CN107614549A - 用于从烷烃分离烯烃的改进的膜 - Google Patents

用于从烷烃分离烯烃的改进的膜 Download PDF

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CN107614549A
CN107614549A CN201680032925.1A CN201680032925A CN107614549A CN 107614549 A CN107614549 A CN 107614549A CN 201680032925 A CN201680032925 A CN 201680032925A CN 107614549 A CN107614549 A CN 107614549A
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ionomer
carbon
film
sulfonic acid
alkene
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N·上官
A·E·费林
S·马宗达
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Cam Pat Film Systems Co
Compact Membrane Systems Inc
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Abstract

包括来自偏二氟乙烯的重复单元的第11族金属的离聚物，其可在包含一层膜时将烯烃与烷烃分离。这些膜在烯烃与烷烃的分离中对烯烃具有优异的渗透性和/或选择性。

Description

用于从烷烃分离烯烃的改进的膜
发明领域
当用于从这些类型的化合物的混合物中的烷烃分离烯烃时，与其他膜相比，含有包含衍生自偏二氟乙烯的重复单元的第11族金属离聚物的膜具有特别好的耐久性和/或选择性。
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
无孔但可透过的膜长期以来已被用于分离各种类型的化学品。例如，某些类型的半透膜用于从海水分离饮用水、或从氮气分离氧气、或从烷烃分离烯烃。
从烷烃分离烯烃通常使用氟化聚合物的银离聚物来实现。通常，因为含氟聚合物比未氟化聚合物对于氧化更稳定，所以氟化聚合物的银离聚物通常比未氟化聚合物更稳定。另外，在例如磺酸基或羧基附近含有氟取代基的聚合物往往是非常强的酸(有时称为“超强酸”)，其银盐可能更稳定。
在炼油厂或烯烃聚合工厂中，有时存在烯烃和烷烃的混合物并且希望从烷烃分离烯烃。如果这两种类型的化合物的沸点具有显著差异，则这可能是相对容易的，但分离具有相似沸点的此类化合物是更困难且昂贵的，当沸点的温度较低时尤其如此。例如，丙烷在-44.5℃下沸腾并且丙烯在-47.8℃下沸腾。由于高设备和能量成本，通过低温蒸馏分离这两种化合物是非常昂贵的。因此，更便宜、更低能量密集的分离方法是合乎需要的。
授予Erikson等人的美国专利5,191,151描述了使用膜从低级烷烃(含有1至6个碳原子)分离低级烯烃(含有2至4个碳原子)，所述膜是四氟乙烯(TFE)和含有磺酸的末端前体基团的全氟乙烯基醚的聚合物的银离聚物。
授予Feiring等人的美国专利申请2015/0025293描述了为氟化聚合物的银离聚物的膜的用途。离聚物包括衍生自全氟化环状单体的重复单元。
L.Sauguet等人,Fluorinated Copolymers and Terpolymers Based onVinylidene Fluoride and Bearing Sulfonic Acid Side-Group,Journal of PolymerScience,Part A:,Polymer Chemistry,第45卷,(2007),第1814-1834页，报道了含有衍生自偏二氟乙烯和烯属磺酰氟的重复单元的广泛范围的氟化聚合物的合成。没有提及使用此类聚合物或它们的离聚物将链烯与烷烃分离，并且仅讨论碱金属(诸如钾)的离聚物。
授予Doyle等人的美国专利6,025,093描述了含有衍生自偏二氟乙烯和全氟化磺酸前体的重复单元的单价金属的离聚物。
本发明得到具有较高的耐久性和分离烯烃/烷烃分离系数，并且具有比先前使用的烯烃/烷烃分离膜更长的使用寿命的膜。
发明概述
本发明涉及一种第11族金属的离聚物，其包含衍生自偏二氟乙烯的重复单元和含有磺酸基团的前体或磺酸基团的单体，并且前提是碳-氟基团是存在于所述离聚物中的所述碳-氟基团和碳-氢基团总数的至少30％。
本文还描述了一种部分氟化聚合物，其包含衍生自偏二氟乙烯的重复单元；和含有磺酸基团的前体或磺酸基团的单体，前提是碳-氟基团是存在于所述离聚物中的所述碳-氟基团和碳-氢基团总数的至少30％。
本文还描述了一种用于从一种或多种烯烃分离一种或多种烷烃的方法，其包括：
(a)提供包含离聚物层的膜，所述离聚物包含衍生自偏二氟乙烯的重复单元和含有磺酸基团的前体或磺酸基团的单体，所述膜具有第一侧和第二侧，前提是碳-氟基团是存在于所述离聚物中的所述碳-氟基团和碳-氢基团总数的至少30％；
(b)将所述第一侧暴露于包含一种或多种烷烃和一种或多种烯烃的混合物的进料组合物；
(c)提供驱动力；以及
(d)在所述膜的第二侧上产生具有比所述第一混合物更高的烯烃与烷烃比率的第二混合物。
发明细节
