CN101883624B - 中空纤维膜 - Google Patents
中空纤维膜 Download PDFInfo
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- CN101883624B CN101883624B CN200880118554.4A CN200880118554A CN101883624B CN 101883624 B CN101883624 B CN 101883624B CN 200880118554 A CN200880118554 A CN 200880118554A CN 101883624 B CN101883624 B CN 101883624B
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
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- BTZJQYVYGCCNHY-UHFFFAOYSA-N calcium;urea Chemical compound [Ca].NC(N)=O BTZJQYVYGCCNHY-UHFFFAOYSA-N 0.000 description 1
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- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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- B01D69/088—Co-extrusion; Co-spinning
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/10—Cellulose; Modified cellulose
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及复合中空纤维毛细管膜,特别用于采用透析液值及其生产方法以及其特别在血液和腹膜透析中的用途。
Description
本发明涉及中空纤维毛细管膜及其生产方法,以及其采用透析液值,尤其对于血和腹膜透析的应用。
已知的是,不同组成的毛细管膜,尤其由于其在透渗析方面日益增加的用途。膜,特别是毛细血管膜在渗透析中的用途和生产,由Samtleben和Lysaght,在等人出版的:Replacement of Renal Function by Dialysis,第五版,Kluwer 2004从第709至724页中举例描述过。
生产中空纤维膜的技术在M.Mulder的Basic Principles of Membrane Technology,第二版,kluwer 1996,71-91页中被举例公开过。典型的方法包括所谓的相转化法(见下文),熔体纺丝方法或者″干-湿纺丝法″(例子参见Hao et al.J,Appl.Polym.Science 62,129-133(1996)).
所谓的中空纤维喷丝头经常被用于毛细管膜的生产,尤其是利用相转化法。当利用中空纤维喷丝头生产一个中空纤维膜时,中空纤维膜是以所谓的沉淀纺丝法方法生产的,其中将被沉淀的高分子从排列的喷丝头的环形缝隙中形成,而相应脱溶物涌入中央的脱溶物钻孔。中空纤维喷丝头的命名类型在DE 10211051A1被举例公开。
由若干具有不同功能的层构成的复合中空纤维膜已经从现有技术公知:
WO 00/78437公开了一种支撑的中空纤维薄膜,其中载体中空纤维膜中支撑层由编织的高分子纤维组成,当用于微量过滤或者超细过滤时,其赋予整体纤维提高的寿命和抗摩擦和张紧性。锻烧过的α氧化铝颗粒分散在其中的高分子膜应用于这些支撑结构。
US 2007/0213665公开了一种含有在肾透渗析时再生透析液的药筒的便携肾状物。在药筒中排列有具有涂层的膜,其由没有更详细描述的在醋酸纤维上的聚砜层组成。
EP 418 432 A1公开了一种支撑的亲水复合膜,其中铜-铵再生纤维素沉淀在例如聚丙烯,聚偏氟乙烯等等的支撑层上。支撑的亲水的复合膜,其中铜-铵再生纤维素置于支撑层上,例如聚丙烯,聚偏氟乙烯等等。铜-铵再生纤维素在其自然状态下是非化学衍生纤维素。该中空纤维膜被涂层,不在其内表面,而是在其外表面。
