance.Regenerate the most time-consuming
(such as 24 hours), and consume energy.Honeycomb structure system, because resistance to mass tranfer (mass transfer resistance) is high,
There is the adsorption low compared with packed bed system.Additionally, honeycomb structure systems bulky and expensive.
The doughnut adsorption system of research and development, compared to packed bed system and honeycomb structure system, has higher in the recent period
Adsorbance and relatively low resistance to mass tranfer.Its low cost and quickly can regenerating in low temperature.Refering to WO2008/110820
(Perera and Tai), WO2007/007051A1 (Perera) and Tai, Novel Adsorbent Hollow Fibers,
Ph.D.thesis,University of Bath,UK(2007).But, because relatively low resistance to mass tranfer, doughnut for
High-speed gas or liquid, have poor adsorption efficiency.Refering to Lee et al., Adsorption Science and
Technology,18,147-70(2000)。
Doughnut also apply be applicable to filter.But it is not particularly suited for filtering high-speed gas or liquid.
Therefore, it is still necessary to research and development can effectively carry out the doughnut adsorbing or filtering.
Summary of the invention
The doughnut of the disclosure have can efficiently carry out little molecule filter or absorption cannot intended effect.
The one side of the disclosure is about doughnut, and it contains (i) and has the tubulose substrate of the first end and the second end, and (ii)
Run through (formed through) this tubulose substrate and bending (winding) channel extended between this first end and the second end
(such as, helical track).
This tubulose substrate is cellular, can be single or multiple lift.Tubulose substrate has 10 to 20000 metre squared per cubic
(m2/m3) surface area to volume ratio (surface-area-to-volume ratio), thickness is 0.05 to 9.95 millimeter
(mm), external diameter is 0.1 to 10mm, the 10 to 90% of this bending channel length a length of.
Another aspect of the present disclosure is about the method manufacturing doughnut.The method comprises the steps: that (1) provides spinning
Head (spinneret), this spinneret includes the first jet (orifice) of body (tube) and this body of ring, this body
The port of export has the mis-cut angle (bevel angle) of 15 ° to 80 °；(2) make endoporus liquid (bore fluid) by this body；
(3) making the first spinning liquid (spinning dope) by this first jet, this first spinning liquid contains inorganic adsorbent；(4) when
When this first spinning liquid and this endoporus liquid leave this spinneret, collect this first spinning liquid and this endoporus liquid, fine to form hollow
Dimension precursor；(5) when this first spinning liquid and this endoporus liquid leave this spinneret, this body of this spinneret is rotated；And (6)
This doughnut precursor is condensed, to form spiral doughnut in condensation water.When this first spinning liquid and this endoporus liquid leave
During this spinneret, this body of this spinneret rotates with the speed of 1 to 200rpm, has 1 to 200mm pitch to be formed
(pitch) helical track.
Detailed description of the invention
Below by way of particular specific embodiment, embodiment of the present disclosure being described, this skilled person can be by this explanation
Content disclosed in book understands further advantage and effect of the disclosure.The disclosure also can be added by other different specific embodiment
To implement or application, the every details in this specification also can not depart from the spirit of this creation based on different viewpoints and application
Under carry out various modification and change.
Disclose herein and be used for adsorbing or filtering the doughnut of little molecule (such as, VOC).This hollow
Fiber can be applicable to various field (including petroleum industry, semiconductor industry and opto-electronics), to carry out filtering, concentrate and dividing
From.
The one side of the disclosure is about doughnut, and it contains (i) and has the tubulose substrate of the first end and the second end, and (ii)
Run through this tubulose substrate and the bending channel (such as, helical track) extended between this first end and the second end.
This tubulose substrate is cellular, can be single or multiple lift.Tubulose substrate has 10 to 20000m2/m3Surface area pair
Volume ratio, thickness is 0.05 to 9.95 millimeter (mm), and external diameter is 0.1 to 10mm, the 10 of this bending channel length a length of to
90%。
The tubulose substrate of doughnut contain (i) can as binding agent (binder), adsorbent (adsorbent) or both
Polymeric material (polymeric material), (ii) inorganic adsorbent, (iii) inorganic bond, or (iv) above-mentioned person
Any combination." binding agent " refers to link the material of the adsorbent in tubulose substrate or form the material of this tubulose substrate.With
After polymer adhesive and adsorbent make doughnut, polymer adhesive can be removed, such as in high temperature (such as 500 DEG C)
Remove, to leave this adsorbent." adsorbent " refer to adsorb have molecular weight be 2000 Doltons (Dalton) or following (the most such as
800 Doltons, 100 Doltons and 18 Doltons) the material of little molecule.All doughnuts of the disclosure were all applicable to
Filter.Doughnut containing adsorbent (polymer absorbant, inorganic adsorbent or both) also can be used for adsorbing.
In one specific embodiment, tubulose substrate contain inorganic adsorbent (count on the basis of the weight of doughnut, 0.1 to
95 weight % (wt%)) and polymer adhesive.In another specific embodiment, it is (fine with hollow that tubulose substrate contains inorganic adsorbent
Count on the basis of the weight of dimension, 0.1 to 95wt%) and inorganic bond.The disclosure also includes containing conductive material
The doughnut of (electrically conductive material), in a specific embodiment, conductive material is positioned at tubulose
The outer layer of substrate.
The example of polymeric material includes, but are not limited to: polyether sulfone (polyether sulfone, PESF), polysulfones
(polysulfone), polyvinylidene fluoride (polyvinylidene fluoride, PVDF), Polyphenylene Sulfone
(polyphenylsulfone, PPSU), polyacrylonitrile (polyacrylonitrile), cellulose acetate, cellulose diacetate,
Pi, Polyetherimide, polyamide (aromatic series), polyvinyl alcohol, polylactic acid, polyglycolic acid, poly-(lactic acid-ethanol)
(poly (lactic-co-glycolic acid)), poly-several lactones, polyethylene hydrogen pyrrolidone (polyvinyl
Pyrrolidone), ethylene-vinyl alcohol copolymer (ethylene vinyl alcohol), polydimethylsiloxane and group thereof
Close.It is preferably PESF, polysulfones, PVDF, Polyphenylene Sulfone and combinations thereof.More preferably PESF and PPSU.