本文使用某些术语，并且其中一些在以下定义：
在离聚物中的碳-氢基团和碳氟基团的总数中，30％或更多是碳-氟基团，优选60％或更多、并且更优选80％或更多是碳氟基团。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。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20摩尔％的CF2＝CFOCF2CF(CF3)OCF2CF2SO2F和80摩尔％的偏二氟乙烯的共聚物中，碳-氢基团是所存在的碳-氟基团加上碳氢基团的总数的27.6％。所存在的碳-氟和碳氢基团的相对量可通过NMR光谱学(例如，使用14C NMR或19F和质子光谱学的组合)来确定。
“含有磺酸基团的前体的单体”意指当聚合后的聚合物的一部分可易于转化为磺酸时的单体。此类基团包括磺酰卤，特别是磺酰氟、磺酰酯、磺酰胺等。本领域的技术人员将理解，在对通过初始聚合形成的聚合物进行化学处理之后，“含有磺酸基团的前体的单体”常常通过水解转化为磺酸基团。此外，在离聚物形式中，“磺酸”基团实际上至少部分地是第11族金属的磺酸盐。本文为了简单起见，在水解的或以其他方式反应的原始聚合物和离聚物中，这些在本文中有时被称为磺酸基团。
通过膜在分离烯烃和烷烃中的“驱动力”通常意指膜的第一(“进料”)侧上的烯烃的有效浓度高于膜的第二(“产物”)侧上的烯烃的有效浓度。如果在气体进料上进行分离，则可通过在膜的进料侧上具有较高的烯烃分压来实现。因此，气体进料可处于比产物侧更高的压力下，并且/或者烯烃可通过“惰性”气体(诸如氮气)从膜的产物侧被吹走，以降低产物侧上烯烃的分压。如果液体进料被分离，则进料侧可处于更高的压力下，并且/或者烯烃可通过惰性液体在产物侧上被冲走。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”的流速，Fa是通过膜的组分a的渗透性，P1a是第一(进料)侧上的a的分压，并且P2a是第二(产物)侧上的a的分压。
含有银离聚物的膜意指包含银离聚物的薄无孔层和物理地支持或加强银离聚物层的一个或多个其他聚合物层的膜。优选地，银离聚物层是约0.1μm至约1.0μm厚，更优选约0.2μm至约0.5μm厚。这些其他层对于待分离的烯烃和烷烃应优选是相对可透过的，并且本身并不具有很多(如果有的话)分离烯烃和烷烃的倾向。
在本发明的一个优选实施方案中，第11族金属是铜或银，更优选银。
在离聚物及其前体酸形式中，含有侧链磺酸基团的重复单元优选为存在的总重复单元的至少约5摩尔％、更优选至少约10摩尔％、非常优选至少约20摩尔％以及特别优选至少约25摩尔％。优选的是含有侧链酸性基团的重复单元不超过银离聚物或其前体酸形式中存在的重复单元的45摩尔％。应理解，此类重复单元的任何最小量和此类重复单元的任何最大量可组合以形成这些重复单元的量的优选范围。
含有磺酸基团或磺酸基团的前体的可用单体包括CF2＝CFOCF2CF2SO2F、CF2＝CFOCH2CF2CF2SO2F和CF2＝CFOCF2CF(CF3)OCF2CF2SO2F中的一种或多种，并且CF2＝CFOCF2CF(CF3)OCF2CF2SO2F是优选的。在含有磺酸或其前体的另一类优选单体中，结合到磺酸基团的碳原子具有结合到此碳原子的至少一个氟原子。
优选地，本文所述的各种形式的VF2共聚物(指的是“Y”究竟是什么，特别是当Y是第11族金属阳离子时)是所谓的“玻璃态”共聚物。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，所述共聚物不具有高于约30℃的熔点，具有3J/g或更高的熔化热。另外，玻璃态共聚物具有高于约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。
优选地，第11族金属离聚物通过在液体介质中使含有侧链磺酸基团(不是金属磺酸盐)的氟化聚合物与第11族金属盐接触来产生，所述第11族金属盐的阴离子共轭布朗斯台德酸在25℃下在水中具有小于1.0的pKa。
离聚物的聚合物部分可含有衍生自其他单体的重复单元，只要存在聚合物的其他组成限制，诸如碳-氟基团的最小分数。可用的单体包括四氟乙烯、三氟氯乙烯、氟乙烯、三氟乙烯、六氟丙烯以及乙烯中的一种或多种。
优选的是衍生自环状或可环化全氟化单体的重复单元不存在于离聚物中。环状全氟化单体意指全氟化烯烃，其中烯烃的双键呈环的形式，或者双键是外双键，其中双键的一个端部位于环碳原子处。可环化全氟化单体意指非环状全氟化化合物，其含有两个烯烃键，并且在聚合时在聚合物的主链中形成环状结构(参见例如N.Sugiyama,PerfluoropolymersObtained by Cyclopolymereization and Their Applications,in J.Schiers编,ModernFiuoropoiymers.John Wiley&Sons，New York，1997，第541-555页，所述文献以引用的方式在此包括在内)。此类全氟化环状和可环化化合物包括全氟(2,2-二甲基-1,3-间二氧杂环戊烯)、全氟(2-亚甲基-4-甲基-1,3-二氧戊环)、全氟链烯基全氟乙烯基醚以及2,2,4-三氟-5-三氟甲氧基-1,3-间二氧杂环戊烯。
