TWI402277B - 具吸附功能之離子交換材料的形成方法 - Google Patents
具吸附功能之離子交換材料的形成方法 Download PDFInfo
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- TWI402277B TWI402277B TW096151448A TW96151448A TWI402277B TW I402277 B TWI402277 B TW I402277B TW 096151448 A TW096151448 A TW 096151448A TW 96151448 A TW96151448 A TW 96151448A TW I402277 B TWI402277 B TW I402277B
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- Prior art keywords
- ion exchange
- exchange material
- forming
- adsorption function
- polymer
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- 238000005342 ion exchange Methods 0.000 title claims description 41
- 239000000463 material Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 32
- 230000000274 adsorptive effect Effects 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000001523 electrospinning Methods 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000578 dry spinning Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000000243 solution Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011630 iodine Chemical group 0.000 description 2
- 229910052740 iodine Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VWHYHPPXJSBSNK-UHFFFAOYSA-M sodium;3-chloropropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCCl VWHYHPPXJSBSNK-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J43/00—Amphoteric ion-exchange, i.e. using ion-exchangers having cationic and anionic groups; Use of material as amphoteric ion-exchangers; Treatment of material for improving their amphoteric ion-exchange properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/014—Ion-exchange processes in general; Apparatus therefor in which the adsorbent properties of the ion-exchanger are involved, e.g. recovery of proteins or other high-molecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
- B01J47/127—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes in the form of filaments or fibres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- Environmental & Geological Engineering (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Description