The example of inorganic adsorbent includes, but are not limited to: type A zeolite, X-type zeolite, y-type zeolite, high-silica zeolite (high
Silica molecular sieve), mesopore molecular sieve, permeability metal organic framework material (porous metal-organic
Framework material), activated carbon, carbon molecular sieve and combinations thereof.Preferably inorganic adsorbent is type A zeolite, X-type boiling
Stone, high-silica zeolite, mesoporous hole molecular sieve, activated carbon and combinations thereof.More preferably type A zeolite, X-type zeolite, high-silica zeolite
And combinations thereof.
The example of inorganic bond includes, but are not limited to: aluminium oxide, silicon dioxide, bentonite (bentonite), china clay
(China clay), oxyhydrogen-base apatite (hydroxylapatite), ball clay (hyplas clay), calcium silicates, magnesium silicate,
Sodium silicate, anhydrous sodium sulfate, Zirconium orthosilicate., opaque zirconium (zircon opaque), carborundum, (Ba, Pb) TiO3, metasilicic acid lead
Frit (lead bisilicate frit), sesquialter lead silicate glass material (lead sesquisilicate frit), low swollen
Swollen frit (low expansion frit), soft borax glass material (soft borax frit), standard borax glass material
(standard borax frit) and combinations thereof.It is preferably aluminium oxide, silicon dioxide, bentonite, china clay, ball clay, silicic acid
Calcium, magnesium silicate, sodium silicate, anhydrous sodium sulfate, Zirconium orthosilicate., opaque zirconium, metasilicic acid lead glass material, sesquialter lead silicate glass material,
Low-expansion glass material, soft borax glass material, standard borax glass material and combinations thereof.
This doughnut contains and runs through tubulose substrate and the bending channel by this tubulose substrate cladding.
A diameter of 0.05 to 9.95mm (such as, 0.1 to 5mm, 0.5 to 2mm, 0.2 to 0.6mm, and 1 of this bending channel
To 3mm), can be z font or shaped form, such as, spiral type.Helical track typically has the pitch of 1mm to 200mm.Pitch refers to
One complete spiral shell shape rotates the width of (spiral turn), is parallel to the axle of this doughnut and measures.
Tubulose substrate, can be straight or curved.10 to 90% (examples of this bending channel length a length of of tubulose substrate
As, 20 to 60%, 20 to 40%, 10 to 80% and 20 to 70%), thickness be 0.05 to 9.95mm (such as, 0.5 to 4mm, 0.5 to
2mm, 0.1 to 9mm, 0.2 to 8mm, 1 to 4mm and 1 to 5mm), external diameter be 0.1 to 10mm (such as, 1 to 5mm, 1 to 3mm, 3 to
8mm, 2 to 4mm, 0.2 to 2.5mm, 0.3 to 6mm and 0.5 to 3mm).
Substrate can have active surface porosity (effective surface porosity) (that is, the table of hole lengths
Face porosity, ε/Lp,m-1) it is 100 to 10000 (such as, 200 to 8000, and 400 to 6000), and hole size (that is, aperture
(pore diameter)) being 1 nanometer (nm), (such as, 0.1 to 10 μm, 1 to 100nm and 10nm are to 50 μ to 50 microns (μm)
m).The porosity of whole doughnut and hole size can be identical or have the biggest difference.Volume ratio is by the surface area of substrate
10 to 20000m2/m3(such as, 10 to 10000m2/m3, 200 to 6000m2/m3, 1000 to 4000m2/m3, 100 to 5000m2/
m3, 250 to 3000m2/m3And 500 to 8000m2/m3).Volume ratio is passed through by active surface porosity, hole size and surface area
Method well known in the art is measured.Refering to Carman, Flow of Gases Through Porous Media
(Butterworths Scientific Publications1956)；Scott and Hughes,Industrial
Membrane Separation Technology(Blackie Academic and Professional1996)；And Li et
al.,Tailor-Made Asymmetric PVDF Hollow Fibers for Soluble Gas Removal,AIChE
Journal,45,1211-19(1999)。
The adsorption efficiency of doughnut is relevant with its surface area.Can be surveyed by the packed density filling the tubing string of doughnut
Fixed.Packed density is the total surface area of the doughnut ratio to tubing string sectional area.Higher packed density and bigger surface
Long-pending to volume ratio, typically result in tubing string more efficiently.
Hole size distribution (pore size distribution) and porosity also affect the performance of doughnut.Hole
Size distribution, the statistical distribution range in the aperture in doughnut, can be 0.005 to 10 μm, 0.05 to 5 μm or 0.5 to 2 μm.
The porosity of doughnut, defines with the void volume percentage ratio in fiber, can be 10 to 200%, 20 to 140% or 40 to 80%.Relatively
Narrow hole size distribution and higher porosity, typically result in the higher flux of doughnut (flux rate).
In one specific embodiment, substrate contains polymeric material, and it is generally as binding agent.With the weight of doughnut it is
Benchmark meter, polymeric material is usually 5 to 100wt% (such as, 5 to 99.9wt%, 7 to 50wt% and 10 to 20wt%).Polymer
Material can be PESF, polysulfones, polyvinylidene fluoride, Polyphenylene Sulfone, polyacrylonitrile, cellulose acetate, cellulose diacetate, poly-sub-acyl
Amine, Polyetherimide, polyamide (aromatic series), polyvinyl alcohol, polylactic acid, polyglycolic acid, poly-(lactic acid-ethanol), poly-several in
Ester, polyethylene hydrogen pyrrolidone, ethylene-vinyl alcohol copolymer, polydimethylsiloxane and combinations thereof.
