CN101356254A - 石油焦炭到甲烷的催化蒸汽气化 - Google Patents

石油焦炭到甲烷的催化蒸汽气化 Download PDF

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CN101356254A
CN101356254A CNA2006800379897A CN200680037989A CN101356254A CN 101356254 A CN101356254 A CN 101356254A CN A2006800379897 A CNA2006800379897 A CN A2006800379897A CN 200680037989 A CN200680037989 A CN 200680037989A CN 101356254 A CN101356254 A CN 101356254A
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petroleum coke
steam
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N·C·纳哈斯
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Abstract

本发明提供了一种用于气化石油焦炭的催化蒸汽气化方法。通过控制进料的催化剂组成来保持所公开的发明的气化反应器内的固体组成。该方法利用来自粗气化产品气的酸性水来回收和循环催化剂。在焦炭处理中产生的微粒被有利地用于提高该方法的效率。

Description

石油焦炭到甲烷的催化蒸汽气化
技术领域
本发明涉及一种将石油焦炭(石油焦，petroleum coke)转化为适用于直接使用或适用于运输的能源的方法。更具体的说，本发明涉及一种将石油焦炭转化为可燃气体如甲烷的方法。
更具体的说，本发明涉及一种将石油焦炭转化为管道输送(pipeline)质量的甲烷的方法，其中往返于反应器的工艺流程(process flow)流有利地用于在没有过量生产废液和损失催化剂的情况下使从石油焦炭进料的收率最大化。
背景技术
长久以来，已知石油储量正在迅速地消耗且新储量勘探变得越来越困难，从而产生了可用原油严重减少的前景。不幸地，这种下降预计与在世界范围内迅速增加的能源需求重合。因此，需要开发另外的能源，特别是形式上与依靠石油基燃料的当前技术相容的能源。一种建议已经将煤转化为可以更容易在管道中、也许甚至在现有管道中可以更容易运输的形式。因此，已经建议了用水或油将煤搅拌成浆料(slurry)以便使其可以通过管道运输。然而，在试图用这种方式运输煤的过程中遇到了许多困难。例如，已经证明了难以使煤作为均匀混合物保持悬浮而不会过度沉降。而且，即使克服了这种困难，非常希望开发可以容易地通过罐车(tanker truck)或管道运输的另外的能源。还非常希望改进当前的原油加工效率以便能够从指定桶数的原油中确保更多的能量值。
在石油炼厂中，原油被转化为包括汽油、燃料油和石油化工原料的产品构成。初始步骤是在大气压力下蒸馏原油以分离和除去轻质烃馏分。非蒸发部分进行真空蒸馏。这些蒸馏过程试图从初始的原油中得到最高产量的液体和气态烃类产品。通过下述方式可以从在真空蒸馏之后剩余的重馏分中提取出另外的液体和蒸气：将这种材料通常在被称为炼焦器的反应器中进行热分解，其中初始原油的最重部分转化为通常被称为石油焦炭的固态产物。
石油焦炭不是非常有价值的炼油厂产品。已经发现其只有少数应用，例如，制造电极。而且，因为它是固体，很难从练油厂中运出。此外，不同于其它碳基固体材料，石油焦炭含有微乎其微的挥发性的材料，使其难以燃烧。因而，石油焦炭不是在需要热量的运行中的炼油厂操作中用于燃烧的良好燃料。
因此，非常需要一种将低价值的石油焦炭转化为更有用的能源的方法。甚至更需要将石油焦炭转化为可以在现有的基础结构如管道中自由运输的能源。而且，由于工业上转向冶炼越来越重的原油，这种将石油焦炭转化为更有用和方便的能源的需要将变得甚至更明显。
一种处理固体含碳材料如煤或石油焦炭的建议是将固体转化为气流如甲烷。在二十世纪七十年代，一种将煤转化为甲烷的方法在授予Koh等的美国专利第4,094,650号中建议。其专利权人暗示，该方法可以应用于其它含碳源如石油焦炭。然而，没有提供关于将该方法应用到石油焦炭上的细节。本领域技术人员将会理解，在将利用煤作为进料源的方法转化为利用石油焦炭的方法中存在显著的困难。例如，在利用煤或焦炭的方法中第一步是将进料粉碎到适当尺寸的颗粒。这种方法总是会产生大量细粉(fines)，其是在美国标准筛尺度上小于325目的固体颗粒。如上所指出的，细煤粉可以用作传统燃烧器的燃料源，所以细煤粉在炼油厂操作中不会呈现过度的负担。然而，石油焦炭细粉含有非常少的挥发物，因此其不适用于在典型的燃烧器中燃烧。
本领域技术人员还将理解，利用煤作为进料源的工艺流程图一定与其中石油焦炭而不是煤作为进料的情况极其不同，因为这些材料的组成不同。例如，煤含有大量矿物质，其必须与相对纯的含碳材料不同地处理。
为此，将看到，Koh方法向进料煤中加入了10-20％碱金属化合物，并且利用了复杂的催化剂再生系统以分离矿物质并重复利用作为部分固体清除物(solid purge)排出的催化剂。其中接近三分之一的排出催化剂与矿物质不可恢复地结合在一起并且被损失掉了。在该方法的过程中产生的大量酸性水直接排到酸性水处理设备中而没有在工艺流程中进一步利用。
授予Nahas的美国专利第4,284,416号公开了一种将煤转化为甲烷的方法，其中将煤颗粒和含水碱金属催化剂的浆料使用过热蒸汽在流化床中干燥以便将大多数浆料水转化为蒸汽，且其中来自浆料干燥器的净蒸汽(net steam)在气化中使用。该方法使用了来自进料浆料水中的未反应蒸汽的冷凝酸性水。然而，催化剂再生方法需要从固体清除物中浸析催化剂并循环到进料混和罐中。酸性水并非用来将催化剂运输回进料中。需要的是如Koh等所教导的，进料浆料水含有足够的溶解的碱金属化合物以在煤上沉积10-20％的碱金属化合物。其中也没有提到关于在最初的固体进料的粉碎过程中产生的细粉的考虑。
授予Nahas的美国专利第6,955,695号公开了一种用于将石油残渣气化为甲烷的改进的催化气化反应器系统。石油残渣定义为含有多于50％的在低于1050°F的大气压等效温度下不会蒸发的残渣的任何原料。所述反应器系统使用了上/下部两阶段方法，其中来自固体颗粒催化剂的下流化床的固体与新鲜进料混和并运输到上部阶段。含有碳和碱金属催化剂的上部阶段内部的颗粒循环到下部阶段，而过热蒸汽和循环氢以及一氧化碳在下部阶段以下进料。两阶段均保持流化态。该公开内容描述了在气化反应器内部将石油残渣转化为石油焦炭，而没有关于利用固体石油焦炭作为生产高质量甲烷流的进料的方法的公开内容。该说明书公开了一种稳态气化器固体的固体组成的优选范围，但没有公开将作为保持气化器固体组成的工具的石油焦炭进料的含水浆料中的催化剂浓度控制在优选范围内。本领域技术人员将理解，当使用与液体石油残渣相反的固体进料时遇到的相当大的差异和困难。该公开也没有提及任何关于利用酸性水将固体含碳进料形成浆料的内容，因此由于该申请不涉及固体进料及其所附带的问题，这是可以理解的。
因此，本发明的一个目标是提供一种将石油焦炭转化为高级能量流的方法。
本发明的一个目标还在于，提供一种将石油焦炭转化为适于在现有网络中运输的形式的方法。
本发明的另一个目标是提供一种将石油焦炭转化为适于在管网或在罐车中运输以便容易地在终端设备等处分配的优质甲烷流的方法。
本发明的另一个目标是提供一种将石油焦炭转化为甲烷而无需复杂的催化剂再生系统的有效的催化气化方法。本文所公开的方法/系统提供了集成的产品纯化和催化剂循环，并且将废固体(spent solids)用于从酸性水中置换氨，从而尽可能减少所需的废物处理。该有效方法得到了生产管道输送质量甲烷的接近100％的碳转化率。
本发明的这些和其它目标将从下面的发明内容和具体实施方式而变得显而易见。
发明内容
本发明提供了一种将石油焦炭转化为甲烷的方法，其中石油焦炭和具有蒸汽气化活性的催化剂被引入到浆料干燥和蒸汽发生区以形成进料浆料。进料浆料被引入到浆料干燥器中，其中该浆料与过热蒸汽流混和以产生来自浆料水的另外的蒸汽和浸有催化剂的石油焦炭的基本上干燥的固体混合物。干燥固体混合物和产生的净(net)蒸汽被引入到气化区，在这里干燥固体混合物与蒸汽流、H2和CO在高温和高压下混合，产生包含CH4、H2S、CO2、CO、H2和H2O的粗制产品流。在另一个实施方式中，石油焦炭和催化剂被直接引入气化区。
从气化区中排出固体清除物，其量足以保持气化区内固体无机化合物的稳态载量。从粗制产品流中除去未反应蒸汽和夹带固体以产生酸性水和冷却的粗制产品流。由催化剂和其它固体组成的固体清除物与酸性水结和以溶解催化剂并形成催化剂的稀水溶液，以及从酸性水中释放氨。从催化剂的稀水溶液中分离固体。含水的催化剂稀溶液用冷却的粗制产品气来汽提，并循环到进料浆料中。
从粗制产品气中回收甲烷。
附图说明
图1是可以在本发明的方法中使用的各区的原理图，其中区100表示图2中所绘的浆料系统，区200表示图3中描绘的气化系统，区300表示图4中描绘的废固体处理，且区400表示没有以其它方式显示的常规气体处理。
图2是浆料干燥和蒸汽发生区的流程图。
图3是气化区的流程图。
图4是废固体处理区的流程图。
具体实施方式
在下面的工艺流程方案中，本发明提供了一种将石油焦炭转化为甲烷的整合方法。该方法有效地利用了在粉碎处理过程中产生的细粉而没有不适当的浪费。此外，在处理过程中产生的酸性水用于捕获和循环催化剂以提供额外的收益。因此，参考图1，该工艺可以包括用于进料浆料干燥和蒸汽发生、气化、废固体处理、以及产品分离的区域。
石油焦炭通常具有这样的组成：约88.6％碳、2.8％氢、7.3％硫、1.1％氮、和0.2％灰分(质量％，干基)。石油焦炭通常通过高压水流从焦炭反应器中除去。石油焦炭进料可以含有至多10wt％的水分。石油焦炭被粉碎为低于30目的粒度，更优选30到100目的粒度，基于美国标准筛尺度(U.S.Standard Sieve Scale)。关于图2中所示的浆料干燥和蒸汽发生区100，将焦炭颗粒从储存或制备区域输送到进料斗中，然后通过管线10输送到浆料混合罐12。固体进料物质可以通过若干方法中的任何一项输送。优选的方法是气动地将固体转移到进料斗中，并通过惰性载气转移到浆料混合罐中。
通过使用常规设备用浆料水洗涤而从气动的转移介质中回收在研碎或粉碎和输送工艺过程中产生的固体细粉。通过用进料浆料水洗涤细粉并直接将混合物送入进料浆料干燥区，可以使细粉凝聚成足够大的颗粒以便在气化区中气化。与其它气化法相比，这样能够得到较高的固体碳到气化产品的总回收率。
经由管线10输送的焦炭颗粒和任何回收的细粉被进料到浆料混合罐12中，在这里它们用具有蒸汽气化活性的催化剂浸渍。合适催化剂可以包括碱金属、碱金属化合物、或其混合物。合适的碱金属化合物包括碱金属的碳酸盐、碳酸氢盐、甲酸盐、草酸盐、氨化物、氢氧化物、乙酸盐、硫化物或类似化合物。催化剂优选包括下述物质中的一种或多种：Na2CO3、K2CO3、Rb2CO3、Li2CO3、Cs2CO3、NaOH、KOH、RbOH或CsOH，更优选包括碳酸钾或氢氧化钾。罐12在100°F到180°F的温度和大气压力下运行。催化剂可以从若干来源引入到罐12中。有利地，根据本发明的一个方面，从废固体处理区300中的分离器101得到的产品冷凝物(其由含水的催化剂稀溶液组成)在约150°F的温度下经由管线95引入浆料混合罐12中。以此方式，含有相当大量酸的产品冷凝物(通常称为酸性水)用于工艺中，从而避免或尽可能减少对昂贵的废物处理操作的需要。
催化剂还可以通过管线24引入罐12中，该管线输送包括离开浆料干燥器20的蒸汽中夹带的所有固体的含水浆料。最后，根据需要可以通过管线11加入补充催化剂(make up catalyst)，以将浆料混合罐12中的催化剂浓度提高到所需水平。在稳态运行中，所需的催化剂浓度在0.5和1.5质量％之间。在测定本文所使用的催化剂的量时，量和比率基于催化剂中的碱量和石油焦炭中的灰分量。
浆料混合罐12中的固体含量为25-35wt％，优选约33wt％。浆料混合罐12中的碳酸钾浓度优选是这样的：在浆料干燥器20中干燥之后，沉积在固体颗粒之上和之内的钾是焦炭含灰分量的3到10倍多，优选是焦炭含灰分量的约5倍多，基于质量。希望在焦炭进料中实现大约5∶1的钾/灰分质量比。根据参考的焦炭组成，考虑到所接收到的焦炭中的水分，浆料水中的碳酸钾浓度是约0.9％K2CO3。
本发明的方法通常以稳态方式运行。然而，应当理解在该方法的初始启动阶段存在不同的必要条件。例如，在初始启动步骤，需要在焦炭颗粒上有较高的钾载量，并且对于约0.2％的焦炭含灰分量来说，浆料水中的含钾量可以增加到约20wt％，这可以通过将浆料水中的碳酸钾浓度调节到约10％K2CO3而实现。
根据稀释固体浓度的需要，可以将补充水直接加入浆料混合罐12中，或其可以与任何液流一起进入浆料混合罐12中。
浆料混合罐12中形成的含碳固体的含水进料浆料通过管线13排出，并且通入排浆泵14或类似装置(其将压力升高到足以使固体能够通过浆料干燥和蒸汽发生区100)中并通过气化区200。该压力通常为约520psig。然后将高压浆料通过热交换器16或类似装置，其中浆料温度升高到接近浆料含水部分的沸点(通常为约480°F)。从热交换器16中排出的预热且增压的进料浆料通过管线17通入流化床浆料干燥器20或类似装置中。
浆料干燥器20含有在内部格栅或类似分配装置之上的容器内向上延伸的含碳固体的流化床。该床通过下述方式保持流化状态：通过底部入口管线34而将过热蒸汽引入到干燥器的底部。流化床浆料干燥器20的压力通常保持在下述范围内：在气化反应器55中所保持的压力到比气化反应器压力高约200psi之间。离开干燥器20的蒸汽温度通常介于蒸汽在干燥器工作压力下的饱和温度到比干燥器工作压力下的饱和温度高约200°F的温度之间。对于进料量为每天2500吨焦炭且流化床干燥器中的固体停留时间为约20分钟的单元来说，床的滞留量可以是约30吨，即，在35lb/ft3的密度下为约2000ft3。通常需要实现约2ft/秒的空塔速度。在这种条件下，浆料干燥器床体直径可以是约14.2ft，且床层深度可以是约12.6ft。
在浆料干燥器20的流化床中，含水进料浆料与通过管线34注入到干燥器中的过热蒸汽接触。该过热蒸汽在约1100°F下注入干燥器。过热蒸汽中的显热可以基本上蒸发掉含水进料浆料中的所有水，从而将其转化为蒸汽。在这些条件下，使用约两磅从管线34注射到浆料干燥器20中的过热蒸汽可以将约一磅浆料进料中的水蒸发到蒸汽中。干燥器20通常运行以使干燥含碳固体含有约0.1到约4.0wt％的水。
离开浆料干燥器20中的流化床的气体主要由蒸汽组成。浆料干燥器可以包括位于流化床之上的一个或多个旋流分离器以便从蒸汽中除去相对大的颗粒。
通过管线21从浆料干燥器20上部排出的蒸汽可以直接通过湿式洗涤器22或类似装置，在这里其与通过线27引入的洗涤水接触。部分洗涤水被冷却并回流到洗涤器的顶部，在这里其将蒸汽从约480°F冷却到约450°F。冷凝足够的蒸汽以便通过管线24而将浆料中被洗涤的细粉携带到进料浆料混合罐12。
被洗涤的蒸汽通过管线28从湿式洗涤器22中排出，并通入压缩机30中，在这里其压力增加到约560psig。加压蒸汽通过管线31而从压缩机30中排出。净蒸汽(其质量流量等于蒸发的浆料水的质量流量)通过管线35而直接通入气化区200。其余的蒸汽(其可以被认为是作为传热介质)通过管线32通入过热器33或类似炉中，在这里蒸汽被过度加热到约1100°F的温度。离开过热器33的过热蒸汽通过管线34通入浆料干燥器20中，在这里其显热用来将进料浆料中的水(包括焦炭孔中的水)转化到蒸汽中同时将进料颗粒、催化剂和未转化的水加热到高温。
如图1所示，净蒸汽从区100通入气化区200，在这里其与H2和CO混和。优选，H2和CO通过将从来自下面讨论的气化区的粗制产品气中回收的氢和一氧化碳循环而得到。通常这些组分通过在本领域是公知的低温蒸镏技术而与产品气体分离。现在参考图3，管线42中的净蒸汽、H2和CO混合物通入到热交换器43中，在这里其通过与来自气化反应器55的热粗制产品气之间的间接热交换而加热到约1150°F，该热粗制产品气通过管线70而在约1300°F下被引入到交换器中。在加热的蒸汽混合物注入气化反应器55之前将其通过管线44通入预热炉45或类似装置中，在这里其被进一步过度加热到约1450°F的过热器出口温度。预热的蒸汽从炉45排出并通过管线46进入气化反应器55。保持过热器出口的实际温度以将气化反应器保持在所需温度，在该实施例中为1300°F。
干燥器20可以运行以便使气化反应器55中所需的基本上所有的蒸汽通过管线35提供，并且不需要来自任何其它来源的补充蒸汽。流化床浆料干燥器20中产生的干燥含碳固体通过管线38而从干燥器中排出，并从区100通入气化区200中。
在气化区200中，若干气化反应器中的任何一个可以用于本发明的方法。一个这种优选反应器是授予Nahas的美国专利第6,955,695号中公开的类型的两阶段流化床反应器。然而，气化反应器55不必用两阶段操作，甚至不必利用流化床操作。气化反应器55中的压力通常为约500psig。气化反应器温度通常保持在约1000°F到约1500°F，优选约1200°F到约1400°F。气化反应器55中使用的提升气体通常是在管线46中引入的过热混合物。管线38中的固体被注入气化反应器55中的上部流化床62中。浆料干燥器20在通常高于气化反应器55的工作压力的压力下运行。因此，固体可以被直接通入气化反应器55中而不需进一步增压。因此，不需要用于对干燥固体加压的复杂系统如闭锁料斗(lockhopper)。然而，根据本发明，可以预期的是干燥固体也可以用于本发明的方法中而不需要区100的浆料干燥操作。如果这是希望的，则干燥石油焦炭进料流可以根据需要使用合适的闭锁料斗或类似机构而直接引入气化反应器中。根据本实施方式，催化剂可以作为与焦炭混合或浸渍在焦炭上的干燥固体引入，或者分别作为干燥固体进料。
再次参考图3所示的气化区200，在气化反应器55中的条件下，蒸汽混合物与约97％的焦炭反应并将其转化为主要由甲烷和二氧化碳组成的气体产物。氢和一氧化碳以平衡状态存在于产品气体中，但被分离和循环，因此不存在这些气体组分的净产品。进料中的硫与氢和一氧化碳反应形成硫化氢和痕量浓度的碳酰硫。进料中的氮与氢定量地反应以形成氨。内旋风分离器66除去了热粗制产品中夹带的较大固体，并将它们返回到气化反应器55。
希望尽可能减少固体清除物60，但是其量应该足以除去新鲜原料中的灰分或矿物质。在每天处理2500吨含有约0.2％灰分的新鲜石油焦炭的单元中，固体清除物60与顶部(overhead)细粉一共可以是约60吨/天。用于抽样或清除的从反应器中排出固体的方法是本领域技术人员所公知的。可以使用例如EP0102828(1984)所教导的一种此类方法。
热粗制产品气包括约32％未反应蒸汽和逃离内旋风器66的夹带细粉。气化反应器粗制产品通过管线70在约1300°F下从气化反应器55中排出，并在交换器43中冷却到约815°F。在管线71中离开热交换器43的粗制产品在废热锅炉72或类似装置中进一步冷却到约400°F。在管线73中离开热交换器72的气体的温度控制在露点以上以保持夹带的细粉干燥直到它们达到细粉洗涤器74。
现在参考图4，管线73中的粗制产品气体流过细粉洗涤器74，其中夹带的细粉被除去且粗制产品通过洗涤水进一步冷却到350°F。将洗涤水从洗涤器74的下部通过管线75泵入洗涤冷却器76，然后通过管线77循环至洗涤器74的顶部。在这些条件下，约10％的未反应蒸汽冷凝，并且与被除去的细粉一起形成细粉和酸性水的浆料，该浆料通过管线79直接通入废固体浆料圆筒(drum)90。
粗制产品通过管线78并在锅炉给水预热器81或类似装置中进一步冷却到约100°F，这冷凝了几乎所有的其余未反应蒸汽。粗制产品通过酸性水分离器80，其中冷凝物形成第二酸性水流并通过管线85直接通入废固体浆料圆筒90。现在仅含有约0.2％未反应蒸汽的冷却粗制产品直接通过管线84通入粗制产品汽提塔101。
通过管线85从酸性水分离器80排出的酸性水与通过管线79从细粉(fines)洗涤器中排出的细粉和酸性水浆料混和，并在废固体浆料圆筒90中与固体清除物60混合。固体混合物具有约58％焦炭、35％钾和7％其它无机物(主要是镍和钒)的稳态组成。大部分钾作为氢氧化钾与一些硫化钾一起溶解。所得浆料的碱度在约100°F的温度下将来自酸性水冷凝物的氨逐出，通过管线96而在顶部(overhead)将来自废固体浆料圆筒90的氨回收。
来自废固体浆料圆筒90的废固体浆料在KOH、K2S和K2CO3的水溶液中含有约2.4％固体，该水溶液通过管线91排到分离器92。对于每天处理约2500吨含有约0.2％灰分的新鲜石油焦炭的单元来说，每天可以通过管线93而排出约40吨/天在淤泥中的固体清除物。通过管线94从分离器92中排出的水溶液与粗制产品汽提塔101中的冷却粗制产品气接触，其中K2S和KOH水溶液被转化为K2CO3水溶液和H2S气体。从催化剂水溶液到碳酸盐形式的转化可以通过与含有CO2的其它气流接触而实现。K2CO3的含水的催化剂稀溶液通过管线95循环到进料浆料混合罐12。冷却的粗制产品气与汽提塔101中形成的H2S一起通过管线110下行到产品分离区400，以便通过传统方法来脱酸性气并从产品CH4中分离H2和CO。甲烷可以通过低温蒸镏来回收，得到高于99.9％的纯度，并且适于在天然气管道中直接运输或作为输送到液化天然气终端设备的液体甲烷而回收。
从以上可见，本文所公开的发明提供了一种将低价值的石油焦炭转化为可以在现有的基础结构如管道中自由输送的甲烷的方法。
通过利用该方法中产生的焦炭末并将它们转化为甲烷，本发明的方法对于指定碳含量的固体起始物料提供了碳到甲烷的更高转化率。本发明的焦炭催化气化方法还提供了一种将石油焦炭转化为甲烷的有效的催化气化方法，该方法不需要复杂的催化剂回收系统并且不存在相关的工艺问题。该方法/系统提供了集成的产品纯化以及尽可能减少所需废物处理的催化剂循环。
本发明还回收了从粗制产品流冷凝的酸性水。这种应用保持了工艺中的酸性水并消除或充分降低了对酸性水废物处理的需要。酸性水有利地用于溶解固体清除物中的催化剂并将催化剂循环到进料中。循环的催化剂溶液是稀释的，这允许较廉价的结构材料。
本发明可以这样运行：基本上所有的进料中的硫均包含在粗制产品气体中，因此可以主要在一个气体处理单元中除去。基本上所有从进料中的任何氮产生的氨都可以从废固体浆料罐中在空中回收。
虽然本发明已经与具体流程方案和操作条件一起进行说明，但在不背离本发明的精神和范围的情况下可以对其作出各种修改和代替。不应该强加任何与以下权利要求所示不同的限制。

Claims (18)

1.一种将石油焦炭转化为甲烷的方法，包括：
将石油焦炭和具有蒸汽气化活性的催化剂在水性介质中混合，以形成进料浆料；
将所述进料浆料和过热蒸汽引入到浆料干燥器中，以产生净蒸汽和浸有催化剂的石油焦炭的基本上干燥的固体颗粒；
使所述干燥固体颗粒与所述净蒸汽在气化反应器中反应，形成包括未反应蒸汽、甲烷、二氧化碳、氢和一氧化碳的粗制产品气；
从所述粗制产品气中回收甲烷；和
根据所述石油焦炭中的灰分量控制所述水性介质中催化剂的浓度。
2.根据权利要求1所述的方法，其中所述具有蒸汽气化活性的催化剂包括一种或多种选自碱金属和碱金属化合物的物质。
3.根据权利要求2所述的方法，其中所述碱金属化合物选自碱金属碳酸盐、碱金属碳酸氢盐、碱金属甲酸盐、碱金属草酸盐、碱金属氨化物、碱金属氢氧化物、碱金属乙酸盐、和碱金属硫化物。
4.根据权利要求2所述的方法，其中所述催化剂包括一种或多种选自Na2CO3、K2CO3、Rb2CO3、Li2CO3、Cs2CO3、NaOH、KOH、RbOH和CsOH的碱金属化合物。
5.根据权利要求2所述的方法，其中所述催化剂包括碳酸钾或氢氧化钾。
6.根据权利要求5所述的方法，其中所述水性介质中所述碳酸钾的含量为约0.9到10wt％。
7.一种将石油焦炭转化为甲烷的方法，包括：
将石油焦炭和具有蒸汽气化活性的催化剂在水性介质中混合，形成进料浆料；
将所述进料浆料和过热蒸汽引入到浆料干燥器中，以产生净蒸汽和浸有催化剂的石油焦炭的基本上干燥的固体颗粒；
使所述干燥固体颗粒与所述净蒸汽在气化反应器中反应，形成包含未反应蒸汽、甲烷、二氧化碳、氢和一氧化碳的粗制产品气；
从所述反应器中排出固体清除物，所述固体清除物包括焦炭物质且其中混合有催化剂；
将所述粗制产品流冷却以使未反应蒸汽冷凝，形成酸性水和冷却的粗制产品气流；
从所述粗制产品气中回收甲烷；
使所述固体清除物与所述酸性水接触以溶解所述混入的催化剂，形成含水的催化剂稀溶液；和
将所述含水的催化剂稀溶液返回到所述进料浆料中。
8.根据权利要求7所述的方法，其中来自气化反应器的固体清除物在浆料容器中与所述酸性水接触，并且从所述浆料容器回收氨蒸汽。
9.根据权利要求7所述的方法，其中所述催化剂稀溶液在回到所述进料浆料中之前与含有CO2的气体接触。
10.根据权利要求7所述的方法，其中所述催化剂稀溶液在回到所述进料浆料中之前用所述冷却的粗制产品气来汽提。
11.一种气化石油焦炭的方法，包括：
粉碎石油焦炭以产生根据美国标准筛尺度其粒度大于约325目的石油焦炭颗粒和石油焦炭细粉流；
将所述石油焦炭颗粒和至少部分所述石油焦炭细粉与具有蒸汽气化活性的催化剂在水性介质中混合，形成进料浆料；
将所述进料浆料和过热蒸汽引入到浆料干燥器中，以产生净蒸汽和浸有催化剂的石油焦炭的基本上干燥的固体颗粒；
使所述干燥固体颗粒和所述净蒸汽在气化反应器中反应。
12.根据权利要求11所述的方法，其中所述石油焦炭颗粒的尺寸为33到100目。
13.根据权利要求11所述的方法，其中所述反应器包括流化床。
14.根据权利要求13所述的方法，其中所述反应器具有上部流化床和下部流化床。
15.一种将石油焦炭转化为甲烷的方法，包括：
将干燥的石油焦炭、具有蒸汽气化活性的催化剂、和过热蒸汽引入到气化反应器中；
使所述焦炭、催化剂和蒸汽反应，形成包含未反应蒸汽、甲烷、二氧化碳、氢和一氧化碳的粗制产品气；
从所述反应器中排出固体清除物，所述固体清除物包括焦炭物质且其中混合有催化剂；
将所述粗制产品流冷却以使未反应蒸汽冷凝，形成酸性水和冷却的粗制产品气流；
将所述固体清除物与所述酸性水在浆料容器中接触；
从所述浆料容器中回收氨蒸汽；和
从所述粗制产品气中回收甲烷。
16.一种从石油焦炭产生甲烷的方法，包括：
将含有一定质量分数(干基)的灰分的石油焦炭、含有一定质量分数的碱的催化剂和过热蒸汽引入到气化反应器中，从而使引入到所述反应器中的碱/灰分比为3到10；
使所述焦炭、催化剂和蒸汽反应，形成包含未反应蒸汽、甲烷、二氧化碳、氢和一氧化碳的粗制产品气；和
从所述粗制产品气中回收甲烷。
17.一种将石油焦炭转化为甲烷的方法，包括：
在具有蒸汽气化活性的催化剂的存在下使石油焦炭与蒸汽在气化反应器中反应，形成包含未反应蒸汽、甲烷、二氧化碳、氢和一氧化碳的产品气；和
根据所述石油焦炭中的灰分量控制所述催化剂与所述石油焦炭的比率。
18.一种将石油焦炭转化为甲烷的方法，包括：
将石油焦炭和具有蒸汽气化活性的催化剂在水性介质中混合，形成进料浆料；
从所述进料浆料中回收干燥固体；
使所述干燥固体与蒸汽在气化反应器中反应，形成包含未反应蒸汽、甲烷、二氧化碳、氢和一氧化碳的粗制产品气；
从所述反应器中排出固体清除物，所述固体清除物包括焦炭物质且其中混合有催化剂；
将所述粗制产品流冷却以使未反应蒸汽冷凝，形成酸性水和冷却的粗制产品气流；
使所述固体清除物与所述酸性水接触以溶解所述混入的催化剂，形成含水的催化剂稀溶液；和
将所述含水的催化剂稀溶液返回到所述进料浆料中。
CNA2006800379897A 2005-10-12 2006-10-05 石油焦炭到甲烷的催化蒸汽气化 Pending CN101356254A (zh)

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CN103391989A (zh) * 2011-02-23 2013-11-13 格雷特波因特能源公司 伴有镍回收的碳质原料加氢甲烷化
CN103391989B (zh) * 2011-02-23 2015-03-25 格雷特波因特能源公司 伴有镍回收的碳质原料加氢甲烷化
CN104711026A (zh) * 2011-02-23 2015-06-17 格雷特波因特能源公司 伴有镍回收的碳质原料加氢甲烷化

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WO2007047210A1 (en) 2007-04-26
CA2624626C (en) 2012-02-28
US20070083072A1 (en) 2007-04-12
CA2624626A1 (en) 2007-04-26
US8114176B2 (en) 2012-02-14
EA012999B1 (ru) 2010-02-26

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