CN102512986A - 气体可透膜 - Google Patents
气体可透膜 Download PDFInfo
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- CN102512986A CN102512986A CN2011104197655A CN201110419765A CN102512986A CN 102512986 A CN102512986 A CN 102512986A CN 2011104197655 A CN2011104197655 A CN 2011104197655A CN 201110419765 A CN201110419765 A CN 201110419765A CN 102512986 A CN102512986 A CN 102512986A
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- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 abstract description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
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- CHJAYYWUZLWNSQ-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;ethene Chemical group C=C.FC(F)=C(F)Cl CHJAYYWUZLWNSQ-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
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- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
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- B01D67/0081—After-treatment of organic or inorganic membranes
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- 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
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Abstract
由疏水性聚合物如Halar制得的多孔性聚合物膜,该膜的孔径足以使0.05微米-5pm的气体和/或蒸气透过,而不允许亲水性液体通过该膜。孔分布是均匀的,孔隙率是高的,在一些情况下可高达80%。该膜例如可呈平板型或中空纤维型,可用于各种领域如HF气体的抽提,苛性碱溶液的脱气,氯气/碱性滤液的脱气,以及脱除自来水中的溶解氯。可采用基本上无毒的溶剂如柠檬酸乙酯或三乙酸甘油酯来进行用于制备这类膜的工艺过程。
Description
本申请是申请日为2005年6月30日、申请号为200580024780.2的中国专利申请(PCT/AU2005/000961)的分案申请。
技术领域
本发明涉及用于气体过滤及有关应用中的聚合物膜的用途和制备,具体地说,本发明涉及Halar(乙烯三氟氯乙烯共聚物,或写为聚(乙烯三氟氯乙烯))以及在苛刻的化学环境情况中使用的有关膜。
背景技术
不能把下面所述内容看作是技术入门的一般知识。
大家都知道,合成聚合物超滤膜和微滤膜有多种用途,其中包括脱盐、气体分离、过滤和渗析。膜的过滤性能取决于膜的形态结构特征(如对称性、孔的形状、孔径)和成膜聚合物材料的化学性质。
微滤和超滤是压力驱动过程,膜的孔径与被膜截留或通过膜的微粒或分子的大小有关。微滤一般可滤出微米级和亚微米级非常细小的直至0.05微米的胶体微粒,而超滤可截留小至0.01微米和以下的微粒。
气体过滤膜或气体可透膜可用来分离溶于液体中的气体。气体分离过程是通过气体扩散产生的,气体扩散过程又构成例如跨膜蒸馏,渗透蒸馏、脱气、干燥及吸附等操作的基础。诸如无泡膜充气以及那些在膜接触器中发生的过程等的逆向过程也是可能的。
膜的化学性质对于气体可透膜来说是极其重要的。
在如下所述的正确组合情况下,液体可被阻止通过多孔膜:
I)适宜小的孔径,及
II)符合要求的膜与液体的亲水性/疏水性的组合。
因此,对于液体是否能通过膜来说,液体分子大小并不是限制因素,而是由液体-液体与液体-膜的力平衡所决定的。
另一方面,气体不存在是否能通过膜的问题,因为气体没有表面张力,所以能通过任何比分子尺寸大的任何尺寸的膜孔隙(通常为0.1纳米级),只要扩散条件适宜(即气体不会向较高压力区扩散)以及没有吸附在膜壁上。
亲水性液体(如水溶液)不会通过小孔径疏水性膜,疏水性液体也不会通过小孔径亲水性膜。例如水分子尺寸虽很小,但由于表面张力需要高压才能通过小孔径疏水性膜。当疏水性膜的孔径变小时,迫使水通过膜所需压力就会上升。
可通过采用足够的压力使水通过疏水性膜,但需很高的压力,对微-超滤膜来说需要150-300磅/平方英寸。在这样高的压力下膜往往会损坏,通常情况下无论如何也达不到均匀润湿。因此,在膜用于水过滤场合时,需要用例如乙醇或二醇那样的试剂使疏水膜亲水化或润湿以使水渗透。如果不润湿膜而保持聚合物的疏水性,则气体过滤膜当然是更好的。
在操作条件很严格的一些工艺过程中常常需要进行气体过滤。例如电子工业中需要气体过滤,如HF气体的抽提或苛性碱溶使用前的脱气,或用于氯/碱电解过程的脱气,此时膜需经受热的浓苛性碱或酸与氯的共同作用。许多用于膜制造的常规材料即使它们能以形成适宜的小孔径膜的方式制成,也经受不起如此高浓度化学品的侵蚀。
甚至在脱除自来水中用于杀死细菌的低浓度溶解氯的过程,也会因为膜运行期间通过大通量自来水而使膜受到大量氯气的作用。最终,膜发黄变脆,这是膜降解的信号。
现今,聚四氟乙烯(PTFE)、聚乙烯(PE)、聚丙烯(PP)和聚(偏二氟乙烯)(PVDF)是最普通的、可商购的疏水性膜材料。
PVDF具有许多适宜于膜用途的理想特性,其中包括耐热性,比较好的耐化学品性(范围涉及腐蚀性化学品,包括次氯酸钠)以及耐候(UV)性。
虽然目前已证实PVDF是许多适用作微孔膜的材料中最理想的材料,但仍需不断寻求具有更好的化学稳定性和特性的,并具有成膜、以适宜方式运行所要求的物理性能的膜材料。
气体过滤膜的局限性是它们在严酷的化学环境下和高温下的稳定性差。因此需继续寻求具有更好化学稳定性和特性的、并具有成膜、以适宜方式运行所要求的物理性能的膜材料。
本发明的一个目的是克服或减轻先有技术中存在的至少一个缺点,或至少提供一种工业用替代品。
发明内容
因此,本发明的第一方面是提供一种由稳定性疏水性膜制成的聚合物膜,其中孔径足以使气体渗透而不允许亲水性液体透过该膜。
本发明还提供一种由稳定性疏水性膜制成的聚合物膜,其中孔径足以使蒸气渗透而不允许亲水性液体透过该膜。
因此,本发明的第二方面是提供一种由Halar成形的聚合物膜,其中孔径足以使气体渗透而不允许液态水分子透过该膜。
Halar即聚(乙烯三氟氯乙烯)是乙烯与三氟氯乙烯的1∶1交替共聚物,该共聚物有如下结构:
-(-CH2-CH2-CFCl-CF2-)n-
虽然本发明是以Halar为例对本发明实施方案作了说明,但本文所用术语Halar包括Halar的等当物,如
-(-(CH2-CH2-)m-CX2-CX2-)n-
其中X各自选自F或Cl,m选自0与1之间以使聚合物中乙烯部分为0-50%。Halar的等当物的实例为PCTFE。
优选的是,孔径为0.05微米-5微米,更优选为0.1微米-1微米,而最优选为0.1微米-0.5微米。
优选的是,本发明膜是不对称膜,该膜具有大孔面和小孔面,孔径沿膜的横截面呈梯度变化。膜可以是平板型膜或更优选为中空纤维膜。
优选的膜是中空纤维膜,更优选的是,本发明膜是通过TIPS(热诱导相分离)法制备的。
优选的是,本发明膜适用于下列技术中一种或多种过程:跨膜蒸馏,渗透蒸馏,脱气,干燥,吸附,无泡膜充气或膜接触器。
膜接触器具有两路或多路由多孔膜隔离的流体(气体或液体)。溶解气体的逸出性会使气体从膜的富气侧向贫气侧扩散。
这类膜也可用来分离两种液体,或用来从二氧化碳中分离水蒸气。
优选的是,本发明膜用于那些化学稳定性要求很高、条件严格或苛刻的环境中。
优选的过程包括HF气体的抽提或苛性碱溶液使用前的脱气,或用于氯/碱电解过程的脱气,此时膜需要经受浓苛性碱或酸与氯的共同作用,以及脱除自来水中的溶解氯。可预期本发明膜适用于许多工业领域,其中包括电子工业。
本发明已出乎意料地发现,Halar可成形为具有这种极小孔的膜。这对于这类疏水性材料来说是异乎寻常的,对于通过TIPS法制成的膜也是异乎寻常的。
出乎意料的是,Halar还可成形为窄孔径分布的膜,即可根据需要制成大小一致的小孔。这样可制成具有小孔径、而孔隙率高达70%,或甚至80%或以上的膜。
优选的是,包含Halar的气体过滤膜的成形不采用有毒溶剂,或有疑惑的溶剂或未能证明是安全的溶剂。本发明膜优选是平板型膜或更优选为中空纤维膜。
优选的是,气体过滤膜是通过TIPS法(热诱导相分离法)形成的,并具有不对称孔径分布。最优选的是,Halar气体过滤膜具有大孔面和小孔面的不对称横截面。
优选的是,气体过滤膜的孔径要结合制造该气体过滤膜的材料极性来加以选择。
优选的是,膜的孔径为0.05微米-5微米,更优选为0.1微米-1微米,而最优选为0.1微米-0.5微米。根据待脱气溶液的疏水性、膜的疏水性以及预期的操作压力来选择适宜的孔径。孔径的选择可尽可能大至在操作压力下能在膜孔中截留液体,或根据实际情况稍小一些-孔径决定于膜制备的方法并取决于所要求分离的速度。
孔径可通过所谓泡点法来测定。
本发明的第三方面是提供一种由Halar和包含一种或多种根据式I或式II化合物的溶液制成的气体过滤膜:
式中R1、R2和R3各自为甲基、乙基、丙基、丁基、戊基、己基或其它烷基。
R4为H、OH、COR5、OCOR5、甲基、乙基、丙基、丁基、戊基、己基或其它烷基、甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基或其它烷氧基。
R5为甲基、乙基、丙基、丁基、戊基、己基或其它烷基。
优选的是R1=R2=R3=乙基,R4=H。
优选的是上述化合物用作孔调节剂,更优选的是上述化合物是柠檬酸乙酯(CitroflexTM-2)或三乙酸甘油酯。
这类化合物可用作聚合物溶剂,或单独使用上述化合物的混合物,或与其它适宜的试剂一起使用。
本发明的气体过滤膜或微滤膜既可以是疏水的也可以是亲水的,并可包含与原料聚合物(优选为Halar)相容的其它材料。疏水膜优选用于水溶液,亲水膜优选用于非极性溶液。
也可添加适用于对膜的化学性质进行改性的其它材料。在一个很优选的替换选择中,本发明气体过滤膜还包含用来改进膜的亲水性/疏水性平衡的改性剂。这样可得到亲水的多孔性聚合物膜,或者疏水的多孔性聚合物膜。
优选的是,本发明多孔性聚合物气体过滤膜具有良好的宏观整体性,均匀的壁厚和高的机械强度(例如断裂拉伸力大于1.3牛)。
本发明的第四方面是提供一种制造气体过滤膜的方法,该方法包括下列步骤:
a)对包含Halar和溶剂体系的混合物进行加热,其中溶剂体系初始包含作为Halar潜溶剂的第一组分和任选包含对Halar是非溶剂的第二组分,其中升高温度时Halar溶于该溶剂体系中形成光学透明的溶液;
b)使溶液迅速冷却,以发生非平衡的液-液相分离而形成连续的聚合物富相和连续的聚合物贫相,该两相间相互迁移成为大的界面面积双连续基质;
c)继续冷却直至聚合物富相凝固;
d)从固态聚合物材料中除去聚合物贫相,其中实施各步骤的条件是根据所制造的气体过滤膜的膜极性结合要达到的孔径进行选择的。
本发明的第五方面提供了一种由包含Halar的聚合物组合物经流延制膜步骤制造微滤膜或超滤膜的方法。
本发明的第六方面提供了一种形成Halar中空纤维膜的方法,该方法包括:
形成Halar与相容溶剂的混合物;
将所述混合物成形为中空纤维;
使所述混合物的内腔表面与形成内腔的流体相接触;
对所述混合物实施热诱导相分离以形成中空纤维膜;
从膜中除去溶剂;以及
其中实施各步骤的条件是根据所制造的气体过滤膜的膜极性结合要达到的孔径进行选择的。
优选的是,混合物中Halar的含量为14-25%,最优选为约16-23%。优选的是,形成内腔的流体是二甘醇。在很优选的实施方案中,该过程是在高温下,优选高于200℃下进行的,更优选高于220℃。
本发明的第七个方面提供了一种形成Halar中空纤维膜的方法,该方法包括:
形成Halar与相容溶剂的混合物;
将所述混合物成形为中空纤维;
使所述混合物的外表面与涂敷流体相接触;
使所述混合物的内腔表面与形成内腔的流体相接触;
对所述混合物实施热诱导相分离以形成中空纤维膜;
从膜中除去溶剂;以及
其中实施各步骤的条件是根据所制造的气体过滤膜的膜极性结合要达到的孔径进行选择的。
本发明涉及Halar用于形成气体过滤膜的用途,并涉及通过上述任何一方面制造的多孔性聚合物Halar气体过滤膜。
本文所用术语“环境友好”是指在与用于同样目的的其它产品或设施相比较时,对人类健康和环境影响较小的材料。具体地说,“环境友好”是指对植物和动物,特别是对人类是低毒的材料。环境友好也包括可生物降解的材料。
优选的是,用于本发明的环境友好溶剂不会对人类健康或其它有机体造成危害,暴露在这类溶剂下既不会有急性毒性(短期/高剂量),也不会有长期慢性毒性(通常较低的剂量)。
优选用于本发明的溶剂的急性毒性是很低的,即溶剂有高的LD50是优选的。对本发明来说,优选的LD50高于1000毫克/千克,更优选高于2000毫克/千克。
然而,除了急性毒性外,还极希望溶剂没有长期的,低剂量接触的危害,也没有致癌性,致突变性或致畸性。虽然LD50不可能反应这么多的因素(虽然也是一个因素),但反映了诸如溶剂的生物积累性以及它的固有毒性和致突变性质等的因素。优选的是,本发明溶剂不具有生物积累性。关于这方面,溶剂的生物降解性是很重要的,具有高的生物降解性的溶剂是优选的。
也有必要考虑其它生态毒性效应如对非人类/非哺乳动物的毒性以及诸如溶剂是否是一种耗臭氧化合物等的因素。
从结构来说,可发现合适的环境友好溶剂的结构特性类型包括:存在有降解性基团例如可水解基团如酯(尤其是存在这些基团会产生小得多的分子如C4或以下),不存在卤素(如氯),以及不存在芳环。
本发明优选的溶剂具有上述三个有利的特征。
实施本发明的最佳方法
Halar,或聚(乙烯三氟氯乙烯)是乙烯与三氟氯乙烯的1∶1交替共聚物,具有下列结构:
-(-CH2-CH2-CFCl-CF2-)n-
虽然本发明是以Halar为例对本发明的实施方案作了说明,但本文所用的这一名词包括Halar等当物,如
-(-(CH2-CH2-)m-CX2-CX2-)n-
式中X各自选自F或Cl,m选择在0-1之间,以使聚合物的乙烯部分为0-50%。Halar等当物的实例是PCTFE。已知制造Halar平板膜已有一段时间了,Halar的性能使它成为超滤和微滤领域中特别理想的材料。具体地说,Halar具有极好的耐氯和苛性碱溶液的性能,还具有耐臭氧和其它强氧化剂的性能。
Halar中空纤维型微滤膜是根据PCT AU94/00198(WO94/17204)和AU653528中公开的方法制造的,这些公开内容已列入本文供参考。
在本发明中,本发明者业已找到一种对由卤化聚合物(如Halar)制备的膜进行改性的方法,以拓宽它们的应用范围,而同时仍保持其优良的耐化学降解,物理降解和机械降解性能。
本发明的气体可透膜特别适宜制成中空纤维膜,并可通过相转化制得。
中空纤维超滤膜和微滤膜通常是通过扩散诱导相分离(DIPS法)或通过热诱导相分离(TIPS法)制造的。
PCTAU94/00198(WO94/17204)和AU653528已对TIPS法作更详细的说明,该两专利内容已列入本文供参考。
形成微孔体系的最快捷方法是两组分混合物的热沉淀法,在该过程中,先将热塑性聚合物溶于溶剂中形成溶液,该溶剂在高温下能溶解聚合物而在较低温度时不能溶解该聚合物。这类溶剂常称为聚合物的潜溶剂。然后使溶液冷却,在冷却至特定温度(随冷却速率而定)时发生相分离,聚合物富相从溶剂中分离出来。在本发明的一个过程中,将Halar溶在适宜的溶剂或适宜的溶剂/非溶剂混合物中,形成具有适宜粘度的溶液。可先将该聚合物溶液铸塑成薄膜或中空纤维,然后浸入凝固浴(如水)中。从而使均匀的聚合物溶液分离成为固态聚合物和液态溶剂相。凝固的聚合物形成了包含孔均匀分布的网络的多孔结构。影响膜结构和膜性能的制造参数包括聚合物浓度、凝固介质和温度,以及聚合物溶液中溶剂与非溶剂的含量。
