CN103228342A - 生产碳膜的方法 - Google Patents
生产碳膜的方法 Download PDFInfo
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- CN103228342A CN103228342A CN2011800570828A CN201180057082A CN103228342A CN 103228342 A CN103228342 A CN 103228342A CN 2011800570828 A CN2011800570828 A CN 2011800570828A CN 201180057082 A CN201180057082 A CN 201180057082A CN 103228342 A CN103228342 A CN 103228342A
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- ethylenically unsaturated
- temperature
- pyrolysis
- carbon film
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- 238000000034 method Methods 0.000 claims description 32
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Classifications
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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- C04B2111/00801—Membranes; Diaphragms
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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Abstract
本发明涉及烯属不饱和聚酯的溶液在生产适用于气体分离的碳膜中的用途,以及一种生产适用于气体分离的碳膜的方法,该方法包括以下步骤:a)用烯属不饱和聚酯的溶液涂覆多孔基材,b)通过除去溶剂将多孔基材上的聚酯涂层干燥,c)使多孔基材上的聚酯涂层热解,以形成适用于气体分离的碳膜,其中可将步骤a)-c)中的任意步骤或按步骤a)-c)的顺序进行超过一次。
Description
本发明涉及生产适用于气体分离的碳膜的方法,可通过该方法获得的碳膜以及特定聚合物溶液在这类碳膜生产中的用途。
通过有机材料热解合成的碳被称作次晶碳,因为其显示了与理想晶体结构的较大或较小偏离。其具有小的周期环域,但显示了X射线漫反射并因此被称作X射线无定形。玻璃状微孔碳具有比结晶石墨(2.2g/cm3)较低的密度(1.2-1.6g/cm3)以及窄的孔径分布。由于高比例的开孔率,碳作为吸附剂具有优异的适用性。
无定形或微晶碳膜具有高的化学惰性。它们包含sp2和sp3键并因此显示介于石墨和钻石性能之间的性能。石墨状结构包含其中微晶通过高变形和无序的石墨层连接的湍层无序层序列。
过去已经建立了关于在X射线无定形碳中确切键合条件的不同理论。Robertson和O’Reilly传播了其中无定形碳包含经由sp3键相互联网的sp2键簇的模型,与之相反,和Liu发表了无定形碳仅包含呈三维网状的sp2键的理论。实验支持分散交联的sp2键的推测。根据Lossy等人,在无定形和纳米晶体碳中,存在sp2和sp3键类型的混合物。如果这些簇变得足够大,则可形成纳米晶体石墨和钻石结构。
