CN101148251A - 用于生产合成气的催化剂构造和方法 - Google Patents
用于生产合成气的催化剂构造和方法 Download PDFInfo
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- CN101148251A CN101148251A CNA2007101537536A CN200710153753A CN101148251A CN 101148251 A CN101148251 A CN 101148251A CN A2007101537536 A CNA2007101537536 A CN A2007101537536A CN 200710153753 A CN200710153753 A CN 200710153753A CN 101148251 A CN101148251 A CN 101148251A
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Abstract
揭示了一种经过改进的烃催化部分氧化产生氢气和一氧化碳的方法。该方法还使用一种具有新颖构造的催化剂设备,该设备包括第一阶段反应器和第二阶段反应器,所述第一阶段反应器含有两层,第一层是在载体上的贵金属或过渡金属催化剂,第二层是负载在洗涂于载体上的稳定无机金属氧化物之上或之中的还原金属催化剂,所述第二阶段反应器是转移反应器。
Description
技术领域
烃转化为含有氢气和一氧化碳的气体在本领域是众所周知的。这类方法的例子包括催化蒸汽转化、自热催化重整、催化部分氧化和非催化部分氧化。这些方法各自具有优点和缺点,制得各种比例的氢气和一氧化碳,也被称为合成气(syngas)。本发明涉及催化部分氧化方法。
背景技术
部分氧化法也是众所周知的,该领域包括各种催化部分氧化法。部分氧化是放热反应,在此反应中,甲烷之类的烃类气体和空气之类的含氧气体在升高的温度下与催化剂接触,产生包含高浓度氢气和一氧化碳的反应产物。这些过程中使用的催化剂通常是贵金属(例如铂或铑)和其它过渡金属(例如镍),它们都在合适的载体上。
部分氧化法将天然气之类的包含烃类的气体转化为氢气、一氧化碳以及其它痕量组分,例如二氧化碳和水。该过程通常是通过以下步骤进行的:将预热的烃类和含氧气体注入燃烧室内,烃类在燃烧室内发生氧化,反应时氧气的含量小于完全燃烧所需的化学计量。该反应在极高的温度下进行,例如超过700℃,经常超过1000℃,压力高达150个大气压。在一些反应中,还可将蒸汽或二氧化碳注入燃烧室中,以改良合成气产物,并调节氢气与一氧化碳的比例。
近来已经揭示了一些部分氧化法,在这些方法中,在存在催化剂[例如沉积在陶瓷整体型(例如泡沫体或蜂窝状结构)载体上的金属]的情况下,使烃类气体和含氧气体以高空速接触。所述整料载体浸渍了铂、钯或铑之类的贵金属,或者浸渍了镍、钴、铬之类的其它过渡金属。通常这些整料载体由氧化铝、氧化锆、氧化镁等之类的固体耐火材料或陶瓷材料制备。在这些反应的运行过程中,烃类进料气体和含氧气体起初在超过400℃、通常超过600℃的温度下,以超过100000/小时的标准气时空速(GHSV)与金属催化剂接触。
甲烷和其它烃的部分氧化是放热的,在理想的条件下,可以方程式1的化学计量比进行,产生H2∶CO比例为2∶1的合成气混合物,平衡温度小于1100℃。
CH4+1/2O2→CO+2H2(1)
有人提出,在催化部分氧化床中,部分氧化反应在催化床的第一段中发生,该阶段的长度为几毫米。参见Hickman和Schmidt,Syngas Gas Formation byDirect Oxidation of Methane Over Pt Monoliths,138J.Catalysis 267,275(1992)。因此,理论上认为催化该反应只需要利用催化剂床的很小的一部分。
