TWI232131B - Reverse osmosis membrane having excellent anti-fouling property and method for manufacturing the same - Google Patents
Reverse osmosis membrane having excellent anti-fouling property and method for manufacturing the same Download PDFInfo
- Publication number
- TWI232131B TWI232131B TW090119208A TW90119208A TWI232131B TW I232131 B TWI232131 B TW I232131B TW 090119208 A TW090119208 A TW 090119208A TW 90119208 A TW90119208 A TW 90119208A TW I232131 B TWI232131 B TW I232131B
- Authority
- TW
- Taiwan
- Prior art keywords
- aqueous solution
- particles
- reverse osmosis
- film
- solution
- Prior art date
Links
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 8
- 239000012528 membrane Substances 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 15
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 claims 1
- 244000005700 microbiome Species 0.000 abstract description 11
- 239000000356 contaminant Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- XZQYTGKSBZGQMO-UHFFFAOYSA-I rhenium pentachloride Chemical compound Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910021571 Manganese(III) fluoride Inorganic materials 0.000 description 1
- 229910019804 NbCl5 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910004537 TaCl5 Inorganic materials 0.000 description 1
- -1 Ti [〇CH (CH3) 2] * Chemical class 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 210000002429 large intestine Anatomy 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- SRVINXWCFNHIQZ-UHFFFAOYSA-K manganese(iii) fluoride Chemical compound [F-].[F-].[F-].[Mn+3] SRVINXWCFNHIQZ-UHFFFAOYSA-K 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- UAIHPMFLFVHDIN-UHFFFAOYSA-K trichloroosmium Chemical compound Cl[Os](Cl)Cl UAIHPMFLFVHDIN-UHFFFAOYSA-K 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
- B01D69/14111—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix with nanoscale dispersed material, e.g. nanoparticles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- 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
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2181—Inorganic additives
- B01D2323/21813—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