可通过改变这些因素来制造大孔径范围(从0.1微米至0.005微米)的微孔膜。出乎意料的是,这些膜发现都是优良的气体过滤膜。
所有实用的热沉淀方法都遵循这一通用工艺,该工艺已由Smolders等人在Kolloid Z.U.Z Polymer,43,14-20(1971)中作了评述。该文章区分了聚合物溶液的旋节分解与双节分解。
液-液相分离的平衡条件已由聚合物/溶剂体系的双节曲线所确定。对于发生双节分解来说,聚合物在溶剂中的溶液在以极缓慢的速率冷却直至温度低于发生相分离温度,聚合物富相即从溶剂中分离出来。
通常,分离的两相不会是纯溶剂和纯聚合物,这是因为聚合物在溶剂中仍有一定程度的溶解度,溶剂在聚合物中也有一定程度的溶解度,因此存在聚合物富相和聚合物贫相。为了便于讨论,称聚合物富相为聚合物相,称聚合物贫相为溶剂相。
当冷却速率较快时,发生相分离的温度通常低于双节情况时,称发生的相分离为旋节分解。根据U.S.Specification No.4247498所公开的方法,聚合物和溶剂的相对浓度要使相分离的结果在连续聚合物相中形成细小的溶剂液滴。这些细小液滴成为膜的微孔。当继续冷却时,聚合物在溶剂微滴四周冻结。
当温度下降时,溶解度随之下降,在聚合物基体中会出现越来越多的溶剂微滴。溶剂从聚合物中离浆会导致收缩和龟裂,由此形成互连或在微孔间形成空隙。进一步冷却使聚合物固化。最后从结构中除去溶剂。
已知的形成多孔性膜的热沉淀法基于从溶剂中分离聚合物富相,然后再冷却以使固化的聚合物可从溶剂中分离出来。当从聚合物中除去溶剂时,溶剂呈液态还是呈固态决定于实施分离的操作温度和溶剂的熔融温度。
真溶液需包含溶剂和溶质。溶剂构成连续相,溶质均匀地分布在溶剂中而没有溶质-溶质间的相互作用。而聚合物溶液情况下不完全如此。长的聚合物链与其它聚合物链接触往往会发生暂时的相互作用或相互键合。因此聚合物溶液很少是真溶液,而是有点介于溶液与混合物之间。
在许多情况中,也难以说明谁是溶剂,谁是溶质。在技术上可以接受的是,如果是光学透明的没有明显的一相夹杂在另一相中,则也可实际称聚合物与溶剂的混合物为溶液。所谓光学透明,技术人员都知道,聚合物溶液由于存在大聚合物链,因而会产生光散射。发生相分离的温度称为浊点,浊点是光学上可检测的相分离温度。另一个可接受的是,实际上也可称聚合物为溶质,称与聚合物混合形成均匀溶液的材料为溶剂。
本发明中,本发明者也找到一种制备具有极小孔径的、可用作气体过滤膜的Halar膜的方法。
大家知道如何制备平板型Halar膜已有若干时间,制备方法已公开在例如US4702836中。以前的方法不适合于制备中空纤维,而且所用溶剂例如1,3,5-三氯苯、邻苯二甲酸二丁酯和邻苯二甲酸二辛酯等是具有高毒性的,对环境有很大影响。
Halar的优良性能使它成为气体过滤领域中极理想的膜材料。具体地说,Halar是高度疏水的(例如比PVDF更疏水),不仅具有极好的耐氯和耐苛性碱溶液的性能,而且也耐臭氧和其它强氧化剂,优选的是在制备Halar气体可透膜时不采用高毒性溶剂。
由于大多数气/液转移领域都涉及气体从水相或极性相中分离,因此理想的膜是疏水性的。这就是说,具有高表面张力的液体(主要是水溶液)不能透过膜孔。然而,由于气体没有表面张力,溶于液体中的气体或液体蒸气可透过多孔膜壁。在中等压力下发生扩散,如果在膜的两面有适当的压差,则扩散更快。例如,稍采用负压会促使气体透过膜。
气体过滤膜也可用来使微分散形态的气体在几乎没有或没有流体阻力的情况下通过液体。稍采用一点正压可加速液体的鼓气过程。
一般来说,疏水微孔膜的特征在于它们具有极好的耐化学品性,生物相容性,低溶胀性和良好的分离性能。
如上所述,气体过滤膜的微结构是不对称的,即孔径沿膜的横截面呈梯度变化,是不均匀的,而是相对于膜内横截距离而发生改变。中空纤维膜优选是不对称膜,膜的一个外表面或两个外表面上具有紧密排列的小孔,向着膜壁内边缘分布有较大的开孔。
已发现这类不对称微结构的优点在于膜的机械强度与过滤效率之间达到了令人满意的平衡。
作为一般原则,在需要过滤大量滤液时,就需要大的表面积。缩小设备体积的通用技术是形成中空多孔纤维膜。本发明根据本发明的一种设备的膜组件中置有大量经集束排列的这种中空纤维(高达数千根)。这些纤维是并列排列的,其作用在于当溶液与组件中所有纤维的外表面接触时可从溶液(通常为水溶液)中除去气体。对气体过滤来说,气体被迫进入每一根纤维的中心通道或内腔,而水和其它溶解物质被截留在纤维的外侧。滤过的气体集中在纤维内侧,并通过终端排出,或以简单方法吹出,流动的空气产生的低压有助于气流通过膜排出。
纤维组件构型是一种很理想的构型,因为这种构型能使组件的每单位体积具有很高的表面积。
根据本发明制得的膜具有优良的耐pH(酸和碱)和耐氧化(氯、臭氧等)性能。
虽然根据具体的实施方案已对本发明作了说明,但技术人员都知道,本文公开的发明构思并不只限于公开的那些具体的实施方案。
附图说明
图1a和1b是用于制备HF膜的可替代TIPS法流程图。
TIPS法的细节已公开在PCT AU94/00198(WO94/17204)和AU653528中,该两专利内容已列入本文供参考。本文将对制造本发明膜的一种优选方法作简要的说明。
在本发明的一个优选形态中,将聚(乙烯三氟氯乙烯)成形为中空纤维。为此将聚(乙烯三氟氯乙烯)溶于适宜溶剂中,然后通过环形共挤塑机头挤出。
中空纤维的制备
有两种可能的途径来实施本发明制备中空纤维的方法。其中一种途径是经具有三个连接通路的共挤塑机头,其横截面如图1b所示,另一种途径是经具有四个连接通路的四路共挤塑机头,其横截面如图1a所示。这两种途径的原理大致相同,除了骤冷流体与纤维接触方式不同以外。
对于这两种途径来说,轴向通路1可包含形成内腔的液流11。第一同心外通路2包含用于成膜的聚合物与溶剂体系的均匀混合物12,接着的同心外通路3包含涂敷液流13。在三通路挤塑机头情况中,骤冷浴或是直接邻接挤塑机头或是稍低于机头,中间有空气间隙。在四通路挤塑机头情况中,最外侧的通路4是对纤维实施骤冷的骤冷液流14。
在仔细进行热控制的条件下,形成内腔的流体、成膜溶液和涂敷液流在预定温度(和流速,如果骤冷液体是借助最外侧同心通路施加的)与骤冷流体相接触。于是聚(乙烯三氟氯乙烯)溶液在中空纤维内侧与形成内腔的流体相接触,在中空纤维的外侧与涂敷流体和/或骤冷浴溶液相接触。
形成内腔的流体和涂敷流体包含一种或多种溶剂体系的组分,可采用单一溶剂或采用按所选比例与其它溶剂相混合(可没有第一种组分)的混合溶剂。涂敷流体和形成内腔的流体的组成预先决定了膜的孔径,膜表面上孔的多少。
每种流体借助各自的计量泵输送到挤塑机头。三种组分是分别加热的,并沿绝热的伴热管(heat traced pipe)输送。挤塑机头有多个温度区。内腔流体、成膜溶液(成纤液体)和涂敷流体进入严格控制的温度基本相同的温度区内,成纤液体在此区域形成纤维。如上所述,骤冷液的确切性质取决于采用四通路或三通路的挤塑机头。对于四通路挤塑机头来说,骤冷液经过外同心通路导入。纤维以明显不同于骤冷液流的线速度下行至骤冷管。然后,根据需要,纤维中可通入更多的骤冷流体。
在三通路挤塑体系中,纤维通过模头挤出,模头可任选管状以有助于测定纤维结构。纤维进入骤冷浴前可任选地通过空气隙。本文中公开的大部分纤维是通过三通路挤塑机头制得的,很明显,制备纤维的参数包括空气隙距离。
当骤冷流体与成纤液体接触时,成纤液体经历非平衡的液-液相分离而形成两种液体的大界面面积的双连续基体,其中在可发生聚集分离成为小界面面积不同的相之前,聚合物富相凝固。
优选的是,在挤塑期间应排除任何空气、气体或蒸气(不是作为内腔液流的气体或蒸气),并对纤维施加轴向应力以将纤维拉伸1.5-5倍,从而使表面孔隙伸长。
离开挤塑机头的中空纤维膜已完全成形,除了通常在制膜过程中的挤塑后操作中除去膜中的溶剂体系外,不需任何进一步的成形处理。在一种优选的方法中,采用一种不会溶解聚合物但能与成纤液体中溶剂互溶的适宜溶剂来除去成品膜中聚合物的溶剂体系。
形成内腔的流体可选自如本文公开的各种物质。同样物质也可用作涂敷流体和骤冷流体。水或实际上任何其它液体都可用作骤冷液体。如果希望是高度不对称结构,则采用水。
不对称膜可偶而通过TIPS法制得。在膜的外表面发生分层的速率较快,而离界面越远分离速率越慢。这就导致在表面形成较小的孔而向中心的孔变大,形成孔径梯度。中空纤维界面上的孔是纤维的外层,而内腔壁在某些情况下可能是很薄以致成为“皮层”区域。该区域约1微米厚,是过滤的重要区域。因此,纤维外侧的孔是较小孔径的孔,而聚合物区域的中心的孔是较大径孔的孔。
聚(乙烯三氟氯乙烯)膜是采用三乙酸甘油酯(GTA)或Citroflex2作为溶剂通过挤塑进入水骤冷浴中制成的。通过SEM观察该膜结构的结果显示,形成了优良的膜,尽管有一定程度的结皮。
聚(乙烯三氟氯乙烯)膜是通过上述TIPS法经挤塑制成的。成纤液体是以Citroflex或GTA为溶剂(21-24%的聚合物成纤液体)制成的,再经Citroflex或GTA涂敷。未涂敷的膜试样的SEM显示有不可渗透的皮层,并有高的断裂伸长(BE)及断裂力(BF)值。
含GTA试样具有高的泡点,说明由许多较小的孔而不是由少数较大的孔来达到高的液流。涂敷Citroflex2的膜在SEM中可见具有良好的孔结构。
因此,采用GTA作为Halar纤维的涂料可显著地调节纤维的表面结构和孔隙度。较低的涂料流动速率仍能保持纤维的渗透性并增强不对称性,而较高的涂料流动速率可获得多得多的开孔表面感兴趣的是渗透性为1立方厘米/分钟的试样与5立方厘米/分钟的试样没有很大差别,纤维表面的孔隙似乎少得多。这样就可假定内部孔径是很小的。因此,如果精确地控制表面孔隙度,则可降低聚合物浓度或采用Citroflex2作为溶剂就能提高渗透性,而仍能保持纤维的优良的泡点/保留特性。
平板型膜的制备
将大约160克溶剂(GTA或Citroflex2)放入玻璃反应器中,用热电偶控制温度。在连续搅拌下,将溶剂加热至230℃,然后向其中加入约40克Halar901LC。聚合物迅速溶解并混合10-15分钟后将聚合物溶液试样从反应器中倾倒在已预热至120℃的玻璃板上。用已预热至120℃的玻璃棒将成纤液体快速地在玻璃板上铺展开。玻璃棒两端绕有粘胶带以在铺展成纤液体时使玻璃棒保持高于玻璃板的一致的高度,因此可得到厚度均匀的平板膜。使铸膜迅速冷却、固化形成平板型膜,然后用乙醇洗涤并在空气中干燥。
按上述方法制备Halar膜,采用约21%Halar在GTA溶剂中的溶液,流动速率为22-35立方厘米/分钟,内腔流体二甘醇的流动速率为5立方厘米/分钟。涂敷是任选的,当进行涂敷时,Citroflex2或GTA的流动速率均为10立方厘米/分钟。膜在水中进行骤冷。不对称膜的壁厚为150-250微米。断裂伸长率优良(超过90%),BF(牛)约1.3,PB(千帕)约490及应力约4.5兆帕。
虽然已参考具体实施方案对本发明作了说明,但技术人员都知道,本文公开的发明构思不仅限于那些公开的具体实施方案。
Claims (42)
1.一种多孔性聚合物膜,其由疏水性聚合物制成,其膜孔尺寸足以使气体和/或蒸气透过,但不允许亲水性液流通过该膜。
2.根据权利要求1的多孔性聚合物膜,其中膜孔径的选择要使气体和/或蒸气透过,但不允许液态水分子流过膜。
3.根据权利要求1或2的多孔性聚合物膜,其中膜孔径要结合制成气体过滤膜的膜材料的极性做出选择。
4.根据前述任一项权利要求的多孔性聚合物膜,其是由Halar制成。
5.根据前述任一项权利要求的多孔性聚合物膜,其中孔径为0.05微米-5微米。
6.根据权利要求5的多孔性聚合物膜,其中孔径为0.1微米-1微米。
7.根据权利要求6的多孔性聚合物膜,其中孔径为0.1微米-0.5微米。
8.根据前述任一项权利要求的多孔性聚合物膜,其具有窄的孔径分布。
9.根据前述任一项权利要求的多孔性聚合物膜,其孔隙率高达70%。
10.根据前述任一项权利要求的多孔性聚合物膜,其孔隙率高达80%。
11.根据前述任一项权利要求的多孔性聚合物膜,其孔隙率为70-80%。
12.根据前述任一项权利要求的多孔性聚合物膜,其孔隙率高于80%。
13.根据前述任一项权利要求的多孔性聚合物膜,其为具有大孔面、小孔面并且其孔径沿膜横截面呈梯度变化的不对称膜形式。
14.根据前述任一项权利要求的多孔性聚合物膜,其为平板型。
15.根据权利要求1-13任一项的多孔性聚合物膜,其为中空纤维膜型。
16.根据前述任一项权利要求的多孔性聚合物膜,由热诱导相分离法制得。
17.根据前述任何一项权利要求的多孔性聚合物膜,该多孔性聚合物膜用于一种或多种选自跨膜蒸馏、渗透蒸馏、脱气、干燥、吸附、无泡膜充气的过程。
18.根据权利要求1-16任一项的多孔性聚合物膜,用作气体过滤膜。
19.根据权利要求1-16任一项的多孔性聚合物膜,用于HF气体汽提。
20.根据权利要求1-16任一项的多孔性聚合物膜,用于苛性碱溶液脱气。
21.根据权利要求1-16任一项的多孔性聚合物膜,用于氯气/碱过滤。
22.根据权利要求1-16任一项的多孔性聚合物膜,用于将自来水中脱气以除去溶解氯。
23.根据权利要求1-16任一项的多孔性聚合物膜,用于膜接触器中。
24.根据前述任一项权利要求的多孔性聚合物膜,不含有毒性溶剂残留物。
26.根据权利要求25的气体过滤膜,其中R1=R2=R3=乙基,R4=H。
27.根据权利要求26的气体过滤膜,其中根据式I或式II的化合物起孔调节剂的作用。
28.根据权利要求27的气体过滤膜,其中根据式I的化合物是柠檬酸乙酯。
29.根据权利要求27的气体过滤膜,其中根据式II的化合物是三乙酸甘油酯。
30.根据前述任一项权利要求的多孔性聚合物膜,其是疏水的。
31.根据前述任一项权利要求的多孔性聚合物膜,其是亲水的。
32.根据前述任一项权利要求的多孔性聚合物膜,包含基础聚合物材料和与基础聚合物材料相容的材料。
33.根据前述任一项权利要求的多孔性聚合物膜,其中基础聚合物材料是Halar。
34.一种多孔性聚合物膜,其断裂力范围大于1.3牛。
35.一种制造气体过滤材料的方法,该方法包括下列步骤:
(a)对包含Halar和溶剂体系的混合物进行加热,其中溶剂体系初始包含作为Halar潜溶剂的第一组分和任选包含对Halar是非溶剂的第二组分,其中升高温度时Halar溶于该溶剂体系中形成光学透明的溶液;
(b)使溶液迅速冷却,以发生非平衡的液-液相分离而形成连续的聚合物富相和连续的聚合物贫相,该两相相互混合成为具有大的界面面积的双连续基体;
(c)继续冷却直至聚合物富相凝固;
(d)从固态聚合物材料中除去聚合物贫相;其中选择实施的条件以达到与膜极性相结合提供气体过滤膜的孔尺寸。
36.一种形成中空纤维Halar膜的方法,该方法包括:
形成Halar与相容溶剂的混合物;
将所述混合物成形为中空纤维;
使所述混合物的内腔表面与成腔的液体相接触;
对所述混合物实施热诱导相分离以形成中空纤维膜;
从膜中除去溶剂;以及
其中选择实施的条件以达到与膜极性相结合提供气体过滤膜的孔尺寸。
37.根据权利要求36的方法,其中混合物中Halar的含量为14-25%。
38.根据权利要求37的方法,其中混合物中Halar的含量为16-23%。
39.根据权利要求36-38任一项的方法,其中成腔的液体为二甘醇。
40.根据权利要求36-39任一项的方法,其中在高于200℃的高温下实施该方法。
41.根据权利要求36-39任一项的方法,其中在高于220℃的高温下实施该方法。
42.一种形成Halar中空纤维膜的方法,该方法包括:
形成Halar与相容溶剂的混合物;
将所述混合物成形为中空纤维;
使所述混合物的外表面与涂敷液体相接触;
使所述混合物的内腔表面与成腔的液体相接触;
对所述混合物实施热诱导相分离以形成中空纤维膜;
从膜中除去溶剂;以及
其中选择实施的条件以达到与膜极性相结合提供气体过滤膜的孔尺寸。
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US (1) | US7819956B2 (zh) |
EP (1) | EP1773476A4 (zh) |
JP (1) | JP2008504122A (zh) |
CN (2) | CN1988949B (zh) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111068463A (zh) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | 一种有机废气的处理方法 |
