CN107683273B - 用于分离烷烃和烯烃的薄膜复合膜 - Google Patents
用于分离烷烃和烯烃的薄膜复合膜 Download PDFInfo
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- CN107683273B CN107683273B CN201680035437.6A CN201680035437A CN107683273B CN 107683273 B CN107683273 B CN 107683273B CN 201680035437 A CN201680035437 A CN 201680035437A CN 107683273 B CN107683273 B CN 107683273B
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Abstract
由至少两个层构成的复合膜特别适用于烷烃与烯烃的所述分离,所述层中的一个层是银离聚物并且第二层是具有一定渗透性特性的氟化聚合物,特别可用的是其中多孔层被层压到所述第二层的三层复合膜。
Description
发明领域
描述了具有某种类型的银离聚物的一个或多个层并且可将烷烃与烯烃分离的薄膜复合膜。
政府权利
由能源部奖颁发DE-SC0004672和DE-SC0007510提供支持。美国政府对本专利申请享有权利。
技术背景
含有某些含磺酸聚合物(特别是氟化聚合物)的银离聚物层的膜已被用于从烯烃分离烷烃。这些类型的化合物(特别是具有相同碳原子数的那些化合物,诸如乙烯从乙烷、丙烯从丙烷和戊烯从戊烷)的分离通常难以通过其他方法分离,因为例如烷烃和烯烃的沸点是相似的,从而导致高能量需求。对于含有2至4个碳原子的低沸点材料尤其如此,这将需要通常非常耗能的低温蒸馏。
在膜分离过程中,经常使用薄膜复合膜。薄膜复合膜(TFC)通常由不同材料层连接在一起以形成单个膜。这种分层结构允许使用优化膜的性能和耐久性的材料组合。对于使用银离聚物的烷烃-烯烃分离方法同样如此,本文描述的是用于此类分离的新的TFC。
作为最低要求,人们可能认为具有银离聚物的单层,“分离层”(SL)的膜将是可用的。然而,这种类型的膜具有两个重要的缺点,银离聚物是昂贵的,并且在膜所需要的具有足够强度的更厚的膜中,对烯烃的渗透性,每单位时间可通过膜的烯烃的量是相对较低的。因此,实际的膜需要一个(或多个)薄分离层。可添加具有另一层材料的复合膜,其物理地支撑整个TFC,并且层合接触分离层。此其他层是无孔的,并且通过TFC(在这种情况下为一种或多种烯烃)的材料也优选通过此其他层快速地扩散。本文此其他层称为高扩散速率层(HDR)。
具有银离聚物分离层的各种复合膜用于从烯烃分离烷烃的用途是已知的,例如参见A.van Zyl等人,Journal of Membrane Science,133,(1997),第15-26页,O.I.Eriksen等人,Journal of Membrane Science,85(1993),第89-97页和A.J.van Zyl,Journal ofMembrane Science,137(1997),第175-185页以及美国专利5,191,151。然而,这些参考文献均没有描述TFC,其中银离聚物的分离层与本文所述的HDR层组合使用。
在TFC中使用某些层,即有时称为“沟槽层”的层,并且通常描述于M.Kattula等人,Designing ultrathin film composite membranes:the impact of a gutter layer,Scientific Reports,5,文章号15016(2015)中。不存在关于使用银离聚物的烷烃-烯烃分离的具体信息。
发明内容
本发明涉及一种用于从烯烃分离烷烃的薄膜复合膜,其包括:
(a)包含聚合物磺酸的银离聚物的分离层;以及
(b)具有至少约250GPU的对于氮的渗透性的氟化聚合物的高扩散速率层,其中所述分离层和所述高扩散速率层彼此层压。
