CN1286550C - 用于分离气体的混合基质膜及其生产和用途 - Google Patents
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Abstract
一种用于分离气体的改良的混合基质膜,其包括聚乙二醇、硅橡胶与多孔载体介质上的活性碳。该膜优选也包括碳酸盐(如碳酸钾)。可被膜分离的气体包括氧和氮的混合物以及二氧化碳和氮的混合物。这样设计的膜可用于处理天然气或其它气体。
Description
发明背景
将如氧和氮的气体彼此分离或将它们从其它气体混合物中分离经常是必要或是希望的。其用途可包括从对从可燃气体流中除去氧的需要、除去氮气以增加医疗用氧的氧含量的需要,到为在石油化工过程中实施分离或作为制备纯净气体流过程的一部分。
为了实施这种分离,已开发了几种技术,包括吸收入溶剂相中、压力摆动吸附(PSA)和膜分离。膜分离是基于一种气体分子比另一种气体分子通过若非如此不能透过的膜的高得多的相对渗透性。在气体分离中的应用中,聚合物膜已吸引了许多注意力。例如,所用的一些膜包括用于分离氧/氮的聚硅氧烷膜,用于从天然气中除去二氧化碳的醋酸纤维素膜以及用于从各种废弃物流中回收氢的聚硅氧烷涂覆的聚砜膜。在典型的操作中,维持聚合物膜两边的压差并以此为渗透驱动力。膜的两种性能对于决定膜所具有的性能特点具有决定性的重要性。第一种性能是气体在膜中的溶解性,而第二种性能是气体在膜材料中的扩散性。这两种性能(即溶解性和扩散性)的积称作渗透性。膜的渗透性越高,膜在气体分离过程中的应用越有吸引力。正如本文会非常详细地说明的,通过形成混合基质膜,聚合物膜的渗透性会增加和改变,从而提供本发明的新型的膜。
就迄今已知的一些气体分离膜而言,US-A-4,243,701中指出某些膜也可用于分离各种气体。通过使原料流横穿过膜的表面来实现利用膜的对气体混合物的分离。由于原料流具有比排出流更高的压力,因而混合物中更易渗透的组分会以比较不易渗透的组分更快的速度穿过膜。因此,穿过膜的渗透流富含更易渗透的组分,相反地,剩余流富含原料中更不易渗透的组分。
多篇参考文献对在分离膜中引入不同物质作出了公开。US-A-3,457,170、US-A-3,878,104、US-A-3,993,566、US-A-4,032,454承US-A-4,341,605讲述了用于帮助膜抵抗反渗透过程中所用的高压的支撑结构或增强纤维或织物的使用。US-A-3,556,305中显示了“三明治”式的反渗透膜,它包括覆盖有阻挡层的多孔基片,该基片使用粘合剂聚合物层覆盖有结合到阻挡层上的聚合物或薄膜。US-A-3,862,030显示了具有的无机填料(如二氧化硅)的聚合物基质,其中无机填料分散至全部聚合物基质中的各处,这产生了具有0.01至100微米的微孔或空隙的、能够过滤亚微米尺寸的微观或超细颗粒的网络。Jakabhazy等的US-A-4,302,334公开了包括与赋予膜亲水性能的聚乙烯醇共混的疏水氟碳聚合物的膜“合金”。
US-A-4,606,740描述了可用于分离气体混合物的、含有聚乙二醇的多组分膜的组成和制造。该文献也公开了聚砜载体的使用。US-A-5,127,925描述了使用由其中混入固体颗粒吸附剂的聚硅氧烷构成的混合基质膜的气体的分离。
现在我们已经发现了一种制备混合基质膜的新型的和非常有利的方法。我们也已发现,当根据本发明的方法制备混合基质膜时,由于膜的稳态渗透性以允许得到所希望的选择性的方式改变而具有独特性质(上述选择性是就预定流体(特别是气体)从流体或气体的混合物中通过混合基质膜而言的)。我们还开发了一种构成在本发明之前还没有过的混合基质膜的具体成分的组合。
发明概述
本发明是具有改善的稳定性和分离性能的混合基质膜。本发明也包括一种制造该改善的膜的方法。这些改善起因于在含有聚乙二醇的配方中包括了活性碳或类似地起作用的物质。本发明涉及用于天然气或其它气体的处理(例如从可燃气体流中除去氧、除去氮气以增加医疗用氧的氧含量到为在石油化工过程中实施分离或作为制备纯净气体流过程的一部分)中的膜。本发明还涉及制备膜的方法和膜的用途。
因此,本发明包括以下内容:
1、一种制造膜的方法,其包括以下步骤:将聚乙二醇与含有碳酸钾的吸附剂颗粒混合以形成第一混合物,将硅橡胶与溶剂混合以形成第二混合物,将第一和第二混合物混合以形成第三混合物,将第三混合物浇铸到多孔担载介质上并将该膜干燥和固化。
2、根据1的方法,其中所述吸附剂颗粒选自活性碳颗粒、沸石、氧化铝、无机氧化物和二氧化硅。
3、根据2的方法,其中所述吸附剂颗粒是活性碳颗粒。
4、根据3的方法,其中膜含有1至40%的活性碳或等量的其他吸附剂。
5、根据1的方法,其中所述多孔担载介质包括聚砜、聚醚砜、聚酰亚胺或醋酸纤维素。
6、一种用于分离气体的多组分膜,该膜包括载于多孔担载介质上的硅橡胶、碳酸钾和聚乙二醇及其颗粒状固体载体的混合物。
7、根据6的膜,其中聚乙二醇的固体载体选自氧化铝、二氧化硅、沸石和活性碳。
8、根据6的用于分离气体的多组分膜,其中所述膜还包括活性碳。
9、一种分离气体混合物的方法,包括在促进分离的条件下使增压的气体混合物与根据8的膜相接触。
附图简述
图1是两种气体的混合基质膜分离的示意图。