In another specific embodiment, counting on the basis of the weight of doughnut, (such as, tubulose substrate contain 5 to 100wt%
5 to 99.9wt%, 7 to 50wt% and 10 to 20wt%) inorganic bond.Example includes, but are not limited to: aluminium oxide, titanium dioxide
Silicon, bentonite (such as, potassium matter bentonite, sodium bentonite, calcium bentonite and aluminum matter bentonite), china clay are (such as,
Al2O3.2SiO2.2H2O), oxyhydrogen-base apatite (such as, Ca10(PO4)6(OH)2), ball clay (such as, 20%Al2O3.70%
SiO2.0.8%Fe2O3.2.3%K2O.1.6%Na2O), calcium silicates (such as, Ca3SiO5、Ca3Si2O7And CaSiO3), magnesium silicate (example
As, Mg3Si4O10(OH)2), sodium silicate (such as, Na2SiO3And hydrate (hydrate), SiO2: Na2The ratio of O is between 2:1
And between 3.75:1), anhydrous sodium sulfate, Zirconium orthosilicate. (such as, ZrSiO4), opaque zirconium (such as, 53.89%SiO2.4.46%
Al2O3.12.93%ZrO2.9.42%CaO.2.03%MgO.12.96%ZnO.3.73%K2O.0.58%Na2O), carborundum (SiC),
(Ba,Pb)TiO3, metasilicic acid lead glass material (such as, 65%PbO.35%SiO2), sesquialter lead silicate glass material (such as, 71.23%
PbO.28.77%SiO2), low-expansion glass material (such as, 0.1%Li2O.3.6%CaO.3.3%ZnO.2.4%MgO.8.2%
Al2O3.63.6%SiO2.17.8%B2O3), soft borax glass material (such as, 10.3% (Li2O+Na2O+K2O) .14% (CaO+
MgO).3.3%ZnO.7.5%Al2O3.50%SiO2.18%B2O3), standard borax glass material (such as, 14.22%CaO.0.16%
MgO.1.56%K2O.9.01%Na2O.7.63%Al2O3.49.45%SiO2.17.93%B2O3) and combinations thereof.
In still another embodiment, substrate contains inorganic adsorbent, preferably fine particulate form, and having particle diameter is 0.005
To 500 μm (such as, 0.01 to 100 μm and 0.1 to 10 μm).Counting on the basis of the weight of doughnut, inorganic adsorbent is 0.1
To 95wt% (such as, 75 to 90wt%, 80 to 90wt%, 50 to 95wt%, 65 to 80wt% and 80 to 95wt%).Inorganic adsorbent can
For type A zeolite (such as, 3A, 4A and 5A), X-type zeolite (such as, 10X), y-type zeolite (such as, 13X), high-silica zeolite (example
As, ZSM-5, tripoli stone (Silicalite), HiSiv1000, HiSiv3000, HiSiv6000, Abscent1000,
Abscent2000, Abscent3000, USK Y-700 and USYZ2000), mesoporous hole molecular sieve (such as, MCM-41,48 and
50), MOF material (such as, the organic framework of metal), activated carbon, carbon molecular sieve or a combination thereof.Refering to Tai, Ph.D.thesis
(2007)；Perry et al.,Materials Research Bulletin,2,409-18(1967)；Harlick et
al.,Microporous and Mesoporous Materials,76,71-79(2004)；Rouquerol et al.,
Adsorption by Powders and Porous Solids(Academic Press1998)；Ruthven,
Principles of Adsorption and Adsorption Process(Wiley-Interscience1984)；Yang,
Gas Separation by Adsorption Processes(Butterworth Publishers1987)；Beck et
al.,Chemistry of Materials,6,1816-21(1994)；And Haber et al., Overview of
Transitional Ceramics,Engineered Materials Handbook,Volume4(The Materials
Information Society,2000)。
Substrate can be multilamellar, such as, double-deck, three layers and four layers.Each layer contains one or more material, its can with his layer contained by
Person is identical or different.When two-layer contains identical material, it has different aperture degree or hole size.Those skilled in the art exist
The material of each layer, porosity, hole size and thickness can be determined in the case of needn't excessively testing.
Substrate also can comprise conductive material.When the doughnut little molecule of absorption to maximal absorptive capacity (adsorption
Capacity), time, remove little molecule by heat and regenerate.Conductive material produce heat thus make little desorbing molecules and make doughnut
Regeneration.Execute voltage between the two ends of doughnut to regenerate.Conductive material can be with inorganic adsorbent or Polymer adsorption
Agent is mixed in same layer, or forms stratum disjunctum with binding agent.In multilayer hollow fiber, this material may be present in each layer.It is also
Can exist only in one layer, be preferably in relatively outer layer, thickness be 0.05 to 9.95mm (such as, 0.1 to 4mm and 0.2 to
2mm).Conductive material typically has 10 to 100000 ohm-sq centimetre (ohm/cm2) resistance (such as, 10 to
40000ohm/cm2And 500 to 10000ohm/cm2).Conductive material example include, but are not limited to: activated carbon, carbon black, stone
Ink, metal-oxide (such as, CuO and (Ba, Pb) TiO3), metal and combinations thereof.
The method that the disclosure also includes manufacturing doughnut.The method comprises the steps: that (1) provides spinneret, and this spins
Silk head includes the first jet (orifice) of body (tube) and this body of ring, and the port of export of this body has 0 ° to 90 °
Mis-cut angle (such as, 15 ° to 80 °, 20 ° to 60 ° and 40 ° to 50 °)；(2) make endoporus liquid (bore fluid) by this body；
(3) making the first spinning liquid (spinning dope) by this first jet, this first spinning liquid contains inorganic adsorbent；(4) when
When this first spinning liquid and this endoporus liquid leave this spinneret, collect this first spinning liquid and this endoporus liquid, fine to form hollow
Dimension precursor；(5) when this first spinning liquid and this endoporus liquid leave this spinneret, this body of this spinneret is rotated；(6) in solidifying
Knot liquid condenses this doughnut precursor, to form spiral doughnut.When this first spinning liquid and this endoporus liquid leave this and spins
During silk head, this body of this spinneret rotates with the speed of 1 to 200rpm (such as, 5 to 100rpm and 10 to 40rpm).Therefore
Formation has the helical track of 1 to 200mm (such as, 3 to 150mm and 6 to 100mm) pitch.
This body of this spinneret has the internal diameter (inside of 1 to 10mm (such as, 2 to 8mm and 3 to 5mm)
diameter).This body is by first jet institute ring, and this first jet has 0.1 to 9.6mm (such as, 0.3 to 6mm and 0.6
To 3mm) internal diameter and the external diameter (outer diameter) of 0.4 to 9.8mm (such as, 0.6 to 7mm and 0.8 to 4mm).
First spinning liquid is by this first jet.First spinning liquid is by by inorganic adsorbent, inorganic bond, polymer
(such as, the weight ratio of inorganic adsorbent/inorganic bond/polymeric material is 50/30/20 to 95/2.5/ for material or a combination thereof
2.5,75/15/15 to 90/5/5, or 80/10/10 to 88/6/6) it is scattered in blending solvent, and optionally (the most such as,
84 hours) stir (such as, with 50 to 100rpm) and obtain.Blending solvent is soluble polymeric thing material and can be with following endoporus
The solvent that liquid and condensation water dissolve each other.The example blending solvent includes, but are not limited to: dimethyl acetylamide (DMAc), 1-methyl-2-
Pyrrolizidine ketone (NMP), dimethylformamide (DMF), 1,4-dioxane (1,4-dioxane), dichloromethane, acetone and group thereof
Close.