本發明係有關於一種離子交換材料，且特別是關於一種具有吸附能力的離子交換材料以及應用此材料吸附過濾重金屬離子之方法。
近年來，由於工業如電鍍、光電、印刷電路板及半導體產業快速發展，造成日益嚴重的重金屬廢水污染問題。重金屬廢水不僅會對人體造成嚴重的傷害，還會破壞人類生存的環境，因此重金屬廢水污染的處理變得相當重要。目前世界上大多數的工業國家都面臨嚴重的重金屬污染問題，因此開發有效的技術，移除廢水中的過量重金屬已是刻不容緩的事情。
目前處理重金屬廢水的方法，有空氣蒸發、離子交換、電透析或電解法。離子交換樹脂法是目前處理重金屬廢水的基本製程方法之一，其原理係利用分析物在不同酸鹼性下所帶的電荷，與樹脂上的陰陽離子進行交換。離子交換樹脂法的優點在於質傳速率快、選擇性高、反應後的廢液可再回收利用、設備與操作簡單。然而，離子交換樹脂材料本身多數反應官能基位於樹脂的內部，離子可以移動到樹酯的內部的深度有限，因此侷限了離子交換的容量，所以近年來在發展新型離子交換纖維的材料，除其有較大的表面積，能有效提高離子交換的容量，還具有易加工成模組的優點。
在目前已有離子交換纖維商品中，日本的Nitivity公司，在美國專利號4125486和4264676中把PVA(polyvinyl alchol)纖維在高溫下交聯，經過磺酸化後，所得到離子交換容量約2－4 meq/g。日本的Toray公司則是複合紡方式，PP(polypropylene)當軸心，外層為PS(Polystyrene)纖維再經磺酸化後，得到離子交換纖維，其交換容量約2 meq/g。俄羅斯的IFOCH NASB公司也是將PP(polypropylene)或PAN(polyacrylonitrile)纖維磺酸化等處理得到離子交換纖維，其交換容量約2－6 meq/g。
上述提及的商品纖維型材料，多是利用接枝或是修飾的方式直接或間接將特殊官能基鍵結到纖維上，使材料具有離子交換的特性。所用於支撐的纖維則無離子交換的功能。再者，上述的製備方式，皆先將材料製成纖維後，再將其官能化，這樣的製備方式也較為複雜。本發明即是開發一種具有高交換容量且製程簡易之離子交換材料，此離子交換材料具有可以直接紡絲的特性。
本發明目的係提供一種具離子吸附功能之材料，其兼具吸附性與離子交換的特性，因此具有高交換容量。
本發明的另一目的就是提供一種使用上述材料吸附過濾重金屬離子的方法。
為達上述目的，本發明之離子交換材料係由化學式(I)與式(Ⅱ)之重複單元所組成之高分子：
其中R1
為苯環磺酸基或烷鏈磺酸基；R2
係擇自於以下所構成之族群：
R3
為碳數1－7之烷基、胺基、醯胺基、羧酸基或磺酸基；X為氯、溴或碘；以及m與n為重複單元之數目，m/n為1－99/99－1。
本發明利用高分子單體之官能基設計，形成兼具吸附與離子交換功能之過濾材料，其高分子結構由化學式(I)與式(Ⅱ)之重複單元所組成：
其中R1
為苯環磺酸基或烷鏈磺酸基；R2
係擇自於以下所構成之族群：
R3
為碳數1－7之烷基、胺基、醯胺基、羧酸基或磺酸基；X為氯、溴或碘；以及m與n為重複單元之數目，m/n為1－99/99－1。
在此高分子結構中具有含有氮、硫、氧等原子，具有吸附與交換能力。本發明之具吸附功能之離子交換材料可以製成各種形式，例如薄膜或纖維。舉例而言，可將合成得到的高分子製成薄膜或將溶液以含浸方式與不織布複合，即得一具吸附功能之離子交換複合纖維膜。
本發明的高分子亦可做成交聯結構，可與習知的交聯劑如環氧樹脂或二鹵素類結構之化合物進行交聯。
此外，當上述材料的聚合分子量較大時，材料具有可紡絲性。這樣的製程較傳統方式(先進行紡絲後再官能化)簡單，減少製程上繁瑣的步驟，因而降低製備的成本。
本發明的纖維製備方式如下：首先合成單體材料，經由聚合後得到高分子，之後經由紡絲技術，得到纖維形式的過濾材料，其纖維直徑範圍可從0.1 μm~100 μm。紡絲技術例如可利用乾式紡絲法、濕式紡絲法、溶液紡法、溶液噴紡或靜電紡絲法等，其中具較高表面積者為溶液噴紡及靜電紡絲法。
本發明之另一實施例為使用上述具吸附功能之離子交換材料吸附過濾重金屬離子廢水的方法，可應用於工業廢水處理、農業廢水處理、核能廢水處理或貴重金屬回收。一般而言，本發明之離子交換材料對重金屬離子的交換容量約為2－17 meq/g的範圍。
為使本發明之上述目的與特徵能更明顯易懂，下文特舉較佳實施例並配合所附圖式做詳細說明。
實施例1取20g苯乙烯磺酸鈉(sodium styrenesulfate)、10g 4－乙基吡啶(4－vinyl pyridine)、1 g硫酸十二酯鈉(sodium dodecyl sulfate,SDS)以及100g去離子水於反應瓶中，通入氮氣，在恆溫70℃下攪拌，取0.3 g過硫酸鉀(potassium persulfate,KPS)溶於10毫升去離子水中，利用加入反應溶液中，恆溫3小時。聚合反應完成後加入去離子水進行稀釋。將稀釋後之聚合物溶液滴入氫氧化鈉水溶液中進行再沉澱純化乾燥，即可得高分子29克，分子量為899599 g/mole。