图2显示出了本发明的固体/液体/聚合物膜的示意图。
图3是制备本发明混合基质膜的流程图。
详细描述和优选实施方案
本发明涉及到对分离气体、特别是分离氧和氮具有改善的选择性的多组分或混合基质膜。这种膜在下述的各种工业和消费者应用中都有实用性。任何特定的膜的实用性都与如选择性和渗透性的性能参数紧密联系在一起。膜分离气体物质的能力是受溶解性(S)和扩散性(D)控制的。渗透性(P)等于S乘以D。组分1和2的选择性通过以下等式来限定:
下表中显示出了利用这些膜可分离的一些正常的气体物质,以及气体分子的动力学直径(动力学直径是涉及其进入混合基质膜固体组分中的能力的一种影响因素)。沸石或其它气体吸附性物质的固体组分不用作膜中的吸附剂,但是起到了增加复合膜中所希望渗透的气体分子的溶解度的功能。这增加了选择性定义中的S1∶S2比率。
表1
分子 | 分子直径() |
NH3H2OH2C2H2O2SO2N2COCH4C2H4 | 2.62.652.893.33.463.63.643.763.83.9 |
图1表示了组分1和2的膜分离。它显示出,将含有等量1和2组分的气体混合物送入左侧的装置中,组分2优先通过膜使得于装置底部离开的产物气体中浓缩了气体组分2。该例中,组分2是所希望渗透分子。少部分组分1与组分2一起通过了膜,而大部分组分1没有通过膜。分散于聚合物相中的固体或液体(术语“混合基质膜”起源于此)增加了组分2的选择性。因为该固体不用作吸附剂,它对所希望渗透物的选择性不需要非常强。虽然它应该对所需渗透物应是选择性的,但固体作为吸附剂的强选择性对混合基质膜仅有很少的贡献。
现有技术的混合基质膜中,已显示了两种不同类型的混合膜-聚合物中含有固体的混合膜和聚合物中含有液体的混合膜。在一种现有技术的膜中,含有固体的膜包含分散在醋酸纤维素中的硅酸盐。液体-聚合物混合基质膜的一个例子是分散在硅橡胶中的聚乙二醇。先前引用的US-A-4,606,740和许多文献如Tantekin-Ersolmaz等的Journal ofMembrane Science 175(2000)285-288、Sungpet等的Journal of MembraneScience 136(1997)111-120中都描述了这些现有技术的混合基质膜。这些文献关于用于气体分离的混合基质膜的组成和制造的讲述被特意结合于此。
图2是旨在图示本发明的在气体分离方面提供了优于现有技术膜的意想不到的优点的固体-液体-聚合物膜的总体结构和组成。因此该膜是固体聚合物与液体聚合物共混物的混合基质膜。图2显示出了膜介质的层,此处包括分散在硅橡胶中的聚乙二醇(PEG)和固体颗粒。该层位于提供强度的聚砜纤维上并形成膜。聚砜纤维有许多通过其中的由空隙表示的小开孔。该膜介质连接了这些空隙上以形成抵抗气体流动的固体层。
本发明的膜含有增塑剂,优选分子量为200至600的二元醇增塑剂。优选聚乙二醇(PEG)。其它合适的二元醇增塑剂包括四甘醇、丙二醇和聚丙二醇。
该膜也含有硅橡胶(SIL)。硅橡胶可以被描述为与二元醇增塑剂形成乳状液,其中PEG分散于硅橡胶中。
该膜含有5至50%的增塑剂和40至85%的硅橡胶。增塑剂含量的优选范围为10至30%。硅橡胶含量的优选范围为60至80%。除非另外指明,否则此处所有百分率为重量百分率。
本发明的膜也含有以活性碳为例的吸附剂组分。该组分被显示为不溶的非常小的分散在膜的整个浇铸部分的颗粒。该膜应含有1至40%的活性碳或等量的吸附剂。碳含量的优选范围为5至25%。优选活性碳具有0.1与5微米之间的颗粒度,并具有0.1至200微米范围内的宽颗粒度分布。将Calgon Carbon Corporation市售的、产品名为CAL的活性碳用于本文报道的配方中。也可使用其它类型的吸附剂组分(如沸石和碳酸盐)。
活性碳被认为起PEG的基底或载体的作用。因此PEG被认为是被吸附在碳颗粒的表面上的。包括无机氧化物的其它物质也可以这种方式有效地起作用,从而稳定PEG或其它增塑剂。例如,精细研磨的氧化铝、二氧化硅或沸石可以这种方式起作用。正如以下实验结论所表明的,硅橡胶-PEG膜中活性碳的存在改善了气体分离的选择性。碳也改善了稳定性。膜的稳定性通过分离氮然后分离二氧化碳,每24小时改变所选择的渗透物来测试。稳定性试验是在70℃下、在膜两边的压力在172和345kPa之间变化的条件下进行的。
膜也可含有碳酸盐,无机和有机的碳酸盐均可。合适的碳酸盐的例子包括碳酸钠和碳酸钾。当希望从原料气体混合物(如含有氮、氧或如甲烷的轻质烃的气体)中分离二氧化碳时碳酸盐的存在是有益的。这种情况下原料气流含有水是重要的,虽然已发现原料的相对湿度在相对湿度区间30至70%并不显著地改变膜从氮中分离二氧化碳的选择性。可以用水饱和原料气流。
本发明的膜组合物的一个实施方案包括5%的碳酸钾、15%的活性碳和80%的硅橡胶。
本发明的膜组合物的第二个实施方案包括20%的活性碳、10%的PEG和70%的硅橡胶。
本发明的膜组合物的第三个实施方案包括5%的碳酸钾、15%的活性碳、10%的PEG和70%的硅橡胶。