Endoporus liquid this body by this spinneret.The example of endoporus liquid includes, but are not limited to: water, methanol, ethanol, third
Alcohol, isopropanol, acetone and combinations thereof.When endoporus liquid is by this body, and rotary spinning head is to form helical track.
When this endoporus liquid and this first spinning liquid leave this spinneret, collect this endoporus liquid and this first spinning liquid (i.e.
Order contacts with each other), to form doughnut precursor, condense to form spiral hollow fine after it in condensation water (such as, water)
Dimension.
In one specific embodiment, this first jet by second nozzle (orifice) institute ring, and, when the first spinning liquid
By this first jet, the second spinning liquid by this second nozzle, with make when this two spinning liquid leaves this spinneret this first
Spinning liquid contacts this second spinning liquid.This second spinning liquid can comprise conductive material.
Use above-mentioned same program can prepare double-layer hollow fiber as follows.Use the spinneret with second nozzle.Second
Nozzle ring around first jet, and can have the internal diameter of 0.6 to 9.6mm (such as, 1 to 7.8mm and 1.4 to 4.8mm) and 0.8 to
The external diameter of 9.8mm (such as, 1.2 to 8mm and 1.6 to 5mm).Except endoporus liquid and the first spinning liquid, also provide for the second spinning liquid.
Such as the first spinning liquid, the second spinning liquid also can be by by conductive material, inorganic adsorbent, inorganic bond, polymeric material
Or a combination thereof is scattered in and prepares in blending solvent.Second spinning liquid can optionally contain conductive material and polymeric material.
Endoporus liquid this body by this spinneret, the first spinning liquid is by this first jet, and the second spinning liquid passes through
Second nozzle.When this first spinning liquid, endoporus liquid and this second spinning liquid leave this spinneret, this first spinning liquid is made to contact
This endoporus liquid and this second spinning liquid, to form doughnut precursor, its condensation becomes double-layer hollow fiber.
Similarly, by making three or more spinning liquid by having three or more nozzles (such as, four nozzle)
Spinneret, the doughnut with three layers or more layers can be prepared.
What the doughnut of the disclosure had improvement tradition doughnut usefulness cannot intended effect.First, bending letter
Road is upset gas stream or liquid stream and moves it to hollow fiber walls to carry out adsorbing or filtering.Furthermore, bending makes path length
Degree increases, and the time therefore extended through, to strengthen adsorption.Additionally, the doughnut of the disclosure is at high temperature (such as, 250
DEG C) it is stable.
The doughnut of the below example only illustrative disclosure is prepared with it, not for limiting the disclosure.
Above-described embodiment all can be modified under the spirit and the scope of the disclosure and change by this skilled person any
Become.Therefore, the rights protection scope of the disclosure, should be as contained in claims.
Embodiment 1 to 7
Preparing of 7 doughnuts A, B, C, D, E, A-25 and A-28 containing inorganic adsorbent is as follows.
First, the constituent containing solvent, polymer and inorganic adsorbent as shown in table 1 below is used to prepare spinning liquid.
Table 1. spinning liquid constituent
Use rotary pump little with 100rpm stirring polymer (100 grams (g)) 24 in solvent (400 to 500 milliliters (mL))
Time or until be completely dissolved as settled solution.Filtering solution.IKA Werke agitator is used to stir with 500 to 3000rpm,
It is slowly added inorganic adsorbent (400 to 700g) simultaneously.Gained mixture stirs 6 to 48 hours with identical speed.It is then used by
Rotary pump in 100rpm degasification 24 to 48 hours to form uniform spinning liquid.
The spinning liquid so prepared is used to prepare doughnut.Use has body (diameter 0.72mm, mis-cut angle 45 °)
And the body nozzle spinneret (tube-in-orifice spinneret) of nozzle (orifice) (external diameter 2.0mm) manufactures monolayer
Doughnut.Spinning liquid is moved in rustless steel container, with vacuum pump degasification 10 to 30 minutes, be forced into 0.5 to 8 bar with nitrogen
(bar), make it with 1 to 10 ml/min (mL/min) by this nozzle.Water (as endoporus liquid) is made to lead to 1 to 30mL/min
Cross this body.This body of spinneret rotates with the speed of 1 to 200rpm.Spinning liquid is met with endoporus liquid phase in spinneret terminal,
Form doughnut precursor, its by the air gap (air gap) between spinneret terminal Yu coagulation bath (such as, water) (0 to
10cm, such as, 3cm).Precursor solidify to form doughnut in the time of 48 hours in water (as coagulation bath).In the second bath
In thoroughly clean obtained by doughnut, soak 24 to 96 hours in clear water, be dried 1 to 7 day in environmental condition.
Doughnut A to E, A-25 and A-28 is prepared with program as above.Spinning liquid constituent is as listed in Table 1.
Preparing the doughnut of two comparative examples again, it respectively has straight channel rather than helical track.
More specifically, in the way of identical with doughnut A-25 and A-28, prepare the doughnut A-25 ' of comparative example
And A-28 ', but use the spinneret with smooth body, and non-usage has the spinneret of body of cutting sth. askew.
7 doughnuts and two comparative example doughnuts are made to carry out permeability test
(permeation test) and adsorption test (adsorption test), described in below embodiment 16,17 and 20.
Embodiment 8 to 10
Prepare 3 double-layer hollow fibers C-12, C-16 and C-19 with same program as above, but use two spinning
It is (outer that liquid and use have body (diameter 0.8mm, mis-cut angle 45 °), inner nozzle (external diameter 2mm, internal diameter 1.2mm) and outer nozzle
Footpath 4mm, internal diameter 3mm) twin-jet nozzle spinneret.
The first spinning liquid in first container is forced into 2bar and makes it pass through inner nozzle
(orifice).The second spinning liquid in second container is forced into 2.5 to 3bar and makes it pass through outer nozzle
(orifice).The doughnut formed by first and second spinning liquid is carried out post processing same as described above.
According to this etc. program manufactures doughnut C-12, C-16 and C-19:
In embodiment 8, by the first spinning liquid (13X/PESF, 10/1 (weight)) and the second spinning liquid (13X/PESF, 4/1
(weight)) both prepare doughnut C-12.Using NMP as solvent, consumption is 4 times of PESF weight.
