CN111225736A - 含第13族金属的碳分子筛膜和其制造方法 - Google Patents
含第13族金属的碳分子筛膜和其制造方法 Download PDFInfo
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- CN111225736A CN111225736A CN201880067597.8A CN201880067597A CN111225736A CN 111225736 A CN111225736 A CN 111225736A CN 201880067597 A CN201880067597 A CN 201880067597A CN 111225736 A CN111225736 A CN 111225736A
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Classifications
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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Abstract
一种具有改进的分离特征以用于将烯烃与其对应的烷烃分离的碳分子筛(CMS)膜,其包含具有至多痕量的硫和第13族金属的碳。可以通过热解不含硫的前体聚合物制造所述CMS膜,其中所述前体聚合物中并入有第13族金属,其中所述金属处于还原态。在非氧化气氛中并且在使得所述金属处于还原态(例如共价键合到碳或氮上或处于金属态)的加热速率和温度下对并入有所述第13族金属的所述前体进行热解。
Description
技术领域
本发明涉及用于气体分离的碳分子筛(CMS)膜。确切地说,本发明涉及一种用于产生具有改进的选择性、渗透性和稳定性的CMS膜的方法。
背景技术
膜广泛用于气体和液体的分离,包括例如从天然气中分离酸性气体,如CO2和H2S,以及从空气中去除O2。通过所述膜的气体传输通常由吸附-扩散机制建模。聚合膜已经得到充分研究,并且由于容易加工的能力和低成本而广泛用于气相分离。然而,已经显示出CMS膜具有超过聚合膜的吸引性分离性能特性。
通常通过聚合物前体的热解来产生CMS膜。举例来说,已知可以通过热解纤维素中空纤维来产生无缺陷中空纤维CMS膜(JE Koresh和A.Soffer,分子筛渗透选择性膜.第一部分:演示一种用于气体混合物分离的新装置.(J.E.Koresh and A.Soffer,Molecularsieve permselective membrane.Part I.Presentation of a new device for gasmixture separation.)《分离科学和技术(Separation Science and Technology)》,18,8(1983))。此外,已使用许多其它聚合物来产生呈纤维和致密薄膜形式的CMS膜,其中聚酰亚胺受到青睐。聚酰亚胺具有高玻璃态转变温度,容易加工,且甚至在热解前在其它聚合膜中具有最高的分离性能之一。
聚酰亚胺中空纤维已经在真空下热解形成CMS膜,如美国专利第6,565,631号所描述。美国专利第6,565,631号还公开使用CMS膜在1000psia和50℃下从含有10%CO2的甲烷物料流中分离CO2的方法,其选择性为约45,即远高于典型商业聚合膜的选择性。描述用于产生碳膜(不对称中空“丝状”和平片两者)的方法和气体分离的应用的其它专利包括例如美国专利第5,288,304号和EP专利第0459623号。
为了改进由聚酰亚胺形成的CMS膜的分离特性,研究主要集中于所用的特定聚酰亚胺和用于碳化特定聚酰亚胺的条件。例如,Steel和Koros关于热解温度、热浸时间和聚合物组合物对碳膜性能的影响进行了详细研究。(K.M.Steel和W.J.Koros,碳材料的孔隙率及其对气体分离性能的影响研究(Investigation of Porosity of Carbon Materials andRelated Effects on Gas Separation Properties),《碳》(Carbon),41,253(2003)。)在空气气氛中以0.05mm Hg的压力产生膜。结果展示出,温度和热浸时间的增加提高了选择性,但降低了CO2/CH4分离的渗透率。此外,Steel等人展示,与较不致密的前体聚合物相比,具有致密填充结构的前体聚合物往往会使得CMS膜具有更高的选择性。