可以通过室温在适当溶剂存在下混合(搅拌或振摇)所需成分、然后以常规的方法将液相混合膜介质成分覆盖在多孔担载介质上浇铸膜从而形成膜。也可以将膜浸入或通过混合原料池。随后,除去过量的膜介质并使剩余的膜介质在暴露于最高可达100℃的升高的温度之后固化。优选的载体介质为属于织物的或属于非织物的可耐受膜将暴露于其中的化学物质和温度的聚合物纤维。醋酸纤维素、聚砜、聚醚砜和聚酰亚胺就是这类材料。以多孔聚砜为优选的载体介质。可以通过与多元醇(如乙二醇、邻苯二酚或丙二醇)接触来处理聚砜。优选的多元醇是丙三醇。可以通过使载体介质暴露于液体多元醇下1至4小时、然后在室温下风干完成所述处理。
图3显示了生产含有PEG、碳酸钾、活性碳和硅橡胶的膜的步骤。它显示出了形成分离混合物的两个初始混合步骤。硅橡胶与环己烷溶剂混合,并制备分开的与碳酸钾混合的PEG和活性碳的混合物。随后将这两种混合物混合在一起形成浇铸溶液,然后将其浇铸在载体介质(如处理过的多孔聚砜)上。然后将经浇铸后的浇铸溶液在热空气中固化。
本发明的优选实施方案中,在添加增塑剂之前将碳加入硅橡胶中。这一添加操作是在适当溶剂的存在下进行的。将氟代烃(如三氟三氯乙烷)用作溶剂,但由于对环境的担忧,非氟代的烃(如环乙烷)是优选的,但从环保方面说,按照现今的标准,它是不能被接受的。溶剂以提供适于浇铸的可加工混合物的量使用。在80至95%的范围内的容积含量通常是适用的。在固化步骤中从膜中除去溶剂。US-A-4,606,740中关于膜的制造方法的讲述结合于此。所得膜介质的层优选30密耳厚(1密耳等于0.001英寸)。层的厚度可按需要变化。
因此,本发明膜的特征可被归纳成用于分离气体的多组分膜,该膜包含悬浮于多孔担载介质上的均匀厚度层中的增塑剂(优选聚乙二醇)、硅橡胶和增塑剂的颗粒状固体载体的混合物。增塑剂的固体载体可选自氧化铝、二氧化硅、沸石和活性碳。
可利用本发明的膜分离的气体包括氧和氮。利用这些膜可从轻质链烷烃中分离轻质烯烃。这种膜也可用于从其它气体混合物中分离氮气,包括从含有甲烷、乙烷和类似轻质烃(如天然气流)的气体烃混合物中分离氮或氢。这种膜可用于制造在医疗或工业应用中可能有用的较纯的氧或氮。它们可用于制造用于生产氮和/或氧的低温气体分离过程的原料流,或与压力摆动吸附(PSA)单元组合使用。该膜可用于制备PSA单元的原料或处理关于PSA单元的流出物以产生再循环料流。
根据本发明制备的膜也可用于分离极性和非极性气体。因此,该膜可用于分离含有硫化氢、二氧化碳、一氧化碳、二氧化硫、氨、氢及其它的气体混合物。这样该膜在从燃烧产物(如燃料气体流)中除去污染物或其它化合物中具有实用性。
通过混合16%的硅橡胶、79%的环己烷溶剂和5%的PEG来制备用于以下试验中的膜。通过混合约17%的硅橡胶、78%的环己烷和5%的活性碳来制备本发明的膜。从约47%的硅橡胶、41%的环己烷、9%的活性碳和3%的碳酸钾的混合物配制本发明的第二种膜。从17%的硅橡胶、76%的环己烷、2%的PEG和5%的活性炭的混合物制造本发明的另一种膜。从含有约17%的硅橡胶、76%的环己烷、2%的PEG、4%的活性碳和1%的碳酸钾的膜介质混合物生产本发明的另一种膜。
表2给出了使用所示组成的三种不同膜来分离二氧化碳和氮气得到的试验数据。括号内的数据是从引用的US-A-4,606,740计算得到的数字。这些数据仅出于比较的目的而显示。然而,它确实也表明了PEG存在的益处。
表2
膜 | PCO2/PN2 | PCO2/d*106cm3(STP)/cm2-秒-cm(Hg) |
SIL-PSPEG/SIL MMMPEG/SIL Gly-P MMM | 11(11.4)42(67)61(100) | 14.3(61)4.89(13.6)5.45(13.2) |
SIL-PS=涂覆在多孔聚砜上的硅橡胶
PEG/SIL MMM=涂覆在多孔聚砜上的聚乙二醇/硅橡胶
PEG/SIL Gly-P MMM=涂覆在丙三醇处理过的多孔聚砜上的聚乙二醇/硅橡胶
表3给出了额外试验的数据,这些试验结果表明将活性碳加入配方中所得的益处。第二种和第四种膜与第一种和第三种相同,但加入了活性碳。下表中的第四种膜表明本发明所显示出的优异性能。由于加入了碳,选择性和渗透性都增加了,加入PEG和活性碳后改善的程度甚至更好了。
表3
膜 | PCO2/PN2 | PCO2/d*106cm3(STP)/cm2-秒-cm(Hg) |
SIL-PSAct.C/SIL MMMPEG/SIL MMMPEG/Act.C/SIL MMM | 11154247 | 14.329.44.924.2 |
Act.C/SIL MMM=涂覆在多孔聚砜上的活性碳/硅橡胶
PEG/Act.C/SIL MMM=涂覆在多孔聚砜上的聚乙二醇/活性碳/硅橡胶
表4给出了测定膜的分离性能的额外试验的数据,其中以碳酸钾作为最后的膜试验中的添加组分。同样,除了存在另外的膜组分之外,第二和第四膜组合物与第一和第三是相同的。
表4
膜 | PCO2/PN2 | PCO2/d*106cm3(STP)/cm2-秒-cm(Hg) |
Act.C/SIL MMMK2CO3/Act.C/SIL MMMPEG/Act.C/SIL MMMPEG/K2CO3/Act.C/SIL MMM | 1520.134.640.5 | 29.416.226.214.3 |
K2CO3/Act.C/SIL MMM=涂覆在多孔聚砜上的K2CO3/活性碳/硅橡胶
