CN1638859A - 蒸汽重整催化结构 - Google Patents
蒸汽重整催化结构 Download PDFInfo
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- CN1638859A CN1638859A CNA038057077A CN03805707A CN1638859A CN 1638859 A CN1638859 A CN 1638859A CN A038057077 A CNA038057077 A CN A038057077A CN 03805707 A CN03805707 A CN 03805707A CN 1638859 A CN1638859 A CN 1638859A
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- catalyst
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- hydrogen
- membrane
- gas
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种在一堆或一排成对的相互连接的高(1a)和低(1b)压反应器室中用于产生纯氢的反应器/净化器,其中用蒸汽重整催化剂(2)洗涂的气体多孔促进湍流的筛结构为在每个高压反应器室的高压反应器室(1b)内,平的氢选择钯合金膜(3)和平的气体不能渗透的热传导金属板(1)中间的夹层结构;其中每个高压室(1a)的催化剂涂覆的结构(2)与蒸汽和烃燃料,如甲醇或合成气,和/或一氧化碳,在每个高压(1a)反应器室中,约200℃到650℃之间适当控制的温度下的等温温度范围内反应,以生产氢和碳氧化物,同时在那里通过膜(3)将纯氢渗透到相应的连接的低压反应器室(1b),而往返于催化剂的必需的热传递主要通过原位相应的金属板(1)的传导来提供。
Description
技术领域
本发明广泛涉及蒸汽重整催化结构和氢的产生,更特别涉及新颖的整体催化结构以及通过在适度升高的温度下蒸汽与气态的或气化的矿物烃燃料等反应产生氢的方法,还尤其涉及包括钯承载膜的钯承载膜纯氢发生器。
背景技术
正如在2002年3月12日提出的临时专利申请60/363,672中所解释的,在该申请和提出的优先权基础上,现有技术主要集中于在适度高温下,通过蒸汽(这里指“蒸汽重整”)与气态的或气化的矿物燃料,包括天然气、丙烷、甲醇、一氧化碳(如通过煤的部分氧化制得)以及包括一氧化碳和氢(这里指“合成气”)的混合物和包括甲醇和乙醇等的衍生物反应用于生产氢的催化剂的描述上。此外,通过此方法即通过氢选择性的钯承载膜的渗透制取纯氢,在本领域是众所周知的,正如共同受让人的美国专利第6,171,574 B1(2001)号中所评论的,该专利并入本文作为参考。
由矿物燃料制得的节省成本的氢产品正在环境接受的、通过形成燃料电池系统进行电力生产的领域中变得越来越重要;更特别地,低成本的纯氢,即不含碳氧化物的氢是在优选的PEM燃料电池中使用所需的。
传统的催化结构是颗粒的,例如陶瓷的小球。近年来,昂贵的陶瓷催化整料已被引入到汽车的催化反应器中,那里它们低的压降(与球床相比)是“必不可少”的。低压降催化的金属整料和泡沫材料也被大家所熟知。这些结构体积大,这样不适合与紧凑的利于与上面所提到的纯氢膜发生器结合的催化反应器的结合。
通常理想的全部蒸汽重整反应为:
对于碳氢化合物燃料为:
对于含氧燃料如醇以及气化的燃料来说,通常为:
通常称为水-气转化(这里以“WGS”表示)反应。