优选地，当使用ASTM测试D3418-12e1，使用10℃/min的加热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，第11族金属离聚物不具有高于约0℃的熔点，具有3J/g或更高的熔化热。还优选地，离聚物不具有高于50℃的玻璃化转变温度(Tg)。根据ASTM测试D3418-12e1以10℃/min的加热速率测量Tg，并且将Tg作为转化中点。优选地，不存在高于30℃并且更优选高于10℃的Tg。可选地，当实际上从一种或多种烯烃分离一种或多种烷烃时，离聚物(如果存在的话)的Tg低于所述方法运行的温度。
离聚物可通过描述于本申请、授予Feiring等人的美国专利申请2015/0025293、授予Erikson等人的美国专利5,191,151以及Sauguet等人,Fluorinated Copolymers andTerpolymers Based on Vinylidene Fluoride and Bearing Sulfonic Acid Side-Group,Journal of Polymer Science,Part A:,Polymer Chemistry,第45卷,(2007),第1814-1834页中的方法产生，所有这些以引用的方式在此包括在内。可用于本发明中的聚合物的一些组成也由Feiring等人描述，并且含有侧链酸性基团的其中所述的此类聚合物也可如本文所述被处理以形成银离聚物。
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和1.70psig(8.3至11.7kPa)之间。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，使用某些缩写，并且它们是：
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
VF2-偏二氟乙烯(H2C＝CF2)
比较实施例A
PDD/SEFVE(进料比率；100/200总)共聚物的合成和水解在0℃下在氩气吹扫5分钟之后，向100mL梨形玻璃反应烧瓶中放入磁性搅拌棒、4.0g PDD、29.3g SEFVE、10mL 2,3-二氢十氟戊烷(XF specialty fluid,E.I.DuPont de Nemours&Co.公司,Wilmington,DE 19898,USA)和0.8mL由CF3CF3CF3OCF(CF3)CFO与碱性过氧化氢反应制备的六氟环氧丙烷(HFPO)二聚体过氧化物(0.12M)(参见美国专利7112314，其以引用的方式在此包括在内，用于合成这种过氧化物)的XF中的引发剂溶液。将反应混合物用橡胶隔膜密封，用氩气球保护、搅拌并且在水浴中温热至室温。在搅拌过夜之后，通过注射器将4.0g PDD和0.8mL HFPO二聚体过氧化物溶液(0.12M)加入到反应混合物中。在再搅拌一天之后，将烧瓶向环境空气打开，并且将40mL丙酮加入到混合物中。在搅拌15分钟之后滗出液体，并且加入40mL新鲜丙酮。在搅拌15分钟之后，再次滗出液体，并且将固体残渣转移至表面皿。在100℃下的烘箱中干燥过夜，产生10.0g白色固体PDD/SEFVE共聚物。
向250mL圆底玻璃烧瓶中加入10.0g在以上程序中合成的PDD/SEFVE共聚物、60mL去离子水、60mL乙醇、3.0g氢氧化钾和磁性搅拌棒。将反应混合物加热至回流并搅拌过夜。将混合物中的乙醇蒸发，并且将100mL 2.0M盐酸加入到混合物中。将固体从混合物中过滤，并且然后浸入100mL 2.0M盐酸两次。将所得固体用100mL去离子水洗涤三次并且在每次洗涤后过滤。最后将其在100℃下的烘箱中干燥3小时，以产生9.4g褐色固体，含有磺酸基团的水解共聚物PDD/SEFVE。此共聚物具有39℃的Tg。
向玻璃瓶中加入1g在前一段FC770(可从3M公司，3M中心，St.Paul,MN,USA获得)中制备的聚合物和30mL 30％过氧化氢。将反应混合物在环境温度下搅拌过夜，并且然后滤出聚合物并真空干燥。将干燥的聚合物(0.1g)加入到含有3.5g异丙醇和1.5g7300的瓶中，并且然后加入47mg AgNO3，并将初始混合物搅拌1-2小时直到聚合物完全溶解且固体AgNO3不可见。然后通过具有1.2μm标称孔尺寸的玻璃纤维滤器过滤溶液。
将在770(可从3M公司，3M中心，Sty.Paul,MN,USA获得)中的AF2400的0.3％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,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)涂覆到(由Nanostone Water,10250Valley View Rd.,EdenPrairie,MN 53344,USA制备的)PAN350膜(据信PAN350膜由聚丙烯腈制成，并且据信这是一种微孔膜)上以形成双层膜，并且然后在100℃下干燥1小时。优选地，Teflon AF2400层的厚度为约0.1至约0.2μm。在相对湿度<30％的情况下，将在前一段中制备的银离聚物溶液涂覆到双层膜的Teflon AF2400层上，并且然后在100℃下干燥1小时。
实施例1
VF2/SEFVE(进料比率；200/100)共聚物的合成和水解银离聚合物的膜