實施例2取10g苯乙烯磺酸鈉(sodium styrenesulfate)、20g 4－乙基吡啶(4－vinyl pyridine)、2 g硫酸十二酯鈉(sodium dodecyl sulfate,SDS)以及100g去離子水於反應瓶中，通入氮氣，在恆溫70℃下攪拌，取0.3 g過硫酸鉀(potassium persulfate,KPS)溶於10毫升去離子水中，利用加入反應溶液中，恆溫3小時。聚合反應完成後加入去離子水進行稀釋。將稀釋後之聚合物溶液滴入氫氧化鈉水溶液中進行再沉澱純化乾燥，即可得高分子28.7克，分子量為648596 g/mole。
實施例3取10g苯乙烯磺酸鈉(sodium styrenesulfate)、10g 1－乙基咪唑(1－vinyl imidazole)、1 g硫酸十二酯鈉(sodium dodecyl sulfate,SDS)以及100g去離子水於反應瓶中，通入氮氣，在恆溫70℃下攪拌，取0.2 g過硫酸鉀(potassium persulfate,KPS)溶於10毫升去離子水中，利用加入反應溶液中，恆溫3小時。聚合反應完成後加入去離子水進行稀釋。將稀釋後之聚合物溶液滴入氫氧化鈉水溶液中進行再沉澱純化乾燥，即可得高分子18.4克，分子量為530,000 g/mole。
實施例4取15g 2－甲基丙烯磺酸鈉(2－Methyl－2－propene－1－sulfonic acid sodium salt)、10g 4－乙基吡啶(4－vinyl pyridine)、1 g硫酸十二酯鈉(sodium dodecyl sulfate,SDS)以及100g去離子水於反應瓶中，通入氮氣，在恆溫70℃下攪拌，取0.25 g過硫酸鉀(potassium persulfate,KPS)溶於10毫升去離子水中，利用加入反應溶液中，恆溫3小時。聚合反應完成後加入去離子水進行稀釋。將稀釋後之聚合物溶液滴入氫氧化鈉水溶液中進行再沉澱純化乾燥，即可得高分子24克。
實施例5取15g 2－甲基丙烯磺酸鈉(2－Methyl－2－propene－1－sulfonic acid sodium salt)、10g 1－乙基咪唑(1－vinyl imidazole)、1 g硫酸十二酯鈉(sodium dodecyl sulfate,SDS)以及100g去離子水於反應瓶中，通入氮氣，在恆溫70℃下攪拌，取0.25 g過硫酸鉀(potassium persulfate,KPS)溶於10毫升去離子水中，利用加入反應溶液中，恆溫3小時。聚合反應完成後加入去離子水進行稀釋。將稀釋後之聚合物溶液滴入氫氧化鈉水溶液中進行再沉澱純化乾燥，即可得高分子23.5克。
實施例6取10g實施例1樣品、1g 2－氯－乙醯胺以及100g N,N－二甲基乙醯胺於反應瓶中，通入氮氣，在恆溫60℃下攪拌24小時。反應完成後聚合物溶液滴入氫氧化鈉水溶液中進行再沉澱純化乾燥，即可得高分子10.4克。
實施例7取10g實施例1樣品、0.8g 2－氯－乙基胺以及100g N,N－二甲基乙醯胺於反應瓶中，通入氮氣，在恆溫60℃下攪拌24小時。反應完成後聚合物溶液滴入氫氧化鈉水溶液中進行再沉澱純化乾燥，即可得高分子10.3克。
實施例8取10g實施例1樣品、1.2g 3－氯－丙基磺酸鈉以及100g N,N－二甲基乙醯胺於反應瓶中，通入氮氣，在恆溫60℃下攪拌24小時。反應完成後聚合物溶液滴入氫氧化鈉水溶液中進行再沉澱純化乾燥，即可得高分子10.5克。
實施例9將實施例1之純化後高分子溶於N,N－二甲基乙醯胺(N,N－dimethyl－acetamide,DMAc)與四氫呋喃(tetrahydrofuran,THF)混合溶劑中製備10%紡絲液，利用靜電紡絲技術，在放電電壓為39 KV，吐量75 μL/min/孔，距離20cm的條件下得到。之後將該吸附離子交換奈米纖維置於pH＝5的硫酸銅，經7小時後對銅離子交換容量如第1表。
實施例10將實施例1之純化後高分子溶於N,N－二甲基乙醯胺(N,N－dimethyl－acetamide,DMAc)與四氫呋喃(tetrahydrofuran,THF)混合溶劑中，利用溶液噴紡技術，在噴量為430 μL/min，空氣壓力8 kg/cm2
，收料帶速度距離60 cm的條件下，紡絲得到吸附離子交換纖維。
實施例11將實施例1及實施例2之純化後高分子溶於水中，取40 ml之金屬離子溶液(pH＝3之銅離子321 ppm、pH＝5之銅離子341 ppm、pH＝3之鎳離子325 ppm、pH＝5之鎳離子324 ppm、pH＝7之鎳離子331 ppm、pH＝2之鐵離子207 ppm)對金屬離子交換容量如第1圖。
比較例1取市售的IFOCH NASB K－1離子交換纖維置於pH＝5之硫酸銅水溶液中，經7小時後其銅離子交換容量如第1表。
比較例2取市售的DIAIONUBK 08之離子交換樹脂置於pH＝5之硫酸銅水溶液中，經7小時後其銅離子交換容量如第1表。