Families Citing this family (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6641733B2 (en) * | 1998-09-25 | 2003-11-04 | U. S. Filter Wastewater Group, Inc. | Apparatus and method for cleaning membrane filtration modules |
AUPR421501A0 (en) | 2001-04-04 | 2001-05-03 | U.S. Filter Wastewater Group, Inc. | Potting method |
AUPR692401A0 (en) | 2001-08-09 | 2001-08-30 | U.S. Filter Wastewater Group, Inc. | Method of cleaning membrane modules |
AUPS300602A0 (en) | 2002-06-18 | 2002-07-11 | U.S. Filter Wastewater Group, Inc. | Methods of minimising the effect of integrity loss in hollow fibre membrane modules |
AU2003903507A0 (en) | 2003-07-08 | 2003-07-24 | U. S. Filter Wastewater Group, Inc. | Membrane post-treatment |
WO2005021140A1 (en) | 2003-08-29 | 2005-03-10 | U.S. Filter Wastewater Group, Inc. | Backwash |
US8808540B2 (en) | 2003-11-14 | 2014-08-19 | Evoqua Water Technologies Llc | Module cleaning method |
WO2005092799A1 (en) | 2004-03-26 | 2005-10-06 | U.S. Filter Wastewater Group, Inc. | Process and apparatus for purifying impure water using microfiltration or ultrafiltration in combination with reverse osmosis |
WO2006002479A1 (en) * | 2004-07-05 | 2006-01-12 | U.S. Filter Wastewater Group, Inc. | Hydrophilic membranes |
JP4838248B2 (ja) | 2004-09-07 | 2011-12-14 | シーメンス・ウォーター・テクノロジーズ・コーポレーション | 逆洗液体廃棄物の低減 |
NZ553742A (en) | 2004-09-14 | 2010-09-30 | Siemens Water Tech Corp | Methods and apparatus for removing solids from a membrane module |
NZ553771A (en) * | 2004-09-15 | 2010-11-26 | Siemens Water Tech Corp | Continuously variable aeration of membrane filtration system and flow control device when used in such application |
EP1835985B1 (en) | 2004-12-24 | 2012-03-14 | Siemens Industry, Inc. | Cleaning in membrane filtration systems |
US8758622B2 (en) | 2004-12-24 | 2014-06-24 | Evoqua Water Technologies Llc | Simple gas scouring method and apparatus |
NZ562786A (en) | 2005-04-29 | 2010-10-29 | Siemens Water Tech Corp | Chemical clean for membrane filter |
JP2009504399A (ja) | 2005-08-22 | 2009-02-05 | シーメンス・ウォーター・テクノロジーズ・コーポレーション | 管状マニホールドを使用して逆洗を最小化する水濾過のためのアセンブリ |
WO2008001300A2 (en) * | 2006-06-27 | 2008-01-03 | Koninklijke Philips Electronics N.V. | A liquid droplet spray cleaning system for teeth with temperature and filter controls |
WO2008051546A2 (en) | 2006-10-24 | 2008-05-02 | Siemens Water Technologies Corp. | Infiltration/inflow control for membrane bioreactor |
ES2739858T3 (es) * | 2007-01-19 | 2020-02-04 | Circassia Ab | Dispositivo de análisis y método para detectar monóxido de nitrógeno en una fase gaseosa |
WO2008123972A1 (en) | 2007-04-02 | 2008-10-16 | Siemens Water Technologies Corp. | Improved infiltration/inflow control for membrane bioreactor |
US9764288B2 (en) | 2007-04-04 | 2017-09-19 | Evoqua Water Technologies Llc | Membrane module protection |
HU4544U (en) | 2007-05-29 | 2015-05-28 | Evoqua Water Technologies Llc | Structural arrangement of a membrane assembly unit placed in a fluid tank |
JP2009195764A (ja) * | 2008-02-19 | 2009-09-03 | Daicel Chem Ind Ltd | 中空糸分離膜の製造方法 |
US8382981B2 (en) | 2008-07-24 | 2013-02-26 | Siemens Industry, Inc. | Frame system for membrane filtration modules |
WO2010021959A1 (en) | 2008-08-20 | 2010-02-25 | Siemens Water Technologies Corp. | Improved membrane system backwash energy efficiency |
US10240013B2 (en) | 2008-12-19 | 2019-03-26 | 3M Innovative Properties Company | Microporous material from ethylene-chlorotrifluoroethylene copolymer and method for making same |
AU2010257526A1 (en) | 2009-06-11 | 2012-01-12 | Siemens Industry, Inc | Methods for cleaning a porous polymeric membrane and a kit for cleaning a porous polymeric membrane |
WO2011015517A1 (en) * | 2009-08-03 | 2011-02-10 | Solvay Solexis S.P.A. | Process for the preparation of ethylene/chlorotrifluoroethylene polymer membranes |
EP3572801A1 (de) * | 2009-08-25 | 2019-11-27 | Hach Lange GmbH | Prozess-analysegerät |
ES2738898T3 (es) | 2010-04-30 | 2020-01-27 | Evoqua Water Tech Llc | Dispositivo de distribución de flujo de fluido |
SG189035A1 (en) * | 2010-09-22 | 2013-05-31 | Oasys Water Inc | Osmotically driven membrane processes and systems and methods for draw solute recovery |
CN103118766B (zh) | 2010-09-24 | 2016-04-13 | 伊沃夸水处理技术有限责任公司 | 膜过滤系统的流体控制歧管 |
JP6016785B2 (ja) * | 2011-03-30 | 2016-10-26 | 国立研究開発法人国立長寿医療研究センター | 膜分取培養器、膜分取培養キット、およびこれを用いた幹細胞分取方法、ならびに分離膜 |
EP2763776B1 (en) | 2011-09-30 | 2021-07-28 | Rohm & Haas Electronic Materials Singapore Pte. Ltd | Improved filtration module assembly |
HUE058060T2 (hu) | 2011-09-30 | 2022-07-28 | Rohm & Haas Electronic Mat | Szigetelõ szelep |
WO2014004645A1 (en) | 2012-06-28 | 2014-01-03 | Siemens Industry, Inc. | A potting method |
CN104684632A (zh) | 2012-09-14 | 2015-06-03 | 伊沃夸水处理技术有限责任公司 | 用于膜的聚合物共混物 |
US9962865B2 (en) | 2012-09-26 | 2018-05-08 | Evoqua Water Technologies Llc | Membrane potting methods |
US9764289B2 (en) | 2012-09-26 | 2017-09-19 | Evoqua Water Technologies Llc | Membrane securement device |
WO2014052139A1 (en) | 2012-09-27 | 2014-04-03 | Evoqua Water Technologies Llc | Gas scouring apparatus for immersed membranes |
US10427102B2 (en) | 2013-10-02 | 2019-10-01 | Evoqua Water Technologies Llc | Method and device for repairing a membrane filtration module |
CN106145231A (zh) * | 2015-03-24 | 2016-11-23 | 通用电气公司 | 用于除氧的装置和方法 |
US10322375B2 (en) | 2015-07-14 | 2019-06-18 | Evoqua Water Technologies Llc | Aeration device for filtration system |
JP6202231B2 (ja) * | 2015-09-30 | 2017-09-27 | 東レ株式会社 | 分離膜、セルロース系樹脂組成物および分離膜の製造方法 |
CN105540765B (zh) * | 2016-02-02 | 2018-08-03 | 东华大学 | 一种电容吸附脱盐用分子筛/多孔碳复合电极材料及其制备方法 |
CN110102153A (zh) * | 2019-04-25 | 2019-08-09 | 成都同创紫气科技有限公司 | 一种膜式除臭器及其组件、系统和除臭方法 |
CN111888946B (zh) * | 2020-08-17 | 2022-08-30 | 杭州科百特科技有限公司 | 一种用于血液氧合的非对称疏水性聚烯烃中空纤维膜及其制备方法与用途 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003068374A1 (en) * | 2002-02-12 | 2003-08-21 | Us Filter Wastewater Group, Inc. | Halar membranes |
Family Cites Families (289)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1994135A (en) | 1933-12-18 | 1935-03-12 | John Schrott | Diaper |
US2732357A (en) | 1949-11-25 | 1956-01-24 | Suspensions of polymeric chlorotri- | |
DE123476C (zh) | 1960-09-19 | |||
NL137371C (zh) | 1963-08-02 | |||
US3556305A (en) | 1968-03-28 | 1971-01-19 | Amicon Corp | Composite membrane and process for making same |
US3625827A (en) | 1968-09-27 | 1971-12-07 | Monsanto Co | Water-soluble polymer-enzyme products |
US3693406A (en) | 1970-01-26 | 1972-09-26 | Air Intake Renu | Method for inspecting filters |
US3708071A (en) | 1970-08-05 | 1973-01-02 | Abcor Inc | Hollow fiber membrane device and method of fabricating same |
US3654147A (en) | 1971-03-16 | 1972-04-04 | Biospherics Inc | Nitrate removal from sewage |
US3864289A (en) | 1971-04-07 | 1975-02-04 | Koratec Inc | Preparation of cellulosic semi-permeable membranes |
US3728256A (en) | 1971-06-22 | 1973-04-17 | Abcor Inc | Crossflow capillary dialyzer |
FR2236537B1 (zh) | 1973-07-11 | 1977-12-23 | Rhone Poulenc Ind | |
US3876738A (en) | 1973-07-18 | 1975-04-08 | Amf Inc | Process for producing microporous films and products |