已经研究了热解气氛的影响。Suda和Haraya在不同环境下公开了CMS膜的形成。(H.Suda和K.Haraya,通过衍生自Kapton Polyimide的碳分子筛膜的微孔的气体渗透(GasPermeation Through Micropores of Carbon Molecular Sieve Membranes DerivedFrom Kapton Polyimide),《物理化学期刊B》(J.Phys.Chem.B),101,3988(1997)。)在1000℃下在氩气或真空中由聚酰亚胺制备CMS致密薄膜。根据它们的气体分离特性,在不同气氛下形成的6个膜之间的O2/N2分离结果几乎相同。Suda和Haraya没有公开气氛对CO2从天然气中分离的影响,也没有公开分离特性如何随能力和低成本而变化。类似地,Geiszler和Koros公开了由氟化聚酰亚胺在氦气和氩气中热解产生的CMS纤维进行O2/N2和H2/N2分离的结果。(V.C.Geiszler和W.J.Koros,聚酰亚胺热解气氛对碳分子筛膜的分离性能的影响(Effects of Polyimide Pyrolysis Atmosphere on Separation Performanceof Carbon Molecular Sieve Membranes),《工业工程化学研究(Ind.Eng.Chem.Res.)》(Ind.Eng.Chem.Res.),(1996))。所述文件公开真空热解的选择性略高于吹扫热解过程的选择性。此外,Geiszler和Koros表明,吹扫气体的流速影响性能。在美国专利第8,486,179号中,描述了在热解气氛中使用具有少量氧气的气氛的影响。
已经对改变聚酰亚胺的化学性质进行了有限的研究,如并入可能对所关注特定气体分子(例如乙烯和丙烯)具有亲和力的金属。已由J.N.Barsema等人在《膜科学期刊(J.Mem.Sci.)》219(2003)47-57中描述,在由P843,3'-4,4'-二苯甲酮四甲酸二酐-二异氰酸甲苯酯/亚甲基二异氰酸酯(BTDA-TDI/MDI)共聚酰亚胺形成的碳膜中混合银粒子的填料粒子(簇)以分离He、CO2、O2和N2。如M.Teixeira等人,《化学工程研究设计(ChemEng.Res.Des.)》90(2012)2338-2345所描述,将氧化铝和银的填料粒子装载到碳化酚系树脂中以分离C3H6、C3H8、He、N2、CO2和O2。特定金属(如银、铝和铜)已并入到磺化聚合物(如磺化聚(亚苯基氧化物))中,其中在将磺化聚合物碳化以分离H2、He、N2、CO2和O2后立即形成金属,但残余硫可潜在地有毒,如M.Yoshimune等人在《淡化(Desalination)》193(2006)66-72中所描述。
希望提供一种CMS膜和一种制造CMS膜的方法,以改进特定气体的分离,如烯烃与烷烃的分离并且特别是丙烯与乙烷的分离。
发明内容
本发明的第一方面是一种碳分子筛膜,其包含具有第13族金属和至多痕量的硫的碳,其中所述第13族金属以还原态存在。当提及第13族金属时,所述族是按照IUPAC新记法(周期表)、按照《化学与物理手册(Handbook of Chemistry and Physics)》,第66版,CRCPress Inc.(1985)的。
第二方面是一种用于从进料气体中分离气体分子的过程,所述进料气体包含所述气体分子和至少一种其它气体分子,所述过程包含
(i)提供第一方面的碳分子筛膜;以及
(ii)使所述气体进料通过并越过所述碳分子筛膜流动,以产生所述气体分子浓度提高的第一渗透物料流和所述气体分子浓度降低的第二保留物料流。在优选实施例中,所述气体进料包含丙烯和乙烷,其中所述气体分子为丙烯且另一气体分子为乙烷。
本发明的第三方面是一种制造碳分子筛膜的方法,其包含,