In embodiment 9, by the first spinning liquid (13X/PESF, 10/1 (weight)) and the second spinning liquid (13X/PESF, 3/1
(weight)) both prepare doughnut C-16.NMP consumption is the same as in Example 8.
In embodiment 10, by the first spinning liquid (13X/PESF, 10/1 (weight)) and the second spinning liquid (13X/PESF, 3/2
(weight)) both prepare doughnut C-19.NMP consumption is the same as in Example 8.
Test the absorption property of these 3 double-layer hollow fibers, shown in below embodiment 19.
Embodiment 11 to 13
3 doughnut S-01, S-02 and S-03 containing organic and/or inorganic materials are prepared with following program.
First, with NMP, PESF, Al2O3And silica gel/magnesium oxide of being fuming prepares spinning liquid.Use 3 kinds of Al2O3(respectively there is grain
Footpath 1,0.3 and 0.01 to 0.02).Its weight ratio is as shown in table 2 below.
Table 2 spinning liquid constituent
For preparing spinning liquid, mixing NMP and PESF and in rotary pump stir 24 to 48 hours to form polymer solution, its
Then stir with 500 to 1000rpm in IKA Werke agitator.Add Al2O3.Gained mixture stirs 2 to 4 days uniformly to divide
Dissipate Al2O3.Add SiO2(that is, silicon of being fuming) and/or MgO (that is, magnesium oxide) and stir 1 to 2 day to form uniform dispersion, its
Bulky grain is removed to filter by the Nylon filter paper (filter paper) of 100 μm.Filtered dispersion liquid uses rotary pump
Degasification is to obtain spinning liquid.
Then, gained spinning liquid is used to prepare doughnut.Spinning liquid is moved in rustless steel container, in room temperature with vacuum
Pump degasification 30 minutes.Container is forced into 2bar with nitrogen.Using water as endoporus liquid and as coagulation bath.It is (straight that use has body
Footpath 0.72mm, mis-cut angle 45 °) and the body nozzle spinneret (tube-in-of nozzle (orifice) (external diameter 2.0mm)
orifice spinneret).The air gap between spinneret and coagulation bath is 3cm.When endoporus liquid with 8mL/min by being somebody's turn to do
When body and spinning liquid are by this nozzle, this body rotates with the speed of 30rpm.Make doughnut precursor by the air gap also
In coagulation bath, tubule (tubule) it is solidify to form in the times of 48 hours.Tubule obtained by thoroughly cleaning in the second bath,
Soak 48 hours in clear water, be dried 3 to 4 days in environmental condition.
Finally, this tubule is calcined to obtain inorganic hollow fibers.It is heated according to temperature program(me) in heating furnace.
Tubules are heated 5 hours at the beginning in 600 DEG C.With the speed of 1.5 DEG C/min, temperature is risen to 900 DEG C, then with 2.5 DEG C/min
Rise to 1100 DEG C, then rise to 1550 DEG C with 1 DEG C/min.Tubule calcines 10 to 12 hours to obtain final hollow in 1550 DEG C
Fiber.
3 doughnuts S-01, S-02 and S-03 are prepared according to said procedure.Spinning liquid constituent is as above shown in table 2.
Embodiment 14 and 15
2 inorganic hollow fibers HF-14a and HF-14b are prepared with following program.
In embodiment 14, use (i) by mixing metasilicic acid lead frit and tripoli stone (weight ratio 15/85) in NMP
First spinning liquid and (ii) of preparation are prepared with tripoli stone (weight ratio 40/60) also through mixing metasilicic acid lead frit in NMP
The second spinning liquid, prepare doughnut HF-14a.Doughnut HF-is prepared according to the program described in above-described embodiment 11 to 13
14a, it is calcined 18 hours in 660 DEG C.
In embodiment 15, prepare doughnut HF-14b preparing the same procedure of doughnut HF-14a, but in 660
DEG C calcining 24 hours rather than 18 hours.
Embodiment 16
Use the doughnut prepared by following method feature embodiment 1 to 5,11 and 12.
Gas permeation test (Gas permeation test)
Carry out blocking gas permeation analyzing (dead-end gas permeation assay) to measure the flat of doughnut
All hole size, active surface porosity and gas permeabilities (gas permeability), its one end with
(Epoxy) seal.Nitrogen is used outside the doughnut other end.By Brooks mass flowmenter (mass flow
Indicator) it is measured in different transmembrane pressures (trans-membrane pressure).Refering to Li et al.,
Tailor-Made Asymmetric PVDF Hollow Fibers for Soluble Gas Removal,AIChE
Journal,45,1211-19(1999)；And Tai, Ph.D.thesis, (2007).
Use following equation calculate doughnut two important parameters, average cell size (r, i.e. average pore size) and
Active surface porosity (ε/Lp):
r=(16/3)(P0/K0)(8RT/πM)1/2μ (l)
ε/Lp=8μRTP0/r2 (2)。
In this two equation, R is gas constant, and T is absolute temperature, and M is molecular weight, and μ is gas viscosity, and K0And P0
It is respectively intercept and slope, by pressure normalised osmotic flow (pressure-normalized permeation flux) to flat
All pressure is mapped and is measured.Refering to Carman, Flow of Gases through Porous Media (Butterworth
Scientific Publications1956)；Shih et al.,Morphology of Microporous Poly
(Vinylidene Fluoride),Membranes Studied by Gas Permeation and Scanning
Microscopy, Journal of Membrane Science, 50 (3), 299-317 (1990) (describe two kinds of methods, i.e.
Poiseuille discharge method (flow mehtod) and Knudsen discharge method)；And Hatim et al., Pd/
Al2O3Composite Hollow Fiber Membrances:Effect of Substrate Resistances on
H2Permeation Properties,Chemical Engineering Science,66,1150-58(2011).Use such as
Lower Equation for Calculating gas permeability (Ji).Refering to Carman (1956) and Shih (1990).
Ji=(2/3(8RT/πM)1/2(I/RT)(rε/Lp))+(P/8μRT)(r2ε/Lp) (3)。
Doughnut A to E, the average cell size of S-01 and S-02, active surface porosity and the value of gas permeability
As shown in table 3 below and 4.The characteristic (using Poiseuille method) of the doughnut A to E of table 3. embodiment 1 to 5 preparation
The characteristic of doughnut S-01 and S-02 of table 4. embodiment 11 and 12 preparation
Embodiment 17
The absorption property of the doughnut A to C of testing example 1 to 3 preparation.
