CN103882536A - 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
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- CN103882536A CN103882536A CN201310184692.5A CN201310184692A CN103882536A CN 103882536 A CN103882536 A CN 103882536A CN 201310184692 A CN201310184692 A CN 201310184692A CN 103882536 A CN103882536 A CN 103882536A
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- doughnut
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- 238000001914 filtration Methods 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 title abstract description 26
- 239000012510 hollow fiber Substances 0.000 title abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 49
- 235000012489 doughnuts Nutrition 0.000 claims description 156
- 238000009987 spinning Methods 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 66
- 239000003463 adsorbent Substances 0.000 claims description 44
- 229910021536 Zeolite Inorganic materials 0.000 claims description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 36
- 239000010457 zeolite Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 32
- 238000005452 bending Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 15
- 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 15
- 239000004020 conductor Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 10
- 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 10
- 230000035699 permeability Effects 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 9
- 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
- 229920002492 poly(sulfone) Polymers 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
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 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
- 239000005355 lead glass Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 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
- 229920000219 Ethylene vinyl alcohol Polymers 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
- 235000012241 calcium silicate Nutrition 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 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
- 239000013384 organic framework Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000005368 silicate glass Substances 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
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920000954 Polyglycolide Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000004633 polyglycolic acid Substances 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229910052586 apatite Inorganic materials 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002596 lactones Chemical class 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
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims 1
- 239000004632 polycaprolactone Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000395 magnesium oxide Substances 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
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229940092782 bentonite Drugs 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 210000005239 tubule Anatomy 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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
- 238000011049 filling Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 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
- 229910052700 potassium Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution 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
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 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
- 239000012621 metal-organic framework Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 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
- 239000012855 volatile organic compound Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 229910004762 CaSiO 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
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 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
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 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
- 239000004927 clay Substances 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
- 238000003795 desorption 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
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process 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
- 239000011368 organic material Substances 0.000 description 1
- 230000003204 osmotic effect Effects 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
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 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
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A hollow fiber for adsorption or filtration. The hollow fiber includes a tubular matrix having a first end and a second end, and a tortuous channel extending through the tubular matrix and between the first end and the second end. 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 is about doughnut and method for making thereof, especially spiral doughnut and method for making thereof.
Background technology
Zeolite in general using molecular sieve or use packed bed system or honeycomb structure system carries out little Molecular Adsorption.
Packed bed system has high adsorption capacity.After reaching its complete adsorbance, system can regenerate.Not only (for example 24 hours) consuming time of regeneration, and power consumption.Honeycomb structure system, because resistance to mass tranfer (mass transfer resistance) height has the adsorption low compared with packed bed system.In addition honeycomb structure systems bulky and expensive.
The doughnut adsorption system of research and development in the recent period, compared to packed bed system and honeycomb structure system, has higher adsorbance and lower resistance to mass tranfer.Its cost is low and can regenerate fast in low temperature.Consult WO2008/110820 (Perera and Tai), WO2007/007051A1 (Perera) and Tai, Novel Adsorbent Hollow Fibers, Ph.D.thesis, University of Bath, UK (2007).But because lower resistance to mass tranfer, doughnut, for high-speed gas or liquid, has poor adsorption efficiency.Consult Lee et al., Adsorption Science and Technology, 18,147-70 (2000).
Doughnut also can be applicable to filter.But itself and be not suitable for and filter high-speed gas or liquid.
Therefore the doughnut that, still needs research and development effectively to adsorb or to filter.
Summary of the invention
Doughnut of the present disclosure has the effect that cannot expect that can efficiently carry out micromolecular filtration or absorption.
One side of the present disclosure is about doughnut, the tubulose matrix that it contains (i) tool first end and the second end, and (ii) bending (winding) channel (for example, spiral channel) that runs through (formed through) this tubulose matrix and extend between this first end and the second end.
This tubulose matrix is cellular, can be single or multiple lift.Tubulose matrix has 10 to 20000 metre squared per cubic (m
2/ m
3) 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, length is 10 to 90% of this bending channel length.
Another aspect of the present disclosure is about the method for manufacturing doughnut.The method comprises the steps: that (1) provides spinneret (spinneret), this spinneret comprises first nozzle (orifice) of body (tube) and this body of ring, and the port of export of this body has the mis-cut angle (bevel angle) of 15 ° to 80 °; (2) make endoporus liquid (bore fluid) by this body; (3) make the first spinning solution (spinning dope) by this first nozzle, this first spinning solution contains inorganic adsorbent; (4) in the time that this first spinning solution and this endoporus liquid leave this spinneret, collect this first spinning solution and this endoporus liquid, to form doughnut precursor; (5), in the time that this first spinning solution and this endoporus liquid leave this spinneret, rotate this body of this spinneret; And (6) this doughnut precursor that condenses in condensation water, to form spiral doughnut.In the time that this first spinning solution and this endoporus liquid leave this spinneret, this body of this spinneret is with 1 to 200rpm speed rotation, to form the spiral channel with 1 to 200mm pitch (pitch).
The specific embodiment
By particular specific embodiment, embodiment of the present disclosure is described below, these those skilled in the art can understand other advantage of the present disclosure and effect by content disclosed in the present specification.The disclosure also can be implemented or be applied by other different specific embodiment, and the every details in this description also can, based on different viewpoints and application, not carried out various modifications and change under the spirit departing from this creation.
Disclose for absorption herein or filter the doughnut of little molecule (for example, volatile organic compounds).This doughnut can be applicable to various fields (comprising petroleum industry, semiconductor industry and opto-electronics), to filter, to concentrate and to separate.
One side of the present disclosure is about doughnut, the tubulose matrix that it contains (i) tool first end and the second end, and (ii) the bending channel (for example, spiral channel) that runs through this tubulose matrix and extend between this first end and the second end.