Description
1232131 案號 90119208 曰 修正 五、發明說明（1) 發明背景 【發明領域】 本發明是 更具體地說， 製備方法，其 代表，其面對 有抵抗微生物 【先前技術】 水的去 化處理 為觀點 之美國 編號第 其能夠 此 積問題 致薄膜 出當將 質，如 費大部 能會造 污 微粒狀 情況中 般而言 鹽作用 等等。 來搜尋 專利編 4, 983, 增加可 外，使 。垢積 性能改 操作壓 可透水 份是用 成的傷 垢可分 物質和 ，垢積 關於一種具有絕佳抗垢積性的逆滲透薄膜， 是關於一種極微結構形式的逆滲透薄膜及其 中，是將光觸媒加入薄膜表面，以T i 02作為 各種有機污染物時不僅具有分解活性，且具 之抗菌活性。 ，逆滲透薄膜已被應用在各種領域中，如海 ，廢水處理，超純水之生產，家庭用水之淨 以增加薄膜之可透水性及改良鹽之排除情況 跟逆滲透作用有關之文獻，T 〇 m a s h k e所申請 號第4, 872, 984號及Chau所發表之美國專利 2 9 1號揭示一種新穎的聚醯胺逆滲透薄膜， 透水性並改善鹽的排除情形。 用逆滲透薄膜來處理水的過程中，會遇到垢 是指污垢沈積在薄膜表面上或其孔洞中，導 變，甚至使薄膜完全被堵塞。這些現象顯示 力提高一段時間後，反而使降低水的滲透性 性或脫鹽效果。因此，水處理設備的操作花 在修理此類垢積所產生之問題及預防垢積可 害上。因此，需要基本的預防估計措施。 為幾種形式，包括無機晶體，有機污染物， 膠體，以及微生物。在聚醯胺逆滲透薄膜的 問題歸咎於微生物，其中最重要的原因是因
第6頁 1232131 案號 90119208_年月日__ 五、發明說明（2) 為水中的微生物會被薄膜表面吸收，而因此形成一生物 膜。
為了降低垢積情況，則預先處理水，改變薄膜表面的 電子性質，改變模組程序條件，以及定期清理等作法皆被 廣泛利用。尤其，據報導，可利用消毒劑（如氯）來有效減 少微生物在逆滲透薄膜所產生的垢積情形。然而，氯卻會 產生致癌物質。因此，若在飲用水之生產過程中加入氯， 可想而知會發生許多問題。最近，對於具有抗垢積性之薄 膜製造的研究重點集中在改變薄膜表面的電荷特性。但事 實上，並沒有發展出一種能夠徹底降低垢積情況的新穎薄 膜。 另外，Ti02是一種高效力光觸媒，其在紫外光或曰光 輻射下可殺死微生物，並可分解有機污染物。在許多專利 及文獻中皆有敘述許多利用此類抗菌性質所應用之案例， 如包裝薄膜，儲藏箱，壁紙，座椅，汽車之内部材料， 燈，眼罩，空氣調節器，電子爐，底層材料，冰箱等等。
另外，在水處理過程中，將T i 02粉末直接加入水中藉 以分解有機污染物並殺死微生物之技術亦為習知。傳統使 用T i 02的水處理過程可分解有機污染物及殺死水中微生 物，而不會產生有害的副產品，使得許多研究皆針對水處 理程序的可應用性。然而，在水處理過程中，將T i 0 2粒子 加入水中以產生分解作用之作法卻具有需要第二次程序來 還原T i 02粒子之缺點，且T i 02粒子難以再利用。所以，此 類作法無法完全適用於水處理上。 發明概述
第7頁 1232131
所以，本發明之一目的為克服先前技術所遇到之問題 而提供一種具有絕佳抗垢積性質之新穎逆滲透薄膜，其藉 由使具有光催化性質之T i 〇2極微粒子與固定形式之薄膜結 合’以防止薄膜使用期間所產生之垢積問題發生。 本發明之另一目的為提供一種製造具有絕佳抗垢積性質之 逆滲透薄膜的製造方法。 、 實施例之詳細說明 在本發明中，藉由將鈦化合物（如Ti [〇CH(CH3)2] *， TiClr TiOS〇4或TiOClg)添加至酸性水溶液，以發生水解作 用末產生極被的T i 02粒子。就其本身而言，使用ρ η值q . 5 一 3 的強酸水溶液會產生較佳的極微粒子。然後，馬上將所得 的鈦酸水溶液調整至ρ Η 1 - 6或9 - 1 3，藉以產生具有穩定 Τ 1 02散佈的溶液。然而，理想上，因為考慮到不純淨所引 發的物質攙雜問題，故會將Ti〇2粒子從鈦化合物分解所得 之鈦酸水溶液分離出來，並乾燥，而產生T i 〇 2的白色粉 末’然後將此白色粉末加入ρ Η 1 - 6的酸性溶液或ρ Η 9 - 1 3 的驗性水溶液，藉以得到散佈有穩定T i 〇2的溶液。在使用 pH值小於1或超過丨3的水溶液情況中，而薄膜可被強酸或 強驗分解。換言之，若水溶液之pH值超過6且小於9，則會 聚集極微的T i 〇2例子並因此使粒子沈澱。所以，散佈溶液 的穩定性變差。 本發明並不限制將T i 〇2粒子從鈦酸水溶液分離出來及 將Τ 1 〇2粒子乾燥的方法，且所有的分離及乾燥方法皆可利 用°就這點而言，可將水溶液直接蒸發並乾燥。 此外’鈦化合物因水解作用而產生T i 02後，可將各種
1232131 _案號90119208_年月曰 修正_ 五、發明說明（4) 金屬氧化物以重量比例為0 . 1 - 1 . 0 %添加量加入水溶液， 藉以得到攙有金屬離子的T i 0 2極微粒子。當以此類粒子來 製備穩定T i 0 2散佈的溶液時，可提高T i 0 2的光催化效力。