(i)提供不含任何硫的前体聚合物;
(ii)将第13族金属并入到所述前体聚合物中以形成带有第13族金属的前体聚合物,
(iii)将所述带有第13族金属的前体聚合物加热至足以形成含有所述第13族金属的所述碳分子筛膜的最终热解温度和非氧化气氛;以及
(iv)将所述碳分子筛膜冷却至室温。
本发明的第四方面是一种碳分子筛模块,其包含包括以下的可密封外围:多个碳分子筛膜,其包含至少一种第一方面的所述碳分子筛膜,所述碳分子筛膜被含有在所述可密封外围内;用于引入由至少两种不同气体分子构成的气体进料的入口;用于准许渗透气体物料流流出的第一出口;和用于保留气体物料流流出的第二出口。
气体分离方法尤其适用于分离气体进料中具有非常相似的分子尺寸的气体分子,如乙烷/乙烯和丙烷/丙烯,并且特别是丙烯与乙烷。它也可以用于分离其他气体,例如从大气中分离氧气或分离天然气进料中的气体(例如甲烷)。
具体实施方式
聚酰亚胺前体聚合物可以是任何聚酰亚胺聚合物,其可用于制造不含硫的CMS膜,并且其中可以添加第13族金属。在一个实施例中,聚酰亚胺含有允许将第13族金属离子地并入到聚酰亚胺结构的部分(例如,极性部分,如3,5-二氨基苯甲酸(DABA)和5,5'-亚甲基-双(邻氨基苯甲酸)(MBAA))。聚酰亚胺可以是常规或氟化的聚酰亚胺。理想的聚酰亚胺通常含有选自以下的至少两个不同部分:2,4,6-三甲基-1,3-苯二胺(DAM)、氧基二苯胺(ODA)、二甲基-3,7-二氨基二苯基-噻吩-5,5'-二氧化物(DDBT)、3,5-二氨基苯甲酸(DABA)、2.3,5,6-四甲基-1,4-苯二胺(均四甲苯)、间苯二胺(m-PDA)、2,4-二氨基甲苯(2,4-DAT)、四甲基亚甲基二苯胺(TMMDA)、5,5'-[2,2,2-三氟-1-(三氟-甲基)亚乙基]-1,3-邻苯二甲酸酐(6FDA)、3,3',4,4'-联苯四甲酸二酐(BPDA)、苯均四酸二酐(PMDA)、1,4,5,8-萘四甲酸二酐(NTDA),以及二苯甲酮四甲酸二酐(BTDA),其中优选6FDA、BPDA和DAM中的两种或更多种。
命名为6FDA/BPDA-DAM的示例性聚酰亚胺可以通过热或化学方法从三种单体的组合合成:DAM;6FDA和BPDA,各自可以例如从西格玛-阿尔德里奇公司(Sigma-AldrichCorporation)商购获得。下式1展示具有调整X与Y之间的比率以调节聚合物性质的潜能的6FDA/BPDA-DAM的代表性结构。如下文实例中所使用,组分X与组分Y的1:1比率也可以缩写为6FDA/BPDA(1:1)-DAM。
指定为6FDA-DAM的另一种示例性聚酰亚胺不含BPDA,使得在以上式1中Y等于零。下式2展示这一聚酰亚胺的代表性结构。
对离子并入第13族金属特别有用的聚酰亚胺是如以下式3中所示的4,4'-六氟亚异丙基二邻苯二甲酸酐(6FDA)、2,4,6-三甲基-1,3-苯二胺(DAM)和3,5-二氨基苯甲酸(DABA),并且其可以缩写为6FDA-DAM:DABA(3:2):
为了获得本发明的CMS膜,将第13族金属并入到前体聚合物中以形成带有第13族金属的前体聚合物。可以通过任何有用的方法并入,由此可以将第13族金属并入到聚酰亚胺中。希望第13族金属以精密标度并入到聚酰亚胺中。可以通过物理混合或掺混并入第13族金属。举例来说,可以将聚合物和第13族金属盐溶解在溶剂中、混合并去除溶剂。在特定实施例中,将第13族金属盐和具有极性部分的聚酰亚胺前体溶解在溶剂中,并在有或没有进一步加热的情况下去除溶剂时,盐分解并且第13族金属通过极性部分离子交联聚酰亚胺聚合物。此类并入的实例说明如下:
在聚酰亚胺合成过程中也可以并入第13族金属。举例来说,将第13族金属盐添加到具有极性部分的聚酰胺酸溶液中,并将所述混合物铸造成薄膜。当薄膜在高温下热固化时,聚酰胺酸转化为聚酰亚胺,并且金属离子与极性部分反应以形成离子聚合物。
也可以通过注入来实现并入第13族金属。举例来说,可以通过注入溶解在溶剂(例如水、乙醇、甲醇、己烷、HCF3和超临界CO2)中的金属化合物将金属并入到固体聚合物前体中。除了前面提到的那些之外,在聚酰亚胺合成期间可用于注入或并入的金属化合物的实例是金属茂,例如二茂铁。