在氩气吹扫5分钟之后，全部在0℃下向150mL不锈钢压力容器中加入磁性搅拌棒、6.69g SEFVE、20mLXF、0.7mL HFPO二聚体过氧化物溶液(0.12M)和1.92g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，并且将30mL氟化溶剂(甲基全氟丙基醚，其可从3M公司，Electronic Materials Solutions Div.,St.Paul,MN 55144,USA获得)加入到反应混合物中。将全部溶液转移至玻璃皿，并且在室温下在通风橱中干燥3小时并且然后在100℃下在烘箱中干燥过夜以产生7.0g为无色粘性泡沫的VF2/SEFVE共聚物。此聚合物具有39℃的Tg。
向250mL圆底玻璃烧瓶中加入5.4g在以上程序中合成的VF2/SEFVE共聚物、20mL去离子水、40mL甲醇、2.7g碳酸铵和磁性搅拌棒。搅拌反应混合物并且保持在50℃-60℃下过夜。将混合物中的甲醇蒸发，并且将50mL 2.0M盐酸加入到混合物中。在搅拌15分钟之后滗出液体，并且添加50mL 2.0M盐酸。在搅拌15分钟之后，再次滗出液体并且添加50mL去离子水。重复两次水洗涤，并且将固体残渣在100℃下在烘箱中干燥过夜。获得的5.0g褐色固体是具有游离磺酸基团的VF2/SEFVE共聚物。此聚合物具有39℃的Tg。
通过与比较实施例A中所述相同的方法制备具有在前一段中制备的含有磺酸的聚合物的银离聚物的层的膜。
实施例2
VF2/SEFVE(进料比率；100/100)共聚物的合成和水解，以及银离聚合物的膜。
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、8.92gSEFVE、15mLXF、0.5mL HFPO二聚体过氧化物溶液(0.12M)，并且然后在0℃下加入1.28g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，并且将30mL7100氟化溶剂加入到反应混合物中。将全部溶液转移至玻璃皿，并且在室温下在通风橱中干燥3小时并且然后在100℃下在烘箱中干燥过夜以产生7.0g为无色粘性泡沫的VF2/SEFVE共聚物。
向250mL圆底玻璃烧瓶中加入7.0g在前一段中合成的共聚物、30mL去离子水、60mL甲醇、3.5g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，将混合物中的甲醇蒸发，并且将50mL 2.0M盐酸加入到混合物中。在搅拌15分钟之后滗出液体，并且添加50mL 2.0M盐酸。在搅拌15分钟之后，再次滗出液体并且添加50mL去离子水。重复两次水洗涤，并且将固体残渣在100℃下在烘箱中干燥过夜。获得含有游离磺酸基团的褐色固体共聚物(5.5g)。共聚物具有52℃的Tg。
除了仅使用31mg的AgNO3之外，通过与实施例1中所述相同的方法制备含有银离聚物层的膜。
实施例3
表1列出来自实施例A、实施例1和实施例2的膜的初始渗透性。用于渗透测量的膜单元使用47mm直径的平膜片。进料气体组合物由通过水性起泡器来增湿，并且在室温下为20摩尔％丙烯(聚合物合成级)和80％丙烷。两种气体的总流速是200mL/min。进料气体(丙烯和丙烷的混合物)压力是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FTIR分析来自膜的第二侧的渗透物以确定丙烷和丙烯的总渗透量。渗透性(GPU)以cm3/cm2/sec/cm Hg x 106的单位给出。
表1
表1显示本发明组合物的离聚物令人惊讶地具有比现有技术膜更优异的烯烃渗透性和/或选择性。

Claims (10)

1.一种第11族金属的离聚物，其包含衍生自偏二氟乙烯的重复单元和含有磺酸基团的前体或磺酸基团的单体，前提是碳-氟基团是存在于所述离聚物中的所述碳-氟基团和碳-氢基团总数的至少30％。
2.如权利要求1所述的离聚物，其中所述第11族金属是银。
3.如权利要求2所述的离聚物，其中存在含有所述侧链磺酸基团或含有至少约10摩尔％所述重复单元的磺酸基团前体的单体的重复单元。
4.如权利要求2所述的离聚物，其中所述碳-氟基团是存在于所述离聚物中的所述碳-氟和所述碳氢基团总数的至少约60％。
5.根据权利要求1至4中任一项所述的离聚物，其中所述前体是CF2＝CFOCF2CF2SO2F、CF2＝CFOCH2CF2CF2SO2F和CF2＝CFOCF2CF(CF3)OCF2CF2SO2F中的一种或多种。
6.根据权利要求1至4中任一项所述的第11族金属的离聚物，其中所述离聚物另外包含衍生自四氟乙烯、三氟氯乙烯、氟乙烯、三氟乙烯、六氟丙烯以及乙烯中的一种或多种的重复单元。
7.一种用于使用膜从一种或多种烯烃分离一种或多种烷烃的方法，其中所述改进包括使用包含如权利要求1至6中任一项所述的离聚物的无孔层的膜。
8.如权利要求7所述的方法，其中所述烷烃和烯烃是气体。
9.一种膜，其包含含有如权利要求1至6中任一项所述的离聚物的无孔层。
10.如权利要求1所述的离聚物，其中不存在衍生自环状或可环化全氟化单体的重复单元。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111804157A (zh) * 2019-01-07 2020-10-23 卡姆帕特薄膜系统公司 薄膜复合膜和用于从气态进料混合物中分离烯烃的方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112018002467T5 (de) 2017-05-12 2020-01-30 Compact Membrane Systems, Inc. Verbesserte membranen zur trennung von alkenen von anderen verbindungen