发明细节
本文使用某些术语,并且其中一些在以下定义。
氟化聚合物或离聚物意指在离聚物中的碳-氢基团和碳氟基团的总数中,约20%或更多是碳-氟基团,优选约50%或更多、非常优选约70%或更多、特别优选约90%或更多,并且非常特别优选95%或更多是碳氟基团或最优选是全氟聚合物。碳-氢基团意指氢原子直接结合到碳原子,而碳-氟基团是氟原子直接结合到碳原子。因此,-CF2-基团含有2个碳氟基团,而-CH3基团含有3个碳-氢基团。因此,在偏二氟乙烯的均聚物中,其中重复基团是-CH2CF2-,碳-氢基团和碳氟基团各自是所存在的碳-氢加上碳-氟基团的总数的50%。在50摩尔%全氟(2,2-二甲基-1,3-间二氧杂环戊烯)和50摩尔%乙烯的共聚物中,碳-氢基团是所存在的碳-氟加上碳氢基团的总数的33.3%,并且碳-氟基团是所存在的碳-氟和碳-氢基团的66.7%。所存在的碳-氟和碳氢基团的相对量可通过元素分析、NMR光谱学(例如,使用14CNMR)或这些中的任何组合来确定。
在分离呈气态的烯烃和烷烃中的“驱动力”通常意指膜的第一(“进料”)侧上的烯烃的分压高于膜的第二(“产物”)侧上的烯烃的分压。例如,这可通过若干方法或其组合来实现。一种是对第一侧加压以增加第一侧上的烯烃的分压,第二种是通过惰性气体(诸如氮气)吹扫第二侧以降低第二侧上的烯烃的分压,并且第三种是通过真空泵减小第二侧的压力以降低第二侧上的烯烃的分压。可使用这些方法和本领域中施加驱动力的其他已知方法。
这可通过数学关系在一定程度上对气体的分离进行量化:
QaαFa(P1a-P2a)
其中Qa是通过膜的组分“a”的流动速率,Fa是通过膜的组分a的渗透性,P1a是第一(进料)侧上的分压,并且P2a是第二(产物)侧上的分压。
“层压”意指所涉及的两个层彼此紧密接触。这通常被称为“粘合在一起”,尽管通常不采用单独的粘合剂。
优选地,SL是约0.1μm至约1.0μm厚,更优选约0.2μm至约0.5μm厚。如上所述,此层的相对薄度有助于提高每单位面积膜的整个分离过程的生产率。
可用于SL的聚合物是含磺酸聚合物的银离聚物。此类离聚物在本领域中以及在已知将烷烃与烯烃分离的一些情况下是熟知的,参见例如美国专利申请14/334,605、美国临时申请62/159,646、62/159,668和62/262,169(现在分别为PCI申请________________________________),A,van Zyl等人,Journal of MembraneScience,133,(1997),第15-26页,O.I.Eriksen等人,Journal of Membrane Science,85(1993),第89-97页和A>J.van Zyl,Journal of Membrane Science,137(1997),第175-185页以及美国专利5,191,151,所有这些以引用的方式在此包括在内。AF的优选等级是AF 2400,其据报道含有83摩尔%PDD和17摩尔%四氟乙烯。还可采用PDD与其他共聚单体(诸如全氟(丙基乙烯基醚)和CF2=CFOCF2CF(CF3)OCF2CF2SO2F)的聚合物,在PDD与这些替代单体的共聚物中,优选的是PDD含量为至少90摩尔%。
在SL中形成银离聚物的含磺酸聚合物优选是氟化聚合物,并且更优选50%或更多、非常优选70%或更多且真正优选90%或更多是碳氟基团,并且当然离聚物本身优选是氟化聚合物。特别优选地,此聚合物是全氟聚合物,即所有被聚合成重复单元的单体均不含氢。此类全氟聚合物可能具有非常少量的来自不纯单体的“外来”碳氢基团,或诸如键合到链的引发剂片段的基团。
在HDL中的含氟聚合物中,并且优选50%或更多、更优选70%或更多,并且非常优选90%或更多是碳氟基团。特别优选地,此聚合物是全氟化的聚合物,即所有被聚合成重复单元的单体均不含氢。此类全氟聚合物可能具有非常少量的来自不纯单体的“外来”碳氢基团,或诸如键合到链的引发剂片段的基团。