US 4,276,172公开了使用铜纤维素用于血液透析的无涂层的纤维素膜,它包括至少一层含二烷基铵纤维素。这里出现的问题涉及层之间的结合强度。这里所述的膜的孔隙是如此之大,以致于它是相对于低分子量的有机化合物或者尿素阳离子没有特定性。这样膜的内层内壁厚度是中空纤维膜整体壁厚的10-50%。
EP 286 091 B1公开了聚砜中空纤维膜,其用乙基纤维素溶液涂层,在工业生产过程中用于液体分离。
EP 359 834 B1同样地描述了聚砜类和醋酸纤维层的多层中空纤维膜,其中醋酸纤维通过溶液沉淀施加在已经准备好的(预先形成)的聚砜类中空纤维膜上,用于工业生产过程。
US 5,156,740进一步公开了复合膜,其由无孔的交联的聚乙烯醇的分离层和聚砜支撑层组成,用于渗透蒸发加工。
在医学处理,例如腹膜和血液透析中,装载有***毒素的透析液,为了最小化高纯度透析液溶液的消耗量,例如提供给便携透析***,例如可以使用吸附材料再生。它同样正常地用于被丢弃的透析液。
人每天新陈代谢产生的大约20到30g的尿素的大部分量通过使用吸附材料消耗。代表性地或者在水相中采用阳离子交换剂或者——如上所述在现有技术中——具有选择性尿素渗透性的中空纤维膜,当其利用透析液值(US 2007/0213665A1)时在便携的透析***中尤其方便。然而,采用上述-命名***,对于单价和二价阳离子令人不满意的尿素选择性,导致在跟随膜布置的吸附材料上的竞争反应。这种减少吸附能力和反之需要大量吸附材料,迫使较高的吸附材料重量,其虽然是不符合要求的,仍是必须的。
先前已知的通过涂层生产的复合膜还有其生产上的缺点,即尤其它们的结构只能通过复杂的和昂贵的工序得到。
此外,现有技术已知的中空纤维膜,不能得到选择性层的如此薄的层厚度,特别是对于尿素的选择性层。因而限制了它们的选择性,即期望物质分离的最大化和非期望的透过选择性层混合物的最小化。特别是迄今已知的用于分离尿素的复合中空纤维膜,尿素的扩散途程太长了,结果是分离不彻底和延长。
因此,目标是获得可用的多分层的(复合的)中空纤维毛细管膜,其对尿素带电混合物选择性分离尤其有利,例如从溶液中分离阳离子。特别是该膜相对单价或者二价金属阳离子对尿素选择性分离,即对于人有机体尤其必需的碱和碱土的阳离子。为了被分离的物质的扩散途程最小化,该膜将尤其具有选择层的小的层厚并且因而提高了物质的分离效率,特别例如尿素。
通过包括共压物(coextrudate),包括支撑层和选择层的支撑复合中空纤维膜实现本发明的目标。选择层布置在或者网眼-侧或者在外表面上。
术语“共压物(coextrudate)”含义是指支撑层和选择层通过本领域技术人员已知的共挤出法同时生产,两个层形成固态结合(复合物)。
包括支撑层和选择层的共压物允许支撑和选择层在单一工序中同时生产,导致在支撑层和选择层之间用机械方法固态结合。
术语“选择层”含义是指该层对于来自物质(液体)混合物至少一个选择的物质可以选择性地渗透,并且对于该物质混合物的其它物质不能渗透。
此外共压物的使用使得形成800nm以下的超薄层成为可能。分离效率因此提高。根据本发明的薄层意味着被分离的混合物的扩散途程可以被最小化,选择层的壁厚优选是中空纤维膜整体壁强度的2-5%。
在本发明的优选实施方式中,选择层是尿素-选择性,即仅对尿素可渗透,尤其相对例如Na+、K+、Ca2+、Mg2+等碱和碱土金属阳离子不能通过该层,结果是根据本发明的中空纤维膜可以特别优选用于血和腹膜透析的透析液再生。可以理解的是,低于或者在检测极限下,这些阳离子的极少数还可以扩散通过。
因为高的尿素膜选择性需要更少的吸附器数量,当使用根据本发明的膜时,还获得了在便携透析装置中的重要的重量优势,例如微量过滤***中。
根据本发明的层厚,尤其是尿素—选择性—选择层,在100nm至5nm之间,优选在200至800nm之间,更优选在300至600nm之间,层厚度特别优选大约500nm,结果是尿素或者其它的不带电的混合物的扩散途程,可以最小化,由于尿素传送速率因此最优化。
选择层的壁厚基于两个相对的条件。更大的选择性层的厚度导致高选择性。然而,扩散途程随着选择性层的厚度也同时变长,结果是分离过程减慢并变成更低效。根据本发明,最佳的层厚度在于上述-定义的范围,结果是选择性和扩散都没有被过强地限制。
