CN1142410A - 改进聚合物膜 - Google Patents
改进聚合物膜 Download PDFInfo
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- CN1142410A CN1142410A CN95115063A CN95115063A CN1142410A CN 1142410 A CN1142410 A CN 1142410A CN 95115063 A CN95115063 A CN 95115063A CN 95115063 A CN95115063 A CN 95115063A CN 1142410 A CN1142410 A CN 1142410A
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- polymer
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- fibre membrane
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- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0074—Inorganic membrane manufacture from melts
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/08—Hollow fibre membranes
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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
- B01D69/08—Hollow fibre membranes
- B01D69/085—Details relating to the spinneret
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1212—Coextruded layers
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0251—Physical processing only by making use of membranes
- C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
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- C01B21/0433—Physical processing only
- C01B21/0438—Physical processing only by making use of membranes
- C01B21/0444—Physical processing only by making use of membranes characterised by the membrane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0476—Purge gas treatment, e.g. for removal of inert gases or recovery of H2
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- B01D2323/30—Cross-linking
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0046—Nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Filtering Materials (AREA)
Abstract
本发明公开了具有一高熵效应的分离层的聚合物气体分离膜,这种膜增强了气体分离特性。本发明还公开了制造改进气体分离膜的方法。
Description
本发明涉及聚合物复合物或非平衡气体分离膜,特别是膜形态设计成利于增加膜的熵选择性效应的聚合物气体分离膜,还涉及这种膜的制造方法。
在许多工业生产中需要从多组分气体混合物中分离出一种或多种气体。目前工业上这种分离是通过例如冷冻法、压力回转吸收和膜分离来进行的。在这些类型的气体分离方法中,膜分离是比其它方法更为经济可行的方法。
在一个压力驱动的气体膜分离方法中,气体分离膜一侧接触的是多组分混合气体,该混合气体中一定组分渗透过膜的速率要比其它气体快。因此气体分离膜允许某些气体穿透它而在某种意义上对其它气体起到了屏障作用。渗透过膜的相对气体渗透速率是膜材料组成及形态的一个性能参数。先有技术认为,一种聚合物膜的内在渗透性是气体透过该膜的扩散性(部分地由该材料的填充状况及其分子自由体积所控制)以及气体在该材料内的可溶性的组合作用。选择性被认为是被一种材料所分离的两种气体的渗透性之比。
人们认识到,气体对的分离因子与该气体对中易渗透气体的渗透性呈反比。在一篇题为“Correlation of Separation Factor VersusPermeability for Polymeric Membranes”,Journal of Membrane Sci-ence,62(1991)165-185 Elsevier Science Publishers B.V.,Ams-terdam,Lloyd M.Robeson.的文章中,报道了对于He、H2、O2、N2、CH4及CO2的二元气体混合物分析数据资料,并说明了对于这些混合物的上界关系。Robeson进一步报道,这些结论表明了扩散系数控制着聚合物对这些气体的分离能力。随着聚合物链段间距变得紧密,其渗透性由于扩散系数的降低而降低,但分离特性被加强。
已经知道膜、例如一些碳纤维膜或沸石膜,可以提供超过Robeson所描述的上界的分离特性。例如,美国专利No.4,685,940使用碳膜于分离过程。碳膜具有预定的孔径大小,起到分子筛的作用。碳膜即使在升高温度的情况下也发挥良好功用并提供优异的气体分离特性。然而,这些膜可能价格昂贵,难以生产,易破碎和或对在待分离的气体混合物中杂质例如油高度敏感。
由此,需要能克服先有技术膜上述缺点的聚合物膜及其生产方法。本发明针对于改进薄膜、特别是中空纤维膜。虽然可应用于一般的膜,本发明特别可用于中空纤维非平衡和复合膜。该改进膜通过增加膜的熵选择性效应而生产出来以提供一种更具渗透特性的膜形态。
本发明提供一种用一种或多种成膜聚合物溶液制备的气体分离膜。该膜可以是非平衡的或复合的。成膜聚合物没有限制,例如可以选自聚砜,聚醚砜、聚醚酰亚胺、聚酰亚胺或聚酰胺类的聚合物。
改进气体分离膜通过可控地调整膜的形态来生产。其优异性能是通过增加膜的致密分离层的熵选择性效应大于1.3而达到的。熵选择性效应是待分离的气体分子间的熵能之间差异的函数,并且有降低一个分子相对于另一个分子的转动和或平动自由度的效应。这可以通过例如消除待分离的大的气体分子的转动自由度来达到。这种情况在具有大于O2转动直径的厚度尺寸但小于N2的长度尺寸的狭长缝状孔隙中发生。
对于聚合物膜,理想的膜形态可以通过调整膜中聚合物随意取向的平面间的平均间距来达到。例如,类似上述狭长缝状孔隙的情况,可以调整聚合物链段间的间距,以使得该间距小到不能使最大分子进行所有的自由转动而分离,但此间距却允许所有或至少一种小气体分子进行自由转动。相似的效应也可按下述方式达到,将膜形态调整到通过该膜选择性扩散会出现的气体分子尺寸大小时,它能阻止两种渗透组分中尺寸小的组分的平均自由度。
制造本发明的多组分中空纤维气体分离膜的优选方法由以下几步组成:
a.将第一种聚合物或聚合物混合物溶解在适宜溶剂中以形成核溶液;
b.将第二种聚合物或聚合物混合物溶解在一种溶剂中形成壳溶液;