优选地,HDL层是约0.05μm至约0.5μm厚,更优选约0.05μm至约0.2μm厚。
用于HDL的特别优选的聚合物是全氟(2,2-二甲基-1,3-二氧杂环戊烯)、(PDD)(特别是如果包含在全氟聚合物中)的共聚物。在PDD的任何共聚物中,优选的是总重复单元的至少约50摩尔%、更优选至少80摩尔%衍生自PDD。一般来说,所有PDD共聚物均需要更高摩尔百分比的PDD,这与能够将聚合物加工成膜中的层一致。优选的共聚物是PDD与四氟乙烯的共聚物,可作为AF(The Chemours公司,Wilmington,DE 19899,USA)获得,并且关于AF的进一步信息,参见P.R.Resnick等人,Teflon AF AmorphousFluoropolymers,J.Schiers编,Modern Fluoropolymers,John Wiley&Sons,New York,1997,第397-420页,所述文献以引用的方式在此包括在内。AF的优选等级是AF2400,其据报道含有83摩尔%PDD和17摩尔%四氟乙烯。
HDL中的其他潜在可用的聚合物包括可从Asahi Glass,1-5-1,Marunouchi,Chiyoda-ku,Tokyo 100-8405,Japan获得的含氟聚合物树脂(据报道是1,1,2,4,4,5,5,6,7,7-十氟-3-氧杂-1,6-庚二烯的均聚物)和可从Solvay,SA,RUE DE RANSBEEK,310,1120Bruxelles,Belgium获得的DA-型含氟聚合物树脂(据报道是四氟乙烯和全氟(3-甲氧基-1,3-间二氧杂环戊烯)的共聚物)。
优选地,HDL中的聚合物是所谓的“玻璃态”聚合物。这意味着当使用ASTM测试D3418-12e1,使用10℃/min的加热和冷却速率通过差示扫描量热法测量时并且是在第二次加热中测量,所述聚合物不具有高于约30℃的熔点,具有3J/g或更高的熔化热。另外,玻璃态聚合物具有高于约40℃、更优选约40℃的玻璃化转变温度(Tg)。根据ASTM测试D3418-12e1以10℃/min的加热和冷却速率测量Tg,并且将Tg作为第二次加热中的转化中点(拐点)。优选地,Tg小于约220℃,因为例如如果Tg太高,则可能难以溶解聚合物以形成涂层或层。
用于HDL的聚合物可含有官能团,但优选地这些官能团相对难以氧化并且将不与SL中的银离子络合或反应。可用的基团包括全氟醚和氯(特别是当以三氟氯乙烯存在时)。优选不存在的基团是伯醇和仲醇、碘、溴和醛。
HDL在约25℃下具有至少250GPU的对于氮的持久性。优选地,此持久性应为至少约500GPU并且更优选至少约1000GPU、特别优选约1500GPU,并且非常优选至少约2500GPU且最优选至少约5000GPU。如果对于烯烃的持久性足够高,则可使用相对厚的HDL材料层,并且这将支撑仅具有HDL和SL两个层的膜。
然而,这种无孔非常高渗透性的材料难以找到,并且因此在许多情况下,第三层是添加了(微)多孔层,其是含有期望的物质可相对畅通地流动通过的许多小孔的层,而HDL非常薄,使得TFC的每单位面积的生产率高。这种多孔层(PL)可被制备得足够厚以物理地支撑整个三(或更多)层TLC而不牺牲很多生产率。
当这三种类型的层,SL、HDL和PL被组合成单个TLC时,TLC的结构按照层的顺序通常是SL/HDL/PL(斜杠表示层表面在那里被层压在一起)L,其中SL暴露于待分离一种或多种组分的混合物,并且分离的产物通过HDL且从PL的“自由表面”出来,反之亦然,在这种类型的构造中,HDL通常被称为“沟槽层”。已知的是这种沟槽层通常提高每单位面积TLC的TLC通过量,参见M.Kattula等人,Designing ultrathin film composite membranes:theimpact of a gutter layer,Scientific Reports,5,文章号15016(2015),所述文献以引用的方式在此包括在内。