这个转化反应(3)典型地与上面的反应(1)或(2)同时发生,但是传统上来说,在较低的温度下,二级蒸汽重整反应器内要比一级反应器内反应完全。这是由于反应1和2为吸热反应,高温下有利于反应物的转化,而反应3为放热反应,低温有利于反应物的转化。就“气化”过程而论,碳承载燃料的高温部分氧化导致了主要为CO和H2的气体混合物。根据反应(3),通常在二级、低温反应器中,这个混合物能又进一步与蒸汽反应使得氢的产生达到最大。
虽然上述的反应(1)-(3)传统上在填充床催化反应器内进行,但是近来的技术已经证明了在氢渗透膜反应器中操作这些反应,氢在原位即可移除的优势。可以意识到的是,在操作温度的选择上允许弹性增加的全部3种情况下,产品氢的移除同样利于反应物的转化。特别地,在氢渗透膜反应器中,当反应(3)在较高温度下进行的同时,反应(1)和(2)则可以在较低温度下有效地进行。具体文献可参见这里作为参考而全部并入本文的美国专利第6,180,081 B1号、上述的共同受让人的6,171,574、5,326,550、5,639,431、6,033,634,其中每个专利都描述了膜蒸汽重整反应器不同的实施方案。
上述的有关膜反应器技术的大多数依赖于上面提到的传统的颗粒催化结构例如半球或者小球。相反,本发明试图合并非颗粒的、整体洗涂的(washcoated)催化结构,例如将要在下面详细描述的金属筛。催化剂洗涂至整体结构上在本领域是周知的,催化洗涂的陶瓷整料商业上被装配在汽车排气的“催化式排气净化器”上。此外,金属结构如金属丝、筛或者金属整料的洗涂在该领域中也是周知的。与本发明特殊关联的是美国专利第4,464,482和4,456,702号,其中每个都公开了使用催化剂洗涂的金属筛或丝结构,这里也是作为参考而并入本文。
标题为“Plate Type Shift Reformer and Shift converter withHydrogen Permeate Chamber”的美国专利第6,033,634(2000)号(发明人M.Koga)中的构造展示了使用传统的颗粒重整和转化催化剂,用于天然气的吸热蒸汽重整反应(见第3栏,第13-14行)和/或放热的水-气转化反应(见第3栏,第23-24行)的带有原位热传递室的钯承载膜反应器。在此发明中,两股气流(一股为热传递气体,另一股为反应气体)通过一排交互的相互连接的气体通路而接触。热传递气体室“充满了氧化铝球.....用于促进热传递”,而反应气体室则充满了颗粒催化剂材料。与之相反,本发明使用一个扁平的用催化剂洗涂的整体湍流促进结构,所述催化剂夹在钯承载膜和控制厚度的热传导金属板之间。这种金属夹层结构除去了Koga的加热室,并且简化了在适当的等温温度范围内氢产生反应的加热或冷却,这将根据具体情况而定。本发明的设计也易于制造,并且需要更少的专业机械加工操作。
正如之前所说的,在由矿物燃料生产氢这一点上节约成本变得愈加重要,不仅可以替代液态或压缩氢的昂贵和危险的货运,而且尤其能够通过燃料电池实现环境接受的电力生产,并且,尤其是低成本纯(也就是无碳氧化物的)氢可用于上述的优选PEM燃料电池系统。膜反应器有希望能够满足这些日益增长的用于分布式的氢的生产的需求,但是过去由于膜中高的钯含量而受到限制。根据也并入本文作为参考的共同受让人的美国专利第6,103,028号,通过使用载体的薄平面钯合金,例如,特别是钯铜合金箔代替现有技术中原有厚得多的管状钯-银膜,可以使钯的成本实际上降低。
和现有技术相比,本发明直接针对包含平的整体催化结构的膜反应器,它主要通过传导视具体情况而允许反应区域的加热(不存在内部的空气氧化)或者冷却,以保持氢的产生和净化在一个可接受的温度范围内(这里称为“等温范围”),提高的氢渗透产量下进行。