第1表為實施例9與比較例1和2的交換容量比較表。顯示本發明之離子交換纖維的交換容量明顯優於市售的離子交換纖維。
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
第1圖為實施例1及實施例2純化後之高分子對金屬離子交換容量比較圖。
Claims (8)
- 一種具吸附功能之離子交換材料的形成方法，包括：將一第一類型單體與一第二類型單體進行一聚合反應以形成一聚合物而獲得一具吸附功能之離子交換材料，其中該第一類型單體包括苯乙烯磺酸鈉或甲基丙烯磺酸鈉，而該第二類型單體包括乙基吡啶或乙基咪唑。
- 如申請專利範圍第1項所述之具吸附功能之離子交換材料的形成方法，更包括：將該聚合物與一交聯劑混合以進行一交聯作用，使該具吸附功能之離子交換材料具有一交聯結構。
- 如申請專利範圍第2項所述之具吸附功能之離子交換材料的形成方法，其中該交聯劑包括環氧樹脂或二鹵素類結構之化合物。
- 如申請專利範圍第1項所述之具吸附功能之離子交換材料的形成方法，其中該材料針對重金屬離子的交換容量約為2-17 meq/g。
- 如申請專利範圍第1項所述之具吸附功能之離子交換材料的形成方法，其中該材料係以薄膜或纖維的形式存在。
- 如申請專利範圍第5項所述之具吸附功能之離子交換材料的形成方法，其中該纖維之分子量大於50,0000。
- 如申請專利範圍第5項所述之具吸附功能之離子交換材料的形成方法，其中該纖維係利用乾式紡絲法、濕式 紡絲法、溶液紡法、溶液噴紡或靜電紡絲法製得。
- 如申請專利範圍第5項所述之具吸附功能之離子交換材料的形成方法，其中該纖維直徑約為0.1 μm~100 μm。
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| TWI497801B (zh) | 2012-12-12 | 2015-08-21 | Ind Tech Res Inst | 應用於電池隔離膜之微米或奈米纖維結構或其纖維複合結構 |
| CN105061703B (zh) | 2013-01-14 | 2019-03-15 | 科腾聚合物美国有限责任公司 | 阴离子交换嵌段共聚物，其制造及其用途 |
| US9061254B2 (en) | 2013-01-14 | 2015-06-23 | Kraton Polymers U.S. Llc | Block copolymers, their manufacture and their use |
| CN106061577B (zh) * | 2013-12-18 | 2018-09-28 | 碧然德公司 | 用于倾倒时过滤器过滤的过滤器介质 |
| US10654725B2 (en) | 2013-12-18 | 2020-05-19 | Brita Lp | Filter assembly for filter as you pour filtration |
| CN105088377B (zh) * | 2014-05-13 | 2018-03-20 | 财团法人纺织产业综合研究所 | 静电纺丝液、聚乙烯醇纳米纤维及离子交换膜 |
| WO2017055915A1 (en) | 2015-09-30 | 2017-04-06 | Brita Lp | Filter cartridge placement in filter as you pour system |
| CN105923828B (zh) * | 2016-06-08 | 2018-11-09 | 浙江奇彩环境科技股份有限公司 | 一种吡啶类废水的处理方法 |
| WO2018056928A2 (en) * | 2016-07-19 | 2018-03-29 | Akkas Kavakli Pinar | A method for obtaining poly(4- vinylpyridine) nanofibers |
| CN106944016B (zh) * | 2017-03-18 | 2019-10-18 | 华南理工大学 | 一种pH响应性油水分离泡沫及其制备方法 |
| FI127747B (en) | 2017-05-24 | 2019-01-31 | Fortum Power & Heat Oy | New ion-exchange materials |
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| JP2005327703A (ja) * | 2004-03-23 | 2005-11-24 | Mitsubishi Gas Chem Co Inc | 固体高分子電解質、固体高分子ゲル膜、固体高分子電解質膜、および燃料電池 |
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