This tubulose matrix is cellular, can be single or multiple lift.Tubulose matrix has 10 to 20000m
2/ m
3surface area to volume ratio, thickness is 0.05 to 9.95 millimeter (mm), external diameter is 0.1 to 10mm, length is 10 to 90% of this bending channel length.
The tubulose matrix of doughnut contains (i) and can be used as adhesive (binder), adsorbent (adsorbent) or both polymeric materials (polymeric material), (ii) inorganic adsorbent, (iii) inorganic bond, or (iv) any combination of above-mentioned person." adhesive " refers to link the material of the adsorbent in tubulose matrix or the material that forms this tubulose matrix.Make after doughnut with polymer adhesive and adsorbent, polymer adhesive can be removed, for example, for example, remove in high temperature (500 ℃), to leave this adsorbent." adsorbent " refers to adsorb and has the micromolecular material that molecular weight is 2000 Doltons (Dalton) or following (for example 800 Doltons, 100 Doltons and 18 Doltons).All doughnuts of the present disclosure are all applicable to filter.The doughnut that contains adsorbent (polymer absorbant, inorganic adsorbent or both) also can be used for adsorbing.
In one specific embodiment, tubulose matrix contains inorganic adsorbent (take the weight of doughnut as benchmark, 0.1 to 95 % by weight (wt%)) and polymer adhesive.In another specific embodiment, tubulose matrix contains inorganic adsorbent (take the weight of doughnut as benchmark, 0.1 to 95wt%) and inorganic bond.The disclosure also comprises the doughnut that contains conductive material (electrically conductive material), and in a specific embodiment, conductive material is positioned at the skin of tubulose matrix.
The example of polymeric material comprises, but be not limited to: polyether sulfone (polyether sulfone, PESF), polysulfones (polysulfone), polyvinylidene fluoride (polyvinylidene fluoride, PVDF), PPSU (polyphenylsulfone, PPSU), polyacrylonitrile (polyacrylonitrile), cellulose acetate, cellulose diacetate, pi, PEI, polyamide (aromatic series), polyvinyl alcohol, PLA, polyglycolic acid, poly-(lactic acid-ethanol) (poly (lactic-co-glycolic acid)), poly-several lactones, polyethylene hydrogen pyrrolones (polyvinyl pyrrolidone), ethylene-vinyl alcohol copolymer (ethylene vinyl alcohol), dimethyl silicone polymer and combination thereof.Be preferably PESF, polysulfones, PVDF, PPSU and combination thereof.More preferably PESF and PPSU.
The example of inorganic adsorbent includes, but are not limited to: A type zeolite, X-type zeolite, y-type zeolite, high-silica zeolite (high silica molecular sieve), mesopore molecular sieve, the organic framework material of permeability metal (porous metal-organic framework material), activated carbon, carbon molecular sieve and combination thereof.Preferred inorganic adsorbent is A type zeolite, X-type zeolite, high-silica zeolite, mesoporous hole molecular sieve, activated carbon and combination thereof.More preferably A type zeolite, X-type zeolite, high-silica zeolite and combination thereof.
The example of inorganic bond comprises, but be not limited to: aluminium oxide, silica, bentonite (bentonite), china clay (China clay), oxyhydrogen-base apatite (hydroxylapatite), ball clay (hyplas clay), calcium silicates, magnesium silicate, sodium metasilicate, anhydrous sodium sulfate, zirconium silicate, opaque zirconium (zircon opaque), carborundum, (Ba, Pb) TiO
3, metasilicic acid lead glass material (lead bisilicate frit), sesquialter lead silicate glass material (lead sesquisilicate frit), low-expansion glass material (low expansion frit), soft borax glass material (soft borax frit), standard borax glass material (standard borax frit) and combination thereof.Be preferably aluminium oxide, silica, bentonite, china clay, ball clay, calcium silicates, magnesium silicate, sodium metasilicate, anhydrous sodium sulfate, zirconium silicate, 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 combination thereof.
This doughnut contains the bending channel that runs through tubulose matrix and be coated by this tubulose matrix.
The diameter of this bending channel is 0.05 to 9.95mm (for example, 0.1 to 5mm, and 0.5 to 2mm, and 0.2 to 0.6mm, and 1 to 3mm), can be z font or shaped form, for example, and spirality.Spiral channel generally has the pitch of 1mm to 200mm.Pitch refers to the width of a complete spiral shell shape rotation (spiral turn), is parallel to the axle of this doughnut and measures.
Tubulose matrix can be straight or curved.The length of tubulose matrix be this bending channel length 10 to 90% (for example, 20 to 60%, 20 to 40%, 10 to 80% and 20 to 70%), thickness is 0.05 to 9.95mm (for example, 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 is 0.1 to 10mm (for example, 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).
Matrix can have active surface porosity (effective surface porosity) (, the surface porosity of hole lengths, ε/L
p, m
-1) be 100 to 10000 (for example, 200 to 8000, and 400 to 6000), and hole size (, aperture (pore diameter)) be 1 nanometer (nm) to 50 microns (μ m) (for example, 0.1 to 10 μ m, 1 to 100nm and 10nm to 50 μ m).The porosity of whole doughnut and hole size can be identical or have very large difference.The surface area of matrix is 10 to 20000m to volume ratio
2/ m
3(for example, 10 to 10000m
2/ m
3, 200 to 6000m
2/ m
3, 1000 to 4000m
2/ m
3, 100 to 5000m
2/ m
3, 250 to 3000m
2/ m
3and 500 to 8000m
2/ m
3).Active surface porosity, hole size and surface area are measured by method well known in the art volume ratio.Consult 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 measure by the packed density of the tubing string of filling doughnut.Packed density is the total surface area of the doughnut ratio to tubing string sectional area.Higher packed density and larger surface area, to volume ratio, cause more efficient tubing string conventionally.