但是,本发明人发现,在催化部分氧化的过程中,第一段的几毫米催化剂中的实际温度远远高于预期的温度。已经发现,在该第一段的几毫米催化剂中可以实现几乎完全的氧转化,当催化剂床的长度增加时,可以提高反应性能。
根据以上的观察,似乎直接部分氧化是燃烧、部分氧化、蒸汽和CO2重整、水煤气转移反应的组合效应。在进料气体第一次接触催化剂(可能只是在第一段的几微米范围内)的反应区之前,如方程式2所示的燃烧之类的氧化反应和如方程式1所示的部分氧化反应相互竞争,导致几乎完全的氧转化。
CH4+2O2→CO2+2H2O (2)
由放热氧化反应释放的热量可提供足够的能量,通过吸热的蒸汽和CO2重整反应(3)和(4)以及一些水-气体转移反应或逆向的水-气体转移反应(5),进一步将未反应的烃物质与燃烧反应产生的蒸汽或CO2转化为合成气。
CH4+H2O→CO+3H2(3)
CH4+CO2→2CO2+2H2(4)
H2O+COCO2+H2(5)
这解释了在超过1450℃的反应区前部的过量热量导致前层(front layer)中极高的温度。重整反应的吸热性质迅速将随后的催化剂冷却到小于1100℃。结果,催化区域的温度在前层中极高,在随后的下游区域较低。
当使用网状整体型催化剂在超过1450℃的高温下进行部分氧化过程时,会出现明显的问题,本发明人发现网状整料载体,例如那些由部分稳定的氧化锆(PSZ)或Al2O3制成的载体,对于高温和热冲击非常敏感,最终导致催化剂不稳定以及在反应后变脆。网状整体型催化剂的脆性可以归咎于以下几个可能的原因:中空网状类型的结构本身在高温时是脆弱的,PSZ材料发生相转变,等等。但是,当反应温度控制在小于1100℃时,网状整料载体[例如部分稳定的氧化锆(PSZ)或Al2O3]能够维持其机械强度,得到极佳的反应性能。
已经发现,在具有商业吸引力的的条件下,用于烃的催化部分氧化的催化剂最合适的固定形式是它保持网状整体结构。用于这种方法的催化剂包含一种或多种负载在耐火氧化物载体上的催化活性组分,该载体的形式是网状整料。
但是,目前已经发现,当使用网状整体型催化剂时,在进行部分氧化的过程中,会出现各种问题。特别是已经发现,耐火整体型催化剂结构对于催化部分氧化过程中普遍的热冲击和高温非常敏感,容易导致结构变脆,最终引起催化剂分解,特别是在使用氧气而非空气时更是如此。因此,本发明的一个目的是提供一种催化部分氧化方法,该方法结合了部分氧化反应阶段1和转移反应阶段2,以获得催化剂的长期稳定性。
发明内容
本发明提供一种烃部分氧化产生氢气和一氧化碳的方法,该方法包括:使含烃的进料气体和含氧气体的混合物与两阶段反应器接触,该两阶段反应器包括:第一阶段反应器,其包括具有两层的催化剂组合物,第一层是分散在惰性载体上的催化活性金属,第二层是主要由负载在洗涂(washcoat)于载体上的稳定无机金属氧化物之上或之中的过渡金属组成的还原金属催化剂;第二阶段反应器,其包括转移反应器。本发明还提供一种设备,该设备包括第一阶段反应器和第二阶段反应器。
第二阶段反应器是转移反应器,可选自整体型催化剂和转移催化剂。整体型催化剂可以是主要由位于陶瓷整料上的二氧化铈涂层支撑的金属组成的金属催化剂;所述金属选自镍、钴、铁、铂、钯、铱、铼、钌、铑和锇中的至少一种;陶瓷材料选自氧化锆、氧化铝、氧化钇、氧化钛、氧化镁、二氧化铈和董青石中的至少一种;相对于陶瓷整料,二氧化铈涂层的重量百分数约为5%至30%。在一个实施方式中,陶瓷选自氧化锆、氧化钇、氧化钛、氧化镁、二氧化铈和董青石中的至少一种。
第二反应器中的转移催化剂可以是低温转移催化剂或水-气体转移反应器催化剂。
用于进料气体的烃通常是具有1-4个碳原子的烷烃。最佳地,烃选自天然气和甲烷。
附图说明
图1是本发明的整体化的两阶段反应器的示意图。
图2是使用本发明的两阶段反应器的工艺方案的示意图。
图3是使用本发明的两阶段反应器的另一种工艺方案的示意图。
具体实施方式
本发明提供了使用两阶段反应器系统,由含烃的进料气体流和含氧的进料气体流的混合物,经过烃的部分氧化反应,产生氢气和一氧化碳或合成气的方法。