第13族金属盐可以是任何可用于并入到聚酰亚胺中的盐,但通常是有机盐,如第13族金属乙酰丙酮化物、金属乙酸盐或金属氯化物。可以使用不同盐和不同第13族金属的混合物。
第13族金属如以上所定义。优选地,第13族金属为硼或铝,并且最优选地为铝。第13族金属以还原状态(如金属或共价键合到碳或氮上而非作为氧化物)存在于CMS膜中。
CMS膜中第13族金属的量可以是任何可用于增强打算分离的所需气体分子(例如分离乙烷和丙烯)的渗透率和选择性的组合的量。通常,第13族金属的量为CMS膜的0.01重量%到15重量%。合意地,第13族金属的量为CMS膜的至少约0.1重量%、0.5重量%或1重量%到12重量%、10重量%或8重量%。
在形成CMS膜时,并入有第13族金属的聚酰亚胺形成中空纤维膜或薄膜式膜。这些形成的膜(即尚未热解)基本上无缺陷。“无缺陷”是指通过中空纤维膜或薄膜式膜的气体对(通常为氧气(O2)和氮气(N2))的选择性是通过致密薄膜的相同气体对的选择性的至少90%,所述致密薄膜由与用于制造聚合前体中空纤维膜的组合物相同的组合物制备。作为例证,6FDA/BPDA(1:1)-DAM聚合物的固有O2/N2选择性(也称为“致密薄膜选择性”)为4.1。
可以使用制造聚酰亚胺中空纤维或薄膜的常规程序。举例来说,包括如干喷湿式纺丝工艺(其中在喷丝头的尖端和凝固或淬火浴之间存在气隙)或湿式纺丝工艺(具有零气隙距离)的共挤出程序可以用于制造中空纤维并且溶液铸造可以用于制造薄膜。
特定的加热速率、最终热解温度、冷却速率和它们的组合在某种程度上取决于所用的特定聚酰亚胺、第13族金属和进行的所需分离。然而,通常已经发现特别是为了分离烯烃与烯烃的烷烃类似物,并且特别是分离丙烯与乙烷,希望加热至最大热解温度并保持在所述温度下,以使第13族金属趋于还原,从而它将不以氧化物形式存在。通常,这倾向于希望在非氧化条件下(例如在没有任何明显的氧气(如低于100ppm)但优选地氧气不“小于1ppm”的情况下)快速加热,在较低的最高热解温度下短时间保持。
通常,碳化含第13族金属的聚酰亚胺的最大或最终热解温度可以是从400到1000℃的任意位置的温度,但优选是从约500℃到700℃或600℃。加热速率可以是任何合适的,如1℃/分钟到100℃/分钟,但理想地是从约5℃/分钟或10℃/分钟到25℃/分钟,或20℃/分钟。考虑到加热速率,最终热解温度下的时间量理想地是从可行的短时间(例如几秒或一分钟)到约60分钟。在实施例中,最终热解温度下的保持时间为15分钟到60分钟。较长的时间往往不是必需的,并且可能对理想的渗透率和选择性的组合产生负面影响。同样,冷却速率可以是任何合适的方法,如仅被动地冷却炉(通过关闭电源),但是可能需要通过热去除方法快速冷却或加速冷却。
示例性热去除方法包括:使气体直接在炉内的碳分子筛膜上流动;使气体流过炉内的碳分子筛膜;去除炉隔热材料;使液体在炉的至少一部分上流动或使气体在炉的至少一部分上流动。可以使用任何一种或组合的热去除方法,其中希望冷却速率尽可能地高,至少从最终热解温度到约400℃或室温。通常,从最终热解温度到400℃的平均冷却速率至少是约2、4或8℃/分钟。平均加热速率是最终热解温度与400℃之间的温差比达到400℃所需的总时间。从400℃到室温的冷却速率可以是任何可行的,仅为了生产率的缘故而需要更快。
应理解,所有温度、加热速率和冷却速率都是在炉中测量的温度,而不是针对形成的实际CMS膜。所形成的CMS膜的实际温度可能由于炉内的热质量、所用的特定炉等导致的温度滞后而稍微变化,并且本领域技术人员可以容易地确定。
在热解期间可以使用任何合适的用于保持CMS膜的支撑构件,包括夹在两个金属丝网之间或与不锈钢丝组合使用的不锈钢网板,并且如美国专利第8,709,133号第6栏第58行到第7栏第4行,其以引用的方式并入。当支撑致密薄膜而不是中空纤维时,可以理想地使用石英板。
含有第13族金属的聚酰亚胺可以在不同惰性气体吹扫或真空条件下、优选在用于真空热解的惰性气体吹扫条件下、优选在低压(例如,小于0.1毫巴)下碳化。在一个实施例中,在热解期间,热解利用受到控制的吹扫气体气氛,其中低水平的氧气存在于惰性气体中。举例来说,使用惰性气体(例如氩气)作为吹扫气体气氛。其它合适的惰性气体包括但不限于氮气、氦气或其任何组合。通过使用任何合适的方法(如阀门),可以将含有特定浓度氧气的惰性气体引入热解气氛中。举例来说,吹扫气氛中的氧气量可小于约50ppm(百万分率)O2/Ar。或者,吹扫气氛中的氧气量可以小于40ppm O2/Ar。实施例包括具有约8ppm、7ppm或4ppm O2/Ar的热解气氛,但优选的是,如上文所描述基本上不具有氧气(即小于约1ppm的O2)。
膜的气体渗透特性可以通过气体渗透实验确定。两种固有特性可用于评价膜材料的分离性能:其“渗透性”(膜固有产率的量度);和其“选择性”(膜分离效率的量度)。通常用巴(Barrer)为单位确定“渗透性”(1巴=10-10[cm3(STP)cm]/[cm2s cmHg]),其根据将通量(ni)除以膜上游与下游之间的分压差(Δpi),且乘以膜厚度(l)来计算。
另一术语“渗透性”在本文中被定义为不对称中空纤维膜的产率,并且通常以气体渗透单位(GPU)(1GPU=10-6[cm3(STP)]/[cm2s cmHg])来测量,其通过将渗透率除以有效的膜分离层厚度来测定。
最后,“选择性”在本文中定义为一种气体渗透通过膜的能力或相对于另一种气体的相同特性来说的渗透性。其经测量为无单位比率。
在特定实施例中,通过所述方法产生的CMS膜能够使碳中空纤维CMS膜对目标气体分子(渗透物)具有至少5GPU的渗透率和至少10的选择性和稳定性,使得在连续分离由保留物气体分子和渗透物气体分子组成的进料气体10天后,所述渗透率和选择性变化小于20%。合意地,在连续分离由保留物和渗透物气体分子对组成的进料气体10、30或60天后,渗透率和选择性变化小于15%、10%或5%。在特定实施例中,渗透物/保留物气体分子对可以是乙烯/乙烷、丙烯/丙烷、丁烯/丁烷、甲烷/二氧化碳、甲烷/水、氧气/氮气和甲烷/硫化氢。示意性地,进料气体通常包含至少50%的渗透物气体分子(例如,乙烯或丙烯)和25%的保留物气体分子(例如,乙烷或丙烷)。
在特定实施例中,所产生的CMS膜对丙烯(渗透物)具有至少10GPU的渗透率和对丙烯/丙烷至少35的选择性。合意地,在此实施例中,对丙烯的渗透率是至少12、15或甚至18GPU。同样,在此实施例中,对于丙烯/丙烷的选择性为至少40、45或甚至50。在另一特定实施例中,所产生的CMS膜对于乙烯(渗透物)的渗透性为至少10GPU并且对于乙烯/乙烷的选择性为至少6。合意地,在此实施例中,对于乙烯的渗透性为至少15、18或甚至20GPU。同样,在此实施例中,对乙烯/乙烷的选择性是至少8、10或甚至12。在另一实施例中,所产生的CMS膜对丁烯(渗透物)具有至少10GPU的渗透率和对丁烯/丁烷至少5的选择性。合意地,在此实施例中,对丁烯的渗透率是至少20、30或甚至40GPU。同样,在此实施例中,对于丁烯/丁烷的选择性为至少10、15或甚至30。
CMS膜特别适用于分离与如上所述尺寸相似的气体,并涉及使含有所需气体分子和至少一种其它气体分子的气体进料流过CMS膜。第一物料流中的流动结果具有增加浓度的期望气体分子,而第二物料流具有增加浓度的另一气体分子。所述方法可用于分离前述气体对中的任一个,并且特别适用于分离乙烯与乙烷,分离丙烯与丙烷,特别是分离丙烯与乙烷。同样,如上所述,所述方法展现出关于渗透率和选择性随时间的相同稳定性。在实践所述过程时,将CMS膜理想地制成包含可密封外围的模块,所述外围包含多个碳分子筛膜,所述碳分子筛膜包含至少一个通过本发明方法产生的碳分子筛膜,所述碳分子筛膜含于可密封外围内。所述可密封外围具有用于引入包含至少两种不同气体分子的气体进料的入口;用于准许渗透气体物料流流出的第一出口;和用于保留气体物料流流出的第二出口。
实例
实例1:
使用6FDA-DAM:DABA(3:2)聚合物制造CMS膜。6FDA-DAM:从Akron PolymerSystems,Inc.,Akron,OH获得DABA。将聚合物在110℃下真空干燥过夜以去除水分。将干燥的聚合物溶解于含四氢呋喃(THF,>99.9%纯度,西格玛-阿尔德里奇(Sigma-Aldrich),圣路易斯市,密苏里州(St.Louis,MO))的40ml小瓶(小瓶A)中以形成2-3重量%的聚合物溶液。将乙酰丙酮铝(III)(西格玛-奥德里奇,圣路易斯市,密苏里州)溶解在含THF的20ml小瓶(小瓶B)中以形成含Al溶液。将两种溶液分别用0.20微米PTFE过滤器过滤以去除杂质,并将小瓶B中的含Al溶液添加到小瓶A中以形成用于薄膜铸造的含Al聚合物掺杂物。溶液的组合物展示于表1中。
通过在室温下将混合溶液铸造到手套袋(科尔-帕默(Cole-Parmer),VernonHills,IL)内的铁氟龙铸造皿中来制备聚合物致密薄膜。接着用氮气吹扫手套袋,并在铸造前至少等待3个小时使其经THF饱和。在至少3天后,将玻璃化薄膜从袋中取出并在真空烘箱中,在130℃下干燥24小时以去除残余溶剂。接着将干燥后的具有约80微米厚度的薄膜切成0.75英寸直径的圆盘,接着按如下所述进行热解。通过将圆盘放置在每个圆盘之间具有间隔的开槽石英板上,将圆盘热解以形成CMS膜。将圆盘和石英板的组合放入到管式炉的石英管中。在惰性气体下热解薄膜(氩气以200标准立方厘米/分钟(sccm)的速率流动)。在热解之前,用惰性气体吹扫炉以去除氧气至少十小时,以将氧气含量降低至小于1ppm。如表2所示将薄膜以升温速率加热直至达到最终的热解温度,以形成最终的CMS膜。所形成的CMS膜全部被动冷却(关闭炉子且保持相同的惰性气体流,直到炉冷却至约室温,约4-6小时)。
冷却后,通过使用不可渗透的铝胶带和五分钟环氧树脂(3MTM Scotch-WeldTM环氧粘合剂DP110)将CMS膜在致密薄膜渗透槽中掩蔽。然后将渗透槽置于等容渗透系统中,并将系统稳定在35℃。对于每次渗透测试,将整个系统抽空18小时。抽空后,在约50磅/平方英寸绝对压力(psia)下用进料气体加压上游,同时将下游保持在真空。通过压力传感器监测恒定的已知下游容量的压力上升并且由LabVIEW(National Instruments,Austin,TX)随时间记录直到达到稳定状态。
评价实例1的多组分烯烃/烷烃混合物分离。多组分进料含有54.60mol%乙烯、17.00mol%乙烷、15.10mol%丙烯和13.30mol%丙烷。用于多组分进料的实例1的CMS膜的分离特征显示于表3中。
表3还展示了以与实例1相同的方式制备的比较实例,不同之处在于将乙酰基丙酮酸铝(III)、乙酰基丙酮酸铁(II)(西格玛-阿尔德里奇,圣路易斯市,密苏里州)代替用于比较实例2,且将乙酰基丙酮酸铁(III)(西格玛-阿尔德里奇,圣路易斯市,密苏里州)用于比较实例3。比较实例1不采用金属。利用相同制备、热解条件和测试。出人意料的是,实例1具有最高的丙烯/乙烷选择性,这对于批量可商购的烯烃/烷烃分离至关重要。实例1还展示出较高乙烯和丙烯渗透率。
表1:铸造溶液配方
溶剂 | 溶质 | |
小瓶A | 20ml THF | 0.5g聚合物 |
小瓶B | 5ml THF | 0.05g乙酰基丙酮酸铝(III) |
表2:热解条件
实例 | 温度(℃) | 气氛(sccm/Ar) | 加热速率(C/min) | 浸渍时间(min) |
1 | 550 | 200 | 10 | 0 |
表3分离特性
C2”=乙烯;C2=乙烷;C3”=丙烯;C3=丙烷。
ND=未确定,由于气相色谱(GC)的测试限制而无法使用。
Claims (13)
1.一种碳分子筛膜,其包含具有第13族金属和至多痕量的硫的碳,其中所述第13族金属以还原态存在。
2.根据权利要求1所述的碳分子筛膜,其中所述第13族金属为铝。
3.根据前述权利要求中任一项所述的碳分子筛膜,其中所述第13族金属以所述碳分子筛膜重量的0.5%到10%存在。
4.根据前述权利要求中任一项所述的碳分子筛膜,其中所述碳分子筛膜是中空纤维或薄膜。
5.一种用于从进料气体中分离气体分子的过程,所述进料气体包含所述气体分子和至少一种其它气体分子,所述过程包含
(i)提供前述权利要求中任一项所述的碳分子筛膜;以及
(ii)使所述气体进料穿过并越过所述碳分子筛膜流动,以产生所述气体分子浓度提高的第一渗透物料流和所述气体分子浓度降低的第二保留物料流。
6.根据权利要求5所述的过程,其中所述气体分子为丙烯且所述至少一种其它气体分子包含乙烷。
7.一种制造碳分子筛膜的方法,其包含,
(i)提供不含任何硫的前体聚合物;
(ii)将第13族金属并入到所述前体聚合物中以形成带有第13族金属的前体聚合物,
(iii)将所述带有第13族金属的前体聚合物加热至足以形成含有所述第13族金属的所述碳分子筛膜的最终热解温度和非氧化气氛;以及
(iv)将所述碳分子筛膜冷却至室温。
8.根据权利要求7所述的方法,其中所述第13族金属的所述并入是通过将所述第13族金属离子键合到所述前体聚合物中存在的一或多个部分而进行。
9.根据权利要求7或8所述的方法,其中所述前体聚合物为聚酰亚胺。
10.根据权利要求9所述的方法,其中所述前体聚合物为包含3,5-二氨基苯甲酸(DABA)的聚酰亚胺共聚物。
11.根据权利要求8所述的方法,其中所述第13族金属的所述并入是通过在所述聚酰亚胺的合成期间添加所述第13族金属或通过将溶解于溶剂中的所述第13族金属注入到所述聚酰亚胺中而进行。
12.根据权利要求11所述的方法,其中所述第13族金属的所述并入是通过将所述第13族金属与六氟亚异丙基二邻苯二甲酸酐(6FDA)、2,4,6-三甲基-1,3-苯二胺(DAM)和二氨基苯甲酸(DABA)的共聚物的二氨基苯甲酸(DABA)部分的离子键合。
13.一种碳分子筛模块,其包含包括以下的可密封外围:多个碳分子筛膜,其包含至少一种根据权利要求1至4中任一项所述的碳分子筛膜,所述碳分子筛膜被含有在所述可密封外围内;用于引入包含至少两种不同气体分子的气体进料的入口;用于准许渗透气体物料流流出的第一出口;和用于保留气体物料流流出的第二出口。
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KR101919302B1 (ko) * | 2017-07-28 | 2018-11-19 | 한국전력공사 | 이산화탄소 분리막 플랜트 이상 감지 시스템 |
WO2019210159A1 (en) * | 2018-04-26 | 2019-10-31 | Texas A&M University | In situ fabrication of metal-organic framework films and mixed-matrix membranes |
CA3225047A1 (en) * | 2021-07-21 | 2023-01-26 | Abhishek Roy | Methods for manufacturing hollow fiber carbon membranes |
WO2023152362A1 (en) * | 2022-02-14 | 2023-08-17 | Fundacion Tecnalia Research & Innovation | Carbon molecular sieves membranes with atomic aluminum distributed in it |
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EP3703847A1 (en) | 2020-09-09 |
US11504675B2 (en) | 2022-11-22 |
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BR112020007670A2 (pt) | 2020-10-13 |
WO2019089087A1 (en) | 2019-05-09 |
KR102571975B1 (ko) | 2023-08-31 |
US11772053B2 (en) | 2023-10-03 |
CA3079195A1 (en) | 2019-05-09 |
CN115888411A (zh) | 2023-04-04 |
US20200276542A1 (en) | 2020-09-03 |
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