US20210016231A1 (en) * 2018-03-29 2021-01-21 Compact Membrane Systems Inc. Carbon dioxide separation membranes and process
US11040312B2 (en) 2019-05-09 2021-06-22 Pall Corporation Porous membrane having a fluorinated copolymer as surface treatment
WO2021050529A1 (en) * 2019-09-09 2021-03-18 Compact Membrane Systems, Inc. Gas permeable fluoropolymers and ionomers
CN111085120B (zh) * 2019-12-30 2022-02-22 山东天维膜技术有限公司 一种单价选择性阳离子交换膜的制备方法
US20230093327A1 (en) * 2020-02-06 2023-03-23 National University Of Singapore Composite membrane and methods of fabrication thereof
WO2021202255A1 (en) * 2020-03-30 2021-10-07 Compact Membrane Systems, Inc. Method for removing ethylene from agricultural products
CN117751006A (zh) 2021-07-12 2024-03-22 卡姆帕特薄膜系统公司 具有改善的层间粘合性的薄膜复合膜及其用途
WO2023023280A1 (en) * 2021-08-18 2023-02-23 Freeman Benny D Selective and hydrogen-stable facilitated transport membranes for olefin-paraffin separation
WO2023022847A1 (en) 2021-08-19 2023-02-23 Exxonmobil Chemical Patents Inc. Membrane-based separation processes enhanced with an absorption device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5191151A (en) * 1991-12-18 1993-03-02 Phillips Petroleum Company Use of silver-exchanged ionomer membranes for gas separation
CN1297463A (zh) * 1998-04-18 2001-05-30 斯图加特大学 酸碱聚合物共混物和它们在膜制品中的用途
CN1527845A (zh) * 2001-07-13 2004-09-08 ��Ļ���Ű˾ 生成氟化离聚物的方法
CN102264777A (zh) * 2008-12-23 2011-11-30 杜邦公司 使用氟化离聚物的分散颗粒通过含水聚合制备含氟聚合物

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3758603A (en) 1972-05-12 1973-09-11 Standard Oil Co Process for separation of unsaturated hydrocarbons
US3758605A (en) 1972-09-13 1973-09-11 Standard Oil Co Process
US4614524A (en) 1984-12-31 1986-09-30 Monsanto Company Water-free hydrocarbon separation membrane and process
US4731263A (en) 1986-09-26 1988-03-15 The Dow Chemical Company Method for the preparation of ionomer films
US4741744A (en) * 1987-02-20 1988-05-03 The Dow Chemical Company Hydrated metal ionomer membranes for gas separation
US5015268A (en) 1988-10-13 1991-05-14 Exxon Research And Engineering Co. Polymeric membrane and process for separating aliphatically unsaturated hydrocarbons