在本发明相当特别优选的改进中,选定层包括酯化的纤维素,尤其特别优选是醋酸纤维素。典型地,通过在乙酸或者二氯甲烷中使用强酸的纤维素与乙酸酐的间歇法工业生产的纤维素酯被称作醋酸纤维素。作为典型的结果,快速产生了彻底的乙酰化物产品(三乙酸酯分别包含44.8和62.5%乙酰基和结合的乙酸)。也可以采用带有其它酰基的酯,例如丙酰基或者丁酰基酯。类似地,在优选的实施方式中,混合酯可以采用不同的酰基,例如乙酰基、丙酰基、丁酰基、较长的-碳链或者分支的酰基。例如可能提及的乙酰基-丁酰基纤维素酯或者丙酰基丁酰基纤维素酯。
与乙酰化同时发生纤维素主链的酸-催化解聚,结果是一般使用的纤维素仅仅有大约100至350的聚合度。
在本发明范围内,优选的乙酰基纤维素或者混合的酯化纤维素具有从0.5至3的酰化或者酯化度,十分优选从2至3。相应例如三乙酸纤维素的酰化3度,相应例如纤维素二醋酸酯酰化2度。酰化的平均度表明多少酰基被结合到每个重复单元上,其平均释放纤维素OH基团。上至理论上可能的最大值的酰化或者酯化度的高度数,优选酰化度数是3,人们发现尤其是尿素-选择性层的选择性随着酰化或者酯化度而提高。人们发现取代达到例如三乙酸纤维素的更高度,进一步提高酰基纤维素层对于尿素的选择性。同样也适用于相应的上述的混合酯。
选择层,优选醋酸纤维素层或者混合的酯纤维素层,一般具有每天每平米从10至80g的尿素渗透性,尤其优选在每天每平米11至60g。钠渗透性,即对于单价电荷阳离子的渗透性,在每天每平米0至112mmol之间。根据本发明采用的选择层在通常的测量精度的范围内对于二价阳离子是不渗透的,例如Ca2+、Mg2+等。选择层典型地是致密、无气孔的层。在此上下文中,无气孔的含义是指选择层相对高分子量物质由于其体积而具有排除界限。优选地,排除界限在最小可能的体积下就有效,结果是仅仅单分子的物质由于它们的尺寸而能够渗透选择层。
在此业已发现,氯化钠渗透性或者通常对于一价阳离子的渗透性随着酰化或者酯化度的改变而改变。例如,因为酯化度提高,观察到钠存留也随着改进。
根据发明选择层的超薄层是机械性不稳定的,结果是支撑层是必需的。这和其作为共压物的存在,导致根据本发明的复合中空纤维层和现有技术已知的复合膜相比具有提高的机械强度。
支撑层的材料优选自聚乙烯吡咯烷酮(PVP)、聚醚砜(PES)、聚醚酰亚胺(PEI)、聚酰胺(PA)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)、聚偏氟乙烯(PVDF)、聚丙烯腈(PAN)、聚酰亚胺(PI)、聚砜类(PSU)和/或聚氨酯(PU)及其混合物。例如,在本发明优选的实施方式中,聚乙烯吡咯烷酮经常作为亲水成分包含在支撑层中。
当选择支撑层的材料时,重要的是支撑层有足够地强渗透性和亲水性,结果是沿着同等长的输送路径通过支撑层时,由通过的混合物例如尿素引起没有,或者仅仅小的扩散阻力。
根据本发明,优选的支撑层材料是,聚砜、聚乙烯吡咯烷酮及其混合物,因为生产例如聚砜膜的条件十分好检验并且可以通过已知的加工参数有选择地设置不同水平的渗透性。聚砜因此相当尤其优选,选择性地添加聚乙烯吡咯烷酮,由于其好的热力学的兼容性,可以例如与聚氨酯共铸形成纤维束(模)用于微量过滤***。
支撑层的厚度典型地在20至50μm之间,优选在30至40μm之间,其如前所述,可以用聚砜很好地达到。
根据本发明的典型的中空纤维毛细管膜的内径值在20μm至1mm之间,并且该中空纤维毛细管膜的总壁厚从20至100μm。
本发明的目标还通过根据本发明的生产中空纤维膜的方法获得,包括步骤:
a)提供两个纺丝浆状溶液A和B,其中纺丝浆状溶液A是酯化纤维素的溶液,纺丝浆状溶液B溶液选自由聚乙烯吡咯烷酮(PVP)、聚醚砜(PES)、聚醚酰亚胺(PEI)、聚酰胺(PA)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)、聚偏氟乙烯(PVDF)、聚丙烯腈(PAN)、聚酰亚胺(PI)、聚砜类(PSU)和/或聚氨酯(PU)及其混合物组成的组的高分子;
b)设置沉淀槽温度在40至95℃;
c)将纺丝浆状溶液A和B经中空纤维喷丝头与内部的沉淀剂接触;和