For obtaining breakthrough curve (breakthrough curve), use Lee et al., Manufacture and
Characterisation of Silicalite Monoliths,Adsorption Science and Technology,18
(2), the method and apparatus described in 147-170 (2000) carries out dynamic adsorption analysis (dynamic adsorption assay).
Equipment includes tubing string, in order to supply the flow system (flow system) of feedback stream and in order to monitor dividing of eluting gas concentration
Analysis system.
Assembling tubing string is with the doughnut containing 50 fillings, and it respectively has the length of 25cm.In order to compare, use
Another tubing string containing commercial particulate (1.0 × 1.18mm buys from Universal Oil Products) compares.Pipe
Commercial particulate in post has the weight identical with this 50 doughnuts.Select normal butane as VOC.
Before tubing string, with N2(vector gas) mixes with the concentration of 6000ppm.Set gas flow rate as 1.5 liters/min (L/min).
Make admixture of gas by absorption tubing string.Use flame ionic detector (flame ionisation
Detector) (Signal Instruments, model3000) continues to monitor concentration of n-butane and the breakthrough curve of absorption tubing string
Change.All of adsorption analysis is in carrying out in 25 DEG C.Gas up flows through tubing string to adsorb, when tubing string regenerates down
Flow through tubing string.
Mapped (from normal butane stream by the time function of ratio between concentration of n-butane and initial concentration of n-butane after absorption
Start at during beginning) to obtain the breakthrough curve of absorption.Time of break-through is obtained by this breakthrough curve.
Doughnut A, B and C is made to carry out dynamic adsorption analysis as above.Obtain its adsorption penetration time.Hollow is fine
The time of break-through of dimension A is 29 minutes, and the time of break-through of doughnut B is 33 minutes, and the time of break-through of doughnut C is 26 points
Clock.The time of break-through of the commercial particulate for comparing is 22 minutes.3 doughnuts of the disclosure all present more than commercially available
The time of break-through of grain length.
Embodiment 18
The absorption property of two doughnut HF-14a and HF-14b of detection embodiment 14 and 15 preparation.
Using the program described in embodiment 17 to carry out adsorption analysis, except using containing 40 filling doughnuts, (it is each
There is the length of 24cm) tubing string.
Draw breakthrough curve.The commercial particulate tubing string used with embodiment 17 compares, doughnut HF-14a and HF-14b
Both breakthrough curves are the sharpest, represent it and have high matter biography rate (mass-transfer rate) and big active surface
Long-pending.The time of break-through of doughnut HF-14a is 76 minutes, and adsorbance is 8.7%.And the time of break-through of doughnut HF-14b is
58 minutes, adsorbance was 6.8%.Two doughnuts are respectively provided with much larger than commercial particulate that (as shown in Examples below 19, it is only
Have 1.4%) adsorbance.
Embodiment 19
The absorption property of three doughnut C-12, C-16 and C-19 of detection embodiment 8 to 10 preparation.
The same procedure described in embodiment 17 is used to carry out adsorption analysis, except using different tubing strings and with CO2Replace
Normal butane.Assemble three tubing strings respectively to contain the doughnut (37 to 40g, 24cm) of filling.Also filling is containing 13X commercial particulate (4
× 3.2mm) comparison tubing string.Initial CO2Concentration is 3000ppm.Gas flow rate is 1L/min.N2Pressure is 1 or 2atm.Use
Far infrared gas monitor (Infra-Red Gas Monitor) (model RS232interface adaptor,
Edinburgh Sensors Limited) continue to monitor feedback material concentration and the change of breakthrough curve adsorbing tubing string.
The time of break-through shown in table 5 below is obtained by breakthrough curve.Three doughnuts all represent much longer compared with 13X commercial particulate
Time of break-through, and adsorbance is also much larger than 13X commercial particulate.In detail, C-12, C-16, C-19 and 13X commercial particulate in
The time of break-through of 1atm is respectively 149,170,141 and 74 minutes；The adsorbance of C-12, C-16, C-19 and commercial particulate is respectively
It is 2.67%, 2.9%, 2.5% and 1.4%.
Table 5. doughnut C-12, C-16, C-19 and the time of break-through of commercial particulate 13X and adsorbance
Embodiment 20
The absorption property of two doughnut A-25 and A-28 of the disclosure of detection embodiment 6 and 7 preparation.Also enforcement is detected
The absorption property of two comparative example doughnut A-25 ' and A-28 ' (it respectively has straight channel) of example 1 to 7 preparation, and and spiral
Doughnut A-25 and A-28 compares.
Adsorption analysis is carried out, except using different tubing strings and with dampness (moisture) according to the program described in embodiment 17
Replace normal butane.Assemble four tubing strings respectively to contain the doughnut (50g, 24cm) of filling.Dampness and N2Mixing.N2Pressure is
1atm.Flow velocity is 1L/min.
Self-gating curve obtains time of break-through.Spiral doughnut has the absorption property superior far beyond direct attack hollow fiber.
In detail, the time of break-through of spiral doughnut A-28 7 hours is long far beyond direct attack hollow fiber A-28 ' (5.4 hours).In spiral
The time of break-through of hollow fiber A-25 4.8 hours is long far beyond direct attack hollow fiber A-25 ' (3.9 hours).
Claims (17)
1. for absorption or a doughnut for filtration, including:
Have the tubulose substrate of the first end and the second end, and
Run through this tubulose substrate and extend the bending channel between this first end and this second end, and this bending channel is for having
1 to 200mm pitch and the helical track of 0.05 to 9.95mm diameter,
Wherein, this tubulose substrate is cellular, and has 10 to 20000m2/m3Surface area to volume ratio, thickness be 0.05 to
9.95mm, external diameter is 0.1 to 10mm, the 10% to 90% of this bending channel length a length of.
2. doughnut as claimed in claim 1, it is characterised in that this tubulose substrate contains inorganic adsorbent.
3. doughnut as claimed in claim 2, it is characterised in that this tubulose substrate has 200 to 6000m2/m3Surface
Long-pending to volume ratio, thickness is 0.5 to 4mm, and external diameter is 1 to 5mm, and the 20% to 60% of this bending channel length a length of, this is curved
Qu Xindao has 0.1 to 3mm diameter；And, to count on the basis of the weight of this doughnut, this inorganic adsorbent is 0.1 to 95
Weight %.