这里使用的术语“整体的催化结构”,是指基本平坦的但是敞开的用粘附的蒸汽重整催化剂洗涂的催化剂载体,这里使用的术语“尺寸控制”,是指在等温的范围内选择包括厚度和敞开面积的结构尺寸以提供对流的气流用于提高热和物质传递给催化剂和/或从催化剂传回,同时确保其上产生的氢充分地畅通无阻的进入选择性膜。
发明内容
本发明的具体目的是提供一种新颖的薄的整体催化结构,其使用一种包括金属筛、编织的玻璃布以及优选的非平化膨胀金属的廉价催化载体来代替球或整料等,并且在该载体上粘附包括氧化物载体和适宜的蒸汽重整催化剂的催化组合物。
本发明更进一步的目的是把这种整体催化结构结合在纯氢发生膜反应器的高压室中,其中它们又作为湍流促进器使用,正如上面所提到的专利“574B1”中所阐述的。
更广泛地讲,本发明的主要目的是提供一种新的并且改进的蒸汽重整催化剂结构以及包含相同的和对这种发生进行改进的方法的氢发生器,这种氢发生器不受现有技术的上述和其他限制及缺点的影响,而是与之相反,提供了较少的昂贵结构并且改进了氢的产生。
更进一步的目的是提供一种新颖的催化结构,其使用廉价的催化气体多孔结构代替小球或整料等,所述廉价的催化气体多孔结构包括适当的氧化物和蒸汽重整催化剂洗涂的金属筛或优选的非平化膨胀金属。
本发明的另一个目的是提供一种新颖的用蒸汽重整催化剂洗涂的气体多孔金属结构的夹层结构,所述蒸汽重整催化剂介于每个交互的低和高压室的高压室中的一层平的氢选择钯合金膜和一层平的热传导金属板之间,以在高压室中产生氢和碳氧化物并同时在那里将纯氢渗透到每个相连的低压室,并且主要通过所述板的传导原位提供必需的热传递。
对于进一步提高的热传导来说,提供带有夹在一层膜和一层板之间的金属的气体多孔膜载体的每个低压室也是本发明的一个目的。
对于在甲醇蒸汽重整和中等生产量的反应器内的转化反应中常见的对加热或冷却的需求适中的情况来说,另一个目的是提供新颖的非金属结构,如带有适当催化剂和/或膜载体的编造玻璃布、织物等。
其他的和更进一步的目的将在下文和与发明的详细描述相关的内容以及附加的权利要求书中指出。
从它的一个观点概括来说,本发明包括通过蒸汽重整气态的或外部气化的矿物燃料或其衍生物用于生产由氢和碳氧化物组成的混合物的膜反应器/净化器,并且在控制的、适度升高的等温温度范围内,在反应器中通过渗透穿过平的氢选择钯合金膜而产生纯氢,所述的反应器/净化器由一堆包含一排成对的通过一层上述的膜彼此连接的高压和低压室组成,上述成对的高压低压室通过金属热传导板相互连接,对包括氢在内的所有气体来说是密封的,并且每个高压室配有尺寸控制的用蒸汽重整催化剂洗涂的整体结构。
广泛来说,本发明描述了在成堆排列的成对交互的低和高压室的每个高压室中、夹在一层平的氢选择钯合金膜和一层平的气体(包括氢)非渗透热传导金属板之间的气体多孔优选金属结构上洗涂的蒸汽重整催化剂,以便在等温的温度范围内在高压室中产生氢和碳氧化物并同时在那里将纯氢渗透到与之相连的每个连接的低压产品室,并且主要通过所述板的传导原位提供必需的往返于所述催化剂的热传递。
本发明的整体催化结构将薄的催化剂载体与粘附在其上的催化组合物结合在一起。载体为金属筛、编织的玻璃布或者优选的非平化的膨胀金属,催化组合物包括承载铜、铁和/或镍催化剂的氧化物,该氧化物包括铈土。一种主要由氢和碳氧化物组成的蒸汽-甲醇混合物使用该催化结构,其进料达到出人意料的每克铜催化剂每小时约300,000立方厘米甲醇的高催化效率。
广泛的说,与在上面所提到的专利“574B1”中描述的反应器相比,现在纯氢是在提高了效率的紧凑的反应器中,在控制的约200℃到650℃之间宽的温度范围内,通过蒸汽与气态的或气化的矿物燃料在反应器的高压室中的薄的湍流促进整体结构上反应而产生的。