US5062866A (en) 1988-10-13 1991-11-05 Exxon Research And Engineering Co. Polymeric membrane and process for separation of aliphatically unsaturated hydrocarbons
EP0477224B1 (en) 1989-06-15 1993-03-17 Du Pont Canada Inc. Perfluorodioxole membranes
EP0709424A1 (en) 1994-10-31 1996-05-01 Ferro Corporation Color concentrates
US5880241A (en) 1995-01-24 1999-03-09 E. I. Du Pont De Nemours And Company Olefin polymers
AU3284197A (en) * 1996-05-17 1997-12-09 Colorado School Of Mines Membrane separation of components in a fluid mixture
US5670051A (en) * 1996-05-23 1997-09-23 Membrane Technology And Research, Inc. Olefin separation membrane and process
US5914154A (en) * 1997-05-30 1999-06-22 Compact Membrane Systems, Inc. Non-porous gas permeable membrane
US6369178B1 (en) 1998-12-23 2002-04-09 Alliedsignal Inc. Poly (chlorotrifluoroethylene/vinylidenefluoride/vinylester) copolymers with excellent long-term ultraviolet light resistance
US6299777B1 (en) 1999-08-17 2001-10-09 Cms Technology Holdings, Inc. Osmotic distillation process
KR100315894B1 (ko) 1999-12-30 2001-12-24 박호군 고분자 전해질을 이용한 알켄 분리용 고체상 촉진 수송분리막
US7482415B2 (en) * 2000-02-16 2009-01-27 Daikin Industries, Ltd. Process for producing fluoroionomer, method for purification and concentration of the ionomer, and method of film formation
US6592650B2 (en) * 2000-05-19 2003-07-15 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes and PSA
US6361582B1 (en) 2000-05-19 2002-03-26 Membrane Technology And Research, Inc. Gas separation using C3+ hydrocarbon-resistant membranes
US6518476B1 (en) * 2000-09-18 2003-02-11 Union Carbide Chemicals & Plastics Technology Corporation Methods for manufacturing olefins from lower alkans by oxidative dehydrogenation
EP1211288A1 (fr) * 2000-12-01 2002-06-05 Atofina Composition conductrice à base de polymère fluoré
EP1220344B2 (en) 2000-12-26 2012-08-01 Asahi Glass Company, Limited Solid polymer electrolyte membrane, solid polymer fuel cell and fluorpolymer
WO2002062749A1 (fr) 2001-02-01 2002-08-15 Asahi Kasei Kabushiki Kaisha Monomere d'ether perfluorovinylique ayant un groupe sulfonamide
DE60221066T2 (de) 2001-05-07 2008-03-13 Solvay Solexis S.P.A. Amorphe perfluorierte Polymere
KR100444325B1 (ko) 2001-07-16 2004-08-16 한국과학기술연구원 안정성이 향상된 은염이 함유된 올레핀 촉진수송 고분자 분리막 및 이의 제조방법
US7101938B2 (en) * 2002-07-09 2006-09-05 E. I. Dupont De Nemours And Company Method for forming fluorinated ionomers