US3992301A (en) | 1973-11-19 | 1976-11-16 | Raypak, Inc. | Automatic flushing system for membrane separation machines such as reverse osmosis machines |
US3968192A (en) | 1974-04-19 | 1976-07-06 | The Dow Chemical Company | Method of repairing leaky hollow fiber permeability separatory devices |
IT1040274B (it) | 1975-07-30 | 1979-12-20 | Consiglio Nazionale Ricerche | Procedimento di preparazione di membrane anisotrope supportate per osmosi inversa a base di poliammidi sintetiche |
US4192750A (en) | 1976-08-09 | 1980-03-11 | Massey-Ferguson Inc. | Stackable filter head unit |
US4247498A (en) | 1976-08-30 | 1981-01-27 | Akzona Incorporated | Methods for making microporous products |
US4203848A (en) | 1977-05-25 | 1980-05-20 | Millipore Corporation | Processes of making a porous membrane material from polyvinylidene fluoride, and products |
US4519909A (en) | 1977-07-11 | 1985-05-28 | Akzona Incorporated | Microporous products |
US4193780A (en) | 1978-03-20 | 1980-03-18 | Industrial Air, Inc. | Air filter construction |
AU529368B2 (en) | 1978-05-15 | 1983-06-02 | Pall Corporation | Preparing polyamide membrane filter media and product |
JPS5535910A (en) | 1978-09-06 | 1980-03-13 | Teijin Ltd | Permselectivity composite membrane and preparation thereof |
US4188817A (en) | 1978-10-04 | 1980-02-19 | Standard Oil Company (Indiana) | Method for detecting membrane leakage |
JPS5554004A (en) | 1978-10-18 | 1980-04-21 | Teijin Ltd | Selective permeable membrane and its manufacturing |
BE874961A (nl) | 1979-03-20 | 1979-09-20 | Studiecentrum Kernenergi | WERKWIJZE TER BEREIDING VAN EEN MEMBRAAN, ALDUS BEREID MEMBRAAN, ELEKTROCHEMISCHE CEL MET ZULK MEMBRAAN EN TOEPASSING VAN ZULKE ELEKTROchemische cel |
US4218324A (en) | 1979-05-03 | 1980-08-19 | Textron, Inc. | Filter element having removable filter media member |
US4248648A (en) | 1979-07-18 | 1981-02-03 | Baxter Travenol Laboratories, Inc. | Method of repairing leaks in a hollow capillary fiber diffusion device |
JPS5695304A (en) | 1979-12-28 | 1981-08-01 | Teijin Ltd | Perm selective composite membrane and its production |
US4629563B1 (en) | 1980-03-14 | 1997-06-03 | Memtec North America | Asymmetric membranes |
DE3026718A1 (de) * | 1980-07-15 | 1982-02-04 | Akzo Gmbh, 5600 Wuppertal | Hohlfasermembran fuer die plasmaseparation |
JPS5770144A (en) | 1980-10-17 | 1982-04-30 | Asahi Glass Co Ltd | Organic solution of fluorinated copolymer containing carboxyl group |
US4384474A (en) | 1980-10-30 | 1983-05-24 | Amf Incorporated | Method and apparatus for testing and using membrane filters in an on site of use housing |
US4354443A (en) | 1980-11-10 | 1982-10-19 | Dason International Products Inc. | Afghan construction and method |
JPS57102202A (en) | 1980-12-18 | 1982-06-25 | Toyobo Co Ltd | Fluid separator |
JPS6059933B2 (ja) | 1981-05-22 | 1985-12-27 | 工業技術院長 | 無水マレイン酸残基を有する高分子膜 |
US4707266A (en) | 1982-02-05 | 1987-11-17 | Pall Corporation | Polyamide membrane with controlled surface properties |
US4702840A (en) | 1982-02-05 | 1987-10-27 | Pall Corporation | Charge modified polyamide membrane |
US4812235A (en) | 1982-03-29 | 1989-03-14 | Hr Textron, Inc. | Filter element assembly replaceable mesh pack |
US4540490A (en) | 1982-04-23 | 1985-09-10 | Jgc Corporation | Apparatus for filtration of a suspension |
US4431545A (en) | 1982-05-07 | 1984-02-14 | Pall Corporation | Microporous filter system and process |
WO1983003984A1 (en) | 1982-05-13 | 1983-11-24 | Gerhard Kunz | Method for the treatment of a liquid phase, particularly method for desalting aqueous solutions, as well as device for its implementation |
JPS5952507A (ja) | 1982-06-03 | 1984-03-27 | デ−・エル・エム・ドクトル・ミユラ−・アクチエンゲゼルシヤフト | 懸濁液を連続的に濃縮する装置 |
GB2132366B (en) | 1982-12-27 | 1987-04-08 | Brunswick Corp | Method and device for testing the permeability of membrane filters |
CA1221645A (en) | 1983-02-28 | 1987-05-12 | Yoshihiro Okano | Filtration apparatus using hollow fiber-membrane |
GB8313635D0 (en) | 1983-05-17 | 1983-06-22 | Whatman Reeve Angel Plc | Porosimeter |
US4636296A (en) | 1983-08-18 | 1987-01-13 | Gerhard Kunz | Process and apparatus for treatment of fluids, particularly desalinization of aqueous solutions |
DE3333834A1 (de) | 1983-09-20 | 1985-04-04 | Herberts Gmbh, 5600 Wuppertal | Verfahren zur herstellung von lack-kunstharzen und diese enthaltendes elektrotauchlack-ueberzugsmittel |
US4650586A (en) | 1983-09-26 | 1987-03-17 | Kinetico, Inc. | Fluid treatment system |
US4756875A (en) | 1983-09-29 | 1988-07-12 | Kabushiki Kaisha Toshiba | Apparatus for filtering water containing radioactive substances in nuclear power plants |
EP0160014B1 (en) | 1983-09-30 | 1993-01-07 | Memtec Limited | Cleaning of filters |
US4888115A (en) | 1983-12-29 | 1989-12-19 | Cuno, Incorporated | Cross-flow filtration |
US4609465A (en) | 1984-05-21 | 1986-09-02 | Pall Corporation | Filter cartridge with a connector seal |
DE3568946D1 (en) | 1984-07-09 | 1989-04-27 | Millipore Corp | Improved electrodeionization apparatus and method |
JPS6125903U (ja) | 1984-07-24 | 1986-02-15 | 株式会社 伊藤鉄工所 | ろ過装置 |
DE3428307A1 (de) | 1984-08-01 | 1986-02-13 | Filterwerk Mann & Hummel Gmbh, 7140 Ludwigsburg | Anzeigevorrichtung fuer den verschmutzungsgrad von ansaugluftfiltern |
US5192478A (en) | 1984-10-22 | 1993-03-09 | The Dow Chemical Company | Method of forming tubesheet for hollow fibers |
US4618533A (en) | 1984-11-30 | 1986-10-21 | Millipore Corporation | Porous membrane having hydrophilic surface and process |
JPS6338884Y2 (zh) | 1984-12-15 | 1988-10-13 | ||
US5198162A (en) * | 1984-12-19 | 1993-03-30 | Scimat Limited | Microporous films |
GB2168981B (en) | 1984-12-27 | 1988-07-06 | Asahi Chemical Ind | Porous fluorine resin membrane and process for preparation thereof |
US5024762A (en) | 1985-03-05 | 1991-06-18 | Memtec Limited | Concentration of solids in a suspension |
JPH0667459B2 (ja) | 1985-03-05 | 1994-08-31 | メムテック・リミテッド | 懸濁液中の微細固体の濃縮方法及び装置 |
US4642182A (en) | 1985-03-07 | 1987-02-10 | Mordeki Drori | Multiple-disc type filter with extensible support |
EP0216876B1 (en) | 1985-03-28 | 1990-05-16 | Memtec Limited | Cooling hollow fibre cross-flow separators |
US4704324A (en) | 1985-04-03 | 1987-11-03 | The Dow Chemical Company | Semi-permeable membranes prepared via reaction of cationic groups with nucleophilic groups |
DE3671843D1 (de) | 1985-04-10 | 1990-07-19 | Memtec Ltd | Filter mit aenderlichem volumen oder konzentrator. |
CA1247329A (en) | 1985-05-06 | 1988-12-28 | Craig J. Brown | Fluid treatment process and apparatus |
JPS61274709A (ja) | 1985-05-29 | 1986-12-04 | Ebara Corp | 中空糸膜ろ過装置 |
US4660411A (en) | 1985-05-31 | 1987-04-28 | Reid Philip L | Apparatus for measuring transmission of volatile substances through films |
US4656865A (en) | 1985-09-09 | 1987-04-14 | The Dow Chemical Company | System for analyzing permeation of a gas or vapor through a film or membrane |
US4876006A (en) | 1985-10-08 | 1989-10-24 | Ebara Corporation | Hollow fiber filter device |
DE3546091A1 (de) | 1985-12-24 | 1987-07-02 | Kernforschungsz Karlsruhe | Querstrom-mikrofilter |
US4779448A (en) | 1986-01-28 | 1988-10-25 | Donaldson Company, Inc. | Photoelectric bubble detector apparatus and method |
