公开(公告)号：US08048198B2

公开(公告)日：2011-11-01

申请号：US11936951

申请日：2007-11-08

申请人： Chunqing Liu ,  David A. Lesch ,  Stephen T. Wilson

发明人： Chunqing Liu ,  David A. Lesch ,  Stephen T. Wilson

IPC分类号： B01D53/22 ,  B01D61/00 ,  B01D71/02 ,  B01D71/06

CPC分类号： B01D53/228 ,  B01D67/0046 ,  B01D67/0079 ,  B01D69/147 ,  B01D69/148 ,  B01D71/028 ,  B01D2323/12

摘要： The present invention discloses a new type of high performance mixed matrix membranes (MMMs) and methods for making and using the same. The MMMs comprise a continuous polymer matrix and at least two types of molecular sieves dispersed therein. The continuous polymer matrix in the MMM contains at least one type of polymer. The MMM in the form of a dense film, asymmetric flat sheet membrane or otherwise prepared exhibits simultaneously improved selectivity and permeability for gas separations compared to polymer membranes made from a continuous polymer matrix without any molecular sieves or with only one type of molecular sieve. MMMs of the present invention are suitable for a wide range of gas, vapor, and liquid separations such as alcohol/water, CO2/CH4, H2/CH4, O2/N2, CO2/N2, olefin/paraffin, iso/normal paraffins, and other light gases separations.

摘要翻译： 本发明公开了一种新型的高性能混合基质膜（MMM）及其制造和使用方法。 MMM包括分散在其中的连续聚合物基质和至少两种分子筛。 MMM中的连续聚合物基质含有至少一种类型的聚合物。 与由没有任何分子筛或只有一种分子筛的连续聚合物基质制成的聚合物膜相比，致密膜，不对称平片膜或其它方式形成的MMM与气体分离同时改善了选择性和渗透性。 本发明的MMM适用于各种气体，蒸汽和液体分离，例如醇/水，CO 2 / CH 4，H 2 / CH 4，O 2 / N 2，CO 2 / N 2，烯烃/石蜡，异/正构链烷烃， 和其他轻质气体分离。

公开(公告)号：US20100326913A1

公开(公告)日：2010-12-30

申请号：US12879249

申请日：2010-09-10

申请人： Chunqing Liu ,  Raisa Minkov ,  Syed A. Faheem ,  Man-Wing Tang ,  Lubo Zhou ,  Jeffery C. Bricker

发明人： Chunqing Liu ,  Raisa Minkov ,  Syed A. Faheem ,  Man-Wing Tang ,  Lubo Zhou ,  Jeffery C. Bricker

IPC分类号： B01D71/58 ,  B01D53/22 ,  B01D61/02 ,  B01D61/36

CPC分类号： B01D53/228 ,  B01D61/025 ,  B01D61/362 ,  B01D71/62 ,  B01D2323/30 ,  B01D2323/345 ,  C02F1/441 ,  C02F2103/08 ,  C08G69/26 ,  C08G69/32 ,  C08G73/22 ,  C08L79/04 ,  H01M8/1018 ,  H01M8/1025 ,  H01M8/103 ,  H01M8/1032 ,  H01M8/1039 ,  H01M8/106 ,  H01M8/1069 ,  Y02A20/131 ,  Y02C20/20 ,  Y02P70/56

摘要： The present invention discloses high performance polybenzoxazole membranes prepared from aromatic poly(o-hydroxy amide) membranes by thermal cyclization and a method for using these membranes. The polybenzoxazole membranes were prepared by thermal treating aromatic poly(o-hydroxy amide) membranes in a temperature range of 200° to 550° C. under inert atmosphere. The aromatic poly(o-hydroxy amide) membranes used for making the polybenzoxazole membranes were prepared from aromatic poly(o-hydroxy amide) polymers comprising pendent phenolic hydroxyl groups ortho to the amide nitrogen in the polymer backbone. In some embodiments of the invention, the polybenzoxazole membranes may be subjected to an additional crosslinking step to increase the selectivity of the membranes. These polybenzoxazole membranes showed significantly improved permeability for gas separations compared to the precursor aromatic poly(o-hydroxy amide) membranes and are not only suitable for a variety of liquid, gas, and vapor separations, but also can be used in catalysis and fuel cells.

公开(公告)号：US20100311565A1

公开(公告)日：2010-12-09

申请号：US12857308

申请日：2010-08-16

申请人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch

发明人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch

IPC分类号： B01J20/282

CPC分类号： B01D53/228 ,  B01D67/0046 ,  B01D67/0051 ,  B01D67/0088 ,  B01D67/0095 ,  B01D69/10 ,  B01D71/028 ,  B01D2256/24 ,  B01D2257/504 ,  B01D2323/12 ,  B01D2323/14 ,  B01D2323/24 ,  B01D2323/40 ,  B01J20/0292 ,  B01J20/08 ,  B01J20/18 ,  B01J20/2803 ,  B01J20/28033 ,  C01B37/04 ,  C01B39/54 ,  Y02C10/10 ,  Y02P20/152

摘要： The present invention discloses microporous aluminophosphate (AlPO4) molecular sieve membranes and methods for making and using the same. The microporous AlPO4 molecular sieve membranes, particularly small pore microporous AlPO-14 and AlPO-18 molecular sieve membranes, are prepared by three different methods, including in-situ crystallization of a layer of AlPO4 molecular sieve crystals on a porous membrane support, coating a layer of polymer-bound AlPO4 molecular sieve crystals on a porous membrane support, and a seeding method by in-situ crystallization of a continuous second layer of AlPO4 molecular sieve crystals on a seed layer of AlPO4 molecular sieve crystals supported on a porous membrane support. The microporous AlPO4 molecular sieve membranes have superior thermal and chemical stability, good erosion resistance, high CO2 plasticization resistance, and significantly improved selectivity over polymer membranes for gas and liquid separations, including carbon dioxide/methane (CO2/CH4), carbon dioxide/nitrogen (CO2/N2), and hydrogen/methane (H2/CH4) separations.

摘要翻译： 本发明公开了微孔磷酸铝（AlPO4）分子筛膜及其制造和使用方法。 微孔AlPO 4分子筛膜，特别是小孔微孔AlPO-14和AlPO-18分子筛膜通过三种不同的方法制备，包括在多孔膜载体上原位结晶一层AlPO 4分子筛晶体， 多孔膜载体上的聚合物结合的AlPO 4分子筛晶体层，以及通过在多孔膜载体上负载的AlPO 4分子筛晶体的种子层上原位结晶连续的第二层AlPO 4分子筛晶体的接种方法。 微孔AlPO4分子筛膜具有优异的耐热和化学稳定性，良好的耐侵蚀性，高的二氧化碳增塑性，并且对于气体和液体分离，包括二氧化碳/甲烷（CO2 / CH4），二氧化碳/氮气 （CO2 / N2）和氢/甲烷（H2 / CH4）分离。

公开(公告)号：US07815712B2

公开(公告)日：2010-10-19

申请号：US11612366

申请日：2006-12-18

申请人： Chunqing Liu ,  Man-Wing Tang ,  Stephen T. Wilson ,  David A. Lesch

发明人： Chunqing Liu ,  Man-Wing Tang ,  Stephen T. Wilson ,  David A. Lesch

IPC分类号： B01D53/22

CPC分类号： B01D67/0079 ,  B01D61/362 ,  B01D69/148 ,  B01D71/028 ,  B01D2323/21 ,  Y10S55/05

摘要： The present invention discloses a novel method of making high performance mixed matrix membranes (MMMs) using stabilized concentrated suspensions of solvents, uniformly dispersed polymer stabilized molecular sieves, and at least two different types of polymers as the continuous blend polymer matrix. MMMs as dense films or asymmetric flat sheet or hollow fiber membranes fabricated by the method described in the current invention exhibit significantly enhanced permeation performance for separations over the polymer membranes made from the continuous blend polymer matrix. MMMs of the present invention are suitable for a wide range of gas, vapor, and liquid separations such as alcohol/water, CO2/CH4, H2/CH4, O2/N2, CO2/N2, olefin/paraffin, iso/normal paraffins, and other light gases separations.

摘要翻译： 本发明公开了使用稳定的溶剂浓缩悬浮液，均匀分散的聚合物稳定化分子筛和至少两种不同类型的聚合物作为连续共混聚合物基质制备高性能混合基质膜（MMM）的新方法。 通过本发明所述方法制造的致密膜或非对称平板或中空纤维膜的MMM显示出从由连续共混聚合物基质制成的聚合物膜上的分离显着增强的渗透性能。 本发明的MMM适用于各种气体，蒸汽和液体分离，例如醇/水，CO 2 / CH 4，H 2 / CH 4，O 2 / N 2，CO 2 / N 2，烯烃/石蜡，异/正链烷烃， 和其他轻质气体分离。

公开(公告)号：US07758751B1

公开(公告)日：2010-07-20

申请号：US11564672

申请日：2006-11-29

申请人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch

发明人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch

IPC分类号： B01D63/00

CPC分类号： B01D67/0006 ,  B01D53/228 ,  B01D2323/30 ,  B01D2323/345 ,  C10G31/11

摘要： The present invention is for high performance UV-cross-linked membranes from polymers of intrinsic microporosity (PIMs) and the use of such membranes for separations. More specifically, the invention involves the methods of making UV-cross-linked membranes from PIMs. These membranes were prepared by cross-linking the UV-cross-linkable membranes from PIMs by exposure to UV-radiation. Pure gas permeation test results demonstrate that the UV-cross-linked membranes from PIMs exhibit CO2/CH4 performance well above the Robeson's polymer upper bound trade-off curve for CO2/CH4 separation. They have more than doubled selectivity for CO2/CH4 and extremely high permeability of CO2 compared to the original UV-cross-linkable membranes from PIMs. These membranes also show excellent separation performance for CO2/N2, H2/CH4, O2/N2, and propylene/propane separations. These high performance UV-cross-linked membranes are very useful for gas and liquid separations such as CO2/CH4, CO2/N2, H2/CH4, O2/N2, olefin/paraffin, deep desulfurization of gasoline and diesel fuels, and ethanol/water separations.

摘要翻译： 本发明是用于由本征微孔（PIM）的聚合物制成的高性能紫外线交联膜和用于分离的这种膜的用途。 更具体地，本发明涉及从PIM制备UV-交联膜的方法。 这些膜是通过暴露于UV辐射下从PIM交联UV可交联膜来制备的。 纯气体渗透测试结果表明，来自PIM的UV交联膜表现出远远高于Robeson的CO 2 / CH 4分离的聚合物上限折衷曲线的CO2 / CH4性能。 与原来的PIM可交联膜相比，它们对二氧化碳/ CH4的选择性提高了一倍以上，二氧化碳渗透率极高。 这些膜对于CO 2 / N 2，H 2 / CH 4，O 2 / N 2和丙烯/丙烷分离也表现出优异的分离性能。 这些高性能的紫外线交联膜对于气体和液体分离如CO 2 / CH 4，CO 2 / N 2，H 2 / CH 4，O 2 / N 2，烯烃/石蜡，汽油和柴油燃料的深度脱硫以及乙醇/ 水分离。

公开(公告)号：US20100133188A1

公开(公告)日：2010-06-03

申请号：US12491473

申请日：2009-06-25

申请人： Chunqing Liu ,  Raisa Minkov ,  Syed A. Faheem ,  Man-Wing Tang ,  Lubo Zhou ,  Jeffery C. Bricker

发明人： Chunqing Liu ,  Raisa Minkov ,  Syed A. Faheem ,  Man-Wing Tang ,  Lubo Zhou ,  Jeffery C. Bricker

IPC分类号： B01D71/56 ,  C08G73/22 ,  B01D15/00 ,  C02F1/44 ,  B01D61/36

CPC分类号： B01D71/62 ,  B01D53/228 ,  B01D2323/30 ,  B01D2323/345 ,  C08G69/26 ,  C08G73/22 ,  H01M8/1027 ,  H01M8/103 ,  H01M2300/0082

摘要： The present invention discloses high performance polybenzoxazole membranes prepared from aromatic poly(o-hydroxy amide) membranes by thermal cyclization and a method for using these membranes. The polybenzoxazole membranes were prepared by thermal treating aromatic poly(o-hydroxy amide) membranes in a temperature range of 200° to 550° C. under inert atmosphere. The aromatic poly(o-hydroxy amide) membranes used for making the polybenzoxazole membranes were prepared from aromatic poly(o-hydroxy amide) polymers comprising pendent phenolic hydroxyl groups ortho to the amide nitrogen in the polymer backbone. In some embodiments of the invention, the polybenzoxazole membranes may be subjected to an additional crosslinking step to increase the selectivity of the membranes. These polybenzoxazole membranes showed significantly improved permeability for gas separations compared to the precursor aromatic poly(o-hydroxy amide) membranes and are not only suitable for a variety of liquid, gas, and vapor separations, but also can be used in catalysis and fuel cells.

摘要翻译： 本发明公开了通过热环化由芳族聚（邻羟基酰胺）膜制备的高性能聚苯并恶唑膜和使用这些膜的方法。 通过在惰性气氛下在200〜550℃的温度范围内热处理芳族聚（邻羟基酰胺）膜来制备聚苯并恶唑膜。 用于制备聚苯并恶唑膜的芳族聚（邻羟基酰胺）膜是由芳族聚（邻羟基酰胺）聚合物制备的，该聚合物包括聚合物骨架中酰胺氮原子邻位的酚羟基。 在本发明的一些实施方案中，聚苯并恶唑膜可以进行额外的交联步骤以增加膜的选择性。 与前体芳族聚（邻羟基酰胺）膜相比，这些聚苯并恶唑膜显示出显着改善气体分离的渗透性，并且不仅适用于各种液体，气体和蒸气分离，而且还可用于催化和燃料电池 。

公开(公告)号：US20090318620A1

公开(公告)日：2009-12-24

申请号：US12145153

申请日：2008-06-24

申请人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch

发明人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch

IPC分类号： C08G65/32 ,  C08F116/06 ,  C08F12/22 ,  C08B3/06

CPC分类号： C08B15/10 ,  B01D53/228 ,  B01D67/0093 ,  B01D71/16 ,  B01D2323/30 ,  B01D2325/30 ,  C08G18/6484 ,  C08L71/02 ,  C08L81/06 ,  Y02P20/152

摘要： This invention involves a composition, a method of making, and an application of high plasticization-resistant chemically cross-linked polymeric membranes such as cross-linked cellulose acetate (CA) membrane. These cross-linked polymeric membranes with covalently interpolymer-chain-connected rigid networks showed no decrease in CO2/CH4 ideal selectivity under 690 kPa (100 psig) pure CO2 pressure and also no CO2 plasticization up to 3447 kPa (500 psig) pure CO2 pressure. By using the method of chemical cross-linking as described in this invention, the separation characteristics of the polymeric membranes can be decisively improved. These new cross-linked polymeric membranes can be used not only for gas separations such as CO2/CH4 and CO2/N2 separations, O2/N2 separation, olefin/paraffin separations (e.g. propylene/propane separation), iso/normal paraffins separations, but also for liquid separations such as pervaporation and desalination.

摘要翻译： 本发明涉及一种组合物，制备方法，以及应用高耐增塑作用的化学交联聚合物膜，例如交联乙酸纤维素（CA）膜。 这些具有共价互聚链连接的刚性网络的交联聚合物膜在690kPa（100psig）纯二氧化碳压力下没有显示CO 2 / CH 4理想选择性的降低，并且也没有CO2增塑达3447kPa（500psig）纯二氧化碳压力 。 通过使用如本发明所述的化学交联方法，可以确定地提高聚合物膜的分离特性。 这些新的交联聚合物膜不仅可用于气体分离，如CO2 / CH4和CO2 / N2分离，O2 / N2分离，烯烃/石蜡分离（如丙烯/丙烷分离），异/正链烷烃分离，但 还用于液体分离，例如渗透蒸发和脱盐。

公开(公告)号：US20090149313A1

公开(公告)日：2009-06-11

申请号：US11954017

申请日：2007-12-11

申请人： Chunqing Liu ,  Stephen T. Wilson ,  Lisa M. Knight

发明人： Chunqing Liu ,  Stephen T. Wilson ,  Lisa M. Knight

IPC分类号： B01J20/28

CPC分类号： B01D67/0079 ,  B01D53/228 ,  B01D69/147 ,  B01D69/148 ,  B01D2256/24 ,  B01D2257/504 ,  B01D2323/21 ,  Y02C10/10

摘要： The present invention discloses mixed matrix membranes (MMMs) containing polymer-functionalized low acidity, ultra low silica-to-alumina ratio, nano-sized SAPO-34 small pore molecular sieves and a continuous polymer matrix and methods for making and using these membranes. The surface functionalization of these molecular sieves provides a desired interfacial adhesion between SAPO-34 nano-particles and the continuous polymer matrix, which results in either no macrovoids or voids of less than 5 angstroms at the interface of the continuous polymer matrix and SAPO-34 in the MMMs. These MMMs, in the form of symmetric dense film, asymmetric flat sheet membrane, or asymmetric hollow fiber membranes, have good flexibility and high mechanical strength, and exhibit remarkably enhanced CO2 permeability (or CO2 permeance) and maintained CO2/CH4 selectivity over the continuous polymer matrices for CO2/CH4 separation. The MMMs of the present invention are suitable for a variety of liquid, gas, and vapor.

摘要翻译： 本发明公开了含有聚合物官能化低酸度，超低二氧化硅与氧化铝比的纳米级SAPO-34小孔分子筛和连续聚合物基质的混合基质膜（MMM）以及制备和使用这些膜的方法。 这些分子筛的表面官能化提供SAPO-34纳米颗粒和连续聚合物基质之间期望的界面粘合，其导致在连续聚合物基质和SAPO-34的界面处不存在小于5埃的大孔或空隙 在MMM中。 这些以对称致密膜，不对称平板膜或不对称中空纤维膜形式的MMM具有良好的柔韧性和高机械强度，并且显示出显着提高的CO 2渗透性（或CO 2渗透性）并且保持CO 2 / CH 4选择性超过连续 用于CO2 / CH4分离的聚合物基质。 本发明的MMM适用于各种液体，气体和蒸气。

公开(公告)号：US20090127197A1

公开(公告)日：2009-05-21

申请号：US11940599

申请日：2007-11-15

申请人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch ,  Douglas B. Galloway

发明人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch ,  Douglas B. Galloway

IPC分类号： B01D61/14 ,  B01D53/22

CPC分类号： B01D53/228 ,  B01D69/148 ,  B01D71/028 ,  B01D2256/10 ,  B01D2256/12 ,  B01D2256/16 ,  B01D2256/22 ,  B01D2256/24 ,  B01D2257/80

摘要： The present invention discloses polymer functionalized molecular sieve/polymer mixed matrix membranes (MMMs) with either no macrovoids or voids of less than several Angstroms at the interface of the polymer matrix and the molecular sieves by incorporating polymer functionalized molecular sieves into a continuous polymer matrix. The MMMs exhibit significantly enhanced selectivity and/or permeability over the polymer membranes made from the corresponding continuous polymer matrices for separations. The MMMs are suitable for a variety of liquid, gas, and vapor separations such as deep desulfurization of gasoline and diesel fuels, ethanol/water separations, pervaporation dehydration of aqueous/organic mixtures, CO2/CH4, CO2/N2, H2/CH4, O2/N2, olefin/paraffin, iso/normal paraffins separations, and other light gas mixture separations.

摘要翻译： 本发明公开了聚合物官能化分子筛/聚合物混合基质膜（MMMs），其通过将聚合物官能化分子筛掺入连续聚合物基质中而在聚合物基质和分子筛的界面处没有大于或等于几埃的大孔或空隙。 相对于用于分离的相应的连续聚合物基质制成的聚合物膜，MMM显示出显着增强的选择性和/或渗透性。 MMM适用于各种液体，气体和蒸气分离，如汽油和柴油的深度脱硫，乙醇/水分离，水/有机混合物的渗透汽化脱水，CO2 / CH4，CO2 / N2，H2 / CH4， O2 / N2，烯烃/石蜡，异/正链烷烃分离和其他轻质气体混合物分离。

公开(公告)号：US20090126570A1

公开(公告)日：2009-05-21

申请号：US11940554

申请日：2007-11-15

申请人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch ,  Douglas B. Galloway

发明人： Chunqing Liu ,  Stephen T. Wilson ,  David A. Lesch ,  Douglas B. Galloway

IPC分类号： B01D53/22

CPC分类号： B01D69/148 ,  B01D71/028

摘要： The present invention discloses polymer functionalized molecular sieve/polymer mixed matrix membranes (MMMs) with either no macrovoids or voids of less than several Angstroms at the interface of the polymer matrix and the molecular sieves by incorporating polyethersulfone (PES) or cellulose triacetate (CTA) functionalized molecular sieves into a continuous polyimide or cellulose acetate (CA) polymer matrix. The MMMs, in the form of symmetric dense film, asymmetric flat sheet membrane, or asymmetric hollow fiber have good flexibility and high mechanical strength, and exhibit significantly enhanced selectivity and/or permeability over the polymer membranes made from the corresponding continuous polymer matrices for carbon dioxide/methane (CO2/CH4) and hydrogen/methane (H2/CH4) separations. The MMMs are suitable for a variety of liquid, gas, and vapor separations such as deep desulfurization of gasoline and diesel fuels, ethanol/water separations, pervaporation dehydration of aqueous/organic mixtures, CO2/CH4, CO2/N2, H2/CH4, O2/N2, olefin/paraffin, iso/normal paraffins separations, and other light gas mixture separations.

摘要翻译： 本发明公开了通过加入聚醚砜（PES）或三乙酸纤维素（CTA），在聚合物基体和分子筛的界面处没有大于或等于几埃的大孔或空隙的聚合物官能化分子筛/聚合物混合基质膜（MMM） 官能化分子筛成为连续的聚酰亚胺或醋酸纤维素（CA）聚合物基质。 以对称致密膜，不对称平板膜或不对称中空纤维的形式的MMM具有良好的柔韧性和高的机械强度，并且相对于由相应的碳的连续聚合物基体制成的聚合物膜显示出显着增强的选择性和/或渗透性 二氧化碳/甲烷（CO2 / CH4）和氢/甲烷（H2 / CH4）分离。 MMM适用于各种液体，气体和蒸气分离，如汽油和柴油的深度脱硫，乙醇/水分离，水/有机混合物的渗透汽化脱水，CO2 / CH4，CO2 / N2，H2 / CH4， O2 / N2，烯烃/石蜡，异/正链烷烃分离和其他轻质气体混合物分离。