c.通过一种具有至少一个中空纤维纺丝喷嘴的喷丝头将核与壳溶液共挤出以提供至少一种初生态的多组分中空纤维膜。
d.通过一空气间隙拉伸上述的初生多组分中空纤维膜。
e.将上述初生多组份中空纤维膜引入一凝固浴中以固化初生多组分中空纤维膜成一中空纤维膜;并且
f.可选择地,通过高温分解、交联、氧化、卤化或结晶交联来处理中空纤维膜以提供出具有大于1.3的熵效应的聚合物分离层的膜。
相应的方法也可以用于制造非平衡气体分离膜。
令人惊讶的是,这种聚合物气体分离膜可以提供超过已知的各种混合气的上界的分离特性。这种膜可以提供比得上或超过碳纤维或沸石膜的气体分离特性。
本发明可以生产改进聚合物膜,尤其是多组分和非平衡气体分离膜。在膜的生产中,许多材料可用于气体分离层。这些材料包括聚酰胺、聚酰亚胺、聚酯、聚碳酸酯、共聚碳酸酯、聚醚、聚醚酮、聚醚酰亚胺、聚醚砜、聚砜、聚偏二氟乙烯、聚苯并咪唑、聚苯并噁唑、聚丙烯腈、纤维素衍生物、聚偶氮芳烃,聚(2,6-二甲基苯氧)、聚苯氧、聚脲、聚氨酯、聚酰肼、聚甲亚胺、聚缩醛、醋酸纤维素、硝基纤维素、乙基纤维素、苯乙烯-丙烯腈共聚物、溴化聚亚二甲苯氧、磺化聚亚二甲苯氧、四卤代聚碳酸酯、四卤代聚酯、聚喹喔啉、聚酰胺酰亚胺、聚酯酰胺、聚硅氧烷、聚炔、聚膦嗪(polyphosphazenes)、聚乙烯、聚苯撑、聚(4-甲基戊烯)、聚(三甲基甲硅烷基丙炔)、聚(三烷基甲硅烷基乙炔)、聚脲、聚氨酯和所谓的梯度聚合物及其共混物、共聚物、取代物等等。进一步认为可聚合的物质、即可以处理成聚合物的物质,例如可硫化的硅氧烷等,也可用于制成本发明的气体分离膜。
本发明多组分膜适宜的基质层材料可包括聚砜、聚醚砜、聚酰胺、聚酰亚胺、聚醚酰亚胺、聚酯、聚碳酸酯、共聚碳酸酯、聚醚、聚醚酮、聚偏二氟乙烯、聚苯并咪唑、聚苯并噁唑、纤维素衍生物、聚偶氮芳烃、聚(2,6-二甲基苯氧)、聚亚芳基氧、聚脲、聚氨酯、聚酰肼、聚甲亚胺、醋酸纤维素、硝基纤维素、乙基纤维素、溴化聚亚二甲苯氧、磺化聚亚二甲苯氧、聚喹喔啉、聚酰胺酰亚胺、聚酯酰酯以及它们的混合物、共聚物、取代物等等。以上材料并不应认为是限制范围,因为任何一种可被制造成各向异性基质膜的材料都可以用于本发明的基质层。用于基质层的优选材料包括聚砜、聚醚砜、聚醚酰亚胺、聚酰亚胺和聚酰胺组合物。特别优选的材料在美国专利5,085,676中有描述。
用于非平衡膜以及多组分膜基质气体分离层的聚合物应当具有足够高的分子量以能形成膜。
本发明的气体分离膜可以以不同的形状例如扁平膜或中空纤维膜而存在。考虑到可获得的表面积大小,最好采用中空纤维膜。可以通过共挤出分离层及骨架层的聚合物溶液,形成一初生态多层膜,来制备扁平膜。
在此以前没有认识到的膜材料的关键特征是熵选择性效应。熵选择性效应是指发生在除了起源于与待渗透两组份A和B激发能之间差异的指数依赖性的运动选择性之外的运动选择性的加强作用。也就是,运动选择性正比于A跃迂频率/B跃迁频率,它正比于:
exp[-(ΔEA-ΔEB)/RT]×exp[(ΔSA-ΔSB)/R]
(I) (II)
能量选择性效应 熵选择性效应这里ΔE是由扩散与温度的Arrhenius关系曲线所决定的分子的活化能,ΔS也是由扩散与温度的Arrhenius关系曲线所决定的熵。因为A与B分子尺寸一般非常相近,各自的跃迁长度也相似,所以A和B的跃迁的相对频率控制着运动选择性。实施一个跃迁的相对频率由与活化能差异(公式I)和跃迁过程中熵差异(公式II)的两个指数函数的乘积所决定的。位于或低于Robeson所描述的上界的聚合物具有类似于刚性碳膜或沸石的指数能量项(I)。这点在表1中有所表明,表1中位于Robeson界线的“上界聚合物”具有等于4.35的“能量效应”项,而碳或沸石的为5.1-7.1。对于聚合物,这一项被归结于聚合物的链段运动。聚合物的大的链段必须运动以容纳相对于小的分子(如O2)大的分子(如N2)的跃迁。如果一种膜能够具有象沸石那样的尺寸刚好的永久缝隙,就不需要能量去使链段或次链段产生运动以产生缝隙。在这种情况下,仅需的活化能归结于渗透组分克服包围在临界缝隙周围的原子的电子云的排拆作用的需要。