JPH0742861B2 (ja) | 1986-03-10 | 1995-05-15 | ヤマハ発動機株式会社 | 内燃機関の吸気装置 |
US4774132A (en) | 1986-05-01 | 1988-09-27 | Pall Corporation | Polyvinylidene difluoride structure |
DE3617724A1 (de) | 1986-05-27 | 1987-12-03 | Akzo Gmbh | Verfahren zur bestimmung des blaspunktes bzw. der groessten pore von membranen oder filterwerkstoffen |
FR2600265B1 (fr) | 1986-06-20 | 1991-09-06 | Rhone Poulenc Rech | Membranes semi-permeables sechables et hydrophiles a base de polyfluorure de vinylidene |
US4670145A (en) | 1986-07-08 | 1987-06-02 | E. I. Du Pont De Nemours And Company | Multiple bundle fluid separation apparatus |
ES2014516A6 (es) | 1986-07-11 | 1990-07-16 | Mentec Ltd | Procedimiento para la limpieza de filtros. |
US4921610A (en) | 1986-09-04 | 1990-05-01 | Memtec Limited | Cleaning of hollow fibre filters |
WO1988001895A1 (en) | 1986-09-12 | 1988-03-24 | Memtec Limited | Hollow fibre filter cartridge and header |
US5094750A (en) | 1986-09-12 | 1992-03-10 | Memtec Limited | Hollow fibre filter cartridge and header |
DE3636583A1 (de) | 1986-10-28 | 1988-05-05 | Draegerwerk Ag | Verfahren zum herstellen eines hohlfaser-stoffaustauschmoduls und nach diesem verfahren hergestelltes modul |
US5019260A (en) | 1986-12-23 | 1991-05-28 | Pall Corporation | Filtration media with low protein adsorbability |
GB8704142D0 (en) | 1987-02-23 | 1987-04-01 | Whitford Plastics Ltd | Protective surface treatment |
US4846970A (en) | 1987-06-22 | 1989-07-11 | Osmonics, Inc. | Cross-flow filtration membrane test unit |
DE3878899T2 (de) * | 1987-07-30 | 1993-07-22 | Toray Industries | Poroese polytetrafluoraethylen-membran, trennvorrichtung unter verwendung dieser membran sowie verfahren zur herstellung. |
US4784771A (en) | 1987-08-03 | 1988-11-15 | Environmental Water Technology, Inc. | Method and apparatus for purifying fluids |
US5221478A (en) | 1988-02-05 | 1993-06-22 | The Dow Chemical Company | Chromatographic separation using ion-exchange resins |
US4904426A (en) | 1988-03-31 | 1990-02-27 | The Dow Chemical Company | Process for the production of fibers from poly(etheretherketone)-type polymers |
US5147553A (en) | 1988-05-04 | 1992-09-15 | Ionics, Incorporated | Selectively permeable barriers |
US4886601A (en) | 1988-05-31 | 1989-12-12 | Japan Organo Co., Ltd. | Column filter using bundles of long fibers |
US5075065A (en) | 1988-08-01 | 1991-12-24 | Chemical Fabrics Corporation | Method for manufacturing of cast films at high productivity |
US5043113A (en) * | 1988-08-05 | 1991-08-27 | Hoechst Celanese Corp. | Process for formation of halogenated polymeric microporous membranes having improved strength properties |
DE3829766A1 (de) * | 1988-09-01 | 1990-03-22 | Akzo Gmbh | Verfahren zur herstellung von membranen |
US4963304A (en) | 1988-09-26 | 1990-10-16 | The Dow Chemical Company | Process for preparing microporous membranes |
US4999038A (en) | 1989-02-07 | 1991-03-12 | Lundberg Bo E H | Filter unit |
DE3904544A1 (de) | 1989-02-15 | 1990-08-16 | Fraunhofer Ges Forschung | Polymermembranen auf der basis von polyvinylidenfluorid, verfahren zu deren herstellung und deren verwendung |
US5032282A (en) | 1989-04-14 | 1991-07-16 | Aligena Ag | Solvent-stable semipermeable composite membranes |
NL8901090A (nl) | 1989-04-28 | 1990-11-16 | X Flow Bv | Werkwijze voor het vervaardigen van een microporeus membraan en een dergelijk membraan. |
US5005430A (en) | 1989-05-16 | 1991-04-09 | Electric Power Research Institute, Inc. | Automated membrane filter sampler |
US5138870A (en) | 1989-07-10 | 1992-08-18 | Lyssy Georges H | Apparatus for measuring water vapor permeability through sheet materials |
DE3923128A1 (de) | 1989-07-13 | 1991-01-24 | Akzo Gmbh | Flach- oder kapillarmembran auf der basis eines homogenen gemisches aus polyvinylidenfluorid und eines zweiten, durch chemische umsetzung hydrophilierbaren polymeren |
US5015275A (en) | 1989-07-14 | 1991-05-14 | The Dow Chemical Company | Isotropic microporous syndiotactic polystyrene membranes and processes for preparing the same |
DE3926059C2 (de) | 1989-08-07 | 1998-01-29 | Basf Ag | Phosphonomethylierte Polyvinylamine, Verfahren zu ihrer Herstellung und ihre Verwendung |
US5194149A (en) | 1989-09-29 | 1993-03-16 | Memtec Limited | Filter cartridge manifold |
US5227063A (en) | 1989-10-03 | 1993-07-13 | Zenon Environmental Inc. | Tubular membrane module |
US5158721A (en) | 1989-11-30 | 1992-10-27 | Millipore Corporation | Porous membrane formed from interpenetrating polymer network having hydrophilic surface |
US5079272A (en) | 1989-11-30 | 1992-01-07 | Millipore Corporation | Porous membrane formed from interpenetrating polymer network having hydrophilic surface |
DE4007383C2 (de) | 1990-03-08 | 1998-10-29 | Seitz Filter Werke | Herstellung von hydrophilen Mikrofiltrationsmembranen aus Polysulfonen |
US5066375A (en) | 1990-03-19 | 1991-11-19 | Ionics, Incorporated | Introducing and removing ion-exchange and other particulates from an assembled electrodeionization stack |
ES2126571T3 (es) | 1990-04-20 | 1999-04-01 | Usf Filtration Limited | Conjuntos de filtros modulares microporosos. |
ES2129245T3 (es) | 1990-05-09 | 1999-06-01 | Usf Filtration Limited | Membrana de poli(fluoruro de vinilideno). |
AU653528B2 (en) | 1990-05-09 | 1994-10-06 | Siemens Water Technologies Corp. | Porous PVdF membranes |
US5017292A (en) | 1990-05-10 | 1991-05-21 | Millipore Corporation | Membrane, process and system for isolating virus from solution |
US5049275A (en) | 1990-06-15 | 1991-09-17 | Hoechst Celanese Corp. | Modified microporous structures |
US5364527A (en) | 1990-06-20 | 1994-11-15 | Heinz Zimmermann | Apparatus and process for treating water |
DE4117281C2 (de) | 1990-06-29 | 1996-02-22 | Gore Enterprise Holdings Inc | Hydrophilierte, mikroporöse Membran aus Polytetrafluorethylen und Verfahren zu ihrer Herstellung |
US5104546A (en) | 1990-07-03 | 1992-04-14 | Aluminum Company Of America | Pyrogens separations by ceramic ultrafiltration |
US5639373A (en) | 1995-08-11 | 1997-06-17 | Zenon Environmental Inc. | Vertical skein of hollow fiber membranes and method of maintaining clean fiber surfaces while filtering a substrate to withdraw a permeate |
US5248424A (en) | 1990-08-17 | 1993-09-28 | Zenon Environmental Inc. | Frameless array of hollow fiber membranes and method of maintaining clean fiber surfaces while filtering a substrate to withdraw a permeate |
US5104535A (en) | 1990-08-17 | 1992-04-14 | Zenon Environmental, Inc. | Frameless array of hollow fiber membranes and module containing a stack of arrays |
US5182019A (en) | 1990-08-17 | 1993-01-26 | Zenon Environmental Inc. | Cartridge of hybrid frameless arrays of hollow fiber membranes and module containing an assembly of cartridges |
JP2904564B2 (ja) | 1990-08-31 | 1999-06-14 | オルガノ株式会社 | 中空糸膜を用いる濾過塔のスクラビング方法 |
FR2666245B1 (fr) | 1990-08-31 | 1992-10-23 | Lyonnaise Eaux | Procede de commande des modes de fonctionnement d'un appareil automatique de filtration d'eau sur membranes tubulaires. |
JP2858913B2 (ja) | 1990-09-26 | 1999-02-17 | オルガノ株式会社 | 中空糸膜を用いる濾過方法 |
USH1045H (en) | 1990-11-19 | 1992-05-05 | The United States Of America As Represented By The Secretary Of The Army | Air bubble leak detection test device |