d)凝结和沉淀由溶入纺丝浆状溶液A和B的物质组成的压出物。
通过采用根据本发明的纺丝过程,共压物的厚度或者形成共压物的两层的厚度可以特别地选择,结果是得到了选择层的高的尿素渗透性和更进一步好的阻止单价或者二价阳离子,并且同时支撑层可以被形成如此之薄,以致于因为在过滤时尿素通过,没有,或者仅仅形成少量的扩散阻力。
这可以特别通过先前命名的纺丝方法的相转化法很好地完成。如已经所述,支撑层的材料由聚砜,聚乙烯吡咯烷酮,或者其混合物组成。十分特别优选的支撑层材料由聚砜组成。
在该方法优选的实施方式中,包含醋酸纤维的纺丝溶液A的粘性是10,000至大约17,000mPas(通过Haake旋转测微器(VTSSO)和量-杯***(MV-ST)测定)。粘性通常来自含量25至40重量%的醋酸纤维例如二甲基乙酰胺中。
含有聚合物作为支撑层的纺丝浆状溶液B的粘度通常位于7,000至13,000mPas之间。
从200至400mm/s的纺丝速度所用的水,根据本发明的方法优选作为内部沉淀剂。
术语″内部的沉淀剂″表示网眼-侧沉淀剂。根据本发明使用了水并且水本身也作为沉淀槽中的沉淀剂。水作为所谓的″硬的″沉淀剂,其导致膜在内侧相对单价或者二价阳离子例如钠、钾、镁或者钙具有增强的不渗透性。通过使用拦网和水表面之间的气隙以及非常缓慢的水分转移通过例如醋酸纤维内层,所谓的″较软的″沉淀发生在该外层,结果是孔隙在外表面形成。沉淀通产包括与水从外及内通过-沉淀,其中孔隙梯度来自从内部(一般地没有微孔)到外部(大微孔)。
没有气隙和沉淀,例如在包括沉淀槽的溶剂中,中空纤维将通过从内及外同时沉淀被得到,结果是大的孔隙将在纤维的中心形成,根据本发明的中空纤维膜的现有目的这是不符合要求的。
纺丝阻块温度设定优选在5至90℃之间,并且沉淀熔体温度在40至95℃的范围内,优选大约40℃,作为共压物由此获得,其具有对于单价和二价阳离子的提高的滞留能力的选择层,并且仍有非常高的尿素渗透性。优选阻块温度位于5至40℃之间的范围内。
本发明还涉及可以根据本发明的方法得到的中空纤维膜以及包括许多根据本发明的中空纤维膜的例如在DE 10 2004 020 226 A1中十分普遍地描述的膜过滤器。
根据本发明的特别优选的膜过滤器用于在纳米和超滤中的分离过程,十分特别优选在透析步骤,例如在血和腹膜透析,尤其用于再生的透析液。
令人惊讶地发现,根据本发明的薄膜对于糖分子,例如葡萄糖还有良好的渗透性。因此根据本发明的薄膜能被优选使用于从反应混合物中,例如在生物乙醇的生产中分离葡萄糖。
本发明采用下述附图和实施例做了更详细的解释。
这里显示了:
图1为根据本发明由共压物组成的双层复合纤维的冷冻切片的REM照片;
图2为图1中冷冻切片的放大的REM照片。
具体实施例
实施例1:
根据本发明,按照所谓的相转化法方法生产的中空纤维。首先,生产两个纺丝浆状溶液A和B。第一纺丝浆状溶液A包括中空纤维膜的网眼-侧选择层的材料和第二纺丝浆状溶液B支撑层材料。
支撑层(外层)的纺丝浆状溶液由20重量%udel 3500聚砜和5重量%聚乙烯吡咯烷酮k90以及1重量%溶入二甲基乙酰胺的水组成。溶液的粘性是大约11,500mPas。
用于网眼-侧选择层的纺丝物质由30重量%、29kD分子量的纤维素二醋酸酯和乙酰含量40%(购自Sigma/Aldrich)组成。在二甲基乙酰胺中通过伴随的搅拌溶解。该溶液的粘性大约15,000mPas。
两个纺丝浆状溶液通过,例如,从现有技术已知的复合空心纤维喷丝头以合适的体积比纺丝。两个溶液通过彼此同心的拉丝模孔引导,其允许内部的和外部的纺丝物质共挤出。两个同心拉丝模孔环绕轴向通道,沉淀剂通过通道引导进入,其作用是凝结两个纺丝物质层。水用作内部的沉淀剂。
模块(纺丝阻块)的温度是20℃,然而可以在根据本发明的方法的范围内更进一步变化。
令人惊讶地发现,在低温(<30℃)纺出的纤维具有较高的尿素选择性相对阳离子例如钠、钾,即一价阳离子。
在离开纺丝阻块之后,中空纤维在浸入温度大约42℃的充满水的沉淀槽之前,通过大约250mm的气隙。然后,由此得到复合中空纤维在温度控制在75℃的洗涤槽中清洗。该纤维的进料速率是250mm/s。
由此得到的中空纤维随后再经大约95℃干燥。
设置得沉淀槽和洗涤槽的体积以及进料速率,以便获得合格的无溶剂的中空纤维。