具体而言,产生纯氢的钯合金承载膜反应器具有(1)配备带有粘附的承载铁或铜催化剂的包含铈土的氧化物组合物的不锈钢筛载体的湍流促进整体结构的高压室,以及(2)在约200℃到550℃之间控制的温度下,蒸汽与甲醇、合成气和/或一氧化碳在其上反应的装置。
然而另一个这样的钯承载膜纯氢发生器具有用在约450℃到650℃之间控制的温度下在其上蒸汽重整气态烃的方式,其中湍流促进整体组件承载镍催化剂(代替铁或铜催化剂)。
优选的和最佳的模式设计以及实施方案将在下文详细介绍。
附图说明
现在将参照附图描述本发明,其中图1为依照本发明建造的三个相同叠层元件的分解图。
具体实施方式
在上面引用的专利第4,464,482号的现有技术案例中,公开了(例如)催化的筛结构可以提供较高的催化剂效率以及较少的倾向于由于催化剂磨损或者颗粒已经在反应物进料中存在而引起的微细颗粒导致的堵塞和过高的压降。应当指出的是,专利482的目的是完成三相反应(气体、液体、固体),其中液体组分在反应器中能够对流动产生相当大的阻力,并且其中筛结构“...给予流动的流体以湍流”。对于本发明,金属筛通常选自市场上可买到的低成本的普通金属“编织金属丝布”。我们注意到,尽管气体流动空间的大多数是曲折的,然而当流动直接沿着布的长度方向进行时,布的结构可以提供优异的流动混合。当然,其他的结构也能够提供类似的弯曲的流动路径。标准的编织金属丝布,当平放时,高度大约是用于形成布的金属丝的直径的两倍。在本发明中,通常的气体流动路径为垂直于这个高度的方向,也就是说气体沿着筛的长度方向流动。
图1为本发明的一种优选形式的分解图横截面。热传导板1限定了两个室;高压反应室1a和低压渗透室1b。高压室填满了整体催化剂结构2。高压和低压室被由膜载体4承载的膜3分隔,其中如果是金属的,可能还需要准备该领域已知的防止载体4和膜3之间金属间扩散的装置。所示热传导板1具有向外延伸至两侧的热传递片,高压反应物的流动路径被定向到进入纸页内的方向(或者从纸页中出来)。多个这些元件如图1中所示通过重复这样的室对组合形成叠层。平行于叠层的反应物的流动可以通过适当的流动分配装置、即集管或簇的排列(header or manifold arrangement)完成。其他的流动配置、即连续或者连续/平行也是可以的。
为了防止装配操作过程中膜的破裂,其中催化的丝布2被覆盖的高压腔1a应当具有等于或优选稍高于催化筛高度的高度尺寸。已经发现尺寸高于筛的高度约5-10%的腔可以使用,同时还会获得气体混合上的曲折的流动路径的优势。
催化的筛2以能够允许在所关心的三个表面之间进行足够的传递的方式制造。提供一个结合的催化剂结构和通道几何结构是本发明的一个目的,这样气流流经通道时能够“同时”与全部三个表面1、2、3接触,以提供在物质传递到催化剂表面2和氢膜表面3以及与热传导表面1和催化剂表面2热传递方面的功效。因此,给定设备的其它尺寸的情况下,流动速率足以完成这个混合是关键性的。因此应存在低流动速率与大的高度的结合;必须避免腔的敞开,因为是气体的混合才能完成本发明的目的。因此本发明中典型的反应通道在流动方向上的长度应等于或者大于它的垂直于流动路径的宽度,其中至少在通道高度的10-100倍范围内,因此是筛。已经确定如果Reynolds值大于约1.0并且少于约1000,优选在约10~约100范围内,可以得到好的反应器性能,这里Reynolds值是按照在反应器温度下并且使用相同管径的标准精确度用于矩形横断面通道的入口气体的性质确定的(这里4倍于被它的周长分开的矩形横截面面积)。
与上面所述的混合影响相一致,催化剂洗涂必须以防止金属丝之间的空间发生不想要的“堵塞”的方式提供。因此想要得到的是提供筛的通路堵塞少于50%的洗涂层(washcoat),优选少于25%,更优选少于5%。我们意识到在全部堵塞的极端情况下,那些筛转变成能够有效堵塞热传递表面和氢膜表面之间气相传递的催化剂“片”。在这种情况下,虽然与催化剂2的接触仍然很充分、全面,但是气相的大部分却很少与氢膜3发生接触,而其它的大部分则很少与热传递表面1发生接触。“通道”的这些情况部分代表了本发明想要以实用的方式所要克服的困难。我们更进一步意识到的是依照本发明的这个反应器装置应该有效地利用作为热传递壁、催化剂结构和氢渗透膜这些部件中的每一个。这样,比如,氢膜3要取得最佳的性能必须提供足够的氢。由于氢是通过催化反应产生的,因此按膜表面的比例来说,足够数量的活性催化剂表面是必需的。高活性催化剂自然是优选的。然而,不使用比必要量更多的催化剂也是所希望的,因为这样不能有效地利用催化剂本身,从而给设备增加了不必要的费用。此外,过多的催化剂能够导致入口处快速的反应,其中在放热反应的情况下,能够导致局部过热和可能的损害。此外,每单位表面膜的大催化剂量需求将要求在热传导板和催化剂之间有大的平均距离,这样进一步增加了无效性。如上面讨论的更薄的氢膜,每单位面积能够渗透更多的氢,因此增加了对催化剂活性上的需求。
就吸热反应而论,必须通过热传导板提供给反应气流足够的热量以保持反应器内的“等温”条件。本文有时使用的术语“等温”确定了一个在等温温度上下约30℃的温度范围。对于放热反应,必须从反应区域消除足够的热能以保持等温条件。由于热主要通过沿着热传导板的传导传递给反应区域或从反应区域去除,因此板的厚度必须足够厚,以沿着它的长度传导必要量的热。此外,由于想要达到最佳的设计,板的厚度不应该过大,因为这将把不必要的重量和热质增加到设备上,以及增加了额外的(材料)成本。我们更进一步意识到的是板本身应该具有高的热导率。板也要求在边缘上提供结构的刚性表面,因此在这个温度下必须保持它的刚性。在一些实例中,利用复合的热传导板可能是合乎需要的,比如衬里结构。将铜的高传导性与钢的强度结合的铜/钢或铜/不锈钢衬里结构很适合这样的应用。
尤其对于高吸热的蒸汽重整反应、如天然气的蒸汽重整来说,总的模块设计经常要在反应物流动的方向上延长。流动将沿着长轴方向,而热传递将主要从侧面指向与主要流动方向垂直的方向。在这些实例中,为了将高热传递速率引入到设计中,热传递板从叠层向外延伸到热源区域,通过使用所谓的热传递增强片以提高传递到叠层的对流热传递是理想的。
通常,外部热源可以通过传导、对流、辐射或者这些方式的结合来提供热量。然而,由于在反应器内达到一种等温的条件是想要得到的,因此从另一个外部产生的气流的热对流是将热提供给吸热反应器的优选方式。用这种方法,外部产生的热气流的温度能够在与膜反应器接触之前控制到预先指定的值。这种方法克服了辐射热传递中的几个潜在的困难,这些困难经常包括外部反应器的表面直接暴露在热火焰或者其它热元件中,从而导致在反应器表面上局部化的高温,这样潜在加速了反应器壳的腐蚀或者损坏反应器外部边界附近的膜和/或催化剂。
所述的外部产生的高温气流可以通过燃料与空气的燃烧,或者通过未渗透的滞留气流与空气的燃烧获得。在第二种情况中,已经认识到通过直接将滞留气流引至燃烧器区域以保持它敏感的热度,从而最好的保持热效率。
在本发明的所有实施方案中,优选将热的进料气流供应给反应器。加入到进料气体中的任何反应物水分也应该是以热的和蒸发的形式提供。对于吸热反应来说,进料的预热和蒸发可以通过将要进料的原料与从高温反应器区域排出的烟道气体适当的接触来完成。这些方法在本领域中是众所周知的,并且典型包括间接的气体/气体热交换设备。
对于放热的水气转化反应,一些情形是可能发生的。在一个案例中,这里提到的作为初级重整的外部的高温处理可能会产生包含CO的气流。初级重整的例子包括高温蒸汽重整、煤的气化等等。通常,与膜反应器相比,初级重整中产生的合成气将达到更高的温度,因此气流在进入到转化反应器之前应优选进行冷却。这样的冷却可以通过直接将任何另外的反应物液态流体注射到热的气流中来完成,流体的汽化和加热提供了一个很好的冷却方法。在不需要另外的反应物流体的情况下(这在初级蒸汽重整中是常有的事),合成气的冷却可以通过一种或多种初级重整进料气流的间接预热和/或汽化来完成。
以下的5个例子更充分地说明了本发明的实施:
实施例1:甲醇蒸汽重整
在开始进行详述更多的实际构造和操作的实施例之前,先描述本发明中优选实施的由承载在两个筛之间的25微米厚的钯铜膜组成的膜反应器,其中一个筛为存在于低压渗透室的膜载体,而另一个为高压反应室中用催化剂涂覆的筛。这种催化剂是一种铜、铈、镧氧化物的共沉淀混合物,其比例为10%的铜,5%的镧,其余为铈氧化物,由脲共沉淀并且在空气中450℃下煅烧12小时制得。面积为38平方厘米大小,高宽比为2∶1的长方形,催化剂重量是150毫克,在具有相同长度和宽度的氧化的标准40目、0.020″厚(涂层之前)的铝筛上涂成一个薄的涂层作为反应器的高压室。筛被安放在高压室中,本身高度为0.030″。高压室一侧和边缘用固体的热传导壁固定,另一侧用钯/铜膜固定。反应器的进料为预混合的甲醇和水,摩尔比为1.5摩尔水/1.0摩尔甲醇。加料首先在压力下泵入到热汽化器单元,完全汽化的混合物然后直接加入到膜反应器中。总的进料速率为0.25ml/分钟液体,对应甲醇的摩尔进料速率为0.004摩尔/分钟。反应器的高压室温度保持在420℃,压力保持在150psig。氢的渗透在大气压下进行。
稳定状态的操作结果表明甲醇的转化率为77%。在包含于催化剂内的每克铜氧化物的基础上,将体现为12.3摩尔甲醇/gm(CuO)-小时的特殊活性。氢穿过膜的渗透率为0.5摩尔/小时,在甲醇进料的基础上体现为约67%的产量(假定加料每摩尔甲醇可能产生3摩尔氢)。
为了比较,在含有由United Catalysts,Inc提供的G66A催化剂球的填充床反应器中进行了单独的实验。G66A是由重量比为33.3%/33.3%/33.3%的铜/锌/铝氧化物组成的复合物。在300℃和150psig压力下,G66A的活性为0.06摩尔甲醇/gm(CuO)-小时,几乎比上述的实验低200倍。校正两个实验之间的温度差别(假定活化能为20kcal/mol)后显示出预期的G66A速率为1.2摩尔甲醇/gm(CuO)-小时,仍然比上述反应器低10倍。实际上,由于活性的损失,G66A不可能在420℃下长期操作。
实施例2:水气转化反应:
膜反应器的几何结构如实施例1。催化剂为WC301B,这是一种专卖的由Louisville,Kentucky的Sud-Chemie,Inc.提供的贵金属基水气转化催化剂。反应器在450℃的等温条件和100psig的压力下运转。膜为10微米厚的Pd/Cu比为60/40重量%。值被记录成2个有意义的数值。渗透压力为环境压力。
类别 | 入口流sccm | 出口流sccm | 渗透流sccm |
H2O | 410 | 260 | 0 |
H2 | 320 | 80 | 390 |
CO | 160 | 11 | 0 |
CO2 | 82 | 230 | 0 |
CH4 | 11 | 14 | 0 |
[CO2][H2]/[CO][H2O] | 0.20 | 6.4 | 37.8(incl.,出口) |
WGS反应在450℃的平衡常数大约为11.9。值37.8代表大约325℃的温度。这样膜反应器有利地为约125℃。
实施例3:水气转化反应:
与实施例2相同的结构、催化剂和膜,350℃等温操作,压力为100psig,渗透在环境压力下进行。
种类 | 入口流sccm | 出口流sccm | 渗透流sccm |
H2O | 540 | 400 | 0 |
H2 | 260 | 90 | 310 |
CO | 140 | 4.0 | 0 |
CO2 | 68 | 200 | 0 |
CH4 | 9.2 | 9.3 | 0 |
[CO2][H2]/[CO][H2O] | 0.23 | 11.3 | 50(incl.,出口) |
实施例4:甲烷蒸汽重整
反应器构造如实施例3;膜厚为18微米,催化剂指定为FCR HC14、WC 723B,也由Louisville,Kentucky的Sud-Chemie Inc.提供。反应条件为200psig,550℃等温操作,渗透压力为环境压力。
种类 | 入口流sccm | 出口流sccm | 渗透流sccm |
H2O | 270 | 120 | 0 |
H2 | 0 | 9.0 | 310 |
CO | 0 | 9.0 | 0 |
CO2 | 0 | 70 | 0 |
CH4 | 120 | 40 | 0 |
值得注意的是,在这些温度和压力的条件下,与本案例的67%相比,平衡时预期的CH4的转化率只为17%。如果在普通的反应器中,在这些条件下取得同样的67%甲烷转化率,就要求温度约为860℃。这样温度下降几乎300℃的益处在膜反应器中是很明显的。
实施例5:甲烷蒸汽重整:
反应器构造如实施例4,膜厚为12微米,570℃,总压力为155psig。
种类 | 入口流sccm | 出口流sccm | 渗透流sccm |
H2O | 217 | 98 | 0 |
H2 | 0 | 25.4 | 243 |
CO | 0 | 6.6 | 0 |
CO2 | 0 | 56 | 0 |
CH4 | 69 | 5.6 | 0 |
在这个实施例中,24%相比92%。92%的转化率要求超过950℃的温度,这就表示几乎400℃的优势。
Claims (21)
1.一种制备包括氢和碳氧化物的混合物的膜反应器/净化器,所述制备包括蒸汽重整气态的或外部气化的矿物燃料或其衍生物,并且在适当控制的、适度升高的等温范围内,通过渗透穿过平的氢选择钯合金膜而产生纯氢,所述反应器/净化器包括含有一排成对的通过一层所述的膜彼此连接的高压和低压室的叠层,所述的成对的高压和低压室通过金属热传导板相互连接,该金属热传导板对包括氢的所有气体是不可渗透的,并且每个高压室配有用蒸汽重整催化剂洗涂的尺寸控制的整体结构。
2.权利要求1的反应器/净化器,其中所述整体结构为金属的,并且成排的高压和低压室对中的每个低压室配有气体多孔金属膜载体,而且每个所述整体结构和每个载体都促进与催化剂的热传递。
3.承载了粘附在其上的催化组合物的整体的薄的催化剂载体结构的组合,其是用于通过燃料的蒸汽重整产生氢的反应器/净化器中,所述载体选自以下组中:金属筛、编织的玻璃布和非平化的膨胀金属,所述催化组合物是包括铈土的、承载选自以下组中的催化剂的氧化物:铜、铁和/或镍催化剂。
4.权利要求3的组合,其中没有用于蒸汽-甲醇混合物在约200℃和550℃之间适当控制的温度范围内在所述的结构上反应以产生主要由氢和碳氧化物组成的混合物的装置。
5.一种氢反应器/净化器系统,其包括承载在两个筛之间的钯承载膜,一个筛在相对低压的渗透室中作为膜载体,另一个是配置在相对高压的反应室中作为催化剂涂覆的筛;以及用于在其上使蒸汽与气态的或气化的烃、甲醇和合成气和/或一氧化碳中的一种在约200℃和650℃之间适当控制的温度下反应的装置,用催化剂涂覆的筛在高压反应器内促进气流的湍流。
6.权利要求5的系统,其中催化剂涂覆的筛包括具有承载铁或铜催化剂的粘附的含铈土的氧化物组合物的不锈钢或者铝筛载体。
7.权利要求5的系统,其中所述湍流促进筛承载镍催化剂,并且所述烃的蒸汽重整在约450℃和650℃之间适当控制的温度下进行。
8.一种产生纯氢的方法,其包括,用蒸汽重整催化剂对薄的气体多孔结构洗涂;在一堆或一排成对的相互连接的低和高压室的每个高压室中,将所述结构夹在平的氢选择钯合金膜和平的气体不能渗透的热传导金属板中间;在高压室中约200℃和650℃之间的适当控制的温度下的等温温度范围内,每对高压室中的用催化剂涂覆的结构与蒸汽和烃燃料和/或一氧化碳反应生产氢和碳氧化物,同时在那里将纯氢通过膜渗透到相应的变换的低压室;往返于催化剂结构所必需的热传递主要是原位通过相应金属板的传导来提供。
9.权利要求8的方法,其中所述催化剂涂覆的气体多孔结构在高压室内产生气流的湍流。
10.权利要求9的方法,其中所述催化剂涂覆的气体多孔结构由选自以下组中的筛结构形成:金属筛、编织的玻璃布以及非平化的膨胀金属筛。
11.权利要求10的方法,其中所述催化洗涂组合物包括含铈土的、承载选自以下组中的催化剂的氧化物:铜、铁和镍催化剂。
12.权利要求9的方法,其中所述蒸汽与甲醇或合成气和/或一氧化碳反应。
13.用于产生纯氢的反应器/净化器,结合存在着:用蒸汽重整催化剂洗涂的气体多孔筛结构;一堆成对的交替连接的相对高压和低压反应器室;在每对交替连接的低和高压反应器室的高压反应器室内,所述结构夹在平的氢选择钯合金膜和平的气体不能渗透的热传导金属板中间;在每个高压反应器室中约200℃和650℃之间的适当控制的温度下的等温温度范围内,每个高压反应器室中使催化剂涂覆的结构与蒸汽和燃料和/或一氧化碳反应生产氢和碳氧化物的装置,同时在那里将纯氢通过膜渗透到相应的变换的低压反应器室;往返于所述催化剂之间所需的热传递主要通过原位相应金属板的传导来提供。
14.权利要求13的反应器/净化器,其中所述催化剂涂覆的气体多孔结构为在高压反应器室中产生气流湍流的筛结构。
15.权利要求14的反应器/净化器,其中经洗涂的筛结构选自以下组中:金属筛、编织的玻璃布以及非平化的膨胀金属筛。
16.权利要求14的反应器/净化器,其中所述催化剂洗涂组合物包括含铈土的、承载选自以下组中的催化剂的氧化物:铜、铁和镍催化剂。
17.权利要求16的反应器/净化器,其中所述蒸汽与甲醇或合成气和/或一氧化碳反应。
18.权利要求14的反应器/净化器,其中所述催化剂涂覆的筛结构包括:具有承载铁或铜催化剂的粘附的含铈土的氧化物组合物的不锈钢筛载体。
19.权利要求14的反应器/净化器,其中所述催化剂涂覆的筛结构承载镍催化剂,所述的燃料是气态的或气化的烃,并且蒸汽重整在约450℃和650℃之间适当控制的温度下进行。
20.权利要求14的反应器/净化器,其中设有用于蒸汽-甲醇混合物在所述结构上于约200℃和550℃之间适当控制的温度范围内反应、产生主要由氢和碳氧化物组成的混合物的装置。
21.权利要求5的系统,其中经催化剂涂覆的筛包括具有基于贵金属的水气转化催化剂的铝筛载体,并且蒸汽重整反应在约300℃和550℃之间适当控制的温度下进行。
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CN100408156C (zh) * | 2006-09-18 | 2008-08-06 | 西安交通大学 | 一种金属泡沫催化重整反应器 |
CN110420644A (zh) * | 2019-08-16 | 2019-11-08 | 广西氢朝能源科技有限公司 | 一种钯膜组件的制作方法及其在甲醇制氢反应器的应用 |
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