在此而言，可使用的金屬氧化物包含LiOH，Mg(C104)2， A1C13， VC13， VOSO4· 3H2〇， V0C13， V0C13， Cr(N03)， MnF3, F2(N〇3)3· 9H2〇，CoF3，NiCl2，Zn(C104)2，Ga(N03)3，Zr [OCH (CH3)2]4，NbCl5，M〇C13，RUC13，Rh(N03)3. 2H2〇，SnCl3， TaCl5，ReCl5，OsCl3，SbCl5等等。理想上，此類金屬氧化 物之添加量為水溶液重量的0 . 1 - 1. 0 % 。 在本發明中，含有T i 02極微粒子的逆滲透薄膜是將逆 滲透薄膜浸入散佈有穩定T i 0 2之水溶液所製備而得。浸沒 時間依溶液之pH值而定，但並不特別限制，只要T i 02粒子 可以成功併入薄膜即可。T i 0 2併入薄膜的反應機構中， T i 02被認為會藉由配位鍵而自身併入薄膜表面上的官能 基，且因此而固定。此外，本發明之逆滲透薄膜可以各種 包括聚醯胺形式之逆滲透薄膜來製造。 本發明揭示了使用具有絕佳光觸媒效力的T i 02而因此 使逆滲透薄膜具有優良的抗垢積性。此外，藉由使用各種 具有與T i 02相似之光催化效力的光催化無機氧化物，如 CdS，W03，SrTi03，MoSe2，和GaAs，而製造出具有絕佳抗 垢積性的逆滲透薄膜。 在概括說明本發明的同時，藉由參考特定具體之範例 可得到進一步的瞭解，然，除非有明確指定，否則這些範 例在此僅供說明而不應據以限制本發明之範圍。 範例一
1232131 _案號 90119208_年月日__ 五、發明說明（5) 將含有111111^[0(：11((：113)2]4完全溶解之2〇1111乙醇慢慢 地滴入2 0 0 m 1 ρ Η 1 · 5的攪動水溶液中，使之水解而產生 T i 02透明溶液。 使用3 5°C的蒸發器來蒸發產生的T i 02水溶液，且在 6 0°C之真空爐中乾燥1小時，以得到白色粉末之Ti 02粒 子，然後以預定比例（0. 5 g/L)將其溶解於水中，且將pH 值調整為2 . 8而產生穩定T i 0 2散佈的溶液。
將重量比例2%的MFD(m-苯二胺）溶液與0. 1%的TMC (三-m e s 〇 y 1 - c h 1 〇 r i d e )溶解於有機溶劑，而得到聚酸胺逆 滲透薄膜，然後將其浸入前述穩定T i 02散佈的溶液1小時， 藉以製備結合有1^02的逆滲透薄膜。 範例二 實行與範例一所述之相同程序，但將白色粉末之T i 02 粒子以預定比例（0. 5 g/L)溶解於水中，且將pH值調整為 1 0而產生結合有T i 0 2之逆滲透薄膜。 範例三
實行與範例一所述之相同程序，但於Ti [OCH(CH3)2]vJc 解而製備出T i Ο 2水溶液後，加入0 . 1 g的L i Ο Η而產生結合有 T i Ο 2的逆參透薄膜。 利用電子發射顯微鏡和可見的紫外光光譜來觀察上述 範例一至三所合成的T i 0 2粒子，而發現到此粒子係為1 0 nm 或更小的極微尺寸。 測量逆滲透薄膜與範例一所合成之T i 02結合前後之鹽 的通量及排除情形。結果顯示於如下之表一。
第10頁 1232131 五 案號 90119208 (6) -上 表一 樣本 通量（gfd) 鹽之棑f 與Ti05結合前 13.2 與TiCb結合德 14.4 修正
為了試驗本發明之逆滲透薄膜的抗 例二所製之Ti〇2的薄膜表面及未含有Ti〇2的’字八結合有範 定濃度之大腸桿菌在紫外光下一起培養。·、刀別與預 菌還原一段時間並在培養盤中培養，然 Μ 4使大腸杯 此決定殘存比例，胃以分析各薄膜之抗菌性顯因^ r心衣一就此而吕，紫外光之發射油具务0 p c 且培養溫度為3 7 °C。 长為365nm， 時問（小時）__ 薄棋與Ti02結石Γ 後之殘存比例 _ 薄膜與Ti02結合 前之殘存比例 100 0.5 1 2 78.9 71.3 43.6 83.7 78.2 51.4
定濃 結合 其浸 垢積 士 了試驗本發明逆滲透薄膜之垢積效 度之大腸桿菌的垢萨、、六、Λ ^ ^ 衣備含有預 有Ti〇2之薄膜，心二。’將範例三所製備之 入時間顯示於表三及^^;〇2之+薄膜浸入垢積溶液， 程度。結果顯示於矣二 々貝丨月I，亚为析 、表二。培養溫度為3 0 °C。
SZmZ5ZxI〇 ~ri〇7~S
滲透 又丄77丨％ 於根據本發明辦制娘V让 薄膜具有較佳的抗菌二 斤衣備之、'、。合有T i 02的 -—Jll政果和分解有機污染物之活# 1232131 _案號90Π9208_年月 曰 修正_ 五、發明說明（7) 同時與習知薄膜在相同情況比較下，仍保有鹽之排除性及 通量。所以，本發明之薄膜可去除水中之微生物且防止此 類微生物被吸收於薄膜上而使垢積情形發生。 本發明係以例證方式來做說明，且應瞭解到這些專門 用語是用來敘述說明而非限制。而按照上述教導即可對本 發明做許多修改及變化。所以，應瞭解到，只要在附加之 申請專利範圍内之情形，皆可以實施本發明而不需特別說 明0
第12頁
第13頁
Claims (1)