然而,在本发明中,沟槽层具有另一个意料不到的效果,从而总体上改善了TLC的分离。不希望受到理论的约束,一般来说,选择用于TLC的各个层的材料(通常为聚合物)部分地被选择,因为在TLC将被使用的条件下,它们在化学和物理上是稳定的。不幸的是,SL层的银离聚物在化学上不是非常稳定,特别是在可相对容易氧化的有机化合物的存在下。用于PL的大多数材料,常常在聚合物本身中含有少量的外来化学物质或可氧化基团的有机聚合物被Ag+氧化,银常常使金属还原,从而使烷烃与烯烃分离变得无效。
这就是为什么据信本文描述的用于HDL的含氟聚合物(特别是全氟聚合物)不仅可能有效改善膜的生产率,而且在适当的构造中有助于保护SL的完整性,从而最初地并且在更长的时间段内改善其“分离性能”,参见例如以下表1。
其他层和层构造可存在于HDL中。例如,可存在另外的HDL层,优选以HDL/SL/HDL/PL构造存在,其中另外的HDL层保护具有SL/HDL/PL的三层HDL的“暴露”表面免受污染以及可能的来自(部分)分离的混合物中的材料的降解。其他可用的层和构造对于本领域技术人员将是显而易见的。
具有一个或多个致密的银离聚物层以将烷烃与烯烃分离的这些类型的膜的使用在本领域中是熟知的。将膜的一侧暴露于一种或多种烷烃和一种或多种烯烃的气态或液体混合物,并且提供驱动力。洗脱液从膜富含烯烃的另一侧流出,即烯烃中的烷烃浓度降低。如果烷烃和烯烃的混合物是气态,则这是优选的。这种分离方法描述于美国专利申请14/334,605、美国临时申请62/159,646、62/159,668和62/262,169(现在分别为PCT申请__________________________),A.van Zyl等人,Journal of Membrane Science,133.(1997),第15-26页,O.I.Eriksen等人,Journal of Membrane Science,85(1993),第89-97页和A.J.van Zyl,Journal of Membrane Science,137(1997),第175-185页以及美国专利5,191,151,所有这些以引用的方式在此包括在内。
HDL必须具有在25℃下至少约500GPU、优选至少约1000GPU、更优选至少约1500GPU并且非常优选至少约2000GPU的对于氮的最小渗透性。为了获得此类层的高渗透性,这些层通常由对所测试的气体(在这种情况下为氮)具有高渗透性的聚合物制成,并且通常相当薄,因为厚度越高渗透性越低。因此,这些SL可以为约0.1至约1.0μm厚,优选约0.2至约0.5μm厚,由于形成和处理此类薄层而受损,可能难以自行测量如此薄的层上的渗透性。因此,HDL的渗透性的测量可用由多孔层支撑的HDL来测量,所述多孔层对所测试的气体具有比HDL本身高得多的“渗透性”。如果可能,具有HDL层和例如多孔层的膜,通过与用于制造烯烃/烷烃分离所使用的实际膜相同的方法来制造,参见例如以下实施例3中的“Teflon AF/PAN”基材的制备。
可通过发现各种其他合适的聚合物对于氮的渗透性来寻找可用于SDL的潜在聚合物。本文的GPU单位具有(1x10-6)sec/cm2 s cm Hg的单位,而渗透性单位通常为Barrer,其为(1x10-10)sec cm/cm2 s cm H测量HDL的氮渗透性的方法
从较大的3英寸平板膜片上冲出47mm平盘膜,其仅含有沟槽层材料作为多孔支撑件上的膜。然后将47mm圆盘放置在由进料口、滞留物口、吹扫入口和渗透物口构成的不锈钢横流测试单元中。使用四个六角螺栓将膜牢牢地固定在具有13.85cm2的总有效区域的测试单元中。
将单元的进料口连接至由4种气体:氮气、氧气、氦气和二氧化碳组成的气体歧管。将滞留物口连接至球形阀,以终止气体流以及吹扫气体。将两个渗透物口中的一个关闭,并且将另一个连接至流量计。
通过气体调节器使氮气加压,并且允许缓慢吹扫1分钟。将渗透物口关闭,并且可从处于大气压下的渗透物进行流量测量。对于5与10psig之间的三个不同进料压力重复此过程,以便可计算平均渗透性。记录进料压力、渗透物流量和温度以便进行计算。渗透性可通过以下公式计算:
Q=F/(A-Δp)
其中,Q=气体渗透性、F=渗透物流速、ΔP=跨膜分压差,并且A是膜的有效面积,在这种情况下是13.85cm2。
烯烃/烷烃分离的渗透性和选择性的测定
对于渗透性(GPU,以sec/cm2s cm Hg的单位报告)和选择性的测定,使用以下程序。从较大的平板3英寸复合膜上冲孔出47mm的平盘膜。然后将47mm圆盘放置在由进料口、滞留物口、吹扫入口和渗透物口构成的不锈钢横流测试单元中。使用四个六角螺栓将膜牢牢地固定在具有13.85cm2的总有效区域的测试单元中。
将单元放置在包括进料管、滞留物管、吹扫管和渗透物管的测试装置中。进料由烯烃(丙烯)气体和石蜡(丙烷)气体的混合物组成。每种气体均由单独的气缸供应。对于烯烃,使用聚合级丙烯(99.5体积%纯度),并且对于石蜡,使用99.9体积%纯度的丙烷。然后将这两种气体进料至各自的质量流量控制器,在那里可制成任何组成的混合物。在200mL/min的总气体流速下,标准混合组成为20体积%的烯烃和80摩尔%的石蜡。将混合气体通过水起泡器以加湿气体混合物,使相对湿度大于90%。在滞留物管中使用背压调节器来控制至膜的进料压力。在背压调节器之后将气体排出,进料压力通常保持在60psig(0.41MPa)。
吹扫管包括纯的潮湿氮气流。将来自气缸的氮气连接至质量流量控制器。将质量流量控制器设定为300mL/min的流量。将氮气进料至水起泡器以使相对湿度大于90%。在起泡器之后,将氮气进料至膜的吹扫口,以将任何渗透气体输送到渗透物口。
渗透管包括通过膜的渗透气体和吹扫气体以及水蒸汽。将渗透物连接至三通阀,因此可进行流量测量。使用具有GS-GasPro毛细管柱(0.32mm,30m)的450GC气相色谱仪(GC)分析渗透物流中烯烃和石蜡的比率。渗透侧的压力通常在1.20与1.70psig(8.3与11.7kPa)之间,但本文中举例来说为0.0至0.3psig(“0”至2.1kPa)。实验在室温下进行。
在实验过程中记录了以下各项:进料压力、渗透压力、温度、吹扫进入流速(氮气+水蒸汽)和总渗透流速(渗透物+氮气+水蒸汽)。
根据记录的结果确定以下各项:基于进料流量和进料压力的所有单独的进料分压;基于测量的渗透流量、吹扫流量和来自GC的组分的所有单独的渗透流量;基于渗透流量和渗透压力的所有单独的渗透分压。由此计算单个组分的跨膜分压差。从渗透的方程式
Qi=Fi/(A.Δpi)
计算渗透性(Qi),其中Qi=物质‘i’的渗透性,Fi=物质‘i’的渗透物流速,Δpi=物质‘i’的跨膜分压差,并且A是膜的面积(13.85cm2)。
在实施例中,使用以下缩写:
HFPO-六氟环氧丙烷(用于制备HFPO二聚体过氧化物,参见美国专利7,112,314,所述专利以引用的方式在此包括在内。HFPO二聚体[206298-8]可从Synquest实验室,Alachua,FL,USA获得)
PDD-全氟(2,2-二甲基-1,3-间二氧杂环戊烯)
SEFVE-CF2=CFOCF2CF(CF3)OCF2CF2SO2F
PPSF-CF2=CFOCF2CF2SO2F
VF2-偏二氟乙烯(H2C=CF)
VF-氟乙烯(H2C=CHF)
PPVE-全氟(丙基乙烯基醚)
实施例1
PDD/VF/SEFVE(进料比率100:100:150)共聚物的合成和水解
在氩气吹扫5分钟之后,向150mL不锈钢压力容器中加入磁性搅拌棒、3.66g PDD、10.04g SEFVE、12mLXF(据报道是1,1,1,2,2,3,4,5,5,5-十氟戊烷并且可从TheChemours公司,Wilmington,DE 19899,USA获得)、0.6mL HFPO二聚体过氧化物溶液(0.12M),并且然后在0℃下加入0.69g氟乙烯气体。将反应混合物密封在压力容器中并且在水浴中在室温下搅拌。在反应3小时之后,将反应容器向环境空气打开,向反应混合物添加10mL丙酮和40mL甲醇。将所得的凝胶样沉淀转移至玻璃皿,并且在100℃下在烘箱中干燥过夜,以产生5.5g为无色固体的PDD/VF/SEFVE三聚物(Tg 37℃)。