PEG/K2CO3/Act.C/SIL MMM=涂覆在多孔聚砜上的聚乙二醇/K2CO3/活性碳/硅橡胶
除非另有说明,本文中的所有试验数据均是在20℃下的。
必须在适当的促进分离的条件下使用膜。在20至100℃的温度下在促进分离的条件下试验了本膜的优选实施方案。需要跨过膜的正压力梯度以驱使气体通过膜。优选172kPa以上的压力差。跨过膜的压力差被膜的强度所限制。这与膜的绝对操作压力(仅被将膜密封的设备的强度所限制)不同。
本发明的膜可用于代替常规设计的分离设备中的现有技术的膜。回收的渗透物的量与所用的膜的面积成正比,因此优选提供大表面积的设备设计(如螺旋盘绕的管束或含有许多小直径管(中空纤维)的管束)。
实施例1
下面的步骤制备了本发明的混合基质膜:部分1:通过在10克环己烷中混合1.08克GE聚硅氧烷RTV-615A和0.12克的GE硅氧烷-615B制备硅橡胶溶液。部分2:通过在0.24克活性碳(颗粒度0.1-5微米,CalgonCarbon Co市售)中加入0.12克的400MW PEG制备聚乙二醇(PEG)浸渍的活性碳。通过将以上部分2中的PEG浸渍的活性碳混入以上部分1中的硅橡胶溶液中来制备浇铸溶液。利用真空泵使浇铸溶液脱气。将脱气溶液倒在多孔聚砜(PS)上。涂覆后,在82℃下将膜固化60分钟。将该膜标记为“A”。该膜是由PEG/活性碳/Sil/PS构成的。
实施例2
为了说明当与其它多组分膜对比使用本发明(从实施例1)的混合基质膜时可以得到的关于分离系数和渗透性的优点,制备了三种多组分膜。这些膜如下:
膜“B”-Sil/PS,该膜根据以上实施例1制备,但是没有PEG浸渍的活性碳。
膜“C”-活性碳/Sil/PS,该膜根据以上实施例2制备,并添加了0.24克的活性碳(Calgon Carbon Co.市售,颗粒度0.1至5微米)。
膜“D”-PEG/Sil/PS,该膜根据以上实施例2制备,并添加了0.12克的400MW PEG。
实施例3
然后通过利用直径为7.5cm的每种膜的样品来试验根据以上实施例1和2制备的膜“A”、“B”、“C”和“D”。置于试验装置中。将被试验的气体(本发明中是二氧化碳和氮)在室温下在345至517kPa(50至75psi)的压力下通过膜。测定并计算二氧化碳和氮气的通量和选择性。试验结果在下表5中列出。
表5
膜 | PCO2/PN2 | PCO2/d*106cm3(STP)cm2-秒-cm(Hg) |
“A”-PEG/活性碳/Sil/PS“B”-Sil/PS“C”-活性碳/Sil/PS“D”-PEG/Sil/PS | 34.6111534.9 | 26.214.329.48.1 |
Claims (9)
1、一种制造膜的方法,其包括以下步骤:将聚乙二醇与含有碳酸钾的吸附剂颗粒混合以形成第一混合物,将硅橡胶与溶剂混合以形成第二混合物,将第一和第二混合物混合以形成第三混合物,将第三混合物浇铸到多孔担载介质上并将该膜干燥和固化。
2、根据权利要求1的方法,其中所述吸附剂颗粒选自活性碳颗粒、沸石、氧化铝、无机氧化物和二氧化硅。
3、根据权利要求2的方法,其中所述吸附剂颗粒是活性碳颗粒。
4、根据权利要求3的方法,其中膜含有1至40%的活性碳或等量的其他吸附剂。
5、根据权利要求1的方法,其中所述多孔担载介质包括聚砜、聚醚砜、聚酰亚胺或醋酸纤维素。
6、一种用于分离气体的多组分膜,该膜包括载于多孔担载介质上的硅橡胶、碳酸钾和聚乙二醇及其颗粒状固体载体的混合物。
7、根据权利要求6的膜,其中聚乙二醇的固体载体选自氧化铝、二氧化硅、沸石和活性碳。
8、根据权利要求6的用于分离气体的多组分膜,其中所述膜还包括活性碳。
9、一种分离气体混合物的方法,包括在促进分离的条件下使增压的气体混合物与根据权利要求8的膜相接触。
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US7291271B2 (en) | 2003-12-09 | 2007-11-06 | Separation Design Group, Llc | Meso-frequency traveling wave electro-kinetic continuous adsorption system |
US7166146B2 (en) * | 2003-12-24 | 2007-01-23 | Chevron U.S.A. Inc. | Mixed matrix membranes with small pore molecular sieves and methods for making and using the membranes |
JP2007518867A (ja) * | 2004-01-20 | 2007-07-12 | バウンドレス・コーポレーシヨン | 高度に微孔質なポリマー及びそれらの製法及び使用法 |
US7589034B2 (en) * | 2004-05-26 | 2009-09-15 | Milliken & Company | Treated activated carbon and process for making same |