对于上界聚合物,它可以也可以不需要运动为让所需要的渗透组分通过而产生出缝隙;然而,环境是使传输控制狭缝太大以至于熵能间差异ΔSA-ΔSB小于或等于零,所以项II熵选择性效应小于或等于1。如果狭缝尺寸比最小渗透组分的最小直径(如3.46A对于O2)足够大但接近或小于最大渗透组分的最小直径(如3.64A对于N2),当大的渗透组分接近狭缝时,将会由于电子排斥被剥夺其平动能。小的渗透组分将不会经历这么强的排斥作用,因为这些力极快地消失,这样,小的渗透组分具有低的ΔSA,而ΔSB是负值。在这种情况下,聚合物的能量选择性可以被提高最大达4.5倍。
对于影响一个转动自由度的聚合物膜中的狭缝或对于影响两个转动自由度的相对圆的环形狭隙,如果尺寸调整到能禁止垂直于分子长轴方向上的转动,类似的效应也会出现。
许多材料对O2和N2混合气在35℃时的熵选择性效应是已知的。例如,沸石的熵效应是14.7,碳分子筛的为4.9。然而,典型的玻璃态聚合物的熵效应小于1.0,Robeson所描述的“上界”聚合物是约1.3。
为了说明本发明,以下以具有两组分—即气体分离组分及基质层组分的多组分膜的制造方法为例来讨论。然而,这不应被认为限定本发明范围,因为这种方法对于生成非平衡膜也是有效的。另外,本发明的多组分膜可以包括超过两组分的膜层。其它的层可做为气体分离层、结构层、相容剂层、基质层、减少环境问题膜层或其组合。这些其它层可以含有用于气体分离层及基质层的材料。
多组分膜的每层材料间应具有足够的相容性,以保证复合膜在加工或气体分离应用中的完整性。
具有中空纤维形式的多组分中空纤维膜可以通过骨架聚合物和分离聚合物溶液的共挤出形成。例如,形成膜层的聚合物溶液可以通过多孔喷丝头共挤出,此间在初生态中空纤维腔中维持气体压力或腔中流体,以维持纤维的结构完整性。这种多孔初喷丝头在以前用于多组分纤维融熔纺丝的工艺中有所描述。聚合物的共挤出及其设备和方法在本领域是熟知的。
在中空纤维膜的制造过程中,为使暴露在气体中的膜表面积最大,分离层优选在纤维的外表面形成。然而,分离层也可以在纤维的内层形成。本发明的多组分中空纤维可以具有约75~1,000μm、优选100~350μm的外径,以及约25~300μm、最好是25-75μm的壁厚。纤维腔直径优选约为纤维外径的1/2-3/4。生成的膜具有足够的孔隙率,使得膜中空隙体积占其本身体积的10%~90%、优选30~70%。如上所述,膜材料的熵效应大于1.0。
在制备中空纤维膜中使用的聚合物具有足够高的分子量,使得生成的纺丝原液能通过一个喷丝头挤出形成自支持的在随后纺丝工艺中能进一步加工的中空纤维。纺丝原液在70℃的零剪切粘度通常超过几百个泊,优选是在100~5000泊范围内。
如上所述,纺丝原液通过喷丝头挤出形成中空纤维膜。纺丝原液通过喷丝头的体积流量(以每单位时间内的立方分米数测定)与纤维的收集速率可以变化,以控制生产速率、纤维尺寸、形态和拉伸比。最好,纺丝原料的体积流量为50~500cc/min、最优选100~300cc/min。
本发明中所使用的喷丝头被恒定的温度应使得纺丝原液的粘度足以利于初生纤维的拉伸牵引。一般情况下,喷丝头温度维持在40~130℃、优选是60~100℃。
在聚合物溶液通过中空纤维喷丝头的挤出过程中,一种腔流体被注射入纤维腔中以便于形成中空纤维的构型。腔流体可以是该聚合物的溶剂和不良溶剂的混合物,以提供一慢速凝集作用及允许纤维牵伸,或者腔流体是一种诸如N2的惰性气体。合适的腔流体包括(但并不限于)水、N一甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)及二甲基乙酰胺(DMAc)。腔流体优选包含诸如DMAc、NMP、DMF等的溶剂与水的混合物。
在喷丝头的出口,初生态的纤维在接触流体凝集浴之前直接暴露在气态环境中的空气间隙中。选择压力、温度、大气组成以及纤维暴露在气态环境中的时间,以控制初生纤维的形态。
初生态纤维通常在室温下通过空气间隙。空气间隙媒质的温度可以变化以利于溶剂从初生态纤维中的蒸发。一般地,空气间隙温度可以是室温或者是升高的温度。空气间隙温度优选为室温。