Hole size distribution (pore size distribution) and porosity also affect the performance of doughnut.Hole size distributes, and the statistical distribution range in the aperture in doughnut, can be 0.005 to 10 μ m, 0.05 to 5 μ m or 0.5 to 2 μ m.The porosity of doughnut, with the void volume percentage definition in fiber, can be 10 to 200%, 20 to 140% or 40 to 80%.Narrower hole size distributes and higher porosity, conventionally causes the flux that doughnut is higher (flux rate).
In one specific embodiment, matrix contains polymeric material, and it is generally as adhesive.Take the weight of doughnut as benchmark, polymeric material is generally 5 to 100wt% (for example, 5 to 99.9wt%, 7 to 50wt% and 10 to 20wt%).Polymeric material can be PESF, polysulfones, polyvinylidene fluoride, PPSU, polyacrylonitrile, cellulose acetate, cellulose diacetate, pi, PEI, polyamide (aromatic series), polyvinyl alcohol, PLA, polyglycolic acid, poly-(lactic acid-ethanol), poly-several lactones, polyethylene hydrogen pyrrolones, ethylene-vinyl alcohol copolymer, dimethyl silicone polymer and combination thereof.
In another specific embodiment, take the weight of doughnut as benchmark, the inorganic bond that tubulose matrix contains 5 to 100wt% (for example, 5 to 99.9wt%, 7 to 50wt% and 10 to 20wt%).Example includes, but are not limited to: aluminium oxide, silica, bentonite (for example, potassium matter bentonite, sodium bentonite, calcium bentonite and aluminium matter bentonite), china clay (for example, Al
2o
3.2SiO
2.2H
2o), oxyhydrogen-base apatite (for example, Ca
10(PO
4)
6(OH)
2), ball clay (for example, 20%Al
2o
3.70%SiO
2.0.8%Fe
2o
3.2.3%K
2o.1.6%Na
2o), calcium silicates (for example, Ca
3siO
5, Ca
3si
2o
7and CaSiO
3), magnesium silicate (for example, Mg
3si
4o
10(OH)
2), sodium metasilicate (for example, Na
2siO
3and hydrate (hydrate), SiO
2: Na
2the ratio of O is between between 2:1 and 3.75:1), anhydrous sodium sulfate, zirconium silicate (for example, ZrSiO
4), opaque zirconium (for example, 53.89%SiO
2.4.46%Al
2o
3.12.93%ZrO
2.9.42%CaO.2.03%MgO.12.96%ZnO.3.73%K
2o.0.58%Na
2o), carborundum (SiC), (Ba, Pb) TiO
3, metasilicic acid lead glass material (for example, 65%PbO.35%SiO
2), sesquialter lead silicate glass material (for example, 71.23%PbO.28.77%SiO
2), low-expansion glass material (for example, 0.1%Li
2o.3.6%CaO.3.3%ZnO.2.4%MgO.8.2%Al
2o
3.63.6%SiO
2.17.8%B
2o
3), soft borax glass material (for example, 10.3% (Li
2o+Na
2o+K
2o) .14% (CaO+MgO) .3.3%ZnO.7.5%Al
2o
3.50%SiO
2.18%B
2o
3), standard borax glass material (for example, 14.22%CaO.0.16%MgO.1.56%K
2o.9.01%Na
2o.7.63%Al
2o
3.49.45%SiO
2.17.93%B
2o
3) and combination.
In another specific embodiment, matrix contains inorganic adsorbent, is preferably fine particulate form, and having particle diameter is that (for example, 0.01 to 100 μ m and 0.1 to 10 μ are m) for 0.005 to 500 μ m.Take the weight of doughnut as benchmark, inorganic adsorbent is 0.1 to 95wt% (for example, 75 to 90wt%, 80 to 90wt%, 50 to 95wt%, 65 to 80wt% and 80 to 95wt%).Inorganic adsorbent (for example can be A type zeolite, 3A, 4A and 5A), X-type zeolite (for example, 10X), y-type zeolite (for example, 13X), high-silica zeolite (for example, ZSM-5, tripoli stone (Silicalite), HiSiv1000, HiSiv3000, HiSiv6000, Abscent1000, Abscent2000, Abscent3000, USK Y-700 and USYZ2000), mesoporous hole molecular sieve (for example, MCM-41,48 and 50), MOF material (for example, the organic framework of metal), activated carbon, carbon molecular sieve or its combination.Consult 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).
Matrix can be multilayer, for example, double-deck, three layers and four layers.Each layer contains one or more material, and it can be identical or different with the contained person of his layer.When two-layer, while containing same material, it has different aperture degree or hole size.Those skilled in the art can determine material, porosity, hole size and the thickness of each layer needn't undo experimentation in the situation that.
Matrix also can comprise conductive material.In the time that doughnut adsorbs little molecule to maximal absorptive capacity (adsorption capacity), remove little molecule by heat and regenerate.Conductive material produces heat thereby makes little molecule desorption and make doughnut regeneration.Execute voltage between the two ends of doughnut to regenerate.Conductive material can be mixed in same layer with inorganic adsorbent or polymer absorbant, or forms separating layer with adhesive.In multilayer hollow fiber, this material can be present in each layer.It also can exist only in one deck, be preferably present in more outer in, thickness is 0.05 to 9.95mm (for example, 0.1 to 4mm and 0.2 to 2mm).Conductive material generally has 10 to 100000 ohm-sq centimetre (ohm/cm
2) resistance (for example, 10 to 40000ohm/cm
2and 500 to 10000ohm/cm
2).Conductive material example include, but are not limited to: activated carbon, carbon black, graphite, metal oxide (for example, CuO and (Ba, Pb) TiO
3), metal and combination thereof.