GB2415047B (en) * | 2004-06-09 | 2008-01-02 | Schlumberger Holdings | Electro-chemical sensor |
US7264650B2 (en) * | 2004-06-24 | 2007-09-04 | North Carolina Agricultural And Technical State University | Ultrahigh-selectivity oxygen enrichment filled elastomeric silicone polymer membrane incorporating nanofillers |
US7344585B1 (en) | 2005-08-31 | 2008-03-18 | Uop Llc | Mixed matrix membrane for gas separation |
US7485173B1 (en) | 2005-12-15 | 2009-02-03 | Uop Llc | Cross-linkable and cross-linked mixed matrix membranes and methods of making the same |
US7846496B2 (en) * | 2006-03-10 | 2010-12-07 | Uop Llc | Mixed matrix membranes incorporating surface-functionalized molecular sieve nanoparticles and methods for making the same |
US20070209505A1 (en) * | 2006-03-10 | 2007-09-13 | Chunqing Liu | High Flux Mixed Matrix Membranes for Separations |
US7897207B2 (en) * | 2006-03-10 | 2011-03-01 | Uop Llc | Nano-molecular sieve-polymer mixed matrix membranes with significantly improved gas separation performance |
US8083833B2 (en) * | 2006-03-10 | 2011-12-27 | Uop Llc | Flexible template-directed microporous partially pyrolyzed polymeric membranes |
US7938893B2 (en) * | 2006-04-18 | 2011-05-10 | Gas Technology Institute | Membrane reactor for H2S, CO2 and H2 separation |
US7572318B2 (en) * | 2006-04-18 | 2009-08-11 | Gas Technology Institute | High-temperature membrane for CO2 and/or H2S separation |
EP2035116A2 (en) | 2006-05-05 | 2009-03-18 | Separation Design Group, LLC | Sorption method, device, and system |
KR100711237B1 (ko) | 2006-06-09 | 2007-04-25 | 한국에너지기술연구원 | 흡착제가 충진된 분리막 및 이를 이용한 이산화탄소 분리방법 |
US7637983B1 (en) | 2006-06-30 | 2009-12-29 | Uop Llc | Metal organic framework—polymer mixed matrix membranes |
US20080011163A1 (en) * | 2006-07-17 | 2008-01-17 | Mcclain Michael S | Sorbent porous polymeric composite materials |
US7943543B1 (en) | 2006-09-29 | 2011-05-17 | Uop Llc | Ionic liquid-solid-polymer mixed matrix membranes for gas separations |
US7758751B1 (en) | 2006-11-29 | 2010-07-20 | Uop Llc | UV-cross-linked membranes from polymers of intrinsic microporosity for liquid separations |
US20080142440A1 (en) * | 2006-12-18 | 2008-06-19 | Chunqing Liu | Liquid Separations Using High Performance Mixed Matrix Membranes |