向250mL圆底玻璃烧瓶中加入3.75g在先前段落中合成的三聚物、20mL去离子水、60mL甲醇、1.85g碳酸铵和磁性搅拌棒。搅拌反应混合物并且保持在50℃-60℃下。在过夜反应之后,获得澄清溶液。将80mL的2.0M盐酸加入到混合物中,并且在加热下蒸发混合物中的甲醇以形成凝胶样沉淀。滗出液体并且添加50mL的2.0M盐酸并搅拌30分钟。滗出液体并且添加80mL的去离子水并且然后搅拌30分钟。在滗出液体之后,重复两次水洗涤,并且将固体残渣在60℃下在真空烘箱中干燥3小时。获得含有游离磺酸基团的褐色固体(2.7g)。
实施例2
PDD/VF/PPSF(进料比率100:100:150)共聚物的合成和水解
在氩气吹扫5分钟之后,向150mL不锈钢压力容器中加入磁性搅拌棒、3.66g PDD、6.3g PPSF、12mLXF、0.6mL HFPO二聚体过氧化物溶液(0.12M),并且然后在0℃下加入0.96g偏二氟乙烯气体。将反应混合物密封在压力容器中并且在水浴中在室温下搅拌。在过夜反应之后,将反应容器向环境空气打开,向反应混合物添加10mL丙酮和40mL甲醇。将所得的凝胶样沉淀转移至玻璃皿,并且在100℃下在烘箱中干燥过夜,以产生6.0g为无色固体的PDD/VF/PPSF三聚物(Tg 58℃)。
向250mL圆底玻璃烧瓶中加入4.0g在先前段落中合成的三聚物、20mL去离子水、60mL甲醇、1.5g碳酸铵和磁性搅拌棒。搅拌反应混合物并且保持在50℃-60℃下。在过夜反应之后,获得澄清溶液。将80mL的2.0M盐酸加入到混合物中,并且在加热下蒸发混合物中的甲醇以形成凝胶样沉淀。滗出液体并且添加50mL的2.0M盐酸并搅拌30分钟。滗出液体并且添加80mL的去离子水并且然后搅拌30分钟。在滗出液体之后,重复两次水洗涤,并且将固体残渣在60℃下在真空烘箱中干燥3小时。获得含有游离磺酸基团的淡褐色固体(3.0g)。
实施例3
膜形成和测试
向玻璃瓶中加入0.1g来自实施例1的聚合物、20mg硝酸银、3.5g异丙醇和1.5g7300(据报道是1,1,1,2,2,3,4,5,5,5-十氟-3-甲氧基-4-三氟甲基戊烷并且可从3M公司,Electronic Markets Materials Div.,St.Paul,MN,55144,USA获得)。搅拌所得溶液1-2小时,并且然后通过具有1.2μm的孔尺寸的玻璃纤维滤器过滤。将此溶液表示为“溶液1”。
向玻璃瓶中加入0.4gD79-25BS(从Sigma-Aldrich,USA获得,并且据报道含有25重量%在水中的聚合物、在聚合物基础上的1.23-1.30meq/g的酸容量)、20mg硝酸银、4.6g异丙醇。搅拌所得溶液1-2小时,并且然后通过具有1.2μm的孔尺寸的玻璃纤维滤器过滤。将此溶液表示为“溶液3”。
向玻璃瓶中加入0.5gD2020(从DuPont Fuel Cells,P.O.Box 80701,Wilmington,DE,19880-0701,USA获得,并且据报道含有20重量%聚合物、约34重量%水和约46重量%1-丙醇、在聚合物基础上的1.03-1.12meq/g的酸容量)、20mg硝酸银、4.5g异丙醇。搅拌所得溶液1-2小时,并且然后通过具有1.2μm的孔尺寸的玻璃纤维滤器过滤。将此溶液表示为“溶液4”。
通过在(由Nanostone Water,10250Valley View Rd.,Eden Prairie,MN 53344,USA制备的)PAN350膜(PAN350膜由聚丙烯腈制成的超滤器)上涂覆在770(可从3M公司,3M中心,Sty.Paul,MN,USA获得)中的0.2重量%的AF2400溶液(可从DuPont公司,Wilmington,DE 19898,USA获得)(关于AF的进一步信息,参见P.R.Resnick等人,Teflon AF Amorphous Fluoropolymers,J.Schiers编,ModernFluoropolymers,John Wiley&Sons,New York,1997,第397-420页,所述文献以引用的方式在此包括在内)来制备基材。将此基材表示为“TeflonAF/PAN”。