空气间隙的气态环境组成一般选择为利于溶剂从纤维中蒸发的组成。可能的气体组成包括(但不限于)空气、N2、如He、Ar、Xe等的惰性气体。另外,空气间隙的压力可低于大气压。空气和惰性气体优选被用于空气间隙中。空气最优选用于空气间隙中。
在接触到空气间隙中的气体环境后、纤维被输入到一凝集浴中,通过提取溶剂而使纤维凝集,然后卷绕到收集辊上。选择浴的组成及温度,以控制纤维的凝集速度及其形态。本发明中采用的可能组成包括(但不限于)水、脂肪醇、脂肪醇混合物、脂肪醇与水的混合物。凝集浴的其它可能组成包括DMF、NMP和DMAc的水溶液。凝集浴组成优选为脂肪醇与水的混合物,最优选为水。凝集浴温度可以变化,以控制凝集速度和纤维形态。浴温一般维持在小于25℃,优选是0~20℃,最优选是5~15℃。对初生膜适宜的组成可根据采用的聚合物溶液的组成和所需生成物而变动。一般地,凝集浴媒质是纺丝原液的溶剂或溶剂混合物,但是聚合物的非溶剂。然而,凝集浴可以变化以使复合膜各层具有希望的特性。例如,对一种多组分膜,与基质层聚合物溶液的溶剂相比,分离层聚合物溶液的溶剂在凝集浴中不那么混溶,以形成不同的溶剂提取速率。因此,凝集浴可以是水及与水和被提取出聚合物的溶剂可混溶的有机溶剂多组分混合物。也可以控制浴温及其组成,以影响凝聚的程度及速率。纤维在凝集浴中处理完后,纤维被缠绕在接收辊或其它适宜收集设备上。
纤维的拉伸速率与纤维的挤出速率之比可以在大范围内变动。一般地,纤维的挤出速率可以在2~100m/min内变动,优选为3~50m/min,最优选是5~20m/min。同样地,纤维的拉伸速率为5~500m/min,最优选为50~150m/min。
初生态的膜可以选择地在特定条件下进行干燥,然后在聚合物非溶剂但是聚合物溶剂的溶剂的凝集浴内沉淀。初生态的膜可通过一个炉子在10℃~200℃、优选25℃~100℃干燥0.01~10min、优选0.05~1.0min。初生态膜然后在凝集浴内沉淀。
生成的纤维膜进行清洗以除去残余的溶剂等杂质,随后进行干燥。清洗一般是将纤维膜放在25℃~100℃、优选25℃~75℃的水中保持足够长时间,以充分地除去所有残余溶剂以及如纺丝原料中残余的添加剂等杂质。随后,纤维被干燥或通过溶剂交换而脱水。例如,聚芳基酰胺纤维可以通过两步法脱水,首先使用甲醇、然后使用FREONF-113进行溶剂交换脱水。本领域中的这类溶剂交换方法是已知的,如在美国专利4,080,743、4,080,744和4,120,098中有所描述。另外,纤维也可以通过在空气等环境中加热来除去水份。
聚合物溶液的典型溶剂包括如二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜等的溶剂。这些溶剂对本发明的适宜聚合物材料即聚砜、聚醚砜、聚酰胺、聚酰亚胺和聚醚酰亚胺是有效的。然而,这些溶剂仅仅是示例,不应视为限定。
溶剂混合物也可以在用于形成膜层的聚合物溶液中采用。例如,两种或更多的溶剂可以被采用,它们的挥发性及溶解力可以不同。
溶剂混合物也可以含另外的组分,如聚合物溶胀剂、不良溶剂组分。这些加入的组分例如可通过使聚合物溶液接近初始凝胶点而达到膜致密分离层理想的各向异性形态。这些添加成份在凝集浴内可以是可提取的也可为不可提取的。可提取的组分即在水基凝集浴内为可提取的材料例如可作为膜层的成孔剂。可提取组分的例子包括无机盐及如聚乙烯基吡咯烷酮的聚合物。可应用的添加组分的例子包括在凝集浴中不溶解的分散单体材料、如可湿固化的硅氧烷的可聚合材料以及相容或不相容聚合物。前面的添加组分例子仅仅是示例,不应视为限定。本发明的多组分膜的制造方法一般决定于膜的主要成分。例如,在生产双组分中空纤维膜时,纺丝参数的选择决定于基质层溶液的可纺性。这意味着本发明形成的双组分膜在基本上与做基础的基质层同样的条件下能容易地进行纺丝。