The disclosure also comprises the method for manufacturing doughnut.The method comprises the steps: that (1) provides spinneret, this spinneret comprises first nozzle (orifice) of body (tube) and this body of ring, the port of export of this body has the mis-cut angle (for example, 15 ° to 80 °, 20 ° to 60 ° and 40 ° to 50 °) of 0 ° to 90 °; (2) make endoporus liquid (bore fluid) by this body; (3) make the first spinning solution (spinning dope) by this first nozzle, this first spinning solution contains inorganic adsorbent; (4) in the time that this first spinning solution and this endoporus liquid leave this spinneret, collect this first spinning solution and this endoporus liquid, to form doughnut precursor; (5), in the time that this first spinning solution and this endoporus liquid leave this spinneret, rotate this body of this spinneret; (6) this doughnut precursor that condenses in condensation water, to form spiral doughnut.In the time that this first spinning solution and this endoporus liquid leave this spinneret, this body of this spinneret for example, with the speed rotation of 1 to 200rpm (, 5 to 100rpm and 10 to 40rpm).Therefore form the spiral channel for example, with 1 to 200mm (, 3 to 150mm and 6 to 100mm) pitch.
This body of this spinneret has the internal diameter (inside diameter) of 1 to 10mm (for example, 2 to 8mm and 3 to 5mm).This body is by the first nozzle institute ring, this first nozzle (for example has 0.1 to 9.6mm, 0.3 to 6mm and 0.6 to 3mm) the external diameter (outer diameter) of internal diameter and 0.4 to 9.8mm (for example, 0.6 to 7mm and 0.8 to 4mm).
The first spinning solution is by this first nozzle.The first spinning solution for example, by combining inorganic adsorbent, inorganic bond, polymeric material or its (, the weight ratio of inorganic adsorbent/inorganic bond/polymeric material is 50/30/20 to 95/2.5/2.5,75/15/15 to 90/5/5, or 80/10/10 to 88/6/6) be scattered in blending solvent, and optionally for a long time (for example, 84 hours) stir (for example, with 50 to 100rpm) and obtain.Blending solvent is soluble polymeric thing material and the solvent that can dissolve each other with following endoporus liquid and condensation water.The example of blending solvent comprises, but be not limited to: dimethylacetylamide (DMAc), 1-methyl-2-Pyrrolizidine ketone (NMP), dimethyl formamide (DMF), 1,4-dioxane (Isosorbide-5-Nitrae-dioxane), carrene, acetone and combination thereof.
Endoporus liquid is by this body of this spinneret.The example of endoporus liquid includes, but are not limited to: water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, acetone and combination thereof.When endoporus liquid is by this body, rotary spinning head is to form spiral channel.
In the time that this endoporus liquid and this first spinning solution leave this spinneret, collect this endoporus liquid and this first spinning solution (even contacting with each other), to form doughnut precursor, after it, for example, in condensation water (, water), condense to form spiral doughnut.
In one specific embodiment, this first nozzle is by second nozzle (orifice) institute ring, and, when the first spinning solution is by this first nozzle, the second spinning solution is by this second nozzle, to make this first spinning solution contact this second spinning solution in the time that this two spinning solution leaves this spinneret.This second spinning solution can comprise conductive material.
Use above-mentioned same program to prepare double-layer hollow fiber as follows.Use has the spinneret of second nozzle.Second nozzle is around the first nozzle, and can have the external diameter of the internal diameter and 0.8 to 9.8mm (for example, 1.2 to 8mm and 1.6 to 5mm) of 0.6 to 9.6mm (for example, 1 to 7.8mm and 1.4 to 4.8mm).Except endoporus liquid and the first spinning solution, also provide the second spinning solution.As the first spinning solution, the second spinning solution also can be by being scattered in conductive material, inorganic adsorbent, inorganic bond, polymeric material or its combination in blending solvent and making.The second spinning solution can optionally contain conductive material and polymeric material.
Endoporus liquid is by this body of this spinneret, and the first spinning solution is by this first nozzle, and the second spinning solution passes through second nozzle.In the time that this first spinning solution, endoporus liquid and this second spinning solution leave this spinneret, make this first spinning solution contact this endoporus liquid and this second spinning solution, to form doughnut precursor, it condenses becomes double-layer hollow fiber.
Similarly, by making three or more spinning solutions for example, there is three layers or more multi-layered doughnut by thering is the spinneret of three or more nozzles (, four nozzles), can preparing.
Doughnut of the present disclosure has the effect that cannot expect of the traditional doughnut usefulness of improvement.First, bending channel is upset gas flow or liquid stream and is moved to hollow fiber walls to adsorb or to filter.Moreover bending increases path, therefore extend the time of passing through, to strengthen adsorption.In addition, doughnut of the present disclosure for example, is stable at high temperature (, 250 ℃).
Following embodiment is illustrative doughnut of the present disclosure and its preparation only, but not for limiting the disclosure.Any these those skilled in the art all can, under spirit of the present disclosure and category, modify and change above-described embodiment.Therefore, rights protection scope of the present disclosure, should be as contained in claims.
Embodiment 1 to 7
7 doughnut A, B, C, D, E, A-25 and A-28 that contain inorganic adsorbent are prepared as follows.
First, use the as shown in table 1 below constituent that contains solvent, polymer and inorganic adsorbent to prepare spinning solution.
Table 1. spinning solution constituent
Use rotary pump in solvent (400 to 500 milliliters (mL)), stir polymer (100 grams (g)) 24 hours with 100rpm or until be dissolved as settled solution completely.Filtering solution.Use IKA Werke agitator to stir with 500 to 3000rpm, slowly add inorganic adsorbent (400 to 700g) simultaneously.Gained mixture stirs 6 to 48 hours with identical speed.Then use rotary pump in 100rpm degasification 24 to 48 hours to form even spinning solution.