将溶液1在<30%相对湿度下分别直接涂覆在PAN350膜上,并且涂覆在Teflon AF/PAN上。
将溶液2在<30%相对湿度下分别涂覆在PAN350膜上,涂覆在Teflon AF/PAN上,并且涂覆在PDMS/PAN上。
将溶液3在<30%相对湿度下分别涂覆在PAN350膜上,涂覆在Teflon AF/PAN上,并且涂覆在PDMS/PAN上。
将溶液4在<30%相对湿度下分别涂覆在PAN350膜上,并且涂覆在Teflon AF/PAN上。
将获得的复合膜按以下方法测量丙烷和丙烯渗透性。
渗透性测量膜是47mm直径的平片。通过将其穿过水起泡器来使进料气体组成20摩尔%丙烯(聚合物合成等级)和80%丙烷潮湿。两种气体的总流速是200mL/min。进料气体(丙烯和丙烷的混合物)是60psig,并且膜的第二侧上的吹扫气体是在0.0至0.3psig的压力下的潮湿氮气。通过GC分析来自膜的第二侧的渗透物以确定丙烷和丙烯的摩尔比率。渗透性(GPU)以cm3/cm2/sec/cm Hg x 106的单位给出。
表1示出渗透性测量结果
表1
从表1可清楚地看出,在复合膜中引入含氟聚合物HDL导致丙烯渗透性和丙烯/丙烷选择性的一致性增加。
实施例4
PDD/PPVE高扩散速率聚合物的合成
在玻璃压力管中加入在Vertrel XF中的8.0g PDD、872mg PPVE、0.8mL HFPO二聚体过氧化物溶液(0.12M)和15mL Vertrel XF。在0℃下用氩气将混合物脱气5分钟之后,将玻璃管密封,使其在水浴中升温至室温并且将反应混合物搅拌过夜。将管向空气打开,并且向混合物中加入30mL丙酮。在搅拌5分钟之后,过滤混合物,并且加入30mL新鲜丙酮以将所有物质冲洗出容器。将滤纸上的固体转移至表面皿。在100℃下的烘箱中干燥过夜之后,收集7.4g白色固体作为PDD/PPVE聚合物。
实施例5
PDD/SEFVE高扩散速率聚合物的合成
在玻璃压力管中加入在Vertrel XF中的4.88g PDD、892mg SEFVE、0.4mL HFPO二聚体过氧化物溶液(0.12M)和15mL Vertrel XF。在0℃下用氩气将混合物脱气5分钟之后,将玻璃管密封,使其在水浴中升温至室温并且将反应混合物搅拌过夜。将管向空气打开,并且向混合物中加入30mL丙酮。在搅拌5分钟之后,过滤混合物,并且加入30mL新鲜丙酮以将所有物质冲洗出容器。将滤纸上的固体转移至表面皿。在100℃下的烘箱中干燥过夜之后,收集4.1g白色固体作为PDD/SEFVE聚合物。
实施例6
高扩散速率层渗透性测量
如实施例3中所述,以不同浓度(表2)由在770中的AF 2400制备溶液并且涂覆在PAN350膜上。据信较低的聚合物浓度导致形成较薄的膜。在10、20和30psig(68.9、137.8和207.7kPa)的进料压力和环境压力(大气压)下在产物侧上测试这些被支撑膜的氮渗透性。表2中所示的每种溶液的结果是三种进料压力的平均值。
表2
Claims (14)
1.一种薄膜复合膜,其包括:
包含氟化聚合物磺酸的银离聚物的分离层;以及
具有至少250GPU的对于氮的渗透性的一种或多种氟化聚合物的高扩散速率层,其中GPU的单位为(1×10-6)cm3/cm2·s·cm Hg,并且其中所述分离层和所述高扩散速率层彼此层压;以及
多孔层,所述多孔层被层压到所述高扩散速率层;并且
其中所述薄膜复合膜的烯烃与烷烃的选择性大于其中所述分离层直接层压到多孔层载体的膜。
2.根据权利要求1所述的薄膜复合膜,其中所述银离聚物是全氟聚合物。