US7815712B2 (en) * | 2006-12-18 | 2010-10-19 | Uop Llc | Method of making high performance mixed matrix membranes using suspensions containing polymers and polymer stabilized molecular sieves |
US20080143014A1 (en) * | 2006-12-18 | 2008-06-19 | Man-Wing Tang | Asymmetric Gas Separation Membranes with Superior Capabilities for Gas Separation |
US7998246B2 (en) | 2006-12-18 | 2011-08-16 | Uop Llc | Gas separations using high performance mixed matrix membranes |
US20080264254A1 (en) * | 2007-04-11 | 2008-10-30 | The Penn State Research Foundation | Novel sorbents and purification and bulk separation of gas streams |
DE102007049203A1 (de) | 2007-10-08 | 2009-04-09 | Werner A. Goedel | Membranen aus partiell eingebetteten Partikeln |
US20090126566A1 (en) * | 2007-11-15 | 2009-05-21 | Chunqing Liu | Polymer Functionalized Molecular Sieve/Polymer Mixed Matrix Membranes |
JP2011516258A (ja) * | 2008-04-08 | 2011-05-26 | フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ | 複合膜 |
US7790803B2 (en) * | 2008-06-02 | 2010-09-07 | Uop Llc | Crosslinked organic-inorganic hybrid membranes and their use in gas separation |
US20110138999A1 (en) * | 2009-12-15 | 2011-06-16 | Uop Llc | Metal organic framework polymer mixed matrix membranes |
US8747521B2 (en) * | 2010-02-10 | 2014-06-10 | Fujifilm Corporation | Gas separation membrane and method for producing the same, and gas separating method, module and separation apparatus using the same |
CN101837228B (zh) * | 2010-06-11 | 2012-06-06 | 苏州信望膜技术有限公司 | 一种混合基质膜及其制备方法 |
US20120048109A1 (en) * | 2010-08-24 | 2012-03-01 | Chevron U. S. A. Inc. | Mixed Matrix Membranes |
WO2013115762A1 (en) | 2012-01-27 | 2013-08-08 | Empire Technology Development, Llc | Accelerating transport through graphene membranes |
DE102012014335A1 (de) * | 2012-07-19 | 2014-01-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Dispersion, Verfahren zur Beschichtung von Gegenstädenmit dieser Dispersion und Verwendung der Dispersion |
US9358506B2 (en) * | 2013-08-29 | 2016-06-07 | V-GRID Energy Systems | Hydrogen separation from synthesis gas near STP |
US9233342B2 (en) * | 2013-11-13 | 2016-01-12 | King Abdulaziz City for Science and Technology (KACST) | Organic-inorganic porous membrane and a method for preparing the same |
US11083989B2 (en) * | 2014-06-04 | 2021-08-10 | Haldor Topsøe A/S | Gas treatment monolith article |
US20180133661A1 (en) * | 2016-11-17 | 2018-05-17 | Uop Llc | High flux, cross-linked, fumed silica reinforced polyorganosiloxane membranes for separations |
WO2022212412A1 (en) * | 2021-03-30 | 2022-10-06 | Entegris, Inc. | Liquid purification membrane including carbonaceous materials and methods of forming them |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3457170A (en) | 1966-04-14 | 1969-07-22 | Havens Intern | Solvent separation process and apparatus |
US3556305A (en) | 1968-03-28 | 1971-01-19 | Amicon Corp | Composite membrane and process for making same |
US4032454A (en) | 1972-03-31 | 1977-06-28 | E. I. Du Pont De Nemours And Company | Permselective membrane apparatus with porous support |
US3862030A (en) | 1972-12-13 | 1975-01-21 | Amerace Esna Corp | Microporous sub-micron filter media |
IL43281A (en) | 1973-08-20 | 1976-09-30 | Comision Para El Aprovechamien | Porous earthenware supporting members for reverse osmosis membranes,process of manufacture and apparatus using same |
US3993566A (en) | 1975-01-08 | 1976-11-23 | Amerace Corporation | Reverse osmosis apparatus |
US4302334A (en) | 1979-05-24 | 1981-11-24 | Abcor, Inc. | Microporous polymeric membrane |
US4243701A (en) | 1979-11-08 | 1981-01-06 | Uop Inc. | Preparation of gas separation membranes |
US4341605A (en) | 1981-01-16 | 1982-07-27 | E. I. Du Pont De Nemours And Company | Process for cation permeable membrane with reinforcement fabric embedded therein and product thereof |
US5127925A (en) | 1982-12-13 | 1992-07-07 | Allied-Signal Inc. | Separation of gases by means of mixed matrix membranes |
US4751104A (en) * | 1984-12-06 | 1988-06-14 | Uop Inc. | Preparation of gas selective membranes |
US4606740A (en) | 1985-04-15 | 1986-08-19 | Uop Inc. | Separation of polar gases from nonpolar gases |
JPS63229061A (ja) * | 1987-03-18 | 1988-09-22 | テルモ株式会社 | 膜型人工肺とその製造方法 |
US5011637A (en) * | 1989-01-23 | 1991-04-30 | The Dow Chemical Company | Preparing cellulose ester membranes for gas separation |