4. doughnut as claimed in claim 3, it is characterised in that this tubulose substrate has 1000 to 4000m2/m3Surface
Long-pending to volume ratio, thickness is 0.5 to 2mm, and external diameter is 1 to 3mm, and the 20% to 40% of this bending channel length a length of, this is curved
Qu Xindao has 0.1 to 2mm diameter；And, to count on the basis of the weight of this doughnut, this inorganic adsorbent is 75 to 90 weights
Amount %.
5. doughnut as claimed in claim 2, it is characterised in that this tubulose substrate also comprises polymeric material.
6. doughnut as claimed in claim 5, it is characterised in that this tubulose substrate has 200 to 6000m2/m3Surface
Long-pending to volume ratio, thickness is 0.5 to 3mm, and external diameter is 1 to 5mm, and the 20% to 60% of this bending channel length a length of, this is curved
Qu Xindao has 0.1 to 3mm diameter；Counting on the basis of the weight of this doughnut, this inorganic adsorbent is 0.1 to 95 weight
Amount %；Counting on the basis of the weight of this doughnut, this polymeric material is 5 to 99.9 weight %；This inorganic adsorbent is A type
Zeolite, X-type zeolite, y-type zeolite, high-silica zeolite, mesopore molecular sieve, permeability metal organic framework material, activated carbon, carbon molecule
Sieve or a combination thereof；And, this polymeric material is polysulfones, polyether sulfone, polyvinylidene fluoride, Polyphenylene Sulfone, polyacrylonitrile, acetic acid fibre
Dimension element, cellulose diacetate, pi, Polyetherimide, aromatic polyamide, polyvinyl alcohol, polylactic acid, polyglycolic acid,
Poly-(lactic acid-ethanol), polycaprolactone, polyvinylpyrrolidone, ethylene-vinyl alcohol copolymer, polydimethylsiloxane or its
Combination.
7. doughnut as claimed in claim 6, it is characterised in that this tubulose substrate has 1000 to 4000m2/m3Surface
Long-pending to volume ratio, thickness is 0.5 to 2mm, and external diameter is 1 to 3mm, and the 20% to 40% of this bending channel length a length of, this is curved
Qu Xindao has 0.1 to 2mm diameter；Counting on the basis of the weight of this doughnut, this inorganic adsorbent is 75 to 90 weight %；
Counting on the basis of the weight of this doughnut, this polymeric material is 10 to 25 weight %；This inorganic adsorbent is type A zeolite, X
Type zeolite, high-silica zeolite, mesopore molecular sieve, activated carbon or a combination thereof；And, this polymeric material is polysulfones, polyether sulfone, gathers
Vinylidene fluoride, Polyphenylene Sulfone or a combination thereof.
8. doughnut as claimed in claim 2, it is characterised in that this tubulose substrate also comprises inorganic bond.
9. doughnut as claimed in claim 8, it is characterised in that this tubulose substrate has 200 to 6000m2/m3Surface
Long-pending to volume ratio, thickness is 0.5 to 4mm, and external diameter is 1 to 5mm, and the 20% to 60% of this bending channel length a length of, this is curved
Qu Xindao has 0.1 to 3mm diameter；Counting on the basis of the weight of this doughnut, this inorganic adsorbent is 0.1 to 95 weight
Amount %；Counting on the basis of the weight of this doughnut, this inorganic bond is 5 to 99.9 weight %；This inorganic adsorbent is A type
Zeolite, X-type zeolite, y-type zeolite, high-silica zeolite, mesopore molecular sieve, permeability metal organic framework material or a combination thereof；And,
This inorganic bond be aluminium oxide, silicon dioxide, bentonite, china clay, oxyhydrogen-base apatite, ball clay, calcium silicates, magnesium silicate,
Sodium silicate, anhydrous sodium sulfate, Zirconium orthosilicate., opaque zirconium, carborundum,
(Ba,Pb)TiO3, metasilicic acid lead glass material, sesquialter lead silicate frit, low-expansion glass material, soft borax glass material, standard boron
Sand glass material or a combination thereof.
10. doughnut as claimed in claim 9, it is characterised in that this tubulose substrate has 1000 to 4000m2/m3Table
Area is to volume ratio, and thickness is 0.5 to 2mm, and external diameter is 1 to 3mm, the 20% to 40% of this bending channel length a length of, should
Bending channel has 0.1 to 2mm diameter；Counting on the basis of the weight of this doughnut, this inorganic adsorbent is 75 to 90 weights
Amount %；Counting on the basis of the weight of this doughnut, this inorganic bond is 10 to 25 weight %；This inorganic adsorbent is A type
Zeolite, X-type zeolite, high-silica zeolite, mesopore molecular sieve or a combination thereof；And, this inorganic bond is aluminium oxide, titanium dioxide
Silicon, bentonite, china clay, ball clay, calcium silicates, magnesium silicate, sodium silicate, anhydrous sodium sulfate, Zirconium orthosilicate., opaque zirconium, metasilicic acid
Lead glass material, sesquialter lead silicate glass material, low-expansion glass material, soft borax glass material, standard borax glass material or a combination thereof.
11. doughnuts as claimed in claim 2, it is characterised in that this tubulose substrate also comprises conductive material.
12. doughnuts as claimed in claim 11, it is characterised in that this conductive material forms the outer layer of this tubulose substrate.
13. doughnuts as claimed in claim 1, it is characterised in that this tubulose substrate contains inorganic bond.
14. doughnuts as claimed in claim 1, it is characterised in that this tubulose substrate contains polymeric material.
15. doughnuts as claimed in claim 1, it is characterised in that this tubulose substrate is bi-layer matrix.
16. 1 kinds of methods manufacturing doughnut, including:
Thering is provided spinneret, this spinneret includes body and the first jet of this body of ring, and the port of export of this body has 15 ° extremely
The mis-cut angle of 80 °；
Make endoporus liquid by this body；
Making the first spinning liquid by this first jet, this first spinning liquid contains inorganic adsorbent；
When this first spinning liquid and this endoporus liquid leave this spinneret, collect this first spinning liquid and this endoporus liquid, to be formed
Doughnut precursor；
When this first spinning liquid and this endoporus liquid leave this spinneret, rotate the body of this spinneret；And
This doughnut precursor is condensed in condensation water, to form spiral doughnut,
Wherein, when this first spinning liquid and this endoporus liquid leave this spinneret, this spinneret revolves with the speed of 1 to 200rpm
Turn, to be formed, there is 1 to 200mm pitch and the helical track of 0.05 to 9.95mm diameter.
