CN1031511A - 从含烃原料生产合成气 - Google Patents
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Abstract
含烃原料通过催化部分氧化法转化成合成气,其
中,含烃原料,氧或一种含氧气体和水蒸汽(可任意选
择)的混合物被送入催化部分氧化段,其温度不低于
自动点火温度以下93℃,其氧/碳摩尔比从0.3∶1
到0.8∶1。催化部分氧化段装有一种催化剂,其几
何表面积与体积之比至少为5cm2/cm3,最好大于
20cm2/cm3,所需催化剂的体积较小,其空速可高达
20,000小时-1到50,000小时-1。
Description
本发明是关于从气态或可汽化的含烃原料生产合成气。特别是关于在低温和低氧耗条件下,通过含烃原料的部份催化氧化来制备合成气。此外,本发明的方法所使用的设备,较之以前在含烃原料的氧化反应中所使用的设备要便宜。
含烃原料,例如从石油矿床附近得到的天然气,转化成工业上有用的瓦斯,已经实现多年了。一般,这种瓦斯的主要成份是甲烷、乙烷、丙烷和丁烷。在有些情况下,也可使低沸点的液体烃类进行这种转化。
为了把含烃原料转化成工业上有用的产品如氨、一氧化碳、甲醇、氢和城市煤气,首先都要把这种原料转化成所谓合成气,其主要成份是一氧化碳、氢、甲烷和二氧化碳。然后,将合成气进行一系列的分离和/或转化过程而得到最终产物。
使含烃原料转化成合成气过去最常用的方法是催化重整。在此方法中,含烃原料在催化剂存在下与水蒸汽反应,催化剂通常为含镍催化剂,反应温度大约在650°和1040℃之间。在这种条件下,烃类与水蒸汽反应生成一氧化碳和氢。催化蒸汽重整是一个费用昂贵的工艺,不仅是含镍催化剂很贵,而且反应是高度吸热的。因此,为了进行反应得到目的产物,需要供给大量的能量。通常,在重整反应中通入空气,以便通过烃类的部份氧化提供能量。
含烃原料的部份氧化在合成气的生产中相当于一种蒸汽重整的代替方法。工业上已经使用的部份氧化方法大多是非催化方法。但是,非催化部份氧化反应其效率是相当低的。它们需要在高温,即1200-1540℃的温度下操作,并需要大量的氧气。一般,在非催化部份氧化中,氧/碳比要求大于0.8∶1,通常要大于1∶1。
Dille等的美国专利No.4,390,374介绍了一个通过一种液体含烃燃料的非催化部份氧化生产合成气的方法。这种含烃原料与一种含有游离氧的气体在水蒸汽存在下进行反应,自生温度维持在925到1650℃之间,压力是100到2300kPa绝对压力。氧/碳摩尔比据报导是从0.7∶1到1.5∶1。
Child等的美国专利No.3,890,113号报导了一种生产富甲烷气的方法,在此方法中是把一种含烃原料在水蒸汽和氧的存在下进行非催化部份氧化。氧化剂中的游离氧与原料中的碳之比是从0.8∶1到1.5∶1。产生的合成气再经过水煤气转换反应以增加气体中的氢含量。
Child等的美国专利No.3,927,998是关于通过一种含烃燃料的部份氧化来生产富甲烷气的,所使用的水蒸汽对燃料油的重量比是2.2∶1到2.9∶1,而氧对碳的分子比是0.8∶1到0.84∶1。部份氧化是在催化剂的存在下进行的。合成气被冷却后,除去水、二氧化碳、碳和其它杂质。气体中的H2和CO在催化甲烷化段反应生成富甲烷气。
部份氧化过程的转化效率可以通过使用催化剂而得到改进。但是,在以前的技术中,催化部分氧化过程一般都使用很贵的催化剂材料。例如Fujitani等的美国专利4,087,259,介绍了一种方法。在此方法中,首先将液体含烃原料汽化,然后与催化剂接触进行部分氧化,该催化剂含有载在担体上的铑。
在部分氧化过程中催化剂的使用要求反应在特定的空速范围内进行。空速可以定义为通过每体积催化剂的体积小的速率。其中,所引用的所有关于体积小时速率的数据都是指在标准的温度和压力条件下。使用先有技术的催化部分氧化方法,为了可以获得可以接受的转化程度所使用的空速必须低于约12,000小时-1。例如,Hwang等的美国专利4,522,894,介绍了一种富氢气体的生产方法,这种富氢气体是被用来作为燃料电池的燃料的,这个方法是使一种烃原料与水蒸汽和一种氧化剂反应,反应是在两段催化剂的自热重整炉中进行。总的小时空速在1,960小时-1和18,000小时-1之间。由于先有技术的方法必须在低空速进行,所以先有技术的催化部分氧化反应器不得不使用很大的催化剂床层,以便在工业操作中达到所需要的处理能力。这就增加了部分氧化反应器的尺寸和成本。
本发明的一个目的是提供一种催化部分氧化方法,这种方法允许在较高的空速下使含烃原料有效地转化成合成气,允许使用的空速可达到20,000小时-1或更高,这样,催化剂床层和部分氧化反应器的尺寸就可以做得很小,而仍能获得工业上可以接受的处理能力。
本发明进一步的目的是提供一种催化部分氧化方法,这种方法可以把含烃原料转化成合成气而只需消耗较少的氧,从而增加了含烃原料的处理能力。
本发明还有一个目的、即提供一种允许使用较便宜催化剂的催化部分氧化方法。
本发明提供一种将气态或可汽化的含烃原料转化为合成气的催化部分氧化方法。本发明的方法是在低的需氧量下操作,所使用的工艺条件和催化剂类型允许过程以高空速进行。
本发明的方法包括:
(a)把一种由含烃原料、氧或一种含氧气体,以及可任意添加的水蒸汽组成的气态混合物通入催化部分氧化段,在气态混合物中水蒸汽/碳的摩尔比是0∶1到3.0∶1,氧/碳摩尔比是0.3∶1到0.8∶1,上述混合物在不低于其自动点火温度93℃的温度下,最好是在等于或高于它的自动点火温度下通入到催化部分氧化段;
(b)将含烃原料在催化部分氧化段进行部分氧化,借助把混合气通过可催化烃类氧化的催化剂,而生成主要含有甲烷,碳的氧化物,H2和水蒸汽的气体产物,该催化剂表面积与体积之比至少为5cm2/cm3。
本发明方法使用的催化剂,是很便宜的材料,而这种材料在以前被认为并不具有足够的催化活性的。
本方法可以在高达20,000小时-1的高空速实施,从而允许使用较小的催化部分氧化反应器而仍然保持较高的处理能力。
图1是反应器的纵剖断面视图,反应器在入口处有一个适合于往催化剂床层通入反应物的混合器和分配器。
图2是图1中的混合器和分配器纵剖断面局部放大视图。
图3是图1中的混合器和分配器的1/4局部顶视图。
图4是图1中的混合器和分配器的1/4局部底视图。
图5是图1和图2中的混合器和分配器的局部纵剖断面的图示说明,它标明了临界尺寸。
图6是在2760KPa的操作压力和三件不同操作温度下的氧/碳摩尔比与水蒸汽/碳摩尔比的关系曲线。
图7是在2760KPa的操作压力和三种不同的操作温度下,在催化部分氧化反应产物中的H2/CO摩尔比与水蒸汽/碳摩尔比的关系曲线。
图8是在2760KPa的操作压力和三种不同操作温度下,在催化部分氧化产物中的甲烷体积(%)与水蒸汽/碳摩尔比的关系曲线。
图9是在2760KPa的操作压力和三种不同操作温度下,在催化部分氧化产物中的二氧化碳体积(%)与水蒸汽/碳摩尔比的关系曲线。
图10是在2760KPa操作压力和三种不同操作温度下,产物中H2+CO总量与原料中H2+C总量摩尔比的关系曲线。
本发明的方法能用于从任何气态的或低沸点的含烃原料生产合成气。一般,用于生产合成气的气态含烃原料是天然气,其近似组成为:甲烷93%,乙烷5%、丙烷1.5%,丁烷及更高级烃类0.5%。
在本发明的方法中,几乎不发生重整反应,也就是说,本发明的方法主要靠部分氧化把含烃原料转化成合成气。本发明的方法能用于在不发生重整反应的情况下把含烃原料转化成合成气,同时如果需要的话,可以做到只有很少量(2%以下)的烃原料未发生反应,对于某些最终的用途,例如生产城市煤气,可能希望留有较多的未反应烃,这也可以用本发明的方法来实现。由于部分氧化反应的转化速率是由传质控制而与所用的催化剂的化学本性无关,因此,只要能满足本发明对催化剂的表面积/体积之比的要求,可以使用较便宜的催化剂材料来进行本发明的方法。
按照本发明的方法,反应气体进入反应段即催化剂床层,其入口温度不低于原料混合物自动点火温度以下93℃。而最好反应气体在(或高于)混合物的自动点火温度进入反应区。本发明另一个重要特点是反应物在反应之前经过充分混合。在适当的温度通入充分混合的反应气体能确保部分氧化反应是由传质控制。因而,反应速度对催化剂活性的依赖相对较小,而主要取决于催化剂的表面积对体积之比。可以使用各种各样的材料作催化剂,只要这种催化剂具有所希望的表面积对体积之比。催化剂不需要具有对水蒸汽重整反应的特殊催化活性。甚至把通常认为是非催化性的物质以适当的结构用作催化剂时也能在规定的反应条件下促进合成气的生成。在这里所用的“催化剂”这一术语,也包括这种物质。
本发明的方法可以参考附图来理解。催化部分氧化段是如图1所示的反应器的催化剂床。如图1所示,用于对气体进料进行部分氧化的反应器包括图中30所指的进料混合器和分配器部分。混合器和分配器把原料与一种氧化剂混合并把混合物分配到32所指的催化反应段的入口,在这里,原料被部分氧化生成产物,然后产物通过34所指的出口部分。
反应器包括由结构金属如碳钢做成的外壳40,带有顶盖42,顶盖用螺栓(图中未画出)或类似件紧固。绝热层44,例如2300°F(1260℃)BPCF陶瓷纤维绝热层被固定在外壳层40的上部(包括顶盖42)的内侧。在反应段32的混合段30和出口段34,在外壳的内侧装有绝热层46,48和50。绝热层46是可浇铸的或与之相当的绝热材料,如2000°F(1090℃)的陶瓷绝热体。绝热层48也是一种可浇铸的或等效的绝热层,但它含有60%的氧化铝以经得住3000°F(1650℃)的高温。内层50是耐火层或有相同功效的绝热层,例如带有陶瓷支座的97%的氧化铝或者97%的氧化铝砖以经得住反应段的内部环境。
催化反应段32含有一个或多个催化剂圆盘54。如图所表明的,反应器内包含一连串的圆盘54,它们被位于相邻两块圆盘间的高含量氧化铝环58分开。这一迭圆盘由带有高含量氧化铝棒56的格栅支撑。在反应段的下端装有采样口60并且有一根管62,它是由309型不锈钢制成,并伸到耐火圆盘54的底部下面以取出产物样品。
出口部分34被装配成适合联接到下游的废热锅炉(图中未画出)和/或其它加工设备。
催化剂含有能催化含烃原料部分氧化的高比表面物质。催化剂的形状要做到其表面积对体积之比至少为5cm2/cm3。催化剂的几何表面积与体积之比最好不小于20cm2/cm3。尽管表面积对体积之比没有严格的上限,但它通常不超过大约40cm2/cm3,许多种物质都能用来做催化剂,包括通常认为不具有催化活性的物质,只要催化剂的结构具有所要求的表面积与体积之比。
催化剂圆盘54,比如说,可以是具有蜂窝状横断面形状的整体结构。这种形式的适宜的整体结构已有工业生产,它的尺寸比用在本发明的方法中的要小,它用作汽车尾气催化转化的结构基质以及作为气体透平的催化燃烧室,或者用于废水的催化氧化。典型的整体结构是一种条状物质,它含有许多紧密排满的通道,这些通道沿结构的长度方向形成蜂窝状结构。通道一般是方形的,并可以被排满到密度高达每平方厘米186个横截面。这种整体结构可以由任何一种材料构成,包括堇青(Mgo/Al2O3/SiO2),Mn/Mgo堇青石
(Mn-Mgo/Al2O3/SiO2),富铝红柱石(Al2/O3/SiO2),富铝红柱石-钛酸铝〔Al2O3/SiO2-(Al,Fe)2O3/TiO2〕,氧化锆尖晶石(ZrO2/Mgo/Al2O3),尖晶石(MgO/Al2O3),氧化铝(Al2O3)和高镍合金。上述整体催化剂可以由这些结构材料的任何一种单独组成,即使这些材料本身通常被认为不具有催化活性。使用蜂窝状的基质,所得到的表面积与体积之比可以达到40cm2/cm3或更高。另一方面,这种整体基质可以涂上已知对氧化反应具有催化活性的任何一种金属或金属氧化物。这些金属或金属氧化物包括,钯、铂、铑、铱、锇、钌、镍、铬、钴、铈、镧及它们的混合物。其它可用来涂镀催化剂圆盘54的金属还包括贵金属和元素周期表上第ⅠA、ⅡA、Ⅲ、Ⅳ、ⅤB、ⅥB或ⅦB族的金属。
催化剂圆盘54也可以由结构填充材料(如用在填充吸附柱中的材料)所组成。这些填充材料一般由波纹金属薄片所组成,它们紧密地装填在一起,形成由其连续而成的延长孔道。这种结构填充材料可以由金属波纹片所组成,所用的金属如高温合金,不锈钢、铬、锰、钼和耐火材料。如果需要的话,这些材料可以涂上金属或金属氧化物,这些金属或金属氧化物是已知对氧化反应具有催化活性的,例如钯、铂、铑、铱、锇、钌、镍、铬、钴、铈、镧以及它们的混合物。
催化剂盘54也可以由密集的金属丝网构成,例如高温合金或白金网。如果需要的话,金属丝网上也可以涂上一层对于氧化反应具有催化活性的金属或金属氧化物,包括钯、铂、铑、铱、锇、钌、镍、铬、钴、镧以及它们的混合物。
上述任何一种催化剂构型都能通过用一种含水浆液涂在它的表面上而增加其表面积与体积之比,这种含水浆液含有大约1%(重量)以下的金属或金属氧化物(如氧化铝)的微粒,或者是第ⅠA、ⅡA、Ⅲ、Ⅳ、ⅤB和ⅦB族的金属,并在高温用火加热涂层后的表面,以便把金属粒子粘附到表面上,但是温度不能高到引起表面烧结。所使用的粒子的BET(Brunnauer-Emmett-Teller)表面积应该大于10米2/克,最好大于200米2/克。
在实施本发明时,是把一种由含烃原料、氧或一种含氧气体(如空气),以及水蒸汽(是否加入可以随意选择)组成的气态混合物通入催化部分氧化段,其温度不低于它的自动点火温度以下93℃。但最好使气体混合物在等于或大于其自动点火温度的温度下进入催化部分氧化段。可以使反应器以传质控制的模式操作,使反应物在略低于自动点火温度的温度下进入反应区,而反应热将为提高反应区内反应物的温度提供必要的能量。但是在这种情况下,通常需要对进入反应区的进料提供热量,例如,通过点火装置或者通过把反应器的内容物(包括催化剂)在引入反应物开始反应之前,予热到超过自动点火温度。如果进到反应区去的反应物的温度比自动点火温度低93℃以上,反应是不稳定的。
当进到催化部分氧化段的反应混合物的温度超过它的自动点火温度时,就必须在混合以后立即把混合物引入催化剂床层;也就是说,最好应在自动点火燃烧滞后期过去之前,把含烃原料和氧化剂的混合物送入催化剂床。气体混合物的彻底混合也是必要的。反应物混合不充分会直接降低产物的质量并能导致过热。图1-5示出了一种装置,这种装置适合于把含烃原料和氧气或含氧气体进行混合和分配,使之做到彻底混合并把加热后的反应物在足够短的时间内送入到反应段。
参见图1,原料气体之一,如含烃气体或含氧气体,由穿过顶盖42的第一入口66送到进料段30,入口66把原料气传送到上部进料锥体68,锥体68形成第一个室。锥体68由支架69固定在顶盖42上。另外一种原料气通过第二入口70被引入到进料段30(第二入口70是通过外壳40的侧口伸入)并传送到第二室72,第二室72位于上室68和催化剂反应段32的入口之间。在室72的上壁75的中心部分安放一个环73,它密封地结合在锥体68的下缘上,致使壁82形成一道位于上室68和下室72之间的公共墙壁。室72的上部有一个在外面的环形部分74,(也见于图2、图3),它被支撑在耐火层50的顶面上。室72的较低部分有一道管状墙76,它向下延伸到耐火套管50。室76的底部是由铸件78构成的。
如果愿义加入水蒸汽,水蒸汽可以加到含烃原料中或者加到氧气或含氧气体中,也可同时加到上述两者中。进到反应器中的气体的相对比例为:水蒸汽/碳的摩尔比是0∶1到3.0∶1,最好是0.3∶1到2.0∶1。氧/碳摩尔比是0.3∶1到0.8∶1,最好是从0.45∶1到0.65∶1。如果希望把制得的合成气用于生产城市煤气,则氧/碳摩尔比最好是从0.3∶1到0.65∶1。对于大多数其它用途,如合成氨,甲醇、氢和一氧化碳,最佳的氧/碳摩尔比是从0.4∶1到0.8∶1。
反应混合物最好在等于或高于其自动点火温度的温度下进入催化反应段32。根据反应气体的特定比例、反应器的操作压力和所用催化剂的不同,该温度通常在大约290°和590℃之间。最好,在通过进口70或66之前,把含烃原料及水蒸汽混合并加热到340℃到650℃。氧或含氧气体(如空气)加热到65℃到650℃,并通过另一个入口66或70。
参见图2,混合和分配的手段包括多根延长管80,其上端在室72的上壁75上。管腔在上部与上面的室68相通。管80的下端固定到构件78上,并以管腔与通道84的上端相通,通道84是垂直穿过构件78形成的。管80的壁上开许多多孔86,其作用是把气流从室72引入管80的管腔15。入口66和70、锥体68、支架69都由通常的耐腐蚀和耐热的金属所制成,而室72、管80和构件78则由通常的高温合金成耐火型材料制造。
管80的数目、管80的内径90(见图5)、以及在每根管上孔86的大小和数目都是根据气体进料的速度和通过入口66和70的压力来选定,以便以超过混合物的回火速度的流速在管80内产生湍流。孔86距管80下端(通往发散形通道84)的最小距离92选定为等于或大于能基本上保证从室68和72来的处于湍流条件下的气流完全混合所需的数值。管80的内径90的大小和管子的长度94的设计,应保证在气体从室68通到反应室时能产生足够的压力降,以便从室68通过管80提供基本均匀的气流。同样,孔86的尺寸也要选成能在室72和管80的内部之间产生足够的压力降(它与气体通过入口70进入的速度和压力有关),以便提供足够均匀的气流量,气流从孔86进入管80。
构件78内的发散通道84的构造,在一定程度上使气体的速度减小,以便在催化剂的入口上方造成均匀的气体分布。随着通道84往下伸展,其横断面的增加率,也就是通道84的壁与管80的直壁形成的角98,一般应等于或小于15°,而最好等于或小于7°,为的是减少或避免在通道84内产生涡流。这样就可以保证基本完全混合的气体在接近或超过自动点火温度下通入催化剂床层,通过时间最好短于自动点火的滞燃时间。通道84下端的构造是圆形的如图4所示。
从出口段34出来的产品气体主要含有甲烷、碳的氧化物(即Co和Co2)、氢和水蒸汽。气体产物中也可能存在痕量的C- 2和更高级的烃类。这里所使用的“痕量”,其含意是大约小于1%(重量)。
在催化反应段32进行的催化部分氧化反应最好在大于690Kpa的压力下进行,压力大于1724Kpa则更好。催化部分氧化反应约在760℃-1090℃的温度下进行。
实例
天然气在一个结构如图1所示的催化部分氧化反应器中转化成合成气。共有九个催化剂园盘54,每个园盘的直径为30英寸(0.76米)厚度为10英寸(0.25米)。园盘是由蜂窝状整体堇青石材料做成的,其几何表面积约为25cm2/cm3。以它为载体,在其上面沉积上一层高表面积的氧化铝,并将分散得很细的催化金属组分分散在载体上。催化金属组分是50%(重量)的铂和50%(重量)的钯。催化剂的空速度是97,000小时-1。
天然气(>95%甲烷)与水蒸汽以各种水蒸汽/碳的摩尔比混合,加热并在2760Kpa的压力下经由直径为25.4厘米的进口66进入反应器。空气加热后,在2830Kpa的压力下经由两个直径为20.3厘米的入口70进入反应器。室72的下部76的直径是27英寸(0.68米),上部74的直径是36英寸(0.91米)。装有261根内径0.5英寸(12.7毫米)长度为20英寸(0.51米)的管80。在每根管上有六个直径0.123英寸(3.2毫米)的孔,其中4个孔在距管子下端4英寸(0.102米)处对称地排布在每根管的周围,其余的两个孔距离管下端6英寸(0.152米)处彼此相对。底部构件78其厚度为5英寸(0.127米),通道部分84是园锥形的,上部直径为0.5英寸(12.7毫米),下部直径为1.75英寸(44.5毫米)。室68和72内的压力基本与入口压力相同。
反应混合气的温度是590℃。图6表明了上述过程氧消耗量和水蒸汽/碳摩尔比的函数关系,反应温度分别是870℃、950℃和1040℃,操作压力是2760Kpa。从图6可以看出,本发明的方法与目前工业上的部分氧化过程相比,以氧/碳摩尔比表示的氧消耗量是比较低的。图6中的虚线25代表这样一种条件,在此条件下会生成积炭,尤其是它表明温度与水蒸汽/碳摩尔比的线性关系,包括从1040℃对应于水蒸汽/碳摩尔比0∶1到870℃对应于水蒸汽/碳摩尔比0.4∶1的范围。
图7表示在产物中H2/CO摩尔比与水蒸汽/碳摩尔比的函数关系,反应温度分别是870℃、950℃和1040℃。
图8和图9分别表示在870℃、950℃和1040℃的反应温度下,产物中甲烷和CO2的量(以体积%表示)与水蒸汽/碳之比的函数关系。
图10是表示本方法生成的有效氢,它是用产品中H2和CO的总摩尔数除以原料中H2和C的总摩尔数来表示。
图6-10表明,本发明的方法能够高效率地生产合成气,它耗氧低,使用较低的氧化温度和比较便宜的催化剂材料。本领域技术人员不难意识到,在本发明的范围内可以对上述例子做出各种变化和改进。这个实例只是描述本发明的方法,在任何方面都未打算限定本发明的范围。
Claims (20)
1、一种从含烃原料生产合成气的方法,它包括:
(a)把充分混合的含烃原料、氧或含氧气体,以及水蒸汽(可任意选择)的气态混合物送入催化部分氧化段,其中水蒸汽对碳的摩尔比是0∶1到3.0∶1,氧对碳的摩尔比是0.3∶1到0.8∶1,所说的送入到催化部分氧化段去的混合物,其温度不低于它的自动点火温度200°F以下;
(b)把含烃原料在催化部分氧化段部分氧化,生产出主要含甲烷、碳的氧化物、氢和水蒸汽的气体产物,其方法是把反应混合物通过一个催化剂,这种催化剂能催化烃类的氧化反应,所说的催化剂其几何表面积对体积之比至少是5cm2/cm3。
2、权利要求1所述的方法,其中,气体反应混合物通过催化剂的空速是20,000小时-1到50,000小时-1。
3、权利要求1所述的方法,其中,送入到部分氧化段去的混合物,其温度至少等于它的自动点火温度。
4、权利要求1所述的方法,其中,气体混合物中水蒸汽对碳的摩尔比是0.3∶1到2.0∶1。
5、权利要求1所述的方法,其中,氧对碳的摩尔比是0.45∶1到0.65∶1。
6、权利要求1所述的方法,其中,催化剂的几何表面积对体积之比是20-40cm2/cm3。
7、权利要求1所述的方法,其中,气态混合物在入口到催化部分氧化段的温度是从340℃到650℃。
8、权利要求1所述的方法,其中,含烃原料和水蒸汽首先混合并加热到340℃-650℃的温度,得到的混合物再与已经加热到65℃-650℃的氧或含氧气体混合,从而产生一种混合物,这种混合物将经受自动点火;把这种含氧混合物在自动点火滞燃时间过去之前通入催化部分氧化段的入口。
9、权利要求1所述的方法,其中,催化剂至少包含一种具有蜂窝横截面的整体结构,所说的结构包括氧化铝、尖晶石、氧化锆尖晶石、富铝红柱石-钛酸铝、富铝红柱石、Mn/Mgo堇青石或堇青石。
10、权利要求1所述的方法,其中,所说的催化剂包括丝网。
11、权利要求1所述的方法,其中,所说的催化剂包括一种结构基质,其上涂有一种材料,这种材料选自一组金属,它们包括铂、铑、铱、锇、钌、钯、镍、铬、钴、铈、镧和它们的混合物。
12、权利要求1所述的方法,其中,催化部分氧化的反应温度是760℃-1090℃。
13、权利要求1所述的方法,其中,催化段的压力大于690Kpa。
14、权利要求1所述的方法,其中,催化部分氧化段的压力大于1724Kpa。
15、权利要求1所述的方法,其中,催化部分氧化反应实际上是在没有水蒸汽重整反应的情况下进行的。
16、权利要求15所述的方法,其中,在部分氧化段中的催化剂,对于水蒸汽重整反应基本上没有活性。
17、权利要求15所述的方法,其中,烃损失不大于2%。
18、权利要求1所述的方法,其中,含烃原料是天然气,把天然气与水蒸汽以水蒸汽对碳的摩尔比在0.3∶1到2.0∶1的范围混合,把天然气和水蒸汽加热到340℃到650℃的温度范围,得到的天然气和水蒸汽的混合物再与已经加热到65°到650℃的氧或含氧气体混合,把天然气、水蒸汽和氧的混合气在自动点火滞燃时间内送入催化部分氧化段,气态混合物通过催化剂的空速为20,000-50,000小时-1,气体混合物在760℃到1090℃的温度下进行催化部分氧化而生成主要含有氢、碳的氧化物、水蒸汽和甲烷的合成气。
19、权利要求18所述的方法,其中,合成气中含有不多于2%的未反应的天然气。
20、权利要求18所述的方法,其中,部分氧化是在-温度范围内完成的,这一温度等于或大于水蒸汽对碳摩尔比的线性关系区间,它包括的范围从1040℃对相应的水蒸汽/碳摩尔比0∶1到870℃对相应的水蒸汽/碳摩尔比0.4∶1。
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| US8516087A | 1987-08-14 | 1987-08-14 | |
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| RU2764097C2 (ru) | 2017-05-23 | 2022-01-13 | Люммус Текнолоджи Ллс | Интеграция окислительного сочетания в метановые установки |
| EP3649097A4 (en) | 2017-07-07 | 2021-03-24 | Lummus Technology LLC | SYSTEMS AND PROCESSES FOR THE OXIDATIVE COUPLING OF METHANE |
| WO2020142595A1 (en) * | 2019-01-02 | 2020-07-09 | Sabic Global Technologies, B.V. | Catalyst activity management in catalytic partial oxidation |
| WO2023034253A1 (en) | 2021-08-31 | 2023-03-09 | Lummus Technology Llc | Methods and systems for performing oxidative coupling of methane |
| EP4321596A1 (en) | 2022-08-12 | 2024-02-14 | Bp P.L.C. | Fischer-tropsch production of hydrocarbons from carbon dioxide through methanol |
| EP4321598A1 (en) | 2022-08-12 | 2024-02-14 | Bp P.L.C. | Fischer-tropsch production of hydrocarbons from carbon dioxide through methanol |
| EP4321597A1 (en) | 2022-08-12 | 2024-02-14 | Bp P.L.C. | Fischer-tropsch production of hydrocarbons from methanol |
| EP4553193A1 (en) | 2023-11-10 | 2025-05-14 | Bp P.L.C. | Integrated production of syngas from carbon dioxide and water |
| WO2025169081A1 (en) | 2024-02-05 | 2025-08-14 | Bp P.L.C. | Production of hydrogen using methanol |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE974909C (de) * | 1954-06-22 | 1961-06-15 | Basf Ag | Verfahren zur flammenlosen Umsetzung von gasfoermigen Kohlenwasserstoffen |
| GB812807A (en) * | 1956-04-13 | 1959-04-29 | Max Gerhold | A method of converting gaseous hydrocarbons |
| GB2015027B (en) * | 1978-02-03 | 1982-06-23 | Haldor Topsoe As | Reforming process |
| NO171409C (no) * | 1982-09-30 | 1993-03-10 | Engelhard Corp | Fremgangsmaate ved fremstilling av en hydrogenrik gass vedautotermisk reformering av et hydrokarbonholdig utgangsmateriale |
| EP0254395B1 (en) * | 1986-05-27 | 1990-11-22 | Imperial Chemical Industries Plc | Method of starting a process for the production of a gas stream containing hydrogen and carbon oxides |
-
1988
- 1988-08-09 EP EP88307342A patent/EP0303438A3/en not_active Withdrawn
- 1988-08-10 IN IN573/MAS/88A patent/IN171834B/en unknown
- 1988-08-11 NO NO883567A patent/NO172886C/no unknown
- 1988-08-12 AR AR88311667A patent/AR244176A1/es active
- 1988-08-12 NZ NZ225819A patent/NZ225819A/xx unknown
- 1988-08-12 JP JP63200253A patent/JPH01145301A/ja active Pending
- 1988-08-12 RU SU884356354A patent/RU1831468C/ru active
- 1988-08-12 BR BR8804093A patent/BR8804093A/pt not_active Application Discontinuation
- 1988-08-12 DK DK453388A patent/DK453388A/da not_active Application Discontinuation
- 1988-08-12 ZA ZA885994A patent/ZA885994B/xx unknown
- 1988-08-12 AU AU20989/88A patent/AU610219B2/en not_active Ceased
- 1988-08-13 CN CN88106072A patent/CN1013430B/zh not_active Expired
- 1988-08-13 KR KR1019880010351A patent/KR890003621A/ko not_active Ceased
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1955268B (zh) * | 2005-10-25 | 2011-05-18 | 庞玉学 | 一种利用煤矿瓦斯气制取合成气或安全燃料气的方法 |
| CN102438940A (zh) * | 2009-05-22 | 2012-05-02 | 沙索技术有限公司 | 用于共同生产合成气体和能量的工艺 |
| CN102438940B (zh) * | 2009-05-22 | 2014-12-31 | 沙索技术有限公司 | 用于共同生产合成气体和能量的工艺 |
| CN103328097A (zh) * | 2010-12-16 | 2013-09-25 | 乔治洛德方法研究和开发液化空气有限公司 | 包含物理固定于载体上的活性颗粒的催化剂 |
| CN111569893A (zh) * | 2020-06-03 | 2020-08-25 | 西南化工研究设计院有限公司 | 一种低成本天然气转化催化剂及制备方法 |
| CN114906809A (zh) * | 2022-03-14 | 2022-08-16 | 大连海事大学 | 一种以丙烷为原料的部分氧化制合成气的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0303438A2 (en) | 1989-02-15 |
| DK453388D0 (da) | 1988-08-12 |
| EP0303438A3 (en) | 1989-12-27 |
| RU1831468C (ru) | 1993-07-30 |
| NO883567L (no) | 1989-02-15 |
| NO172886C (no) | 1993-09-22 |
| AU610219B2 (en) | 1991-05-16 |
| ZA885994B (en) | 1990-01-31 |
| NO172886B (no) | 1993-06-14 |
| JPH01145301A (ja) | 1989-06-07 |
| CN1013430B (zh) | 1991-08-07 |
| AU2098988A (en) | 1989-02-16 |
| AR244176A1 (es) | 1993-10-29 |
| NZ225819A (en) | 1990-02-26 |
| BR8804093A (pt) | 1989-03-07 |
| IN171834B (zh) | 1993-01-23 |
| DK453388A (da) | 1989-02-15 |
| NO883567D0 (no) | 1988-08-11 |
| KR890003621A (ko) | 1989-04-15 |
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