为了给膜材料提供一大于1.3的熵选择性效应,聚合物膜材料在加工中不同步骤进行处理。优选处理干膜以达到理想的熵选择性效应,例如,多组分聚合物的分离层可以用本领域熟知的方法高温分解、交联、氧化、卤化和/或结晶交联。这些步骤不应认为是限定,只要加工修饰后的膜具有一熵选择性效应大于1.3的聚合物分离膜即可。高温降解例如一般可在含碳物质的分解温度到石墨化温度(约3000℃)之间的宽范围内进行。一般地,高温降解在250℃~2500℃范围内进行,优选的范围是约450℃~800℃。
在高温分解过程中,加热最好在有控制氧化作用的惰性气体如N2或稀有气体中进行。控制氧化作用导致了孔开放,因此可以达到预定的孔尺寸范围,适宜于想要进行的分离工艺。适宜的氧化剂包括O2、蒸汽、CO2、氧化氮及氧化氯、硝酸溶液、硫酸溶液、铬酸溶液和过氧化物溶液。氧化处理后膜应在升高温度下进行脱气。
这项处理的目的是调整聚合物链的形态,以提供一种间隙,它至少能限制一种或多种待分离的气体分子的一种转动和/或平动自由度。
聚合物链段及次链段的运动可被视为一种迅速扑动的图像。链段及侧基构象间细微差别的变换经一特定时间进行,除其它因素外,该时间由聚合物骨架的内在刚性以及侧基运动的空阻决定。
已知围绕可动聚合物链节点的所谓摇摆运动可以产生可渗透组分的间隙,以允许吸附着的气体分子的运动。增加聚合物网络骨架间的平均距离的结构变动产生出更为开放的聚合物基体。对于更开放的基质,越大的链段间空隙估计将预先存在于围绕在处于扩散跃迁的渗透组分周围的“吸附笼”内。与比较小开放的基质相比,这些较大平均空隙能以比较小辐度的周围链段摇摆而瞬时开放。这样大和小的渗透组分的平均跃迁频率在较开放的基质内将趋于增加。通过用运动阻禁来压制聚合物周围链段及侧基的角度变换,甚至对于尺寸差异很小的分子也能维持或增加运动选择性。我们已发现调节处于或附于聚合物链的运动节点及产生的空隙,可以改变在处于Robeson界线或其下的材料所达不到的程度上改变待分离的一种或多种气体分子的平动和转动自由度。
我们认为,这一概念的一个证据是,对于聚合物链中含有苯环的聚合物,处于一个或多个苯环间的聚合物节点至少有15的距离、最好是15-20距离,将给膜的分离层提供一增加的熵选择性效应。在这种情况下,这些聚合物链象平面的聚合物带。对于O2/N2体系,这种聚合物膜可以提供大于8.0的选择性、优选大于10.0。这种膜的选择性是由熵选择性效应控制的,而不是由控制扩散跃迁的相对能量阻碍所控制的。这种扩散跃迁由能量除以普适气体常数R与绝对温度的乘积的负指数所决定。这两种效应的相对重要性从表1中可清楚看到,表1中较开放的基质聚合物及沸石和碳分子筛都具有-0.9~-1.2kcal/mol的活化能差距,而只有刚硬的沸石和碳分子筛基体提供明显大于1.0的熵选择性效应。
对于O2与N2的混合气,认为熵效应可以在分子尺寸上加以解释。一个氧气分子有3.73的长度及3.46的最小宽度。氮气分子有4.03的长度及3.64的最小宽度。因此氮气分子比较长。这些分子在他们各自的笼内快速地旋转。在第一种情况下,气体分子的最小跨区尺寸决定着他们渗透过聚合物材料的相对能力。然而,为了降低氮气分子的转动自由度而调整膜中空隙的尺寸和构型将会明显地阻止氮气渗透过膜的能力。类似的原理也适用于平动自由度,因为接近N2尺寸的空隙将超过O2尺寸,并且几乎不会阻止O2分子渗透空隙。
本发明出人意料的优势特能制得具有改进气体分离特性的聚合物膜。我们认为,该气体分离膜的优势性源于降低了待分离气体混合物中最大气体分子的转动和或平动自由度。
在先有技术中,他人也试图提高膜的气体分离性能,他们是通过增加或降低聚合物材料相对于待分离气体的相对能量效应而控制气体的扩散系数而进行的,这借助于控制聚合物链段或亚链段运动以产生瞬时间隙所需的能量,而无需形成可渗透的间隙,这样,选择性地限制原先不能透过的渗透组分的平动和/或转动自由度。
Robeson题为“Correlation of Separation Factor Versus Perme-ability for Polymeric Membranes,”Journal of Membrane Science,62(1991)165-185 Elsevier Science Publishers B.V.,Amsterdam的文章是以前提高聚合物膜的气体分离特性的努力的示型。Robeson在他的文章中如下报道了扩散系数与溶解度常数的相互关系:
“基本渗透性方程(对于非浓度依赖性的费克扩散)是P=DS
这里P是渗透性系数,D是扩散系数,S是溶解度常数。早已知道,普通气体在聚合物中的扩散系数与气体分子的有效分子直径有很强的依赖关系,文献中已指出各种依赖关系。一般气体的溶解度常数遵循Henry法则。Van Amerongen[26]认为,在一特定聚合物中的气体溶解性常数与气体的沸点和临界点有关系。…
“正如本文中将要说明的,上界似乎是由于aij(Pi/Pj)[选择性]与Pi(i=快气体)[渗透性]的关系而存在的。溶解性比值(Si/Sj)的作用似乎很小,主要因素归扩散分离(Di/Dj),如下式所示:
“人们已很好地认识到,扩散系数是决定气体在聚合物中的渗透性的绝对值的主要因素。Van Amerongen[26]认为,气体(在弹性体中)的扩散性随着气体分子的碰撞直径(由气体的粘度值所决定)增加而迅速下降。对比不同的弹性体表明,logD与气体分子直径的关系为正比例关系(尽管不是理想的直线关系)。”
Robeson的注意力集中在气体渗透过聚合物的能量效应。他还公开了多种聚合物与多种气体混合物的渗透特性。
然而,先有技术没有意识到具有高熵选择性效应的膜,以进一步改进对渗透性的选择性。尤其是,先有技术集中在控制气体A相对于气体B的扩散系数上,它通过调节与允许最小尺寸的气体分子透过开孔的运动有关的能量效应,没有认识到转动能力也是一种影响因素,例如一种聚合物也很关键地依赖于气体分子相对于聚合物材料的长度(最长尺寸)。通常认为,调节运动选择性要求严格考虑到待分离的两种气体分子的最小尺寸(“筛分直径”)。这些尺寸决定着渗透组分扩散跃迁过在聚合物基质中处于链段间间隙的大小范围的瞬间开孔的相对能力。
对于大小相近的渗透组分(如O2与N2),跃迁长度项一般被认为是相近的,所以,例如运动选择性应由基质中O2相对于N2的跃迁频率所决定。O2具有3.46的直径,因此产生了相对于N2的0.18的尺寸差异。
例如,高刚性的玻璃态材料对于O2/N2体系可能具有至多8.5的运动选择性。应用沸石筛分直径理论,可以理解控制几种感兴趣的渗透组分在这些常规材料中、甚至在Robeson所述的“上界”材料中的运动选择性是比较困难的。
溶解性效应尽管不是首要的,但也很重要。因此一般来讲,对于超临界气体分离,膜中的渗透选择性虽然受溶解性选择性影响,但由运动选择性控制。
本发明的膜具有高的熵选择性效应,因此具有优异的气体分离特性。
本发明的新颖膜可用于各种气体分离中。例如,本发明膜可用于:分离空气中的O2,以提供富集氧以提供加强燃烧作用;用于分离空气中的N2,以提供惰性气体系统;从精炼厂和氨气厂的烃气体中回收氢气;从合成气体系中将H2与CO分离;从NH3中分离N2;从烃气体中分离CO2或硫化氢。
但是,本发明新颖多组分膜并不限于气体分离。所有已知的膜分离过程一般都可从运用本发明新颖膜。例如,该膜可用于反渗透、微滤、超滤以及其它分离过程如生物分离,这种生物分离要求混合物中的一定组分与膜有一定的亲和力以实现有效分离。
表1
材料 | 在35℃对O2/N2的选择性 | ΔEO2(kcal/mol) | Δ[ΔEO2,N2](kcal/mol) | 能量选择性效应exp[-Δ[ΔEO2,N2]/RT] | 熵选择性效应exp[Δ[ΔSO2,N2]/R] |
4A沸石 | 102 | 4.5 | -1.2 | 7.1 | 14.7 |
碳分子筛 | 25-45 | 5.5 | -1.0 | 5.1 | 4.9-8.8 |
“上界”聚合物 | 4.8-5.1 | 5.3 | -0.90 | 4.35 | 1.1-1.2 |
Claims (7)
1.具有聚合物分离层及大于1.3的熵效应的气体分离膜。
2.根据权利要求1的膜,其中,熵效应大于1.5。
3.根据权利要求1的膜,其中,熵效应大于2.0。