JPH04187224A (ja) * | 1990-11-20 | 1992-07-03 | Mitsubishi Rayon Co Ltd | フッ素系多孔質中空糸膜の製法 |
KR930006968B1 (ko) | 1990-12-22 | 1993-07-24 | 삼성전자 주식회사 | 화상 기록장치 |
US5069065A (en) | 1991-01-16 | 1991-12-03 | Mobil Oil Corporation | Method for measuring wettability of porous rock |
GB2253572B (en) | 1991-02-11 | 1994-12-14 | Aljac Engineering Limited | Flow device in fluid circuits |
JP3238399B2 (ja) | 1991-03-06 | 2001-12-10 | ザルトリウス アクチエンゲゼルシヤフト | 成形体の表面変性方法、該方法によって製造された成形体及びその吸着性物質分離のための使用 |
EP0510328B1 (en) | 1991-03-07 | 1995-10-04 | Kubota Corporation | Apparatus for treating activated sludge |
FR2674448B1 (fr) | 1991-03-26 | 1994-03-25 | Dumez Lyonnaise Eaux | Procede de nettoyage de membranes tubulaires mesoporeuses d'ultrafiltration. |
DE4113420A1 (de) | 1991-04-25 | 1992-10-29 | Bayer Ag | Polyacrylnitril-hohlfaeden aus speziellen spinnloesungen nach dem dry/wet- oder nass-spinnverfahren |
DE4117422C1 (en) | 1991-05-28 | 1992-11-12 | Willi Prof. Dr.-Ing. 7432 Bad Urach De Dettinger | Monitoring contamination level of filter, partic. for hydraulic fluids - in which signal is produced which correlates with quotient of two pressure differences and evaluating device produces signal to change filter when quotient reaches given value |
DE4119040C2 (de) | 1991-06-10 | 1997-01-02 | Pall Corp | Verfahren und Gerät zum Testen des Betriebszustands von Filterelementen |
US5211823A (en) | 1991-06-19 | 1993-05-18 | Millipore Corporation | Process for purifying resins utilizing bipolar interface |
US5137633A (en) | 1991-06-26 | 1992-08-11 | Millipore Corporation | Hydrophobic membrane having hydrophilic and charged surface and process |
US5643455A (en) | 1991-08-07 | 1997-07-01 | Memtel Limited | Concentration of solids in a suspension using hollow fibre membranes |
US5135663A (en) | 1991-10-18 | 1992-08-04 | Loctite Corporation | Method of treating (meth)acrylic monomer-containing wastewater |
US5137631A (en) | 1991-10-22 | 1992-08-11 | E. I. Du Pont De Nemours And Company | Multiple bundle permeator |
WO1993013489A1 (en) | 1991-12-24 | 1993-07-08 | Sierra Semiconductor Corporation | An anti-aliasing method for polynomial curves using integer arithmetics |
US5198116A (en) | 1992-02-10 | 1993-03-30 | D.W. Walker & Associates | Method and apparatus for measuring the fouling potential of membrane system feeds |
DE69316325T2 (de) | 1992-02-12 | 1998-05-28 | Mitsubishi Rayon Co | Hohlfasermembranemodul |
US5411663A (en) | 1992-03-20 | 1995-05-02 | Micron Separations, Inc. | Alcohol-insoluble nylon microporous membranes |
DE69313574T2 (de) | 1992-05-01 | 1998-01-08 | Memtec Japan Ltd | Vorrichtung zur Integritätsprüfung von Membranfiltern |
DK0641247T3 (da) | 1992-05-18 | 1997-04-01 | Minntech Corp | Filterpatron med hule fibre og fremgangsmåde til fremstilling af denne |
EP0581168B1 (en) * | 1992-07-22 | 1996-10-02 | Mitsubishi Rayon Co., Ltd. | Hydrophobic porous membranes, process for the manufacture thereof and their use |
CA2100643A1 (en) | 1992-08-14 | 1994-02-15 | Guido Sartori | Fluorinated polyolefin membranes for aromatics/saturates separation |
US5275766A (en) | 1992-10-30 | 1994-01-04 | Corning Incorporate | Method for making semi-permeable polymer membranes |
US5918264A (en) | 1992-11-02 | 1999-06-29 | Usf Filtration And Separations Group Inc. | Fiber monitoring system |
US5320760A (en) | 1992-12-07 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Method of determining filter pluggage by measuring pressures |
US5288324A (en) | 1992-12-18 | 1994-02-22 | Shaneyfelt Jack L | Multi-color powder coat paint recovery apparatus |
US5401401A (en) | 1993-01-13 | 1995-03-28 | Aquaria Inc. | Hang on tank canister filter |
US5389260A (en) | 1993-04-02 | 1995-02-14 | Clack Corporation | Brine seal for tubular filter |
US5361625A (en) | 1993-04-29 | 1994-11-08 | Ylvisaker Jon A | Method and device for the measurement of barrier properties of films against gases |
US5297420A (en) | 1993-05-19 | 1994-03-29 | Mobil Oil Corporation | Apparatus and method for measuring relative permeability and capillary pressure of porous rock |
FR2705734B1 (fr) | 1993-05-25 | 1995-06-30 | Snecma | Procédé et dispositif pour améliorer la sécurité des filtres à fluide. |
US5419816A (en) | 1993-10-27 | 1995-05-30 | Halox Technologies Corporation | Electrolytic process and apparatus for the controlled oxidation of inorganic and organic species in aqueous solutions |
US5354587A (en) | 1993-11-15 | 1994-10-11 | W. L. Gore & Associates, Inc. | Hydrophilic compositions with increased thermal and solvent resistance |
FR2713220B1 (fr) | 1993-11-30 | 1996-03-08 | Omnium Traitement Valorisa | Installation de potabilisation de l'eau à membranes filtrantes immergées. |
US5403479A (en) | 1993-12-20 | 1995-04-04 | Zenon Environmental Inc. | In situ cleaning system for fouled membranes |
JP3160140B2 (ja) | 1993-12-22 | 2001-04-23 | オルガノ株式会社 | 中空糸モジュールを用いるろ過装置 |
JPH07313850A (ja) | 1994-05-30 | 1995-12-05 | Kubota Corp | 浸漬型セラミック膜分離装置の逆洗方法 |
US5491023A (en) | 1994-06-10 | 1996-02-13 | Mobil Oil Corporation | Film composition |
US6309550B1 (en) * | 1994-06-22 | 2001-10-30 | Fls Miljo A/S | Mass transfer method and apparatus |
US5531900A (en) | 1994-07-07 | 1996-07-02 | University Of Arizona | Modification of polyvinylidene fluoride membrane and method of filtering |
JP3084292B2 (ja) | 1994-07-28 | 2000-09-04 | ミリポア コーポレイション | 多孔質複合膜と方法 |
US5451317A (en) | 1994-09-08 | 1995-09-19 | Kubota Corporation | Solid-liquid separator |
AUPM800694A0 (en) | 1994-09-09 | 1994-10-06 | Memtec Limited | Cleaning of hollow fibre membranes |
US5470469A (en) | 1994-09-16 | 1995-11-28 | E. I. Du Pont De Nemours And Company | Hollow fiber cartridge |
FR2726568B1 (fr) | 1994-11-08 | 1996-12-06 | Atochem Elf Sa | Melanges de polymeres comprenant un polymere halogene et compatibilises par un polyester aliphatique greffe |
US5906742A (en) | 1995-07-05 | 1999-05-25 | Usf Filtration And Separations Group Inc. | Microfiltration membranes having high pore density and mixed isotropic and anisotropic structure |
US5725769A (en) | 1995-07-18 | 1998-03-10 | Bend Research, Inc. | Solvent-resistant microporous polymide membranes |
US6656356B2 (en) | 1998-10-09 | 2003-12-02 | Zenon Environmental Inc. | Aerated immersed membrane system |
WO1997006880A2 (en) | 1995-08-11 | 1997-02-27 | Zenon Environmental Inc. | Vertical skein of hollow fiber membranes and method of maintaining clean fiber surfaces |
US6685832B2 (en) | 1995-08-11 | 2004-02-03 | Zenon Environmental Inc. | Method of potting hollow fiber membranes |
US6193890B1 (en) | 1995-08-11 | 2001-02-27 | Zenon Environmental Inc. | System for maintaining a clean skein of hollow fibers while filtering suspended solids |
US5944997A (en) | 1995-08-11 | 1999-08-31 | Zenon Environmental Inc. | System for maintaining a clean skein of hollow fibers while filtering suspended solids |
RU2119817C1 (ru) | 1995-10-23 | 1998-10-10 | Акционерное общество открытого типа "Полимерсинтез" | Пористая фторуглеродная мембрана, способ ее получения и патронный фильтр на ее основе |