第一阶段反应器是一种具有两层的催化剂组合物。第一层是分散在惰性载体上的催化活性金属。第二层是还原金属催化剂,主要由负载在洗涂于载体上的稳定无机金属氧化物之上或之中的过渡金属组成。第二阶段反应器包括转移反应器。对于本发明,转移反应器可以是整体型催化剂,或者是低温转移催化剂或水-气体转移催化剂之类的转移反应器。将烃和含氧气体流加入到该两级反应器中,反应形成氢气和一氧化碳或合成气。
本发明还提供了一种用于烃部分氧化产生氢气和一氧化碳或合成气的反应器系统设备,该设备包括两阶段反应器系统。
第一阶段包括一种两层的催化剂组合物。第一层是分散在惰性载体上的催化活性金属,第二层是还原金属催化剂,主要由负载在洗涂于载体上的稳定无机金属氧化物之上或之中的过渡金属组成。
反应器系统的第二阶段反应器包括转移反应器。该转移反应器可选自整体型催化剂或低温转移催化剂或水-气体转移催化剂。可用于第二阶段反应器的整体型催化剂是主要由位于陶瓷整料上的二氧化铈涂层支撑的金属组成的金属催化剂。所述金属选自:镍、钴、铁、铂、钯、铱、铼、钌、铑和锇。陶瓷材料选自:氧化锆、氧化铝、氧化钇、氧化钛、氧化镁、二氧化铈和董青石。相对于陶瓷整料,二氧化铈涂层的重量百分数约为5%至30%。在整体型催化剂的一个实施方式中,陶瓷选自:氧化锆、氧化钇、氧化钛、氧化镁、二氧化铈和董青石。
在于2003年1月9日作为US 2003/0007926A1公开的Jiang等的共同待审查申请序列号10/143705中对该金属催化剂整体型陶瓷进行了更详细的说明。
在整体型催化剂的优选实施方式中,用约1-20重量%的二氧化铈涂布锆整料,在二氧化铈涂布的整料上负载0.5-5重量%的铑。
用于烃部分氧化产生氢气和一氧化碳的设备包括:第一阶段反应器,该反应器包括一种两层的催化剂组合物,第一层是分散在惰性载体上的催化活性金属,第二层是还原金属催化剂,主要由负载在洗涂于载体上的稳定无机金属氧化物之上或之中的过渡金属组成;第二阶段反应器,该反应器包括转移反应器。
在进料侧用于第一层的优选催化剂基材是微粒,包括球、丸和环状物;车轮形基材(wagonwheels)、Saint-Gobain Norpro的Ty-Pak、HexPakTM、Snowflake介质和Norton鞍形、细目丝网、蜂窝状整料或任何其它具有任何可接受制造形状(例如文中所述的)的合适载体,然而也可以使用机械强度经过改善的网状整料。对于本发明,机械强度可以描述为“压碎强度”,它是材料在碾压负荷下能够承受的最大应力。碾压负荷是能够压碎或压实催化剂基材的重量和/或压力。本发明的催化剂基材具有能够承受烃部分氧化方法的常规运行条件的碾压强度。因此,本发明的催化剂基材在正常的烃部分氧化过程中,不会丧失碾压强度。在产物一侧的层状催化剂可以催化部分氧化反应,但是主要促进重整和水-气体转移反应,从而获得高碳转化率和高合成气选择性。网状整料更适合用于后面的这些层,特别是用作最后一层。
当使用两层以上时,这些层可以任何顺序层叠,只要第一层对于热冲击和超过1100℃的高温更稳定,而后面各层可进一步催化后面的碳转化反应,产生合成气。整料的孔结构和微粒的粒径符合以下条件:通过催化床没有明显的压降。US 2003/0083198A1描述了一种固体床催化剂系统,该系统包括以堆叠的连续流动方式设置的第一区和第二区,以获得更佳的流动分布,其中第一区域(上游部分)比第二区域(下游部分)对进料物流流动的阻力更大。但是,在本发明中,不使用网状整料,而使用大孔径蜂窝状结构,可以使第一层(上游)对进料物流流动的阻力小于第二层。可以在催化剂层之间设置催化惰性基材,以改善气体分布。
为了避免网状整体型催化剂在高温下发生活性金属烧结或机械强度弱化,可以使用第一层作为燃烧催化剂,使网状整体型催化剂避免接触高温。这种多层催化剂的思路显示在下图中,其中NG表示天然气。
第一催化剂层
第一层催化剂应当能够在氧化和还原环境中、在约1000℃-1800℃的温度范围内有效地工作,而不会明显地失活。第一层催化剂优选包含分散在惰性载体上的催化活性金属。用于本发明催化剂的金属选自元素周期表中的某些过渡金属和贵金属。活性金属可以选自镍、钴、铁、铂、钯、铱、铼、钌、铑和锇之类的过渡金属或贵金属,以及它们的组合。优选的金属是镍和铑。
该组中最优选的金属是铑。金属可以金属、金属氧化物、金属卤化物或其它待还原的金属盐形式位于载体上。如下文所述,在还原后,金属基本上是金属形式。通常,约0.1重量%至8重量%的金属沉积在载体上。任选地,可使用Rh/Pt纱网状催化剂作为放热反应催化剂。
US 2003/0198592A1揭示了多级串联排列的反应区和多种烃进料,用于将烃和氧气进料流转化为合成气。第一反应区催化进料烃的净(net)部分氧化反应,后面的反应区催化水-气体转移反应、净部分氧化反应、蒸汽或干重整反应。由于存在烧结和对成碳的耐受性有限等原因,最常被选用的催化剂中的一些(例如Rh)不能承受热量和保持它们的活性。本发明有利是由于它能够在反应器的前部设置更多的热稳定催化剂,例如混合金属氧化物或稳定的晶体结构,例如尖晶石或钙钛矿,更优选CoCr氧化物,最优选9.9重量%Co0.2Cr0.8氧化物/1重量%Rh/6.1重量%Yb,这些催化剂负载在耐火载体[例如氧化铝或氧化锆,优选部分稳定的氧化锆(PSZ)]上。
在本发明的方法中,在接触第一催化剂层后,放热反应几乎立刻完成。后面的层的主要作用是促进吸热重整反应。“净部分氧化”催化剂区域被认为是包含燃烧催化剂和吸热催化剂的两层。有必要指出,由于在高温下会发生固有的相转变,PSZ网状材料不是优选的材料;而在Al2O3上的透明Rh涂层作为第一层,即使连续工作7个月以上无疑也是稳定的。该催化材料保持其催化活性和机械强度。
惰性载体的优选形式由在高温下能维持其形状和足够的机械强度的耐火、基本惰性的硬质材料制成。通常,选择用作载体的材料具有较低的热膨胀系数、良好的抗热冲击性和高熔点。例如,堇青石材料由于其熔点低(约1450℃)而不适合用作纯氧基部分氧化反应的前层载体。
用于构建这类载体的几种常规材料是已知的。可商购得到不同尺寸和结构的蜂窝状整料载体。也可以商购得到合适形状和尺寸的球状或颗粒状催化剂。这两种类型的载体结构由选自下面的常规耐火或陶瓷材料制成:氧化铝、莫来石、氧化锆、部分稳定的氧化锆、二氧化铈、二氧化硅、碳化硅、氮化硅、SialonTM(氮化硅陶瓷,其中加入了少量氧化铝)、氮化铝、氮化硼、铝硅酸盐、铝硅酸镁和它们的混合物。可以通过合适的方法形成载体,包括模塑、压制、挤出、喷雾干燥或模冲等。惰性载体还包括在高温下作为金属泡沫或金属的烧结颗粒制备的金属整体材料。最优选的载体是作为蜂窝体、球、丸、环、车轮形、Saint-Gobain Norpro的Ty-Pak、HexPakTM、Snowflake介质和Norton鞍或颗粒形式的稳定的氧化铝、碳化硅或部分稳定的氧化锆。较佳地,载体的表面积较小,约为0.1-50米2/克。
后面的催化剂层
位于第一催化剂层下面的后续催化剂层应该能够在氧化和还原环境中、在低于约1100℃的温度范围内有效地工作,而不会明显地失活。吸热反应催化剂包括任何已知适用于此目的的金属催化剂。用于本发明的金属催化剂是主要由以下部分构成的整料载体结构:部分稳定的氧化锆,该氧化锆上洗涂了二氧化铈,浸渍了贵金属或过渡金属,或它们的组合。文中所用的“金属催化剂”指包括金属、无机金属氧化物涂层和整料载体或整体型基材的整个催化剂结构。本发明催化剂中使用的活性金属选自镍、钴、铁、铂、钯、铱、铼、钌、铑和锇之类的过渡金属或贵金属,以及它们的组合。优选活性金属是铑和/或镍。
整料载体通常是由单独的结构单元形成的陶瓷泡沫体状结构或多孔结构,其中的通道以不规则或规则的图案设置,在相邻的通道之间具有间隔。优选的是具有不规则通道的陶瓷泡沫体结构。载体结构通常由选自下面的常规耐火或陶瓷材料制成:氧化铝、莫来石、氧化锆、部分稳定的氧化锆、二氧化铈、二氧化硅、碳化硅、氮化硅、SialonTM(氮化硅陶瓷,其中加入少量氧化铝)、氮化铝或氮化硼、铝硅酸盐、铝硅酸镁和它们的混合物。也可以使用作为金属泡沫体制备的金属整料。最优选的载体是部分稳定的氧化锆或碳化硅。
优选将活性金属结合到高表面积材料上,以提高总的催化剂效率和活性。可以通过浸渍、洗涂、吸附、离子交换、沉淀、共沉淀、沉积沉淀、溶胶凝胶法、浆料浸涂、微波加热等方法沉积高表面积无机金属氧化物(例如γ-氧化铝、二氧化铈等)来提高载体的表面积。用无机金属氧化物涂布基材的方法包括使基材与金属氧化物前体接触,优选将前体涂布的基材保持在平衡涂层的条件下,然后使前体氧化,形成含有金属氧化物的基材。优选通过向洗涂层(washcoat)中添加可分解的有机物质,然后在高温下、在氧化气氛中使其分解来形成大孔。
可进行洗涂的稳定的高表面积无机氧化物选自但不限于:包含一种或多种选自元素周期表中第IA、IIA、IIIA和IVA族和过渡金属的阳离子的氧化物,优选选自第IA、IIA、IIIA、IIIB、IVA、IVB族和镧系元素、更优选选自铈、铝、镧、锆和钡的阳离子的氧化物,以及它们的混合物。可以用不止一种无机氧化物同时或依次地浸渍泡沫体。
合适的浸渍介质的形式是无机氧化物颗粒的水性或有机溶液、浆料、溶胶、凝胶、悬浮液或分散体,优选是胶状无机氧化物颗粒的溶胶。这些洗涂涂料的前体可以是任何能够通过热分解而分解为氧化物的形式。可以向洗涂涂料中加入碱金属或稀土金属氧化物之类的稳定剂,以防止洗涂层在反应或预处理的过程中烧结。
最优选的载体是用约5%-30%无机金属氧化物(最优选二氧化铈)洗涂的部分稳定的氧化锆泡沫整料。任选地,用贵金属涂布的陶瓷蜂窝体或金属整料也可以用作吸热反应催化剂。
一方面,本发明提供一种烃部分氧化生产氢气和一氧化碳的方法,该方法包括使含烃进料气体和含氧进料气体的混合物与催化有效的多层结构在以下条件下接触:压力为1-20大气压,进料气体标准气时空速约为5000-500000/小时,线性速率约为0.2-50.0米/秒(m/s)。另外,进料气体混合物还可以包含蒸汽和/或CO2。反应器设备的两个阶段将在不同的温度下运行,第一阶段在约800℃至100℃的温度下运行,第二阶段在约250℃至600℃的温度下运行。反应气体混合物还可以预热到约10℃-450℃的温度。
现在结合附图进行说明,图1是本发明的整体化的两阶段反应器的示意图。管路1、2和3分别用于蒸汽、天然气和氧气的进料,它们通过管路4进入整体化的两阶段反应器A。A1是第一阶段反应器,进料气体流通过位于其中的两层催化材料。这些气体流继续进入A2,骤冷水通过管路5进入其中,而蒸汽通过管路6进入其中。经过骤冷的气体流继续进入作为转移反应器的部分A3中,通过管路7离开两阶段反应器,进入冷却装置B。通过调节进入第二阶段反应器的蒸汽与碳的比例可以更有效地方式运行转移反应器。冷却的产物流通过管路8离开,进入另一个低温转移反应器C。气体流通过管路9离开,进入冷凝装置D,在此将产物气体流中存在的水冷凝除去。然后使无水气体流通过管路11,通过压缩装置E,然后通过管路12进入分离装置F。该分离装置可以是压力摆动吸附系统或膜系统,该装置将分离出氢产物,该产物通过管路13离开。其余物流通过管路14离开,主要由一氧化碳组成。
图2是本发明的整个过程的示意图。氧气、天然气和蒸汽分别通过管路15、16和17进入第一阶段反应器G。来自第一阶段反应器的产物气体流通过管路18离开,水和蒸汽分别通过管路19和20进入管路18,然后气体流进入第二阶段反应器H。主要由氢气、一氧化碳和二氧化碳组成的产物气体流通过管路21离开第二阶段反应器,通过热交换器或冷却装置I。已经冷却的产物气体流通过管路22离开热交换器,进入低温转移反应器J。低温转移反应器进一步促使剩余的烃和一氧化碳反应产生氢气,该氢气流将通过管路23离开,通过合成气压缩器K,产物气体流将通过管路24离开压缩器,进入气体分离装置L,该气体分离装置可以是压力摆动吸附装置或膜系统,将产物气体流分离为氢气和尾气燃料,氢气通过管路26离开并进入储存装置M,尾气通过管路25离开。
在图3中,氧气、天然气和蒸汽分别通过管路27、28和29进入第一阶段整体反应器N。来自第一阶段反应器的产物流通过管路30离开,水和蒸汽通过管路31和32直接进入管路30中。然后,热交换器或冷却装置O接收气体流,已经冷却的气体流通过管路33进入第二阶段反应器。主要由氢气、一氧化碳和一些二氧化碳组成的产物流通过管路35,进入合成气压缩器R,压缩气体流通过管路36离开,进入气体分离系统,该系统可以是压力摆动吸附装置或膜系统S。尾气通过管路37离开,氢产物可通过管路38回收,储存在装置T中。
尽管已经结合本发明的具体实施方式描述了本发明,但是本发明的许多其它形式和改进对本领域技术人员来说是显而易见的。本发明所附的权利要求书应当理解为包括所有这些显而易见的形式,其改良包括在本发明的实质精神和范围之内。
Claims (14)
1.一种烃部分氧化产生氢气和一氧化碳的方法,该方法包括:使含烃的进料气体和含氧气体的混合物与两阶段反应器接触,该两阶段反应器包括:第一阶段反应器,其包括具有两层的催化剂组合物,其中第一层是分散在惰性载体上的催化活性金属,第二层是主要由负载在洗涂于载体上的稳定的无机金属氧化物之上或之中的过渡金属组成的还原金属催化剂;以及第二阶段反应器,其包括转移反应器。
2.如权利要求1所述的方法,其特征在于,所述催化活性金属选自:镍、钴、铁、铂、钯、铱、铼、钌、铑、锇、以及它们的组合。
3.如权利要求1所述的方法,其特征在于,所述催化活性金属以约0.1-8.0重量%的量沉积在所述惰性载体上。
4.如权利要求1所述的方法,其特征在于,所述惰性载体具有选自下组的形状:蜂窝状、球状、丸状、环形、车轮形、鞍形和颗粒状。
5.如权利要求1所述的方法,其特征在于,所述载体选自:陶瓷泡沫体整料、蜂窝体整料和金属整料。
6.如权利要求1所述的方法,其特征在于,所述载体是洗涂有二氧化铈的部分稳定的氧化锆整料载体。
7.如权利要求1所述的方法,其特征在于,所述过渡金属选自:镍、钴、铁、铂、钯、铱、铼、钌、铑、锇、以及它们的组合。
8.如权利要求1所述的方法,其特征在于,所述过渡金属占所述整料载体的约2-4重量%。
9.如权利要求1所述的方法,其特征在于,所述稳定的无机金属氧化物选自:包含一种或多种选自元素周期表中第IA、IIA、IIIA和IVA族,过渡金属,以及它们的混合物的阳离子的氧化物。
10.如权利要求1所述的方法,其特征在于,所述无机金属氧化物占所述整料载体的约5-30重量%。
11.如权利要求1所述的方法,其特征在于,所述第二阶段反应器选自催化剂整料和转移反应器。
12.如权利要求1所述的方法,其特征在于,该方法还包括位于所述第一阶段反应器和所述第二阶段反应器之间的热交换器。
13.如权利要求1所述的方法,其特征在于,该方法还包括位于所述第一阶段反应器和所述第二阶段反应器之后的热交换器。
14.一种用于通过与含烃的进料气体和含氧气体的混合物接触使烃部分氧化产生氢气和一氧化碳的设备,,该设备包括权利要求1至13中任一项的两阶段反应器。
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2006
- 2006-09-19 US US11/523,360 patent/US20080069765A1/en not_active Abandoned
-
2007
- 2007-07-26 CA CA002595150A patent/CA2595150A1/en not_active Abandoned
- 2007-07-31 SG SG200705530-4A patent/SG141307A1/en unknown
- 2007-08-02 NZ NZ560322A patent/NZ560322A/en unknown
- 2007-08-03 AU AU2007203636A patent/AU2007203636A1/en not_active Abandoned
- 2007-08-20 ZA ZA200706967A patent/ZA200706967B/en unknown
- 2007-09-18 KR KR1020070094679A patent/KR20080026055A/ko not_active Application Discontinuation
- 2007-09-18 EP EP07116687A patent/EP1903001A3/en not_active Withdrawn
- 2007-09-18 CN CNA2007101537536A patent/CN101148251A/zh active Pending
- 2007-09-19 NO NO20074785A patent/NO20074785L/no not_active Application Discontinuation
- 2007-09-19 JP JP2007241803A patent/JP2008074700A/ja active Pending
- 2007-09-19 TW TW096134928A patent/TW200831401A/zh unknown
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103648971A (zh) * | 2011-06-23 | 2014-03-19 | 代表Mt创新中心的斯塔米卡邦有限公司 | 适用于制备氢的合成气中间体的制备方法 |
CN103648971B (zh) * | 2011-06-23 | 2018-04-17 | 代表Mt创新中心的斯塔米卡邦有限公司 | 适用于制备氢的合成气中间体的制备方法 |
CN111566042A (zh) * | 2017-11-15 | 2020-08-21 | 美国燃气技术研究院 | 用于重整甲烷和其他烃类的贵金属催化剂及方法 |
CN111566042B (zh) * | 2017-11-15 | 2024-02-13 | 美国燃气技术研究院 | 用于重整甲烷和其他烃类的贵金属催化剂及方法 |
CN111569857A (zh) * | 2019-02-19 | 2020-08-25 | 现代自动车株式会社 | 寿命性能提高的用于制造氢的纳米复合物及其制造方法 |
CN111569857B (zh) * | 2019-02-19 | 2024-04-30 | 现代自动车株式会社 | 寿命性能提高的用于制造氢的纳米复合物及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
NO20074785L (no) | 2008-03-21 |
AU2007203636A1 (en) | 2008-04-03 |
KR20080026055A (ko) | 2008-03-24 |
EP1903001A3 (en) | 2008-11-05 |
NZ560322A (en) | 2009-03-31 |
CA2595150A1 (en) | 2008-03-19 |
EP1903001A2 (en) | 2008-03-26 |
US20080069765A1 (en) | 2008-03-20 |
JP2008074700A (ja) | 2008-04-03 |
TW200831401A (en) | 2008-08-01 |
ZA200706967B (en) | 2009-09-30 |
SG141307A1 (en) | 2008-04-28 |
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