在使用纳米孔碳作为膜材料的情况下,可在高选择性下同时获得高的渗透性。在碳膜中气体渗透比在聚合物膜中简单,因为气体在碳中不溶。对以下两种碳膜加以区别:分子筛碳膜(MSCM)和吸附选择性碳膜(ASCM)。由于较大分子类型的尺寸排除,MSCM允许具有不同分子直径的气体混合物的分离。
与之相反,ASCM允许具有相似分子半径的气体混合物的分离或甚至从小分子中除去较大分子。
可吸附和不可吸附气体的渗透特征基于不同机理。当在理想情况下未吸附气体的渗透应理解为纯粹的气体扩散,可吸附气体的渗透通过表面扩散方法测定。在可吸附和不可吸附气体的混合物中,未吸附组分的渗透被已吸附的气体分子阻止。未吸附气体首先必须克服潜在阻挡以扩散通过膜。实际上,气体扩散和表面扩散总是同时发生。分离通过一种组分选择性吸附并表面扩散至膜的低压侧(在此该组分最后解吸附)而进行。
碳的另一关键优点为可通过热化学处理对孔径可控调节,这使得能够由相同起始材料生产具有不同渗透和分离性能的膜。碳膜对酸、碱和有机溶剂具有高的化学稳定性。相对于聚合物膜,纳米孔的碳膜可在非氧化条件下,在高达900℃的高温下使用。
碳的一个缺点为其对氧化介质和水蒸气的有限的稳定性。此外,碳膜比聚合物膜更脆且可被吸附气体,如氯气堵塞。吸附气体分子可在≥200℃的温度下再被除去。因此,优选的工艺温度应在该范围内。
玻璃状碳中的第一批代表之一为在规定热处理下由于纤维素高温转化为碳而形成的“纤维素碳”。
来自纤维素纤维的碳纤维膜的通过热解的生产例如描述在中EP-A-0671202。
WO00/62885描述了聚合物酚醛树脂在适用于气体分离的碳膜的形成中的用途。这包括将酚醛树脂溶解在甲醇中。
WO01/97956描述了通过所选聚合物在多孔基材上的热解而生产纳米孔的碳膜。所提及的优选聚合物包括聚糠醇、聚氯乙烯和聚丙烯腈。将它们与添加剂,优选二氧化钛、二氧化硅沸石或聚乙二醇混合并施加至基材上。随后热解。
EP-A-2045001描述了酚醛树脂、三聚氰胺树脂、脲醛树脂、呋喃树脂、聚酰亚胺树脂或环氧树脂,以及基于聚乙烯和纤维素的溶于有机溶剂的树脂在通过膜形成并随后使树脂热解而生产碳膜中的用途。
此外,EP-A-2045001描述了碳膜的构造,其包含多孔基材,随后的多孔陶瓷层以及碳层,其具有碳膜施加其上,由TiO2溶胶制备且孔径为0.3-20nm的最后的夹层。此外,将膜进行试验,仅用于在75℃下通过全蒸发分离水和乙醇。该试验不允许适用于在较高温度下气体分离。
用于合成各向同性碳产物的优选前体通常为基于烃的聚合物,其在热解之后剩下高比例的微晶碳且其在具有尺寸稳定性下降解[1][2][3][4]。碳膜的合成同样如此[5]。关于涂层,此处优点在于热解之后所获得碳层的厚度可经由前体聚合物的层厚更有效地调节。具有尺寸稳定性的降解不仅是复杂载体几何形状的涂覆所希望的,而且防止熔融[6]和重构为石墨的能量上更有利的形式,以及缺陷(如针孔)的发展,其可通过气体降解产物的逃逸而产生[7]。因此,对碳膜[8][9][10]的合成而言,聚合物,如酚醛树脂或聚糠醇是显而易见的,因为热解各自留下了35质量%或55质量%呈碳形式的聚合物[4][3]。
[1]E.Fitzer,“Thermal degradation of polymers to elemental carbon-a path to materials of the future”,Angew.Chem.,92,375-386(1980)。
[2]E.Fitzer,“From polymers to polymeric carbon-A way tosynthesize a large variety of new materials”,Pure&Appl.Chem.,52,1865-1882(1980)。
[3]H.and E.Fitzer,“New forms of carbon”,Naturwissenschaften,57,29-36(1970)。
[4]A.Gardziella,L.Pilato and A.Knop,2000。
[5]W.Koros and D.Vu,San Ramon,美国,2002。
[6]P.Harris,University of Reading,Whiteknights,英国,2001。
[7]A.Soffer,D.Rosen,S.Saguee and J.Koresh,德国,1992。
[8]S.Saufi and Ismail AF,“Fabrication of carbon membranes forgas separation-a review”,Carbon,42,241-259(2004)。
[9]A.Fuertes,“Effect of air oxidation on gas separation propertiesof adsorption-selective carbon membranes”,Carbon,39,697-706(2001)。
[10]C.J.Anderson,S.J.Pas,G.Arora,S.E.Kentisch,A.J.Hill,S.I.Sandler and G.W.Stevens,“Effect of pyrolysis temperature andoperating temperature on the performance of nanoporous carbonmembranes”,Journal of Membrane Science,[322],19-27(2008)。
在热解步骤之前,聚合物膜常经受物理或化学预处理。物理预处理应理解为是指例如中空纤维的拉伸。化学处理方法例如包括用碳化催化剂,如无机酸处理,或用化学物质,如二甲基甲酰胺处理以获得窄的孔径分布。另一预处理方法为在氧化气氛,如在升高的温度下的空气中处理。
合成聚合物在惰性气体气氛下的热解产生高孔隙率的碳,其孔径可由于聚合物类型和形态以及热解条件而大大改变。可控的热处理可调节碳膜的孔径。热解条件对碳的分离性能具有重要影响。加热速率、热解温度和热解时间为可以规定方式调节的参数。热能的供应使聚合物中的键断裂,结果是形成碳膜。
已知的膜还不具有适用于所有分离任务的性能特征。在某些情况下,膜不能以可复制方式产生,即膜性能每一批都变化。
本发明目的为提供一种生产适用于气体分离的碳膜的方法,或提供一种适用于生产碳膜的聚合物,且所得膜应避免现有技术的缺点并应在具有理想的再现性下显示优异的分离性能。
根据本发明,该目的通过烯属不饱和聚酯在生产适用于气体分离的碳膜中的用途而实现,其中所述膜优选额外具有以下分离性能,其用于在150-450℃的温度下从气体混合物中分离氢气,根据混合物-气体测量所测定,氢气渗透性为≥2Nm3/m2/小时/巴,氢气选择渗透性≥30。
渗透性的定义:在标准温度和压力条件下每m2膜面积、时间和压力,气体的立方米流速(Nm3),其中所用压力(驱动力)为相应气体的进料/保留物和渗透物之间的分压差。
渗透选择性的定义:随后渗透选择性由所确定的渗透性的比例给定。
该目的额外通过一种生产适用于气体分离的碳膜的方法实现,该方法包括以下步骤:
a)用烯属不饱和聚酯的溶液涂覆多孔基材,
b)通过除去溶剂将多孔基材上的聚酯涂层干燥,
c)使多孔基材上的聚酯涂层热解,以形成适用于气体分离的碳膜,
其中可将步骤a)-c)中的任意步骤或按步骤a)-c)的顺序进行超过一次。
该目的还通过可通过上述方法获得的碳膜实现。
根据本发明已发现的是,烯属不饱和聚酯溶液的使用导致具有优异分离性能和理想再现性的碳膜。
另外,已发现的是,当所用前体为具有非常高降解程度并因此仅5质量%碳产率的聚酯树脂时,可产生特别高性能的碳膜。
如在开头所引用文献中所述的,该膜可通过已知方法生产。
所用烯属不饱和聚酯可为任何合适的烯属不饱和聚酯。烯属不饱和聚酯优选具有脂族二醇、芳族二羧酸和烯属不饱和二羧酸的重复单元。根据本发明使用的烯属不饱和聚酯可由脂族二醇、芳族二羧酸酐和烯属不饱和二羧酸酐制备。
脂族二醇优选为C2-12链烷二醇,更优选C2-6链烷二醇,特别是C2-4链烷二醇。它们可为其中羟基为端基或非端基的线性或支化的链烷二醇。优选使用其中羟基为端基或非端基的线性脂族链烷二醇。特别优选的是,将1,2-丙二醇用作链烷二醇。
烯属不饱和二羧酸优选为马来酸。将其特别以马来酸酐形式用于制备烯属不饱和聚酯。
芳族二羧酸可选自任何合适的芳族二羧酸。它们例如可为邻苯二甲酸、间苯二甲酸或对苯二甲酸。芳族二羧酸优选为对苯二甲酸,将其以邻苯二甲酸酐的形式用于制备烯属不饱和聚酯。
在烯属不饱和聚酯中,二醇和二羧酸可以等量存在。优选在二醇略微过量下进行,以使所得聚酯具有比羧酸端基更多的醇端基。二醇相对于二羧酸可过量1-20%,优选2-10%,特别是3-7%。
芳族二羧酸和烯属不饱和二羧酸可以任何合适的摩尔比例使用。芳族二羧酸和烯属不饱和二羧酸优选以0.1:1-1:0.1,更优选0.3:1-1:0.3,特别是0.09:1-1:0.9的摩尔比例使用。特别优选在等量的芳族二羧酸和烯属不饱和二羧酸下进行。
在常规条件下将所提及的单体用于制备烯属不饱和聚酯,且烯属不饱和二羧酸的烯属不饱和基团应基本保留。就烯属不饱和聚酯的制备而言,可参考已知方法。
根据本发明优选使用的烯属不饱和聚酯的分子量为100-2000g/mol,更优选200-600g/mol。聚酯的粘度优选为4-200mPas,更优选10-40mPas。
烯属不饱和聚酯的溶液优选额外饱和交联烯属不饱和单体和作为交联引发剂的自由基生成体。交联烯属不饱和单体优选为苯乙烯或α-甲基苯乙烯。所用自由基生成体可为任何自由基聚合引发剂。例如可使用作为自由基生成体的过氧化二苯甲酰。在将烯属不饱和聚酯的溶液施加至多孔基材上时,聚酯优选当时仍未交联或至多部分交联至其仍保持流动性的程度。
有用的溶剂为适用于聚酯的全部溶剂,优选苯乙烯、α-甲基苯乙烯和丙酮。
在本发明的一个实施方案中,将交联烯属不饱和单体用作溶剂,这是指当使用烯属不饱和单体时,省去另一溶剂。在适当调节烯属不饱和聚酯的粘度的情况下,在本发明的一个实施方案中,同样可省略溶剂的加入。特别是当烯属不饱和聚酯在环境温度下(22℃)自由流动时,就是这种情况。
更优选在步骤a)的涂布中,在未加入其它溶剂或稀释剂下将烯属不饱和聚酯与交联烯属不饱和单体一起使用。
在该情况下,交联烯属不饱和单体在烯属不饱和聚酯和烯属不饱和单体的混合物中的比例优选为0.1-5重量%,更优选0.2-2重量%,或优选20-100重量%,更优选40-80重量%。
多孔基材可通过任何合适的涂覆方法涂覆烯属不饱和聚酯的溶液。溶液可通过浸入、喷雾、浸渍方法等施加。优选使用浸涂方法施加烯属不饱和聚酯的溶液。烯属不饱和聚酯的施加也可通过油墨涂布和超声沉积(UD)实现。相应方法例如描述在EP-A-2045001和WO01/97956中。
在用烯属不饱和聚酯的溶液涂覆多孔基材之后,使聚酯涂层在多孔基材上干燥。这样除去所存在的任何溶剂。在使用交联烯属不饱和单体的情况下,该单体的过量部分同样在干燥过程中除去。干燥优选在0-70℃,更优选17-30℃的温度下,特别是在环境温度下进行0.1-50小时,优选2-24小时的时间。
在步骤c)热解之前,在干燥b)之后或当部分干燥时,固化可在略微升高的温度下进行。固化优选在20-150℃或50-250℃,更优选60-100℃的温度下进行1-100小时或4-20小时,优选6-24小时或6-12小时的时间。固化使烯属不饱和聚酯交联。交联阻止熔融以及因此阻止交联聚酯结构重排为石墨的能量上更有利的状态。
在热解步骤之前,聚合物膜也可经受物理或化学预处理。化学预处理方法例如包括用碳化催化剂如无机酸处理,或用化学物质如二甲基甲酰胺处理以获得窄的孔径分布。添加剂,如聚乙二醇、路易斯酸和离子盐已经描述在开头所引用的文献中,特别是EP-A-0671202中。这种预处理也可根据本发明进行,但常常是不必要的,因为合适的孔径结构仅通过根据本发明使用的聚酯的使用而获得。其它合适的造孔剂为SO3NH(C2H5)3、三乙基硝酸铵和(-C(CF3)2-)六氟异亚丙基。膜的渗透性可经由造孔剂的类型和量控制。
在热解时,根据本发明使用的聚酯优选为已在热解的低温范围内交联或固化。在交联之前,优选应从聚合物涂层中除去所有溶剂,因为它们可在加热过程中导致泡形成并在聚合物层中导致缺陷。交联度和交联温度可影响后来膜的渗透性和选择性。
在步骤c)中,在多孔基材上的聚酯涂层热解形成碳膜优选在惰性气体下,在500-900℃,更优选650-750℃的温度下进行。热解进行的时间优选为0.1-24小时,优选0.5-17小时,更优选1-10小时,特别是1-2小时。
在某些情况下,可建议在少量含氧气体存在下进行热解。然而,根据本发明优选在惰性气体下,如在氮气和/或氩气气氛下进行热解。
热解产生高孔隙率的碳,其孔径可由于前体类型和形态以及热解条件而变化。可控的热处理可调节碳膜的孔径。热解条件影响所得碳膜的分离性能。加热速率、热解温度和热解时间为可调节的参数。热能的供应使聚合物中的键断裂。在聚合物降解过程中,形成一系列气体副产物,其结果是产生了明显的质量损失。
在热解之后,需要和希望的话,所得碳膜可经受其它处理步骤。例如,膜可通过在空气下,在100-500℃的温度下热处理而活化。也可根据本发明在二氧化碳流中活化。然而,根据本发明优选在步骤c)的热解之后不进行任何这种后处理,并且由热解所得的碳膜实际上直接适用于气体分离。
根据本发明所得碳膜的平均孔径优选为0.1-0.7nm或0.25-0.4nm,更优选0.25-0.45nm,特别是0.3-0.4nm。这些膜优选仅允许具有较小动力气体直径的,可渗透入膜的孔体系的分子通过。它们特别是氢气、水、氨和氦气。这些气体的分离机理不基于待分离气体的不同吸附和运输特征,但基于形状选择性分离(分子筛)。在该情况下,确保渗透气体的流动以与驱动力线性的方式提高。
特别优选借助根据本发明获得的碳膜,任选与使平衡移动的化学反应组合以进行以下分离:
例如在脱氢中,从来自C1上升气流的烃中分离氢气。
根据本发明,目标使用温度为200-500℃。
本发明碳膜优选以不对称膜的形式产生。多孔基材(载体)的选择首先取决于化学反应性和与碳的相容性,机械稳定性,以及经济因素,如成本和可得到性。合适的多孔基材为多孔材料,如多孔金属、多孔陶瓷、多孔玻璃或其多孔复合物。
多孔基材更优选具有TiO2、ZrO2、Al2O3、SiO2或其混合物的中孔陶瓷氧化物层,其用烯属不饱和聚酯的溶液涂覆。
中孔陶瓷氧化物层更优选由γ-Al2O3形成。
在本发明的一个实施方案中,中孔陶瓷氧化物层具有低于步骤c)中热解温度的烘烤温度。该中孔陶瓷氧化物层优选以未被烘烤的形式,用烯属不饱和聚酯的溶液涂覆,在该情况下中孔陶瓷氧化物层的烘烤与热解同时。这可导致所得碳膜的特别有利的性能谱图。
钢作为载体材料的用途产生了标准化、易控制和可再现生产的优点。然而,在使用钢的情况下,不可由层复合物产生多孔载体,这将使高的渗透性和选择性相互组合。
因此,优选在陶瓷多孔载体上的碳膜。碳膜优选包含具有更细层厚和孔径的复合物。因为在基材表面中的缺陷可引起碳膜中的缺陷,如针孔,其可导致膜的分子筛性能的损失,有利的是通过用中间层涂覆多孔载体而减少载体的表面形态和缺陷结构。
优选的本发明膜的基本结构描述在EP-A-2045001中。特别是可参考其中在说明书中具有相应说明的附图1。
在优选的粗孔Al2O3载体上,在较小孔的层之后优选为γ-Al2O3的中孔陶瓷氧化物层,γ-Al2O3层的孔径优选为2-10nm,更优选3-7nm,特别优选4-6nm。该中孔陶瓷氧化物层的层厚优选为0.1-10μm,更优选0.5-5μm,特别是1-2nm,尤其是1-5nm。
经由多孔基材横截面中的孔径向碳膜降低的事实,可避免多孔基材中的压降,同时在碳膜中建立了合适的孔径。这种膜的设计可确保在特定分离任务中通过膜的高流动性。
本发明通过以下实施例详细说明。
实施例
实施例1
前体溶液通过使二醇与至少一种不饱和羧酸反应,产生不饱和聚酯并随后加入烯烃而制备。在特定情况下,在250ml两颈烧瓶中,将19.98g1,2-丙二醇(0.25mol+5%过量;VWR)、12.26g马来酸酐(0.125mol;VWR)和18.52g邻苯二甲酸酐(0.125mol;VWR)称重加入。随后,将0.01g氢醌(VWR)作为聚合引发剂加入,以防止过早聚合或交联过程。在氮气下,借助油浴将称重加入的原材料加热至200℃的反应温度。为检查链形成,酸值通过用KOH溶液在有规律的间隔下滴定而测定。在约50的酸值下,反应通过快速冷却至140℃而停止。借助滴液漏斗,随后在1分钟内将50g苯乙烯作为交联剂加入,同时激烈搅拌。所加入的苯乙烯已经预先加热至50℃。为防止聚酯-苯乙烯混合物的过早聚合,将不饱和的聚酯树脂溶液在水浴中冷却至室温。随后,将1%作为自由基生成体的过氧化二苯甲酰(VWR)加入聚酯-苯乙烯混合物,随后在室温下将混合物搅拌5分钟。
用于膜的载体为α-Al2O3的长度为105mm,内径为7mm,外径为10mm的陶瓷单通道管,其在内侧具有孔径降低的中间层。所用的最上面的中间层为孔径为5nm,厚度为1-2μm的γ-Al2O3层。
将其在浸涂方法中,用清澈的、粘性的浅黄色前体溶液涂覆。为此,将溶液引入管子并在1分钟停留时间之后,再抽出来。将试样在空气下干燥24小时,然后在空气及80℃的温度下,在干燥箱内固化12小时,并冷却至室温。
在聚合物交联形成热固性树脂之后,使用以下程序将层热解为碳。
1.在氮气下,以0.5K/分钟将温度从室温升至380℃
2.在氮气下,在380℃下停留1小时
3.在氮气下,以0.6K/分钟将温度从380℃升至500℃
4.在氮气下,在500℃下停留10分钟
5.将气氛从氮气转换为氩气
6.在氩气下,以1K/分钟将温度从500℃升至最后的热解温度
7.在氩气下,在最后的热解温度下停留1小时
8.在氩气下,以5K/分钟从最后的热解温度冷却至500℃
9.将气氛从氩气转换为氮气
10.在氮气下,以5K/分钟从500℃冷却至室温
聚酯组成、交联剂比例和最后的热解温度可参见实施例4的表中结果。
实施例2:
根据实施例1的方法,在0.2/0.05/0.25摩尔至0.07/0.43/0.5摩尔范围中改变马来酸酐/邻苯二甲酸酐/1,2-丙二醇反应物的比例。
实施例3:
根据实施例1的方法,使用在300℃,500℃和650℃下烧结的中孔的γ-Al2O3层。
为表征实施例1-3中产生的碳膜的分离性能,单独气体和混合物气体测量在150℃的温度下,在气体测量装置中进行。单独气体的渗透性测量借助压力增加方法进行,其中在该情况下渗透性可由压力随时间的线性增加确定。混合物气体测量使用含80体积%氢气和20体积%丙烷的H2/C3H8混合物进行,其中可透性膜压为1.5巴(进料压力=2.5巴,渗透压力=1.0巴绝对压力)。总的流动速率借助气泡计数仪测量,渗透性借助对来自进料、保留物和渗透物的组合物中的H2和丙烷的进料压力和渗透压力计算。渗透性指每m2膜面积,时间和压力的流动速率,其中所用压力为相应气体的分压差(驱动力)。然后,选择渗透性由所确定的两个渗透性的比给定。
实施例4:
如实施例1中所详细描述的进行制备前体溶液(聚酯:25摩尔%马来酸酐,25摩尔%邻苯二甲酸酐和50摩尔%1,2-丙二醇;溶液:50重量%PES和50重量%苯乙烯),用于涂覆的载体(最上面的夹层:在500℃下烧结的勃姆石溶胶),用前体溶液涂覆,干燥(在空气下,在室温下24小时),交联(在空气下,在80℃下12小时)和最后的热解(在Ar下在650℃下1小时)。
为研究碳膜的分离性能,在150-450℃的温度下以及在1-10巴绝对压力的进料压力下,在实验装置上进行混合物气体测量。测量使用含约50体积%氢气和50体积%丙烷的H2/C3H8混合物进行;渗透压约为1巴绝对压力。总的保留物和渗透物流速借助气体测量仪测量,以及进料、保留物和渗透物的气体组成借助在线的气相色谱测量。此外,记录压力和温度。各自的流速(单位=Nm3/h/m2;Nm3=在标准温度和压力条件下立方米)由总的流速和渗透物的组成计算。然后,渗透性(对驱动力标准化的流速,单位=Nm3/h/m2/巴,驱动力=进料/保留物和渗透物之间的分压差)由进料/保留物和渗透物的组成以及相关压力给定。选择渗透性由所确定的两个渗透性的比率给定。
表2显示了在不同条件下膜所测量和计算的数据。
I:在300℃下,进料/保留物压力在2.6-10.2巴绝对压力之间变化
II:在7.1巴进料/保留物绝对压力下,温度在200-350℃之间变化
结果表明,在300℃的恒定温度下,可透性膜压(TMP=进料压力和保留物压力的算术平均值减去渗透压力)的增加伴随着氢气渗透性从9.9Nm3/h/m2/巴降至5.9Nm3/h/m2/巴以及选择渗透性从930降至400。
在7.1巴绝对压力的恒定进料/保留物压力下的温度增加表明,不仅氢气的流速和渗透性,而且氢气-丙烷的选择渗透性都增加了。
Claims (14)
1.烯属不饱和聚酯的溶液在生产适用于气体分离的碳膜中的用途。
2.一种生产适用于气体分离的碳膜的方法,所述方法包括以下步骤:
a)用烯属不饱和聚酯的溶液涂覆多孔基材,
b)通过除去溶剂将多孔基材上的聚酯涂层干燥,
c)使多孔基材上的聚酯涂层热解,以形成适用于气体分离的碳膜,其中可将步骤a)-c)中的任意步骤或按步骤a)-c)的顺序进行超过一次。
3.根据权利要求2的方法,其中所述烯属不饱和聚酯具有脂族二醇、芳族二羧酸和烯属不饱和二羧酸的重复单元。
4.根据权利要求3的方法,其中所述脂族二醇为C2-12链烷二醇。
5.根据权利要求3或4的方法,其中所述烯属不饱和二羧酸为马来酸。
6.根据权利要求2-5中任一项的方法,其中所述烯属不饱和聚酯的溶液额外包含交联烯属不饱和单体和作为交联引发剂的自由基生成体。
7.根据权利要求6的方法,其中所述交联烯属不饱和单体为苯乙烯或α-甲基苯乙烯。
8.根据权利要求2-7中任一项的方法,其中所述多孔基材选自多孔金属、多孔陶瓷、多孔玻璃及其多孔复合物。
9.根据权利要求2-8中任一项的方法,其中所述多孔基材具有TiO2、ZrO2、Al2O3、SiO2或其混合物的中孔陶瓷氧化物层,其用烯属不饱和聚酯的溶液涂覆。
10.根据权利要求9的方法,其中所述中孔陶瓷氧化物层由γ-Al2O3形成。
11.根据权利要求9或10的方法,其中所述中孔陶瓷氧化物层具有低于步骤c)中热解温度的烘烤温度,且优选以未烘烤形式用烯属不饱和聚酯的溶液涂覆。
12.根据权利要求2-11中任一项的方法,其中步骤c)中的热解在500-900℃的温度下进行。
13.根据权利要求12的方法,其中所述热解在至多500℃的温度及氮气下以及在高于500℃的温度及氩气下进行。
14.一种可通过根据权利要求2-12中任一项的方法获得的碳膜。
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JP2013543433A (ja) | 2013-12-05 |
EP2621616B1 (de) | 2016-11-16 |
JP6219165B2 (ja) | 2017-10-25 |
EP2621616A1 (de) | 2013-08-07 |
WO2012041998A1 (de) | 2012-04-05 |
CN103228342B (zh) | 2016-06-29 |
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