1232131 案號 90119208 曰 務正 替換未 六、申請專利範圍 1 · 一種具有良好抗垢積性之逆滲透薄膜的製備方法，其包 含下列步驟： 使水溶液中之鈦化合物在pH 0. 5 - 3的酸性環境中水 解，以產生極微之T i 0 2粒子； 將產生的TiOdS微粒子散佈於pH 1-6的酸性水溶液 或p Η 9 - 1 3的驗性水溶液中，以產生穩定T i 0 2散佈的溶 液；以及 將聚醯胺化合物之逆滲透薄膜浸入散佈有T i 0 2之溶 液中，使T i 02與薄膜結合。 2 .依申請專利範圍第1項所述之方法，其中該T i 02粒子係 自身併入聚合薄膜表面之官能基且因此固定。 3. 依申請專利範圍第1項所述之方法，其中該鈦化合物是 TiCl4iTi [0CH(CH3)2]4。 4. 依申請專利範圍第1項所述之方法，其中，在一該水解步 驟進一步包含L i 0 Η之添加量為水溶液重量的0 . 0 1 -1.0% 。 5. —種製備具有良好抗垢積性之逆滲透薄膜的製備方法， 其包含下列步驟： 使水溶液中之鈦化合物在pH 0. 5 - 3的酸性環境中水 解，以產生極微之T i 0 2粒子； 將T i 0 2粒子從鈦酸水溶液中分離出來且將T i 0 2粒子 乾燥，以得到白色粉末之T i 02 ; 將T i 0 2粉末分散於P Η值1 - 6之酸性水溶液或p Η值 9 - 1 3之驗性水溶液中，以產生穩定T i 0 2散佈的溶液；以
第14頁 1232131
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2001-0041423A KR100444126B1 (ko) | 2001-07-11 | 2001-07-11 | 안티파울링 특성이 우수한 역삼투 분리막 및 그 제조방법 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TWI232131B true TWI232131B (en) | 2005-05-11 |
Family
ID=36319948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW090119208A TWI232131B (en) | 2001-07-11 | 2001-08-07 | Reverse osmosis membrane having excellent anti-fouling property and method for manufacturing the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100444126B1 (zh) |
| TW (1) | TWI232131B (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100626321B1 (ko) * | 2005-07-26 | 2006-09-20 | (주)씨엔디환경 | 오염도가 낮은 분리막 및 그것의 제조방법 |
| CN102824856B (zh) * | 2012-08-31 | 2015-07-08 | 北京工业大学 | 一种自组装技术原位生成无机纳米粒子杂化膜的制备方法 |
| KR101687667B1 (ko) * | 2014-10-17 | 2016-12-20 | 도레이케미칼 주식회사 | 안티바이오파울링-fo막 개질제, 안티바이오파울링-fo막 및 이의 제조방법 |
| CN105597558B (zh) * | 2015-09-29 | 2018-11-13 | 浙江理工大学 | 一种具有催化降解功能的复合纳滤膜及其制备方法、应用 |
| KR102257887B1 (ko) * | 2019-09-20 | 2021-05-28 | 주식회사 알이디 | 대드존이 제어되는 막증류 장치 |
-
2001
- 2001-07-11 KR KR10-2001-0041423A patent/KR100444126B1/ko active IP Right Grant
- 2001-08-07 TW TW090119208A patent/TWI232131B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR100444126B1 (ko) | 2004-08-09 |
| KR20030005931A (ko) | 2003-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6551536B1 (en) | Reverse osmosis membrane having excellent anti-fouling property and method for manufacturing the same | |
| Chadha et al. | A review of the function of using carbon nanomaterials in membrane filtration for contaminant removal from wastewater | |
| CN103418250B (zh) | 一种在分离膜表面原位生成纳米粒子的方法 | |