FR2741280B1 (fr) | 1995-11-22 | 1997-12-19 | Omnium Traitement Valorisa | Procede de nettoyage d'une installation de filtration du type a membranes immergees |
US6136911A (en) * | 1996-01-11 | 2000-10-24 | E.I. Du Pont De Nemours And Company | Fibers flash-spun from partially fluorinated polymers |
US6074718A (en) | 1996-02-06 | 2000-06-13 | Koch Membrane Systems, Inc. | Self supporting hollow fiber membrane and method of construction |
US6077435A (en) | 1996-03-15 | 2000-06-20 | Usf Filtration And Separations Group Inc. | Filtration monitoring and control system |
EP0814116A1 (de) | 1996-06-19 | 1997-12-29 | Hüls Aktiengesellschaft | Hydrophile Beschichtung von Oberflächen polymerer Substrate |
US6318555B1 (en) | 1996-06-27 | 2001-11-20 | Kimberly-Clark Worldwide, Inc. | Flexible packaging bag with visual display feature |
US5958243A (en) | 1996-07-11 | 1999-09-28 | Zenon Environmental Inc. | Apparatus and method for membrane filtration with enhanced net flux |
US5981614A (en) * | 1996-09-13 | 1999-11-09 | Adiletta; Joseph G. | Hydrophobic-oleophobic fluoropolymer compositions |
USD390726S (en) * | 1996-10-15 | 1998-02-17 | Arvans Robert S | Plate carrier |
JP3686918B2 (ja) | 1996-10-16 | 2005-08-24 | 森村興産株式会社 | 汚水、廃水等の固液分離用濾過装置 |
USD396046S (en) | 1996-10-24 | 1998-07-14 | Allen Scheel | Steer device for an outboard motor |
WO1999067013A1 (fr) | 1996-12-10 | 1999-12-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Film poreux d'une resine de fluorure de polyvinylidene et son procede de production |
AUPO412596A0 (en) | 1996-12-10 | 1997-01-09 | Memtec America Corporation | Improved microporous membrane filtration assembly |
US6045899A (en) | 1996-12-12 | 2000-04-04 | Usf Filtration & Separations Group, Inc. | Highly assymetric, hydrophilic, microfiltration membranes having large pore diameters |
CA2639642C (en) | 1996-12-20 | 2013-01-15 | Siemens Water Technologies Corp. | Scouring method |
US6146747A (en) | 1997-01-22 | 2000-11-14 | Usf Filtration And Separations Group Inc. | Highly porous polyvinylidene difluoride membranes |
USD396726S (en) | 1997-02-06 | 1998-08-04 | Abc Group | Combined air intake manifold and filter |
US6048454A (en) | 1997-03-18 | 2000-04-11 | Jenkins; Dan | Oil filter pack and assembly |
AUPO709797A0 (en) | 1997-05-30 | 1997-06-26 | Usf Filtration And Separations Group Inc. | Predicting logarithmic reduction values |
US5914039A (en) | 1997-07-01 | 1999-06-22 | Zenon Environmental Inc. | Filtration membrane with calcined α-alumina particles therein |
US6354444B1 (en) | 1997-07-01 | 2002-03-12 | Zenon Environmental Inc. | Hollow fiber membrane and braided tubular support therefor |
US6641733B2 (en) | 1998-09-25 | 2003-11-04 | U. S. Filter Wastewater Group, Inc. | Apparatus and method for cleaning membrane filtration modules |
US6083393A (en) | 1997-10-27 | 2000-07-04 | Pall Corporation | Hydrophilic membrane |
US6039872A (en) | 1997-10-27 | 2000-03-21 | Pall Corporation | Hydrophilic membrane |
US6723758B2 (en) | 1997-11-12 | 2004-04-20 | Ballard Power Systems Inc. | Graft polymeric membranes and ion-exchange membranes formed therefrom |
USD400890S (en) | 1997-12-03 | 1998-11-10 | Gambardella C Bruce | Automotive manifold |
JP3866399B2 (ja) | 1997-12-16 | 2007-01-10 | 住友重機械工業株式会社 | 膜ろ過装置及びその運転方法 |
US6838400B1 (en) | 1998-03-23 | 2005-01-04 | International Business Machines Corporation | UV absorbing glass cloth and use thereof |
DE29906389U1 (de) | 1998-04-30 | 1999-06-17 | Cramer Weberei Heek Nienborg G | Mehrschichtiger textiler Baustoff |
US6280626B1 (en) | 1998-08-12 | 2001-08-28 | Mitsubishi Rayon Co., Ltd. | Membrane separator assembly and method of cleaning the assembly utilizing gas diffuser underneath the assembly |
US6096213A (en) | 1998-08-14 | 2000-08-01 | 3M Innovative Properties Company | Puncture-resistant polyolefin membranes |
TWI222895B (en) | 1998-09-25 | 2004-11-01 | Usf Filtration & Separations | Apparatus and method for cleaning membrane filtration modules |
BR9914376A (pt) | 1998-10-09 | 2001-08-07 | Zenon Environmental Inc | Sistema de aeração cìclica para módulos de membrana submersos |
US6550747B2 (en) | 1998-10-09 | 2003-04-22 | Zenon Environmental Inc. | Cyclic aeration system for submerged membrane modules |
WO2000026334A1 (en) | 1998-10-30 | 2000-05-11 | Metrex Research Corporation | Simultaneous cleaning and decontaminating compositions and methods |
CA2290053C (en) | 1999-11-18 | 2009-10-20 | Zenon Environmental Inc. | Immersed membrane module and process |
WO2000030742A1 (en) | 1998-11-23 | 2000-06-02 | Zenon Environmental Inc. | Water filtration using immersed membranes |
JP4107453B2 (ja) | 1998-11-26 | 2008-06-25 | 旭化成ケミカルズ株式会社 | 中空糸膜カートリッジ |
US6156200A (en) | 1998-12-08 | 2000-12-05 | Usf Filtration & Separations Group, Inc. | Gas-scrubbed hollow fiber membrane module |
DE19959916A1 (de) * | 1998-12-30 | 2000-07-20 | Henkel Chile Sa | Füllstoffhaltige Polymerdispersion, Verfahren zu deren Herstellung und deren Verwendung |
AU1689800A (en) | 1999-01-21 | 2000-08-07 | Ebara Corporation | Ethylene-vinyl alcohol hollow fiber membranes |
US6113794A (en) | 1999-01-25 | 2000-09-05 | Kumar; Ashwani | Composite solvent resistant nanofiltration membranes |
JP2000254459A (ja) | 1999-03-05 | 2000-09-19 | Sumitomo Heavy Ind Ltd | 固液分離エレメントの洗浄方法及び固液分離装置 |
US6770202B1 (en) * | 1999-04-14 | 2004-08-03 | Pall Corporation | Porous membrane |
US6322703B1 (en) | 1999-04-20 | 2001-11-27 | Asahi Kasei Kabushiki Kaisha | Method for purifying aqueous suspension |
AUPP985099A0 (en) | 1999-04-20 | 1999-05-13 | Usf Filtration And Separations Group Inc. | Membrane filtration manifold system |
US6221247B1 (en) | 1999-06-03 | 2001-04-24 | Cms Technology Holdings, Inc. | Dioxole coated membrane module for ultrafiltration or microfiltration of aqueous suspensions |
JP2000342932A (ja) | 1999-06-04 | 2000-12-12 | Mitsubishi Rayon Co Ltd | 分離膜のポッティング方法 |
US6277512B1 (en) | 1999-06-18 | 2001-08-21 | 3M Innovative Properties Company | Polymer electrolyte membranes from mixed dispersions |
US6214231B1 (en) | 1999-08-27 | 2001-04-10 | Zenon Environmental Inc. | System for operation of multiple membrane filtration assemblies |
US6761013B2 (en) | 1999-11-08 | 2004-07-13 | Kimberly-Clark Worldwide, Inc. | Packaging article and method |
US6423784B1 (en) | 1999-12-15 | 2002-07-23 | 3M Innovative Properties Company | Acid functional fluoropolymer membranes and method of manufacture |
WO2001047935A2 (en) | 1999-12-22 | 2001-07-05 | Metabasis Therapeutics, Inc. | Novel bisamidate phosphonate prodrugs |
US6830782B2 (en) | 1999-12-28 | 2004-12-14 | Hitoshi Kanazawa | Hydrophilic polymer treatment of an activated polymeric material and use thereof |
US6635179B1 (en) | 1999-12-30 | 2003-10-21 | Nephros, Inc. | Sterile fluid filtration cartridge and method for using same |
US6315895B1 (en) | 1999-12-30 | 2001-11-13 | Nephros, Inc. | Dual-stage hemodiafiltration cartridge |
USD478913S1 (en) | 2000-02-24 | 2003-08-26 | Usf Filtration And Separations Group, Inc. | Manifold header |
US6440303B2 (en) | 2000-03-02 | 2002-08-27 | Chapin Manufacturing, Inc. | Fluid filter |
