公开(公告)号：US08226862B2

公开(公告)日：2012-07-24

申请号：US11954454

申请日：2007-12-12

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： B29D7/00

CPC分类号： B01D69/148 ,  B01D67/0079 ,  B01D69/06 ,  B01D71/028 ,  B01D2325/022

摘要： The present invention discloses an approach for making mixed matrix membranes (MMMs) and methods for using these membranes. These MMMs contain a continuous polymer matrix and dispersed microporous molecular sieve particles. This invention also pertains to control of the thickness of the thin dense selective mixed matrix membrane layer that is equal to or greater than the particle size of the largest molecular sieve particles for making large scale asymmetric MMMs. In particular, the invention is directed to making asymmetric flat sheet MMM by a phase inversion technique. The MMMs of the present invention exhibit at least 20% increase in selectivity compared to the polymer membranes prepared from their corresponding continuous polymer matrices. The MMMs of the present invention are suitable for a variety of liquid, gas, and vapor separations.

摘要翻译： 本发明公开了一种制备混合基质膜（MMM）的方法和使用这些膜的方法。 这些MMM含有连续的聚合物基质和分散的微孔分子筛颗粒。 本发明还涉及等于或大于用于制造大规模不对称MMM的最大分子筛颗粒的粒度的薄致密选择性混合基质膜层的厚度的控制。 特别地，本发明涉及通过相位反转技术制造不对称平板MMM。 与由其相应的连续聚合物基质制备的聚合物膜相比，本发明的MMM显示出至少20％的选择性增加。 本发明的MMM适用于各种液体，气体和蒸气分离。

公开(公告)号：US08132677B2

公开(公告)日：2012-03-13

申请号：US12412649

申请日：2009-03-27

申请人： Chunqing Liu ,  Peter K. Coughlin ,  Man-Wing Tang ,  Raisa Minkov ,  Lubo Zhou

发明人： Chunqing Liu ,  Peter K. Coughlin ,  Man-Wing Tang ,  Raisa Minkov ,  Lubo Zhou

IPC分类号： B01D71/64 ,  B01D71/28 ,  B01D69/00

CPC分类号： B01D71/62 ,  B01D53/228 ,  B01D67/0093 ,  B01D2323/08 ,  B01D2323/30 ,  B01D2323/345 ,  C08G73/1039 ,  C08G73/1042 ,  C08G73/1046 ,  C08G73/1064 ,  C08G73/16 ,  C08L79/08 ,  Y02C20/20

摘要： The present invention discloses a new type of high performance polymer membranes prepared from aromatic polyimide membranes by thermal treating and crosslinking and methods for making and using these membranes. The polymer membranes were prepared from aromatic polyimide membranes by thermal treating under inert atmosphere followed by crosslinking preferably by using a UV radiation source. The aromatic polyimide membranes were made from aromatic polyimide polymers comprising both pendent hydroxy functional groups ortho to the heterocyclic imide nitrogen and cross-linkable functional groups in the polymer backbone. The membranes showed significantly improved selectivity and permeability for gas separations compared to the aromatic polyimide membranes without any treatment. The membranes can be fabricated into any convenient geometry and are not only suitable for a variety of liquid, gas, and vapor separations, but also can be used for other applications such as for catalysis and fuel cell applications.

公开(公告)号：US08127936B2

公开(公告)日：2012-03-06

申请号：US12412629

申请日：2009-03-27

申请人： Chunqing Liu ,  Man-Wing Tang ,  Raisa Serbayeva ,  Lubo Zhou

发明人： Chunqing Liu ,  Man-Wing Tang ,  Raisa Serbayeva ,  Lubo Zhou

IPC分类号： B01D71/64 ,  B01D71/68 ,  B01D71/50 ,  B01D61/00

CPC分类号： C08G75/32 ,  B01D67/0093 ,  B01D71/62 ,  B01D2323/30 ,  B01D2323/345 ,  B01J20/26 ,  B01J20/262 ,  B01J20/267 ,  C08G73/1042 ,  C08G73/22

摘要： In the present invention high performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes and methods for making and using these membranes have been developed. The cross-linked polybenzoxazole and polybenzothiazole polymer membranes are prepared by: 1) first synthesizing polyimide polymers comprising pendent functional groups (e.g., —OH or —SH) ortho to the heterocyclic imide nitrogen and cross-linkable functional groups in the polymer backbone; 2) fabricating polyimide membranes from these polymers; 3) converting the polyimide membranes to polybenzoxazole or polybenzothiazole membranes by heating under inert atmosphere such as nitrogen or vacuum; and 4) finally converting the membranes to high performance cross-linked polybenzoxazole or polybenzothiazole membranes by a crosslinking treatment, preferably UV radiation. The membranes can be fabricated into any convenient geometry. The high performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes of the present invention are suitable for a variety of liquid, gas, and vapor separations.

摘要翻译： 在本发明中，开发了高性能交联聚苯并恶唑和聚苯并噻唑聚合物膜以及制备和使用这些膜的方法。 交联的聚苯并恶唑和聚苯并噻唑聚合物膜是通过以下步骤制备的：1）首先合成聚酰亚胺聚合物，其包含与杂环酰亚胺氮邻接的侧基官能团（例如-OH或-SH）和聚合物主链中的可交联官能团; 2）从这些聚合物制造聚酰亚胺膜; 3）通过在惰性气氛如氮气或真空下加热将聚酰亚胺膜转化为聚苯并恶唑或聚苯并噻唑膜; 和4）最后通过交联处理，优选UV辐射将膜转化成高性能交联聚苯并恶唑或聚苯并噻唑膜。 膜可以制造成任何方便的几何形状。 本发明的高性能交联聚苯并恶唑和聚苯并噻唑聚合物膜适用于各种液体，气体和蒸气分离。

公开(公告)号：US20110278227A1

公开(公告)日：2011-11-17

申请号：US13165939

申请日：2011-06-22

申请人： Chunqing Liu ,  Peter K. Coughlin ,  Man-Wing Tang ,  Raisa Minkov ,  Lubo Zhou

发明人： Chunqing Liu ,  Peter K. Coughlin ,  Man-Wing Tang ,  Raisa Minkov ,  Lubo Zhou

IPC分类号： B01D71/40 ,  B01D61/00 ,  B05D3/06 ,  B05D7/04 ,  B05D3/02 ,  B01D53/22 ,  C08G73/10

CPC分类号： B01D71/62 ,  B01D53/228 ,  B01D67/0093 ,  B01D2323/08 ,  B01D2323/30 ,  B01D2323/345 ,  C08G73/1039 ,  C08G73/1042 ,  C08G73/1046 ,  C08G73/1064 ,  C08G73/16 ,  C08L79/08 ,  Y02C20/20

摘要： The present invention discloses a new type of high performance polymer membranes prepared from aromatic polyimide membranes by thermal treating and crosslinking and methods for making and using these membranes. The polymer membranes were prepared from aromatic polyimide membranes by thermal treating under inert atmosphere followed by crosslinking preferably by using a UV radiation source. The aromatic polyimide membranes were made from aromatic polyimide polymers comprising both pendent hydroxy functional groups ortho to the heterocyclic imide nitrogen and cross-linkable functional groups in the polymer backbone. The membranes showed significantly improved selectivity and permeability for gas separations compared to the aromatic polyimide membranes without any treatment. The membranes can be fabricated into any convenient geometry and are not only suitable for a variety of liquid, gas, and vapor separations, but also can be used for other applications such as for catalysis and fuel cell applications.

摘要翻译： 本发明公开了通过热处理和交联由芳族聚酰亚胺膜制备的新型高性能聚合物膜以及制造和使用这些膜的方法。 聚合物膜由芳族聚酰亚胺膜通过在惰性气氛下热处理制备，然后优选通过使用UV辐射源进行交联。 芳族聚酰亚胺膜由芳族聚酰亚胺聚合物制成，其中包含杂环酰亚胺氮原子的邻接羟基官能团和聚合物主链中的可交联官能团。 与没有任何处理的芳族聚酰亚胺膜相比，膜显示出气体分离的选择性和渗透性显着提高。 膜可以制造成任何方便的几何形状，并且不仅适用于各种液体，气体和蒸汽分离，而且还可以用于其它应用，例如用于催化和燃料电池应用。

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：US07943543B1

公开(公告)日：2011-05-17

申请号：US11537294

申请日：2006-09-29

申请人： Chunqing Liu ,  Santi Kulprathipanja ,  Mark E. Schott ,  Stephen T. Wilson

发明人： Chunqing Liu ,  Santi Kulprathipanja ,  Mark E. Schott ,  Stephen T. Wilson

IPC分类号： B01J20/28 ,  B01D53/22

CPC分类号： B01D53/228 ,  B01D67/0009 ,  B01D67/0011 ,  B01D67/0079 ,  B01D69/148 ,  B01D71/64 ,  B01D71/82 ,  B01D2323/08 ,  B01D2323/21 ,  B01D2323/46 ,  B01D2325/02 ,  Y02C10/10

摘要： New ionic liquid-solid-polymer mixed matrix membranes were proposed for gas separations such as CO2 removal from natural gas or N2. For the new mixed matrix membranes, the solids such as carbon molecular sieves, microporous molecular sieves, MCM-41 type of mesoporous molecular sieves, or polymer of intrinsic microporosity (PIM) are coated (or impregnated) with ionic liquids such as 1-butyl-3-methyl imidazolium bis[trifluoromethylsulfonyl]amide. The ionic liquids coated or impregnated solids are then dispersed in the continuous polymer matrix to form mixed matrix membranes. These hybrid mixed matrix membranes will combine the properties of the continuous polymer phase, the ionic liquids, and the dispersed ionic liquids coated or impregnated solids phase, which will possibly open up new opportunities for gas separation processes such as CO2 separation from natural gas or flue gas.

摘要翻译： 提出了新的离子液固固体混合基质膜用于气体分离，例如从天然气或N2中除去二氧化碳。 对于新的混合基质膜，将诸如碳分子筛，微孔分子筛，MCM-41型介孔分子筛或本征微孔聚合物（PIM）的固体用离子液体例如1-丁基 -3-甲基咪唑双[三氟甲磺酰基]酰胺。 然后将离子液体涂覆或浸渍的固体分散在连续聚合物基质中以形成混合基质膜。 这些混合混合基质膜将结合连续聚合物相，离子液体和分散的离子液体涂覆或浸渍的固体相的性质，这可能为气体分离过程（例如从天然气或烟道中分离CO 2）开辟新的机会 加油站。

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。