4.根据权利要求1的膜,其中,它在室温下对O2/N2选择性大于8.0。
5.根据权利要求1的膜,其中,聚合物分离层包括在聚合物链骨架上具有芳环的聚合物,并且该聚合物在至少两个相距至少为15的芳环之间具有连接链。
6.一种制备多组分气体分离膜的方法,它包括下列步骤:
a.将第一种聚合物或聚合物混合物溶于适宜溶剂中形成核溶液;
b.将第二种聚合物或聚合物混合物溶于溶剂中形成壳溶液;
c.通过具有至少一个中空纤维纺丝孔的喷丝头将核、壳溶液共挤出,以提供至少一种初生多组分中空纤维膜;
d.通过一空气间隙拉伸上述初生多组分中空纤维膜;
e.将上述初生多组分中空纤维膜引入一凝集浴中,将初生多组分中空纤维膜固化成具有致密分离层的中空纤维膜;并且
f.处理中空纤维膜,使其形成具有大于1.3的熵效应的致密分离层。
7.根据权利要求6的方法,其中将中空纤维膜进行高温降解、交联氧化、卤化和/或结晶交联处理,使其形成具有大于1.3的熵选择性效应的致密分离层。
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JP7122775A JPH08155282A (ja) | 1994-05-20 | 1995-05-22 | 改善された高分子メンブレン |
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CN102946981A (zh) * | 2010-05-13 | 2013-02-27 | 气体产品与化学公司 | 聚合物、聚合物膜及其制造方法 |
US8926733B2 (en) | 2010-05-13 | 2015-01-06 | Air Products And Chemicals, Inc. | Polymers, polymer membranes and methods of producing the same |
CN102946981B (zh) * | 2010-05-13 | 2015-11-25 | 气体产品与化学公司 | 聚合物、聚合物膜及其制造方法 |
CN102068915A (zh) * | 2010-06-11 | 2011-05-25 | 苏州信望膜技术有限公司 | 一种双层中空纤维混合基质膜及其制备方法 |
CN104084064A (zh) * | 2014-05-23 | 2014-10-08 | 杭州水处理技术研究开发中心有限公司 | 一种硅烷或卤代硅烷改性纤维素气体分离膜的制备方法 |
CN104084064B (zh) * | 2014-05-23 | 2015-11-25 | 杭州水处理技术研究开发中心有限公司 | 一种硅烷或卤代硅烷改性纤维素气体分离膜的制备方法 |
CN106999861A (zh) * | 2014-09-22 | 2017-08-01 | 佐治亚理工学院 | 具有提高的渗透率的复合纳米颗粒稳定化的芯碳分子筛中空纤维膜 |
CN106999861B (zh) * | 2014-09-22 | 2021-01-05 | 乔治亚技术研究公司 | 具有提高的渗透率的复合纳米颗粒稳定化的芯碳分子筛中空纤维膜 |
CN113975981A (zh) * | 2021-09-07 | 2022-01-28 | 南京工业大学 | 一种聚4-甲基-1-戊烯/聚砜共混中空纤维膜、制备方法及在人工肺中的应用 |
Also Published As
Publication number | Publication date |
---|---|
EP0682977A3 (en) | 2000-01-12 |
US5599380A (en) | 1997-02-04 |
JPH08155282A (ja) | 1996-06-18 |
EP0682977A2 (en) | 1995-11-22 |
CA2149806A1 (en) | 1995-11-21 |
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