干燥的纤维随后进行缠绕。由2300根纤维组成的一束中空纤维,具有总表面面积0.4m2。内部的纤维直径是200μm。外部的纤维直径是261μm。
选择层的厚度大约为500nm。
纤维被浇铸成模具和铸件与聚氨酯成为模块,因此确保纤维网眼的流入物和纤维外部是无关的。
所属技术领域的专业人员普遍熟知这样的模块对血液透析。
图1显示REM图像放大250倍,图2显示从图1中所得的截面放大20,000倍。
通过″冷冻切片″的含义是指根据本发明的中空纤维膜沉浸在液氮中,然后人工地将其横向断开。
如右边所示,可以明显地从图2中看出聚砜支撑层的多孔结构,以及左边显示的薄的纤维素二醋酸酯选择层的几乎无孔结构。
实施例2:
测量根据本发明的薄膜的基本的物理参数。
在实施例1中得到的中空纤维膜的超滤率以及其对于尿素和不同盐类的渗透性被随后检验。
为了测定含水的超滤,过度压力在37℃的温度下作用于网眼侧,并且测量了从中空纤维的网眼侧溢出到中空纤维外侧的水量。
根据本发明从实施例1中实测超滤率处于0.1至0.3[ml/h torr m2]的范围内。
为了测定尿素和盐的渗透性,使用了500-700ml的包括盐溶液的尿素,其包含25mM尿素、141mM氯化钠,2.5mM氯化钙,249mM葡萄糖,并且其通过中空纤维的网眼侧以50ml/min再循环。
在中空纤维网眼侧的溶液位于压力-密封的容器中,结果是测试溶液的体积在实验期间不能变化。
在薄膜外侧,538mM葡萄糖溶液以50ml/min的流速回流泵入。
在室温下两个小时之后,从网眼侧循环溶液中除掉样品,并且用商业分析装置(Cobas Integra 400,Roche)检查。
该薄膜的渗透性和选择性可以由检验的起始溶液的浓度计算出来。
以下结果是在分离上述命名的包含溶液的尿素时,由来自实施例1的薄膜得到的:
表1:根据本发明实施例1的该薄膜的渗透性和选择性
纳 | 尿素 | 钙 | |
起始数值[mM] | 158 | 25 | 2.8 |
2小时之后数值[mM] | 157 | 15 | 3.0 |
测量的变化系数对钠是1%,对钙是3.5%和对尿素是1.8%。
如可以从测量值看到的,尿素通过根据本发明的中空纤维膜被很好的分离,而钠和钙被大量地保留。
实施例3:
为了更进一步的表征薄膜,用纯气体进行渗透试验。为此,中空纤维在网眼侧给予大约1bar的气体过度压力,并且测量经过薄膜的产物气流。以下列表显示典型的结果。
表2:气体在室温下流过根据本发明的薄膜,并且薄膜上经过1bar压力梯度气流。
氮气 | 二氧化碳 | |
气体流量[ml/h torr m2] | 0.1 | 15 |
这些结果表明,根据本发明的薄膜仅有很少的孔隙,由于对通常的薄膜来说一般的通过-流量是几升。
Claims (6)
1.用于制备中空纤维膜的方法,所述中空纤维膜包括支撑层和选择层的共压物,所述方法包括:
a)提供两个纺丝浆状溶液A和B,其中,纺丝浆状溶液A是酯化纤维素的溶液,纺丝浆状溶液B溶液选自由聚乙烯吡咯烷酮(PVP)、聚醚砜(PES)、聚醚酰亚胺(PEI)、聚酰胺(PA)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)、聚偏氟乙烯(PVDF)、聚丙烯腈(PAN)、聚酰亚胺(PI)、聚砜(PSU)和/或聚氨酯(PU)及其混合物组成的组的高分子;
b)设置沉淀槽温度在40至95℃,
c)将纺丝浆状溶液A和B经纺丝速度为200-400mm/s的空心纤维喷丝头与作为内部沉淀剂的水接触;和
d)凝结和沉淀由溶入纺丝浆状溶液A和B的物质组成的压出物。
2.根据权利要求1所述的方法,其中,纺丝浆状溶液A的粘度位于10,000至17,000mPas的范围内。
3.根据权利要求2所述的方法,其中,纺丝浆状溶液A在二甲基乙酰胺中含有25至40重量%纤维素二醋酸酯。
4.根据权利要求1所述的方法,其中,纺丝浆状溶液A的粘度位于7,000至13,000mPas的范围内。
5.根据权利要求4所述的方法,其中纺丝浆状溶液B含有15至35%聚砜,4至8%的聚乙烯吡咯烷酮以及二甲基乙酰胺。
6.根据权利要求1所述的方法,其中纺丝阻块的温度设定在5至90℃。
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