| Zhang et al. | Ag modified gC 3 N 4 composite entrapped PES UF membrane with visible-light-driven photocatalytic antifouling performance | |
| Al-Hinai et al. | Antimicrobial activity enhancement of poly (ether sulfone) membranes by in situ growth of ZnO nanorods | |
| Barzegar et al. | Antibacterial and antifouling properties of Ag3PO4/GO nanocomposite blended polyethersulfone membrane applied in dye separation | |
| Sotto et al. | Preparation and characterization of MOF‐PES ultrafiltration membranes | |
| CN104548969A (zh) | 一种自组装固载金属离子制备抗污染聚砜类多孔膜的方法 | |
| Wu et al. | One-pot assembly tannic acid-titanium dual network coating for low-pressure nanofiltration membranes | |
| CN109803750A (zh) | 氧化石墨烯抗微生物元件 | |
| CN105413499B (zh) | 一种交联改性聚酰胺复合膜及其制备方法 | |
| Jiang et al. | Fabrication of anti-fouling and photocleaning PVDF microfiltration membranes embedded with N-TiO2 photocatalysts | |
| TWI232131B (en) | Reverse osmosis membrane having excellent anti-fouling property and method for manufacturing the same | |
| CN110813100B (zh) | 复合分离膜及其制备方法 | |
| Arif et al. | Development of eco-friendly, self-cleaning, antibacterial membrane for the elimination of chromium (VI) from tannery wastewater | |
| DE102011006753B3 (de) | Verwendung eines Biokompositmaterials zur Entfernung von Arsenverunreinigungen aus Wasser und Verfahren | |
| Le et al. | Melamine sponge-based copper-organic framework (Cu-CPP) as a multi-functional filter for air purifiers | |
| JP2013202606A (ja) | チオ尿素含有水の処理方法および装置 | |
| CN114887494B (zh) | 一种无金属离子浸出的可响应释放型mil-53修饰膜的制备方法和应用 | |
| Bharathi et al. | Improvement of membrane system for water treatment by synthesized gold nanoparticles | |
| CN104128101A (zh) | 一种银掺杂的金属陶瓷复合膜及其制备方法 | |
| Üçel et al. | Modification of PVDF membranes using dopamine/zinc oxide for lead removal from aqueous media | |
| JP6004376B2 (ja) | 分離膜の製造方法 | |
| Missaoui et al. | Removing organic dye by cellulose acetate nanocomposite membrane ultrafiltration: Effect of bio-nanoparticle size | |
| Rameesha et al. | Highly hydrophilic and antifouling poly (vinylidene fluoride) hybrid ultrafiltration membranes incorporated with silver‐loaded iron‐based metal–organic frameworks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |