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1. 发明申请

WO2017189522A1 IMPROVED TRANSITION METAL CONTAINING CARBON MOLECULAR SIEVE MEMBRANES AND METHOD TO MAKE THEM 审中-公开
标题翻译：改进的含碳分子筛膜的过渡金属及其制备方法
公开(公告)号：WO2017189522A1
公开(公告)日：2017-11-02
申请号：PCT/US2017/029325
申请日：2017-04-25
申请人： DOW GLOBAL TECHNOLOGIES LLC , GEORGIA TECH RESEARCH CORPORATION
发明人： CHU, Yu-Han , KOROS, William J. , XU, Liren , BRAYDEN, Mark K. , MARTINEZ, Marcos V.
IPC分类号： B01D53/22 , B01D67/00 , B01D69/02 , B01D69/08 , B01D69/14 , B01D71/02
CPC分类号： B01D53/228 , B01D67/0067 , B01D69/02 , B01D69/08 , B01D69/142 , B01D69/145 , B01D71/021 , B01D71/022 , B01D2257/102 , B01D2257/104 , B01D2257/504 , B01D2257/7025 , B01D2325/20 , C07C7/144 , Y02C20/20
摘要： A carbon molecular sieve (CMS) membrane having improved separation characteristics for separating olefins from their corresponding paraffins is comprised of carbon with at most trace amounts of sulfur and a transition metal, wherein the transition metal is one or more of a group 4-10 and 12 transition metal. The CMS membrane may be made by pyrolyzing a precursor polymer devoid of sulfur in which the precursor polymer has had a transition metal incorporated into it. The pyrolyzing for the precursor having the transition metal incorporated into it is performed in a nonoxidizing atmosphere and at a heating rate and temperature such that the metal has a valence greater than zero (i.e., not metal bonded) to a valence desirably closer to its maximum valence.
摘要翻译：具有改进的用于将烯烃从其相应的链烷烃中分离的分离特性的碳分子筛（CMS）膜由具有至多痕量的硫和过渡金属的碳组成，其中过渡金属为一种或更多的是4-10和12族过渡金属。 CMS膜可以通过热解不含硫的前体聚合物来制备，其中前体聚合物中掺入了过渡金属。具有结合到其中的过渡金属的前体的热解在非氧化性气氛中进行，并且在加热速率和温度下进行，使得金属具有大于零（即不是金属键合）的化合价至理想地接近其最大值价。

2. 发明申请

WO2020041226A1 CROSS-LINKED POLYIMIDE MEMBRANES AND CARBON MOLECULAR SIEVE HOLLOW FIBER MEMBRANES MADE THEREFROM 审中-公开
公开(公告)号：WO2020041226A1
公开(公告)日：2020-02-27
申请号：PCT/US2019/047132
申请日：2019-08-20
申请人： DOW GLOBAL TECHNOLOGIES LLC , GEORGIA TECH RESEARCH CORPORATION
发明人： VAUGHN, Justin T. , QIU, Wulin , KOROS, William J. , XU, Liren , BRAYDEN, Mark K.
IPC分类号： C08G73/10 , B01D53/22 , B01D69/08 , B01D71/64
摘要： A cross-linked polyimide of the reaction product of a crosslinking agent and a polyimide. The cross-linking agent having at least two cross-linking moieties and the polyimide has a plurality of polyimide chains having an aryl constituent with a moiety comprised of a reactive substituent. The polyimide has crosslinks from the reaction of the reactive substituent of the aryl constituents of the polyimide chains and the cross-linking moieties of the cross-linking agent. The cross-linking may be induced by thermally treating a mixture of the polyimide and crosslinking agent above about 150 °C to a temperature where the polyimide begins to decompose under an inert atmosphere. The membrane can be used for separations involving gases such as hydrogen and light hydrocarbons.

3. 发明申请

WO2017165098A1 IMPROVED METHOD OF MAKING CARBON MOLECULAR SIEVE MEMBRANES 审中-公开
标题翻译：改进的碳分子筛膜制备方法
公开(公告)号：WO2017165098A1
公开(公告)日：2017-09-28
申请号：PCT/US2017/020432
申请日：2017-03-02
申请人： DOW GLOBAL TECHNOLOGIES LLC , GEORGIA TECH RESEARCH CORPORATION
发明人： HESSLER, John , KOROS, William J. , XU, Liren , BRAYDEN, Mark K. , MARTINEZ, Marcos V.
IPC分类号： B01D67/00 , B01D53/22 , B01D69/08 , B01D71/02 , B01D71/64
摘要： The invention is an improved method of making a carbon molecular sieve (CMS) membrane in which a polyimide precursor polymer is pyrolyzed to form a carbon molecular sieve membrane by heating, in a furnace, said polyimide precursor polymer to a final pyrolysis temperature of 600 C to 700 C at a pyrolysis heating rate of 3 to 7 C/minute from 400 C to the final pyrolysis temperature, the final pyrolysis temperature being held for a pyrolysis time of at most 60 minutes in a non-oxidizing atmosphere. In a particular embodiment, the cooling rate from the pyrolysis temperature is accelerated by methods to remove heat. The CMS membranes have shown an improved combination of selectivity and permeance as well as being particularly suitable to separate gases in gas streams such methane from natural gas, oxygen from air and ethylene or propylene from light hydrocarbon streams.
摘要翻译：本发明是一种制造碳分子筛（CMS）膜的改进方法，其中通过在炉中加热所述聚酰亚胺前体聚合物来热解聚酰亚胺前体聚合物以形成碳分子筛膜以3-7℃/分钟的热解加热速率从400℃到最终热解温度达到600℃-700℃的最终热解温度，最终热解温度在非热解温度下保持至多60分钟的热解时间氧化气氛。在一个具体实施方案中，通过除去热量的方法来加速来自热解温度的冷却速率。 CMS膜显示出选择性和渗透性的改进组合，以及特别适合于从天然气中分离气体中的气体，例如来自天然气的甲烷，来自空气的氧气和来自轻质烃流体的乙烯或丙烯中的气体。

4. 发明申请

WO2019212647A1 IMPROVED METHOD OF MAKING CARBON MOLECULAR SIEVE MEMBRANES 审中-公开
公开(公告)号：WO2019212647A1
公开(公告)日：2019-11-07
申请号：PCT/US2019/022848
申请日：2019-04-03
申请人： DOW GLOBAL TECHNOLOGIES LLC , GEORGIA TECH RESEARCH CORPORATION
发明人： VAUGHN, Justin T. , QIU, Wulin , KOROS, William J. , XU, Liren , BRAYDEN, Mark K. , MARTINEZ, Marcos V.
IPC分类号： B01D67/00 , B01D53/22 , B01D71/02
摘要： The invention is an improved method of making an improved carbon molecular sieve (CMS) membrane in which a precursor polymer (e.g., polyimide) is pyrolyzed at a pyrolysis temperature to form a CMS membrane that is cooled to ambient temperature (about 40°C or 30°C to about 20°C). The CMS membrane is then reheated to a reheating temperature less than the pyrolysis temperature to form the improved CMS membrane. The improved CMS membranes have shown an improved combination of selectivity and permeance as well as stability for separating hydrogen from gas molecules (e.g., methane, ethane, propane, ethylene, propylene, butane, carbon dioxide, nitrogen, butylene, and combinations thereof).

5. 发明申请

WO2019212647A4 IMPROVED METHOD OF MAKING CARBON MOLECULAR SIEVE MEMBRANES 审中-公开
公开(公告)号：WO2019212647A4
公开(公告)日：2019-11-07
申请号：PCT/US2019/022848
申请日：2019-04-03
申请人： DOW GLOBAL TECHNOLOGIES LLC , GEORGIA TECH RESEARCH CORPORATION
发明人： VAUGHN, Justin T. , QIU, Wulin , KOROS, William J. , XU, Liren , BRAYDEN, Mark K. , MARTINEZ, Marcos V.
IPC分类号： B01D67/00 , B01D53/22 , B01D71/02
摘要： The invention is an improved method of making an improved carbon molecular sieve (CMS) membrane in which a precursor polymer (e.g., polyimide) is pyrolyzed at a pyrolysis temperature to form a CMS membrane that is cooled to ambient temperature (about 40°C or 30°C to about 20°C). The CMS membrane is then reheated to a reheating temperature less than the pyrolysis temperature to form the improved CMS membrane. The improved CMS membranes have shown an improved combination of selectivity and permeance as well as stability for separating hydrogen from gas molecules (e.g., methane, ethane, propane, ethylene, propylene, butane, carbon dioxide, nitrogen, butylene, and combinations thereof).

6. 发明申请

WO2019089087A1 CARBON MOLECULAR SIEVE MEMBRANES CONTAINING A GROUP 13 METAL AND METHOD TO MAKE THEM 审中-公开
公开(公告)号：WO2019089087A1
公开(公告)日：2019-05-09
申请号：PCT/US2018/036597
申请日：2018-06-08
申请人： DOW GLOBAL TECHNOLOGIES LLC , GEORGIA TECH RESEARCH CORPORATION
发明人： CHU, Yu-Han , KOROS, William J. , XU, Liren , BRAYDEN, Mark K. , MARTINEZ, Marcos V.
IPC分类号： B01D67/00 , B01D69/02 , B01D69/14 , B01D71/02 , B01D53/22 , B01D71/64 , C07C7/144 , B01D69/06 , B01D69/08
摘要： A carbon molecular sieve (CMS) membrane having improved separation characteristics for separating olefins from their corresponding paraffins is comprised of carbon with at most trace amounts of sulfur and a group 13 metal. The CMS membrane may be made by pyrolyzing a precursor polymer devoid of sulfur in which the precursor polymer has had a group 13 metal incorporated into it, wherein the metal is in a reduced state. The pyrolyzing for the precursor having the group 13 metal incorporated into it is performed in a nonoxidizing atmosphere and at a heating rate and temperature such that the metal in a reduced state (e.g., covalently bonded to carbon or nitrogen or in the metal state).

7. 发明申请

WO2017105836A1 METHOD OF MAKING CARBON MOLECULAR SIEVE MEMBRANES 审中-公开
标题翻译：碳分子筛膜的制备方法
公开(公告)号：WO2017105836A1
公开(公告)日：2017-06-22
申请号：PCT/US2016/064115
申请日：2016-11-30
申请人： DOW GLOBAL TECHNOLOGIES LLC , GEORGIA TECH RESEARCH CORPORATION
发明人： HESSLER, John , KOROS, William J. , XU, Liren , BRAYDEN, Mark K. , MARTINEZ, Marcos V.
IPC分类号： B01D67/00 , B01D69/08 , B01D71/02 , B01D71/64
CPC分类号： B01D67/0002 , B01D53/22 , B01D53/228 , B01D67/0067 , B01D67/0081 , B01D67/0083 , B01D69/08 , B01D69/088 , B01D71/021 , B01D71/028 , B01D71/64 , B01D2256/10 , B01D2256/24 , B01D2257/104 , B01D2257/7022 , B01D2321/32 , Y02C20/20
摘要： The invention is an improved method of making a carbon molecular sieve (CMS) membrane in which a precursor polymer is pyrolyzed to form a carbon molecular sieve membrane that is then exposed to a conditioning atmosphere comprised of a target permeate gas molecule such as ethylene when the membrane is desired to separate it from a light hydrocarbon gas stream. The exposure to the ethylene desirably occurs prior to the CMS permeance and selectivity combination substantially changing (e.g., within 5 days) of cooling from the pyrolyzing temperature. The CMS membranes have shown an improved combination of selectivity and permeance as well as stability and are useful to separate gases in gas streams such methane from natural gas, oxygen from air and ethylene or propylene from light hydrocarbon streams.
摘要翻译：本发明是一种制造碳分子筛（CMS）膜的改进方法，其中前体聚合物被热解以形成碳分子筛膜，然后暴露于由靶当膜需要将其与轻质烃气流分离时，渗透气体分子如乙烯。乙烯暴露最好在CMS渗透和选择性组合基本上从热解温度变化（例如5天内）内冷却之前进行。 CMS膜显示出选择性和渗透性以及稳定性的改进组合，并且可用于从天然气分离甲烷，来自空气的氧气和来自轻质烃流的乙烯或丙烯的气流中的气体。

8. 发明申请

WO2019036064A1 IMPROVED METHOD TO MAKE CARBON MOLECULAR SIEVE HOLLOW FIBER MEMBRANES 审中-公开
公开(公告)号：WO2019036064A1
公开(公告)日：2019-02-21
申请号：PCT/US2018/023228
申请日：2018-03-20
申请人： DOW GLOBAL TECHNOLOGIES LLC
发明人： XU, Liren , SHARMA, Rahul , FITZGIBBONS, Thomas , BRAYDEN, Mark K. , MARTINEZ, Marcos V.
IPC分类号： B01D53/22 , B01D67/00 , B01D69/08 , B01D71/02
摘要： A method of making a hollow fiber carbon molecular sieve is comprised of heating a hollow polymer fiber to a carbonization temperature in an atmosphere that is non-oxidizing to form a hollow fiber carbon molecular sieve, wherein during at least a portion of the heating a tensile force is applied to the hollow polymer fiber. The method may improve the separation of gases similar in size such a propylene from propane.

9. 发明申请

WO2014160624A1 NOVEL CARBON MOLECULAR SIEVE AND PELLET COMPOSITIONS USEFUL FOR C2-C3 ALKANE/ALKENE SEPARATIONS 审中-公开
标题翻译：用于C2-C3碱金属/碱金属离子的新型碳分子筛和聚烯烃组合物
公开(公告)号：WO2014160624A1
公开(公告)日：2014-10-02
申请号：PCT/US2014/031537
申请日：2014-03-24
申请人： DOW GLOBAL TECHNOLOGIES LLC
发明人： LIU, Junqiang , BRAYDEN, Mark K. , CALVERLEY, Edward M. , LAKSO, Steven R. , LIU, Yujun , MARTINEZ, Marcos V.
IPC分类号： B01J20/20 , B01J20/28 , B01J20/30 , B01D53/04 , B01D53/047 , C01B31/08
CPC分类号： B01J20/20 , B01D53/0462 , B01D53/047 , B01D2253/102 , B01D2253/116 , B01D2253/304 , B01D2257/7022 , B01J20/28042 , B01J20/28078 , B01J20/28085 , B01J20/28092 , B01J20/3007 , B01J20/3028 , B01J20/3042 , B01J20/3078 , C01B31/00 , C01B31/02 , C01B31/08 , C01B32/00 , C01B32/05 , C01B32/30 , C01P2004/54 , C01P2004/60 , C01P2006/16 , C01P2006/17 , C07C7/12
摘要： A novel microporous carbon molecular sieve may be used as the basis for carbon adsorbent pellets that have discrete areas of carbonized binder and of carbonized precursor, macropores having an average pore diameter greater than or equal to 1 micrometer and a total macroporosity of at least 30 percent, both as measured by mercury porosimetry, and micropores that are capable of selectively admitting a C2-C3 alkene and excluding a C2-C3 alkane, and a total microporosity ranging from 10 percent to 30 percent. The pellets may be prepared by pyrolyzing a pellet structure comprising a carbon forming, non-melting binder and a non-porous gel type sulfonated polystyrene precursor at a temperature ranging from 500 °C to 1000 °C, under an inert atmosphere and other conditions suitable to form the described pellets. The pellets are particularly useful in pressure swing and temperature swing adsorption processes to separate C2-C3 alkane/alkene mixtures.
摘要翻译：可以使用新颖的微孔碳分子筛作为具有碳化粘合剂和碳化前体的离散区域的碳吸附剂颗粒的基础，大孔的平均孔径大于或等于1微米，总的大孔隙率至少为30％，通过水银孔率法测量，以及能够选择性地引入C2-C3烯烃并排除C2-C3烷烃的微孔，以及总微孔率为10％至30％的微孔。颗粒可以通过在惰性气氛和其它合适的条件下，在500℃至1000℃的温度范围内热解包含碳形成，非熔融粘合剂和无孔凝胶型磺化聚苯乙烯前体的颗粒结构来制备以形成所述的颗粒。颗粒在用于分离C 2 -C 3烷烃/烯烃混合物的压力摆动和变温吸附方法中特别有用。

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