US5104425A (en) * | 1989-11-14 | 1992-04-14 | Air Products And Chemicals, Inc. | Gas separation by adsorbent membranes |
US5507860A (en) * | 1989-11-14 | 1996-04-16 | Air Products And Chemicals, Inc. | Composite porous carbonaceous membranes |
US5069794A (en) * | 1990-06-05 | 1991-12-03 | Mobil Oil Corp. | Separation of mixture components over membrane composed of a pure molecular sieve |
US5445669A (en) * | 1993-08-12 | 1995-08-29 | Sumitomo Electric Industries, Ltd. | Membrane for the separation of carbon dioxide |
AU6492696A (en) * | 1995-07-14 | 1997-02-18 | U.S. Environmental Protection Agency | Absorbent filled membranes for removal of volatile compounds from wastewater |
US5772735A (en) * | 1995-11-02 | 1998-06-30 | University Of New Mexico | Supported inorganic membranes |
US5753011A (en) * | 1997-01-17 | 1998-05-19 | Air Products And Chemicals, Inc. | Operation of staged adsorbent membranes |
US6503295B1 (en) * | 2000-09-20 | 2003-01-07 | Chevron U.S.A. Inc. | Gas separations using mixed matrix membranes |
US6500233B1 (en) * | 2000-10-26 | 2002-12-31 | Chevron U.S.A. Inc. | Purification of p-xylene using composite mixed matrix membranes |
US6508860B1 (en) * | 2001-09-21 | 2003-01-21 | L'air Liquide - Societe Anonyme A'directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude | Gas separation membrane with organosilicon-treated molecular sieve |
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2002
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- 2002-11-01 WO PCT/US2002/035326 patent/WO2003039728A2/en not_active Application Discontinuation
- 2002-11-01 CA CA2465791A patent/CA2465791C/en not_active Expired - Fee Related
- 2002-11-01 EA EA200400634A patent/EA006480B1/ru not_active IP Right Cessation
- 2002-11-01 CN CN02825964.5A patent/CN1286550C/zh not_active Expired - Fee Related
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WO2003039728A2 (en) | 2003-05-15 |
WO2003039728A3 (en) | 2003-11-13 |
CA2465791C (en) | 2011-08-02 |
EA006480B1 (ru) | 2005-12-29 |
CN1607976A (zh) | 2005-04-20 |
EP1441846A2 (en) | 2004-08-04 |
US6726744B2 (en) | 2004-04-27 |
US20030089228A1 (en) | 2003-05-15 |
AU2002361586B2 (en) | 2007-11-22 |
CA2465791A1 (en) | 2003-05-15 |
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