3.根据权利要求1所述的薄膜复合膜,其中所述高扩散速率层是氟化聚合物,其中碳氟基团和碳-氢基团总数的50%或更多是碳氟基团。
4.根据权利要求1所述的薄膜复合膜,其中所述高扩散速率层氟化聚合物是全氟聚合物。
5.根据权利要求1所述的薄膜复合膜,其中所述高扩散速率层氟化聚合物是全氟(2,2-二甲基-1,3-间二氧杂环戊烯)的全氟共聚物。
6.根据权利要求1所述的薄膜复合膜,其中所述高扩散速率层氟化聚合物是全氟(2,2-二甲基-1,3-间二氧杂环戊烯)和四氟乙烯的共聚物。
7.根据权利要求1所述的薄膜复合膜,其中所述高扩散速率层是0.1至1.0μm厚。
8.一种用于从烯烃分离烷烃的膜方法,所述膜方法包括:
(a)提供薄膜复合膜,所述薄膜复合膜具有进料侧和渗透侧并且包括:
包含氟化聚合物磺酸的银离聚物的分离层;以及
具有至少250GPU的对于氮的渗透性的一种或多种氟化聚合物的高扩散速率层,其中GPU的单位为(1×10-6)cm3/cm2·s·cm Hg,并且其中所述分离层和所述高扩散速率层彼此层压;以及
多孔层,所述多孔层被层压到所述高扩散速率层;
(b)将膜进料侧暴露于包括烯烃和烷烃的流动组合物;以及
(c)产生膜渗透侧组合物,所述膜渗透侧组合物具有比膜进料侧组合物高的烯烃与烷烃之比;以及,
其中所述薄膜复合膜的烯烃与烷烃的选择性大于其中所述分离层直接层压到多孔层载体的膜。
9.根据权利要求8所述的膜方法,其中所述银离聚物是全氟聚合物。
10.根据权利要求8所述的膜方法,其中所述高扩散速率层是氟化聚合物,其中碳氟基团和碳-氢基团总数的50%或更多是碳氟基团。
11.根据权利要求8所述的膜方法,其中所述高扩散速率层氟化聚合物是全氟聚合物。
12.根据权利要求8所述的膜方法,其中所述高扩散速率层氟化聚合物是全氟(2,2-二甲基-1,3-间二氧杂环戊烯)的全氟共聚物。
13.根据权利要求8所述的膜方法,其中所述高扩散速率层氟化聚合物是全氟(2,2-二甲基-1,3-间二氧杂环戊烯)和四氟乙烯的共聚物。
14.根据权利要求8所述的膜方法,其中所述高扩散速率层是0.1至1.0μm厚。
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US62/262,169 | 2015-12-02 | ||
PCT/US2016/031135 WO2016182887A1 (en) | 2015-05-11 | 2016-05-06 | Thin film composite membranes for separation of alkenes from alkanes |
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CN201680032925.1A Pending CN107614549A (zh) | 2015-05-11 | 2016-05-06 | 用于从烷烃分离烯烃的改进的膜 |
CN201680037766.4A Pending CN107835797A (zh) | 2015-05-11 | 2016-05-06 | 用于从烷烃分离烯烃的改进的膜 |
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CN201680037766.4A Pending CN107835797A (zh) | 2015-05-11 | 2016-05-06 | 用于从烷烃分离烯烃的改进的膜 |
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US20180085714A1 (en) | 2018-03-29 |
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US10399044B2 (en) | 2019-09-03 |
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