CN1319916C (zh) * 2002-12-02 2007-06-06 液体空气乔治洛德方法利用和研究的具有监督和管理委员会的有限公司 从与链烷烃的混合物中分离烯烃的方法
US20040173529A1 (en) * 2003-03-07 2004-09-09 Membrane Technology And Research, Inc. Liquid-phase separation of low molecular weight organic compounds
KR100530544B1 (ko) 2003-04-11 2005-11-23 한국과학기술연구원 전이금속염과 프탈릭 구조를 포함한 고분자로 구성된 고체고분자 전해질층 및 다공성 지지막을 포함하는 촉진 수송분리막
CA2426629C (en) 2003-04-25 2012-09-25 Nova Chemicals Corporation Process for the separation of olefins from paraffins using membranes
US20060014887A1 (en) * 2004-07-19 2006-01-19 3M Innovative Properties Company Method of hydrolyzing a dispersion of ionic fluoropolymer
ITMI20050445A1 (it) * 2005-03-17 2006-09-18 Solvay Solexis Spa Membrana ionomerica composta
KR100611682B1 (ko) 2005-07-12 2006-08-14 한국과학기술연구원 은 나노 입자/고분자 나노 복합체를 이용한 올레핀/파라핀분리용 나노 복합 분리막 및 제조 방법
US8497049B2 (en) * 2007-04-02 2013-07-30 GM Global Technology Operations LLC Hydrophilic and corrosion resistant fuel cell components
KR101558027B1 (ko) * 2008-07-02 2015-10-06 유오피 엘엘씨 필러로서 미세다공질 중합체를 포함하는 혼합 매트릭스 멤브레인
US20110266220A1 (en) 2009-01-07 2011-11-03 Cms Technologies Holdings, Inc. Separations with highly selective fluoropolymer membranes
US9079138B2 (en) * 2010-10-25 2015-07-14 Cms Technologies Holdings, Inc. Organic fluid permeation through fluoropolymer membranes
CN103263860B (zh) * 2013-05-26 2015-03-25 北京工商大学 一种聚氟乙烯分离膜的制备方法
AU2013206560A1 (en) * 2013-06-27 2015-01-22 Canon Kabushiki Kaisha Method, system and apparatus for rendering
US10029248B2 (en) * 2013-07-18 2018-07-24 Compact Membrane Systems Inc. Membrane separation of olefin and paraffin mixtures
US9120834B2 (en) * 2013-10-31 2015-09-01 Cms Technologies Holdings, Inc. Membrane separation of ionic liquid solutions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5191151A (en) * 1991-12-18 1993-03-02 Phillips Petroleum Company Use of silver-exchanged ionomer membranes for gas separation
CN1297463A (zh) * 1998-04-18 2001-05-30 斯图加特大学 酸碱聚合物共混物和它们在膜制品中的用途
CN1527845A (zh) * 2001-07-13 2004-09-08 ��Ļ���Ű˾ 生成氟化离聚物的方法
CN102264777A (zh) * 2008-12-23 2011-11-30 杜邦公司 使用氟化离聚物的分散颗粒通过含水聚合制备含氟聚合物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111804157A (zh) * 2019-01-07 2020-10-23 卡姆帕特薄膜系统公司 薄膜复合膜和用于从气态进料混合物中分离烯烃的方法

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