WO2001066474A2 (en) | 2000-03-08 | 2001-09-13 | Zenon Environmental Inc. | Membrane module for gas transfer and membrane supported biofilm process |
AUPQ680100A0 (en) | 2000-04-10 | 2000-05-11 | Usf Filtration And Separations Group Inc. | Hollow fibre restraining system |
US6337018B1 (en) | 2000-04-17 | 2002-01-08 | The Dow Chemical Company | Composite membrane and method for making the same |
AU142387S (en) | 2000-05-31 | 2000-11-27 | Evoqua Water Tech Llc | Manifold header cap |
EP1166871A1 (en) | 2000-06-21 | 2002-01-02 | Fuji Photo Film B.V. | Photocalytic sheet of film and its manufacturing process |
JP2002034126A (ja) | 2000-07-19 | 2002-01-31 | Yazaki Corp | 配線ユニット |
AUPR064800A0 (en) | 2000-10-09 | 2000-11-02 | Usf Filtration And Separations Group Inc. | Improved membrane filtration system |
AUPR094600A0 (en) | 2000-10-23 | 2000-11-16 | Usf Filtration And Separations Group Inc. | Fibre membrane arrangement |
AU2002214877A1 (en) | 2000-11-13 | 2002-05-21 | Mcmaster University | Gas separation device |
AUPR143400A0 (en) | 2000-11-13 | 2000-12-07 | Usf Filtration And Separations Group Inc. | Modified membranes |
US6705465B2 (en) | 2000-11-15 | 2004-03-16 | Kimberly-Clark Worldwide, Inc. | Package for feminine care articles |
US20020078665A1 (en) | 2000-12-21 | 2002-06-27 | Salman Nabil Enrique | Portable packaging device and method for forming individually packaged articles |
ITMI20010421A1 (it) | 2001-03-01 | 2002-09-02 | Ausimont Spa | Membrane porose semipermeabili di fluoropolimeri semicristallini |
AUPR421501A0 (en) | 2001-04-04 | 2001-05-03 | U.S. Filter Wastewater Group, Inc. | Potting method |
DE60236696D1 (de) | 2001-04-27 | 2010-07-22 | Millipore Corp | Neue beschichtete Membranen und andere Artikel |
US20040085300A1 (en) | 2001-05-02 | 2004-05-06 | Alec Matusis | Device and method for selecting functions based on intrinsic finger features |
US6595167B2 (en) | 2001-05-22 | 2003-07-22 | Mtd Products Inc | Internal combustion engine and method of making the same |
AUPR584301A0 (en) | 2001-06-20 | 2001-07-12 | U.S. Filter Wastewater Group, Inc. | Membrane polymer compositions |
AUPR692401A0 (en) | 2001-08-09 | 2001-08-30 | U.S. Filter Wastewater Group, Inc. | Method of cleaning membrane modules |
US6721529B2 (en) | 2001-09-21 | 2004-04-13 | Nexpress Solutions Llc | Release agent donor member having fluorocarbon thermoplastic random copolymer overcoat |
JP4426163B2 (ja) | 2001-10-02 | 2010-03-03 | ユニ・チャーム株式会社 | 吸収性物品の個別包装体およびその製造方法 |
US6790912B2 (en) | 2001-12-11 | 2004-09-14 | 3M Innovative Properties Company | Extrudable fluoropolymer blends |
US6890435B2 (en) | 2002-01-28 | 2005-05-10 | Koch Membrane Systems | Hollow fiber microfiltration membranes and a method of making these membranes |
US7247238B2 (en) | 2002-02-12 | 2007-07-24 | Siemens Water Technologies Corp. | Poly(ethylene chlorotrifluoroethylene) membranes |
CN1642628B (zh) * | 2002-03-19 | 2010-06-16 | 安格斯公司 | 中空纤维膜接触装置及方法 |
US6811696B2 (en) | 2002-04-12 | 2004-11-02 | Pall Corporation | Hydrophobic membrane materials for filter venting applications |
US6851259B2 (en) | 2002-06-12 | 2005-02-08 | The Aerospace Corporation | Inflatable ablation gas cell structure system |
US6994867B1 (en) | 2002-06-21 | 2006-02-07 | Advanced Cardiovascular Systems, Inc. | Biocompatible carrier containing L-arginine |
DE10228148B4 (de) | 2002-06-24 | 2006-08-24 | Saehan Industries Inc. | Selektive Membran mit hoher Fouling-Beständigkeit |
US6828386B2 (en) * | 2002-09-20 | 2004-12-07 | Ballard Power Systems Inc. | Process for preparing graft copolymers and membranes formed therefrom |
US7459085B2 (en) | 2002-10-18 | 2008-12-02 | Asahi Kasei Medical Co., Ltd. | Microporous hydrophilic membrane |
US20040092901A1 (en) | 2002-11-11 | 2004-05-13 | Ronald Wayne Reece | Diaper changing kit |
FR2850297B1 (fr) | 2003-01-29 | 2005-04-15 | Aquasource | Procede de fabrication de membranes pour modules de filtration, notamment pour le traitement des eaux |
JP2004230280A (ja) | 2003-01-30 | 2004-08-19 | Toray Ind Inc | 親水性ポリフッ化ビニリデン系樹脂多孔質膜の製造方法 |
US20040167489A1 (en) | 2003-02-14 | 2004-08-26 | Kellenberger Stanley R. | Compact absorbent article |
US20040159584A1 (en) | 2003-02-18 | 2004-08-19 | Ke Liu | Mini-CPO providing hydrogen for hydrogen desulfurization of hydrocarbon feeds |
US20040167493A1 (en) | 2003-02-21 | 2004-08-26 | Sca Hygiene Products Ab | Arrangement and method for applying elastic element to a material web |
ATE302243T1 (de) | 2003-02-28 | 2005-09-15 | 3M Innovative Properties Co | Fluoropolymerdispersion enthaltend kein oder wenig fluorhaltiges netzmittel mit niedrigem molekulargewicht |
US20050131368A2 (en) | 2003-03-04 | 2005-06-16 | Diaperoos, Llc | Vacuum-packed diaper |
JP4885539B2 (ja) | 2003-03-13 | 2012-02-29 | 株式会社クレハ | フッ化ビニリデン系樹脂多孔膜およびその製造方法 |
US7067058B2 (en) | 2003-04-01 | 2006-06-27 | 3M Innovative Properties Company | Hydrophilic membrane and process for making the same |
AU2003903507A0 (en) | 2003-07-08 | 2003-07-24 | U. S. Filter Wastewater Group, Inc. | Membrane post-treatment |
US20050015052A1 (en) | 2003-07-17 | 2005-01-20 | Michelle Klippen | Compression packed absorbent article |
US20050063895A1 (en) | 2003-09-23 | 2005-03-24 | Martin Perry L. | Production of potassium monopersulfate triple salt using oleum |
US20050142280A1 (en) * | 2003-10-20 | 2005-06-30 | Kim Kwon I. | System and method for synthesizing a polymer membrane |
EP1533325B1 (en) | 2003-11-17 | 2011-10-19 | 3M Innovative Properties Company | Aqueous dispersions of polytetrafluoroethylene having a low amount of fluorinated surfactant |
KR100562050B1 (ko) | 2004-03-30 | 2006-03-17 | 한국화학연구원 | 가교된 폴리비닐알콜계 신규 고분자막 및 이의 제조방법 |
WO2006002479A1 (en) | 2004-07-05 | 2006-01-12 | U.S. Filter Wastewater Group, Inc. | Hydrophilic membranes |
EP1804961B1 (en) | 2004-10-13 | 2016-06-08 | 3M Innovative Properties Company | Method for preparing hydrophilic polyethersulfone membrane |
-
2005
- 2005-06-30 JP JP2007518410A patent/JP2008504122A/ja active Pending
- 2005-06-30 CN CN200580024780.2A patent/CN1988949B/zh not_active Expired - Fee Related
- 2005-06-30 EP EP05756970A patent/EP1773476A4/en not_active Withdrawn
- 2005-06-30 CA CA002571498A patent/CA2571498A1/en not_active Abandoned
- 2005-06-30 CN CN2011104197655A patent/CN102512986A/zh active Pending
- 2005-06-30 US US11/571,100 patent/US7819956B2/en active Active
- 2005-06-30 WO PCT/AU2005/000961 patent/WO2006002469A1/en active Application Filing
- 2005-07-01 MY MYPI20053017A patent/MY149930A/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003068374A1 (en) * | 2002-02-12 | 2003-08-21 | Us Filter Wastewater Group, Inc. | Halar membranes |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111068463A (zh) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | 一种有机废气的处理方法 |
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CN1988949B (zh) | 2012-08-22 |
US20070157812A1 (en) | 2007-07-12 |
EP1773476A1 (en) | 2007-04-18 |
CA2571498A1 (en) | 2006-01-12 |
JP2008504122A (ja) | 2008-02-14 |
MY149930A (en) | 2013-10-31 |
US7819956B2 (en) | 2010-10-26 |
EP1773476A4 (en) | 2007-07-25 |
WO2006002469A1 (en) | 2006-01-12 |
CN1988949A (zh) | 2007-06-27 |
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