Use the spinning solution so making to prepare doughnut.Use has the body nozzle spinneret (tube-in-orifice spinneret) of body (diameter 0.72mm, 45 ° of mis-cut angles) and nozzle (orifice) (external diameter 2.0mm) and manufactures individual layer doughnut.Spinning solution is moved in rustless steel container, with vavuum pump degasification 10 to 30 minutes, be forced into 0.5 to 8 bar (bar) with nitrogen, make it pass through this nozzle with 1 to 10 ml/min (mL/min).Make water (as endoporus liquid) pass through this body with 1 to 30mL/min.This body of spinneret rotates with 1 to 200rpm speed.Spinning solution is met in spinneret terminal and endoporus liquid phase, forms doughnut precursor, and it for example, for example, by the air gap (air gap) between spinneret terminal and coagulation bath (, water) (0 to 10cm,, 3cm).Precursor solidify to form doughnut in the time of 48 hours in water (as coagulation bath).In the second bath, thoroughly clean prepared doughnut, in clear water, soak 24 to 96 hours, in environmental condition, be dried 1 to 7 day.
Prepare doughnut A to E, A-25 and A-28 with program as above.Spinning solution constituent as shown in Table 1.
Prepare the doughnut of two comparative examples, it respectively has straight channel and non-helical channel again.
More specifically, prepare doughnut A-25 ' and the A-28 ' of comparative example in the mode identical with doughnut A-25 and A-28, but use the spinneret with smooth body, but not use the spinneret with the body of cutting sth. askew.
Make 7 doughnuts and two comparative example doughnuts carry out permeability test
(permeation test) and adsorption test (adsorption test), as follows described in embodiment 16,17 and 20.
Embodiment 8 to 10
Prepare 3 double-layer hollow fiber C-12, C-16 and C-19 with same program as above, but use two spinning solutions and use to there is body (diameter 0.8mm, 45 ° of mis-cut angles), inner nozzle (external diameter 2mm, internal diameter 1.2mm) and the twin-jet nozzle spinneret of outer nozzle (external diameter 4mm, internal diameter 3mm).
The first spinning solution in the first container is forced into 2bar and makes it pass through inner nozzle
(orifice)。The second spinning solution in second container is forced into 2.5 to 3bar and make it pass through outer nozzle (orifice).The doughnut being formed by first and second spinning solution is carried out to post processing same as described above.
Supervisor is manufactured doughnut C-12, C-16 and C-19 according to this:
In embodiment 8, by the first spinning solution (13X/PESF, 10/1 (weight)) and the second spinning solution (13X/PESF, 4/1 (weight)), both prepare doughnut C-12.Use NMP as solvent, consumption is 4 times of PESF weight.
In embodiment 9, by the first spinning solution (13X/PESF, 10/1 (weight)) and the second spinning solution (13X/PESF, 3/1 (weight)), both prepare doughnut C-16.NMP consumption is identical with embodiment 8.
In embodiment 10, by the first spinning solution (13X/PESF, 10/1 (weight)) and the second spinning solution (13X/PESF, 3/2 (weight)), both prepare doughnut C-19.NMP consumption is identical with embodiment 8.
Test the absorption property of these 3 double-layer hollow fibers, shown in following embodiment 19.
Embodiment 11 to 13
Prepare 3 doughnut S-01, S-02 and S-03 containing organic and/or inorganic materials with following program.
First, with NMP, PESF, Al
2o
3and the silica gel/magnesia of being fuming is prepared spinning solution.Use 3 kinds of Al
2o
3(respectively thering is particle diameter 1,0.3 and 0.01 to 0.02).Its weight ratio is as shown in table 2 below.
Table 2 spinning solution constituent
For preparing spinning solution, mix NMP and PESF and stir 24 to 48 hours to form polymer solution in rotary pump, it then stirs with 500 to 1000rpm in IKA Werke agitator.Add Al
2o
3.Gained mixture stirs 2 to 4 days with dispersed Al
2o
3.Add SiO
2(, the silicon of being fuming) and/or MgO (, magnesia) also stir 1 to 2 day to form uniform dispersion, and its Nylon filter paper by 100 μ m (filter paper) removes bulky grain to filter.Filtered dispersion liquid uses rotary pump degasification to obtain spinning solution.
Then, use gained spinning solution to prepare doughnut.Spinning solution is moved in rustless steel container, in room temperature with vavuum pump degasification 30 minutes.Container is forced into 2bar with nitrogen.Using water as endoporus liquid and as coagulation bath.Use has the body nozzle spinneret (tube-in-orifice spinneret) of body (diameter 0.72mm, 45 ° of mis-cut angles) and nozzle (orifice) (external diameter 2.0mm).Air gap between spinneret and coagulation bath is 3cm.In the time that endoporus liquid passes through this nozzle with 8mL/min by this body and spinning solution, this body is with the speed rotation of 30rpm.Make doughnut precursor in coagulation bath, solidify to form tubule (tubule) by air gap and in the time of 48 hours.In the second bath, thoroughly clean prepared tubule, in clear water, soak 48 hours, in environmental condition, be dried 3 to 4 days.
Finally, calcine this tubule to obtain inorganic hollow fibers.It is heated according to temperature program(me) in heating furnace.Heat tubules 5 hours in 600 ℃ at the beginning.With the speed of 1.5 ℃/min, temperature is risen to 900 ℃, then rise to 1100 ℃ with 2.5 ℃/min, then rise to 1550 ℃ with 1 ℃/min.Tubule is calcined 10 to 12 hours to obtain final doughnut in 1550 ℃.
Prepare 3 doughnut S-01, S-02 and S-03 according to said procedure.Spinning solution constituent is as above shown in table 2.
Embodiment 14 and 15
Prepare 2 inorganic hollow fibers HF-14a and HF-14b with following program.
In embodiment 14, use (i) by the first spinning solution of mixing the plumbous glass material of metasilicic acid prepare with tripoli stone (weight ratio 15/85) in NMP and (ii) the second spinning solution of also preparing by mix metasilicic acid lead glass material and tripoli stone (weight ratio 40/60) in NMP, prepare doughnut HF-14a.Prepare doughnut HF-14a according to the program described in above-described embodiment 11 to 13, it was in 660 ℃ of calcinings 18 hours.
In embodiment 15, prepare doughnut HF-14b to prepare the same procedure of doughnut HF-14a, but calcine 24 hours but not 18 hours in 660 ℃.
Embodiment 16
Use the prepared doughnut of following method characteristic embodiment 1 to 5,11 and 12.
Gas permeation test (Gas permeation test)
Carry out end-blocking gas permeation analyzing (dead-end gas permeation assay) to measure average hole size, active surface porosity and the gas permeability (gas permeability) of doughnut, its one end with
(Epoxy) seal.Use nitrogen outward at the doughnut other end.Measure in different transmembrane pressure (trans-membrane pressure) by Brooks mass flowmenter (mass flow indicator).Consult 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 two important parameters of following equation calculating doughnut, average hole size (r, i.e. average pore size) and active surface porosity (ε/L
p):
r=(16/3)(P
0/K
0)(8RT/πM)
1/2μ (l)
ε/L
p=8μRTP
0/r
2 (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 K
0and P
0be respectively intercept and slope, by pressure criteria osmotic flow (pressure-normalized permeation flux), average pressure mapped and measured.Consult 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) (having described two kinds of methods, i.e. Poiseuille discharge method (flow mehtod) and Knudsen discharge method); And Hatim et al., Pd/Al
2o
3composite Hollow Fiber Membrances:Effect of Substrate Resistances on H2Permeation Properties, Chemical Engineering Science, 66,1150-58 (2011).Use following equation to calculate gas permeability (Ji).Consult Carman (1956) and Shih (1990).
J
i=(2/3(8RT/πM)
1/2(I/RT)(rε/L
p))+(P/8μRT)(r
2ε/L
p) (3)。
The value of average hole size, active surface porosity and the gas permeability of doughnut A to E, S-01 and S-02 is as shown in following table 3 and 4.The characteristic (using Poiseuille method) of the doughnut A to E of table 3. embodiment 1 to 5 preparation
The doughnut S-01 of table 4. embodiment 11 and 12 preparations and the characteristic of S-02
Embodiment 17
The absorption property of the doughnut A to C of test implementation 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 described method and apparatus of 147-170 (2000) carries out Dynamic Adsorption analysis (dynamic adsorption assay).The analytical system that equipment comprises tubing string, expects the flow system (flow system) of stream and go out gas concentration in order to monitoring stream in order to supply with feedback.
Assembling tubing string is to contain the doughnut of 50 fillings, and it respectively has the length of 25cm.In order to compare, use another tubing string that contains commercially available particle (1.0 × 1.18mm buys from Universal Oil Products) to compare.Commercially available particle in tubing string has and these 50 weight that doughnut is identical.Select normal butane as volatile organic compounds.Before tubing string, with N
2(vector gas) mixes with the concentration of 6000ppm.Setting gas flow rate is 1.5 liters/min (L/min).
Make admixture of gas by adsorbing tubing string.Use flame ionic detector (flame ionisation detector) (Signal Instruments, model3000) to continue to monitor the absorption concentration of n-butane of tubing string and the variation of breakthrough curve.All adsorption analyses are in carrying out in 25 ℃.Gas up flows through tubing string to adsorb, and down flows through tubing string in the time that tubing string is regenerated.
Map (in the time that normal butane stream starts, starting at) by adsorbing the function of time of the ratio between rear concentration of n-butane and initial concentration of n-butane to obtain the breakthrough curve of absorption.Time of break-through is obtained by this breakthrough curve.
Make doughnut A, B and C carry out Dynamic Adsorption analysis as above.Obtain its adsorption penetration time.The time of break-through of doughnut 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 minutes.Time of break-through for commercially available particle is relatively 22 minutes.3 doughnuts of the present disclosure have all represented the time of break-through long more than commercially available particle.
Embodiment 18
Detect two doughnut HF-14a of embodiment 14 and 15 preparations and the absorption property of HF-14b.
Program described in use embodiment 17 is carried out adsorption analysis, except using the tubing strings that contain 40 filling doughnuts (it respectively has the length of 24cm).
Draw breakthrough curve.With the commercially available particle tubing string comparison that embodiment 17 uses, both breakthrough curves of doughnut HF-14a and HF-14b are obviously sharper, represent that it has high matter biography rate (mass-transfer rate) and large effective surface area.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 is 6.8%.Two doughnuts all have much larger than the adsorbance of commercially available particle (as shown in embodiment 19 below, it only has 1.4%).
Embodiment 19
Detect three doughnut C-12, the C-16 of embodiment 8 to 10 preparations and the absorption property of C-19.
Use the same procedure described in embodiment 17 to carry out adsorption analysis, except using different tubing strings and with CO
2replace normal butane.Assemble three tubing strings respectively to contain the doughnut (37 to 40g, 24cm) of filling.Also the comparison tubing string that filling contains the commercially available particle of 13X (4 × 3.2mm).Initial CO
2concentration is 3000ppm.Gas flow rate is 1L/min.N
2pressure is 1 or 2atm.Use far infrared gas monitor (Infra-Red Gas Monitor) (model RS232interface adaptor, Edinburgh Sensors Limited) to continue to monitor the feedback material concentration of absorption tubing string and the variation of breakthrough curve.
Obtain the time of break-through shown in following table 5 by breakthrough curve.Three doughnuts all represent compared with the much longer time of break-through of the commercially available particle of 13X, and adsorbance is also much larger than the commercially available particle of 13X.In detail, the commercially available particle of C-12, C-16, C-19 and 13X is respectively 149,170,141 and 74 minutes in the time of break-through of 1atm; The adsorbance of C-12, C-16, C-19 and commercially available particle is respectively 2.67%, 2.9%, 2.5% and 1.4%.
Time of break-through and the adsorbance of table 5. doughnut C-12, C-16, C-19 and commercially available particle 13X
Embodiment 20
Detect the two doughnut A-25 of the present disclosure of embodiment 6 and 7 preparations and the absorption property of A-28.Also detect two comparative example doughnut A-25 ' of embodiment 1 to 7 preparation and the absorption property of A-28 ' (it respectively has straight channel), and with spiral doughnut A-25 and A-28 comparison.
Carry out adsorption analysis according to the program described in embodiment 17, except using different tubing strings and replacing normal butane with moisture (moisture).Assemble four tubing strings respectively to contain the doughnut (50g, 24cm) of filling.Moisture and N
2mix.N
2pressure is 1atm.Flow velocity is 1L/min.
Self-gating curve obtains time of break-through.Spiral doughnut has the absorption property superior far beyond straight doughnut.In detail, the time of break-through of spiral doughnut A-28 7 hours is long far beyond straight doughnut A-28 ' (5.4 hours).The time of break-through of spiral doughnut A-25 4.8 hours is long far beyond straight doughnut A-25 ' (3.9 hours).
Claims (26)
1. the doughnut for adsorbing or filtering, comprising:
The tubulose matrix of tool first end and the second end, and
Run through this tubulose matrix and extend this first end and this second end between bending channel,
Wherein, this tubulose matrix is cellular, and has 10 to 20000m
2/ m
3surface area to volume ratio, thickness is 0.05 to 9.95mm, external diameter is 0.1 to 10mm, length is 10% to 90% of this bending channel length.
2. doughnut as claimed in claim 1, is characterized in that, this tubulose matrix contains inorganic adsorbent.
3. doughnut as claimed in claim 2, is characterized in that, this tubulose matrix has 200 to 6000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 4mm, external diameter is 1 to 5mm, length is 20% to 60% of this bending channel length; And take the weight of this doughnut as benchmark, this inorganic adsorbent is 0.1 to 95 % by weight.
4. doughnut as claimed in claim 3, is characterized in that, this tubulose matrix has 1000 to 40000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 2mm, external diameter is 1 to 3mm, length is 20% to 40% of this bending channel length; And take the weight of this doughnut as benchmark, this inorganic adsorbent is 75 to 90 % by weight.
5. doughnut as claimed in claim 2, is characterized in that, this tubulose matrix also comprises polymeric material.
6. doughnut as claimed in claim 5, is characterized in that, this tubulose matrix has 200 to 6000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 3mm, external diameter is 1 to 5mm, length is 20% to 60% of this bending channel length; Take the weight of this doughnut as benchmark, this inorganic adsorbent is 0.1 to 95 % by weight; Take the weight of this doughnut as benchmark, this polymeric material is 5 to 99.9 % by weight; This inorganic adsorbent is A type zeolite, X-type zeolite, y-type zeolite, high-silica zeolite, mesopore molecular sieve, the organic framework material of permeability metal, activated carbon, carbon molecular sieve or its combination; And this polymeric material is polysulfones, polyether sulfone, polyvinylidene fluoride, PPSU, polyacrylonitrile, cellulose acetate, cellulose diacetate, pi, PEI, polyamide (aromatic series), polyvinyl alcohol, PLA, polyglycolic acid, poly-(lactic acid-ethanol), polycaprolactone, polyvinylpyrrolidone, ethylene-vinyl alcohol copolymer, dimethyl silicone polymer or its combination.
7. doughnut as claimed in claim 6, is characterized in that, this tubulose matrix has 1000 to 4000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 2mm, external diameter is 1 to 3mm, length is 20% to 40% of this bending channel length; Take the weight of this doughnut as benchmark, this inorganic adsorbent is 75 to 90 % by weight; Take the weight of this doughnut as benchmark, this polymeric material is 10 to 25 % by weight; This inorganic adsorbent is A type zeolite, X-type zeolite, high-silica zeolite, mesopore molecular sieve, activated carbon or its combination; And this polymeric material is polysulfones, polyether sulfone, polyvinylidene fluoride, PPSU or its combination.
8. doughnut as claimed in claim 5, is characterized in that, this bending channel is spiral channel.
9. doughnut as claimed in claim 8, is characterized in that, this tubulose matrix has 200 to 6000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 3mm, external diameter is 1 to 5mm, length is 20% to 60% of this bending channel length; Take the weight of this doughnut as benchmark, this inorganic adsorbent is 0.1 to 95 % by weight; Take the weight of this doughnut as benchmark, this polymeric material is 5 to 99.9 % by weight; This inorganic adsorbent is A type zeolite, X-type zeolite, y-type zeolite, high-silica zeolite, mesopore molecular sieve, the organic framework material of permeability metal, activated carbon, carbon molecular sieve or its combination; And this polymeric material is polysulfones, polyether sulfone, polyvinylidene fluoride, PPSU, polyacrylonitrile, cellulose acetate, cellulose diacetate, pi, PEI, polyamide (aromatic series), polyvinyl alcohol, PLA, polyglycolic acid, poly-(lactic acid-ethanol), poly-several lactones, polyethylene hydrogen pyrrolones, ethylene-vinyl alcohol copolymer, dimethyl silicone polymer or its combination.
10. doughnut as claimed in claim 9, is characterized in that, this tubulose matrix has 1000 to 4000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 2mm, external diameter is 1 to 3mm, length is 20% to 40% of this bending channel length; Take the weight of this doughnut as benchmark, this inorganic adsorbent is 75 to 90 % by weight; Take the weight of this doughnut as benchmark, this polymeric material is 10 to 25 % by weight; This inorganic adsorbent is A type zeolite, X-type zeolite, high-silica zeolite, mesopore molecular sieve, activated carbon or its combination; And this polymeric material is polysulfones, polyether sulfone, polyvinylidene fluoride, PPSU or its combination.
11. doughnuts as claimed in claim 2, is characterized in that, this tubulose matrix also comprises inorganic bond.
12. doughnuts as claimed in claim 11, is characterized in that, this bending channel is spiral channel.
13. doughnuts as claimed in claim 12, is characterized in that, this tubulose matrix has 200 to 6000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 4mm, external diameter is 1 to 5mm, length is 20% to 60% of this bending channel length; Take the weight of this doughnut as benchmark, this inorganic adsorbent is 0.1 to 95 % by weight; Take the weight of this doughnut as benchmark, this inorganic bond is 5 to 99.9 % by weight; This inorganic adsorbent is A type zeolite, X-type zeolite, y-type zeolite, high-silica zeolite, mesopore molecular sieve, the organic framework material of permeability metal or its combination; And this inorganic bond is aluminium oxide, silica, bentonite, china clay, oxyhydrogen-base apatite, ball clay, calcium silicates, magnesium silicate, sodium metasilicate, anhydrous sodium sulfate, zirconium silicate, opaque zirconium, carborundum, (Ba, Pb) TiO
3, metasilicic acid lead glass material, sesquialter lead silicate glass material, low-expansion glass material, soft borax glass material, standard borax glass material or its combination.
14. doughnuts as claimed in claim 13, is characterized in that, this tubulose matrix has 1000 to 4000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 2mm, external diameter is 1 to 3mm, length is 20% to 40% of this bending channel length; Take the weight of this doughnut as benchmark, this inorganic adsorbent is 75 to 90 % by weight; Take the weight of this doughnut as benchmark, this inorganic bond is 10 to 25 % by weight; This inorganic adsorbent is A type zeolite, X-type zeolite, high-silica zeolite, mesopore molecular sieve or its combination; And this inorganic bond is aluminium oxide, silica, bentonite, china clay, ball clay, calcium silicates, magnesium silicate, sodium metasilicate, anhydrous sodium sulfate, zirconium silicate, 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 its combination.
15. doughnuts as claimed in claim 2, is characterized in that, this bending channel is spiral channel.
16. doughnuts as claimed in claim 15, is characterized in that, this tubulose matrix has 200 to 6000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 4mm, external diameter is 1 to 5mm, length is 20% to 60% of this bending channel length; Take the weight of this doughnut as benchmark, this inorganic adsorbent is 0.1 to 95 % by weight.
17. doughnuts as claimed in claim 16, is characterized in that, this tubulose matrix has 1000 to 40000m
2/ m
3surface area to volume ratio, thickness is 0.5 to 2mm, external diameter is 1 to 3mm, length is 20% to 40% of this bending channel length; Take the weight of this doughnut as benchmark, this inorganic adsorbent is 75 to 90 % by weight.
18. doughnuts as claimed in claim 2, is characterized in that, this tubulose matrix also comprises conductive material.
19. doughnuts as claimed in claim 18, is characterized in that, this bending channel is spiral channel.
20. doughnuts as claimed in claim 18, is characterized in that, this conductive material forms the skin of this tubulose matrix.
21. doughnuts as claimed in claim 1, is characterized in that, this tubulose matrix contains inorganic bond.
22. doughnuts as claimed in claim 1, is characterized in that, this tubulose matrix contains polymeric material.
23. doughnuts as claimed in claim 1, is characterized in that, this bending channel is spiral channel.
24. doughnuts as claimed in claim 1, is characterized in that, this tubulose matrix is double-deck matrix.
Manufacture the method for doughnut, comprising for 25. 1 kinds:
Spinneret is provided, and this spinneret comprises the first nozzle of body and this body of ring, and the port of export of this body has the mis-cut angle of 15 ° to 80 °;
Make endoporus liquid by this body;
Make the first spinning solution by this first nozzle, this first spinning solution contains inorganic adsorbent;
In the time that this first spinning solution and this endoporus liquid leave this spinneret, collect this first spinning solution and this endoporus liquid, to form doughnut precursor;
In the time that this first spinning solution and this endoporus liquid leave this spinneret, rotate the body of this spinneret; And
This doughnut precursor that condenses in condensation water, to form spiral doughnut,
Wherein, in the time that this first spinning solution and this endoporus liquid leave this spinneret, this spinneret is with 1 to 200rpm speed rotation, to form the spiral channel with 1 to 200mm pitch.
26. methods as claimed in claim 25, it is characterized in that, this first nozzle by second nozzle institute around, and, when this first spinning solution is by this first nozzle, the second spinning solution is by this second nozzle, with in the time that this first spinning and this second spinning solution leave this spinneret, makes this first spinning solution contact this second spinning solution; And this second spinning solution comprises conductive material.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/719,945 US9114364B2 (en) | 2012-12-19 | 2012-12-19 | Hollow fibers having a winding channel |
| US13/719,945 | 2012-12-19 | ||
| TW102111105A TWI504790B (en) | 2012-12-19 | 2013-03-28 | A hollow fiber for adsorption or filtration and a method for manufacturing the same |
| TW102111105 | 2013-03-28 |
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| CN103882536A true CN103882536A (en) | 2014-06-25 |
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| CN103882536B (en) | 2016-12-28 |
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