17. methods as claimed in claim 16, it is characterised in that this first jet by the cincture of second nozzle institute, and, when this
First spinning liquid is by this first jet, and the second spinning liquid is by this second nozzle, second to spin with this when this first spinning liquid
When silk liquid leaves this spinneret, this first spinning liquid is made to contact this second spinning liquid；And, this second spinning liquid comprises conduction material
Material.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/719,945 | 2012-12-19 | ||
| US13/719,945 US9114364B2 (en) | 2012-12-19 | 2012-12-19 | Hollow fibers having a winding channel |
| TW102111105 | 2013-03-28 | ||
| TW102111105A TWI504790B (en) | 2012-12-19 | 2013-03-28 | A hollow fiber for adsorption or filtration and a method for manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103882536A CN103882536A (en) | 2014-06-25 |
| CN103882536B true CN103882536B (en) | 2016-12-28 |
Family
ID=50951645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310184692.5A Active CN103882536B (en) | 2012-12-19 | 2013-05-17 | Hollow fiber for adsorption or filtration and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103882536B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI520778B (en) * | 2015-03-31 | 2016-02-11 | 財團法人工業技術研究院 | Multi-channel hollow fiber |
| CN105688349B (en) * | 2016-04-18 | 2019-04-19 | 广州拜费尔空气净化材料有限公司 | Virus-proof mask |
| CN108677272B (en) * | 2018-05-15 | 2020-09-22 | 华南理工大学 | Micron-sized inorganic antibacterial fiber and preparation method thereof |
| CN109183242A (en) * | 2018-07-04 | 2019-01-11 | 苏州市天翱特种织绣有限公司 | A kind of preparation method of antistatic filter cloth |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103814A (en) * | 1993-12-18 | 1995-06-21 | 中国科学院生态环境研究中心 | Method for fabricating composite hellow fibre ultrafiltration film and the products |
| JP3844564B2 (en) * | 1997-07-18 | 2006-11-15 | 独立行政法人科学技術振興機構 | Hollow microfiber and method for producing the same |
| CA2473286A1 (en) * | 2002-01-29 | 2003-08-07 | Attila Herczeg | Spiraled surface hollow fiber membranes |
| CN1552507A (en) * | 2003-05-27 | 2004-12-08 | 天津膜天膜工程技术有限公司 | Method and apparatus for primary shaping composite or modified hollow fibre membrane |
| CN2706481Y (en) * | 2004-04-13 | 2005-06-29 | 东华大学 | Spinning plate for spinning profiled hollow fiber |
| EP2083939B1 (en) * | 2006-10-18 | 2010-11-10 | Gambro Lundia AB | Hollow fiber membrane and method for manufacturing thereof |
| GB0704934D0 (en) * | 2007-03-14 | 2007-04-25 | Univ Bath | Regenarable adsorption unit |
| AU2009257503A1 (en) * | 2008-06-10 | 2009-12-17 | Aquatech International Corporation | Preparation of high performance ultra filtration hollow fiber membrane |
| CN101368302A (en) * | 2008-10-15 | 2009-02-18 | 东华大学 | Preparation method for hollow cellulose carbon fibre |
-
2013
- 2013-05-17 CN CN201310184692.5A patent/CN103882536B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103882536A (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI504790B (en) | A hollow fiber for adsorption or filtration and a method for manufacturing the same | |
| EP3075888B1 (en) | Multi-channel hollow fiber | |
| EP1913183B1 (en) | Hollow inorganic porous fibres | |
| EP2164598B1 (en) | Hollow sorbent fiber and method of adsorbing a component from a medium | |
| CN103882536B (en) | Hollow fiber for adsorption or filtration and method for producing the same | |
| Jang et al. | Modified mesoporous silica gas separation membranes on polymeric hollow fibers | |
| JP5599785B2 (en) | Ceramic pervaporation membrane and ceramic vapor permeable membrane | |
| Mubashir et al. | Study on the effect of process parameters on CO2/CH4 binary gas separation performance over NH2-MIL-53 (Al)/cellulose acetate hollow fiber mixed matrix membrane | |
| Xiao et al. | Design and synthesis of Al-MOF/PPSU mixed matrix membrane with pollution resistance | |
| JPS6099328A (en) | Separating apparatus for condensable gas | |
| CN104220151B (en) | Honeycomb shape ceramic porous article, its manufacture method, and honeycomb shape ceramic separation film structure | |
| Yue et al. | Activated carbon fibers from meltblown isotropic pitch fiber webs for vapor phase adsorption of volatile organic compounds | |
| Sun et al. | Rational design of electrospun nanofibers for gas purification: Principles, opportunities, and challenges | |
| Gebreyohannes et al. | Hollow fibers with encapsulated green amino acid-based ionic liquids for dehydration | |
| KR100646312B1 (en) | Hollow fiber membrane for oxygen separation and preparation method thereof | |
| Basile et al. | Current Trends and Future Developments on (bio-) Membranes: Microporous Membranes and Membrane Reactors | |
| KR100725266B1 (en) | Carbon dioxide adsorptive paper and the carbon dioxide adsorbent using the carbon dioxide adsorptive paper and the manufacturing method thereof | |
| Berned‐Samatán et al. | Self‐supported single‐wall carbon nanotube buckypaper membranes applied to air and water filtration | |
| Tavasoli et al. | Gas separation polysulfone membranes modified by cadmium-based nanoparticles | |
| Tai et al. | Development of adsorbent hollow fibres for environmental applications | |
| Alsebaeai et al. | Potential effects of nano‐fumed silica particles (NFS)/PVDF mixed matrix hollow fiber membrane on the performance of direct contact membrane distillation | |
| KR102641726B1 (en) | Hollow ceramic fiber membrane for water treatment, water treatment module, methood of hollow ceramic fiber membrane for water treatment | |
| Shi et al. | Review on the Role of Nanomaterials in Membrane Fabrication via Additive Manufacturing for Gas Separation | |
| JP2001170622A (en) | Desorption method for absorptive substance, concentrator and concentration method | |
| Kamińska | WWTP effluent treatment with ultrafiltration with different mixed matrix nanocomposite membranes: comparison of performance and fouling behavior |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |