CN100381353C - 制备合成气的方法 - Google Patents

制备合成气的方法 Download PDF

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CN100381353C
CN100381353C CNB2004800100818A CN200480010081A CN100381353C CN 100381353 C CN100381353 C CN 100381353C CN B2004800100818 A CNB2004800100818 A CN B2004800100818A CN 200480010081 A CN200480010081 A CN 200480010081A CN 100381353 C CN100381353 C CN 100381353C
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CN1774392A (zh
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T·H·泰欧
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Shell Internationale Research Maatschappij BV
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Abstract

一种由碳质原料制备含氢气与一氧化碳的气体的方法，该方法进行下述步骤：(a)在上端包括燃烧器(52)的垂直取向管式部分氧化反应器(51)中部分氧化碳质原料，从而得到氢气和一氧化碳的第一气态混合物，(b)在包括配有装有重整催化剂的一个或多个管的管式反应器的对流蒸汽重整装置(44)中催化蒸汽重整碳质原料，作为单独的产品得到蒸汽重整产品(39)，其中步骤(b)的原料中蒸汽与碳的摩尔比小于1，(c)将蒸汽重整产品供给部分氧化反应器的上端，得到步骤(a)的流出物和蒸汽重整产品的混合物，和(d)通过在步骤(c)中得到的混合物与蒸汽重整反应器管之间对流换热为步骤(b)中的蒸汽重整反应提供所需的热量，从而得到温度下降的含氢气和一氧化碳的气体。

Description

制备合成气的方法
技术领域
本发明涉及通过进行部分氧化反应和吸热蒸汽重整反应由碳质原料制备包括一氧化碳和氢气的混合物的方法。
背景技术
EP-A-168892描述了一种吸热蒸汽重整反应，该反应在位于至少一个管内的固定床中进行，通过使部分氧化反应的至少部分热产品气沿管运行而使管内温度保持为800-950℃。根据该公开的专利文献，部分氧化反应和吸热生产合成气的组合可以提高合成气的产率，提高H2/CO的比，降低每得到一立方米合成气产品使用的氧气量，降低用于生产含CO和H2的气体混合物的设备的投资费用(与部分氧化相比)。
DE-A-3345088描述了进行蒸汽重整反应的反应器和方法。该公开专利文献描述了由天然气原料开始进行蒸汽重整反应的反应器。该反应器由管板组成，多个充填有合适催化剂的管从管板伸入反应器。通过使天然气部分氧化反应的热流出物从反应器管外部通入反应器，以此提供反应需要的热。这种蒸汽重整反应器也称为所谓的对流蒸汽重整(CSR)反应器。
EP-A-983964描述了一种对流蒸汽重整反应器，其中反应器配有装有催化剂床的多个反应器管。在反应器管周围提供环状套管，用于运输自热重整装置(ATR)的热流出物。通过在该热流出物与经过催化剂床的反应试剂之间间接换热可以进行蒸汽重整反应。
现有技术方法的缺点是得到的合成气(一氧化碳和氢气的混合物)包括较高含量的蒸汽。特别是当合成气用于费-托合成时，这种蒸汽是不希望的。可以在较低的蒸汽与碳的比下操作CSR。但这样会导致较少量的甲烷在CSR反应器中转化，致使合成气中含有大量甲烷。尽管这样的甲烷含量在某些工艺中可以接受，但如果合成气用作费-托工艺的原料，则不希望存在甲烷，因为它作为惰性物质存在，占据反应器的空间。
本发明的目的是提供一种方法，其中CSR反应器可以在较低的蒸汽与碳的比下操作，并且其中得到的合成气中的甲烷含量保持在较低水平，使合成气可以有利地用作如费-托反应的原料。
发明内容
下述方法可以实现本发明的目的。
一种由碳质原料制备含氢气与一氧化碳的气体的方法，该方法进行下述步骤：
(a)在上端包括燃烧器的垂直取向管式部分氧化反应器中部分氧化碳质原料，从而得到氢气和一氧化碳的第一气态混合物，
(b)在包括配有装有重整催化剂的一个或多个管的管式反应器的对流蒸汽重整装置中催化蒸汽重整碳质原料，作为单独的产品得到蒸汽重整产品，其中步骤(b)的原料中蒸汽与碳的摩尔比小于1，
(c)将蒸汽重整产品供给部分氧化反应器的上端，得到步骤(a)的流出物和蒸汽重整产品的混合物，和
(d)通过在步骤(c)中得到的混合物与蒸汽重整反应器管之间对流换热为步骤(b)中的蒸汽重整反应提供所需的热量，从而得到温度下降的含氢气和一氧化碳的气体。
申请人发现：通过将步骤(b)中得到的蒸汽重整流出物供给部分氧化反应器的上部，大部分未转化的甲烷会转化为一氧化碳和氢气，这是因为下述事实：同样存在于部分氧化反应器上部的燃烧器会部分氧化甲烷。
附图说明
图1示出可用于本发明的CSR反应器。
图2示出图1的反应器与部分氧化反应器的组合。
图3示出涉及图2的装置、费-托合成及其下游一些单元操作的集成方法。
具体实施方式
步骤(a)中的碳质原料优选是气态烃，合适的是甲烷、天然气、伴生气或C1-4烃的混合物。气态烃的例子是天然气、炼油气、伴生气或(煤层)甲烷等。合适的气态烃主要包括，即大于90v/v％、特别是大于94v/v％的C1-4烃，特别是包括至少60v/v％的甲烷，优选至少75％，更优选90％的甲烷。优选使用天然气或伴生气。优选脱除原料中所有的硫。
步骤(a)和步骤(b)中的碳质原料优选是上述气态原料。在该优选实施方案中，步骤(a)和(b)的全部气态原料的10-90wt％、优选20-50wt％供给步骤(b)。
在步骤(a)中，可以根据公知的原理如Oil and Gas Journal，1971年9月6日，第85-90页中所述Shell Gasification Process进行部分氧化。描述部分氧化工艺例子的公开文献有EP-A-291111、WO-A-9722547、WO-A-9639354和WO-A-9603345。在这些工艺中，优选在没有催化剂的情况下使原料与含氧气体在部分氧化条件下接触。
含氧气体可以是空气(含有约21％的氧气)，优选富氧空气，合适的是最高含有100％氧气的空气，优选含有至少60vol％的氧气，更优选含有至少80vol％的氧气，更优选含有至少98vol％的氧气。可以用深冷技术生产富氧空气，但是优选用膜基法生产，例如WO93/06041中描述的方法。
在步骤(a)中，原料与含氧气体的接触优选在置于反应器内的燃烧器中进行。为了调节步骤(a)中部分氧化反应得到的气态产品中的H2/CO比，可以在原料中加入二氧化碳和/或蒸汽。以气态产品的量计，至多15vol％，优选至多8vol％，更优选至多4vol％的二氧化碳或蒸汽加入原料。作为合适的蒸汽源，可以使用任选的下游烃合成中生产的水。
步骤(a)中部分氧化反应的气态产品的温度是1100-1500℃，H2/CO摩尔比是1.5-2.6，优选1.6-2.2。在靠近燃烧器的地方供给蒸汽重整产品，所述上部区域中达到的温度适宜为800-1050℃。
可以用公知的蒸汽重整工艺实施步骤(b)，其中蒸汽和气态烃原料在CSR反应器中与合适的重整催化剂接触。对流蒸汽反应器优选包括配有一个或多个装有重整催化剂的管的管式反应器。这种反应器的各种设计都是已知的，都适用于本发明。该设计应当使用于供热的蒸汽重整产品和合成气在该反应器中作为单独的物流得到。这类反应器概念的例子描述在US-A-6224789中。也可以使用如图1所示的设计。
图1示出CSR反应器。包括热气通道(23)的充填有蒸汽重整催化剂床(22)的一个或多个平行放置的反应器管(21)定义出反应器空间。第三个管板(32)位于反应器(44)的下端，定义出空间(33)，空间(33)使用于用于步骤(c)得到的混合物的反应器入口(38)与通道(23)的入口流体连接，通道(23)通过开孔(34)穿过管板(32)，开孔(34)优选比通道(23)本身大。通道不固定在管板(32)上的这一事实是有利的，因为它能使组合的反应器管(21)和通道(23)在启动和冷却条件下在反应器(44)中自由热膨胀。伸入下部空间(33)的通道下端优选用耐热材料如陶瓷制成，因为在所述空间中由于热气态介质通过反应器入口(38)进入反应器而具有很高的温度。
包括催化剂床(22)的反应器管(21)的出口开孔(35)正好位于所述管板(32)的正上方。所述开孔(35)排出的蒸汽重整产品进入空间(36)，空间(36)定义为管板(40)和(32)之间的空间。该空间(36)使用于蒸汽重整产品的反应器出口(39)与开孔(35)流体连接。空间(36)中可以适当设置导流片，引导蒸汽重整产品流以之字形流经所述空间，从而优化热蒸汽重整产品气与所述空间中存在的反应器管(21)外表面的接触。在使用时，开孔(35)排出的部分蒸汽重整产品通过出口(39)离开反应器，通过操作反应器，使空间(36)中的压力高于空间(33)中的压力，使另一部分通过开孔(34)离开空间(36)进入空间(33)。在使用时，由开孔(35)排出的蒸汽重整产品的优选0-60wt％、更优选0-40wt％可以进入空间(33)与热气态介质混合。这是有利的，因为通道(23)中流动气体的蒸汽与碳的比可以提高，从而限制了通道(23)内的金属污染。
图1还示出用于天然气和蒸汽的反应器入口(43)、用于热气态介质的反应器入口(38)、用于蒸汽重整产品的反应器出口(39)和用于由通道(23)排出的气体的反应器出口(42)。存在的管板(40)和(41)是为了固定反应器管(21)，定义通道(23)排出气体的收集空间(45)和入口空间(46)，入口空间(46)使用于天然气和蒸汽的反应器入口(43)和包括催化剂床(22)的反应器管(21)流体连接。
应用于蒸汽重整反应器管的催化剂和工艺条件可以是蒸汽重整领域的普通技术人员熟知的那些催化剂和工艺条件。合适的催化剂包括任选负载在载体如氧化铝上的镍。气态原料的空速优选是700-1000L(S.T.P.)/L催化剂/hr，其中S.T.P.表示15℃的标准温度和1bar(绝对)的标准压力。蒸汽与碳(烃和CO)的摩尔比低于1，优选0.5-0.9。如果在步骤(b)中使用这样低的蒸汽与碳的比，则催化剂优选包括VIII族金属。催化剂更优选包括(a)氧化物载体材料和(b)包括约0.1wt％至约7.0wt％的至少一种选自Pt、Ni、Pd和Co的金属的涂层，金属优选是铂；所述载体材料包括：
(i)至少80wt％的在涂布所述涂层前已经在最高约670℃的温度下煅烧的ZrO2；(ii)0.5-10mol％的至少一种选自Y、La、Al、Ca、Ce和Si的氧化物，优选La2O3。这种催化剂的例子例如描述在EP-A-695279中的催化剂。原料优选还包括一定量的CO2，其中CO2与碳(烃和CO)的摩尔比优选是0.5-2。步骤(b)的产品气的温度优选是600-1000℃，H2/CO摩尔比是0.5-2.5。
在步骤(b)中，含氢气和一氧化碳的气体的温度优选由步骤(a)之后的1000-1500℃降至步骤(c)之后的800-1050℃，在步骤(d)后降至300-750℃。在CSR反应器中，内构件材料的金属壁表面温度优选保持低于1100℃。
任选地，步骤(a)的流出物与步骤(c)中得到的蒸汽重整产品的混合物在所述混合物的高温下进行自热重整步骤，也称为后催化重整步骤，将步骤(c)中得到的气态混合物转化为其H2/CO摩尔比更接近对于所述温度来说所希望的热平衡H2/CO摩尔比值的混合物。这种组合的混合物，任选在该后重整步骤之后，用在步骤(d)中。
上述实施方案示于图2。图2示出CSR反应器。为了清楚起见，图2中没有示出反应器(44)的内构件。图2中还示出配有燃烧器(52)的部分氧化反应器(51)。碳质原料(50)和含氧气体(50′)供给燃烧器(52)。图2还示出步骤(b)的产品气(55)供给反应器(51)的上半部分。
蒸汽重整产品(55)优选靠近燃烧器(52)(即在反应器(51)的上半部分)供给，以最大获益于反应器(51)区域内存在的800-1050℃的高温。相对于步骤(b)的原料(43)中以烃存在的碳，蒸汽重整产品(55)中的甲烷含量可以是5-30mol％碳。当在上述较低的蒸汽与碳的比下操作步骤(b)时，可以得到较高的甲烷含量。因为本发明的方法可以校正甲烷的下滑率，所以也允许CSR反应器中较低的反应温度。较低的反应温度还导致更多未反应的甲烷存在于产品(55)中。步骤(b)中的低温适宜为700-800℃，这是针对离开反应器(44)的蒸汽重整产品(55)测量的。由于反应器(44)内构件中使用的材料强度的原因，需要低温。
图2还示出优选的自热重整装置或存在于反应器(51)下半部分的后催化重整催化剂床(53)。催化剂床(53)可以是任何公知的重整催化剂，如含镍催化剂。任选催化剂床(53)的流出物(56)随后供入反应器(44)的入口(38)，其中气体在通道(23)(图2中未示出)中被冷却，通过出口(42)得到最终的合成气产品(63)。
上述工序得到的合成气(63)可有利地用作费-托合成工艺、甲醇合成工艺、二甲醚合成工艺、醋酸合成工艺、氨合成工艺的原料，或者供给使用合成气混合物作为原料的其它工序如涉及羰基化和加氢甲酰化反应的工序。优选向步骤(a)和(b)中供应再循环气。这些再循环气例如前面例举的使用本发明方法制备的合成气的工艺得到的。这些再循环气可以包括C1-5烃，优选C1-4烃，更优选C1-3烃。这些烃或其混合物在5-30℃(1bar)、特别是20℃(1bar)下是气态。还可以存在氧化化合物如甲醇、二甲醚、醋酸。
本发明特别涉及制备含氢气和一氧化碳的气体(合成气)的方法，其中还可以实施附加步骤(e)、(f)和(g)。在步骤(e)中，用费-托催化剂将合成气催化转化为包括烃的物流。在步骤(f)中，步骤(e)的包括烃的物流分离成烃产品和气态再循环物流。适宜的烃产品是具有5个或更多个碳原子、优选4个或更多个碳原子、更优选3个或更多个碳原子的那些产品。气态再循环物流可以包括合成工艺中生产的普通气态烃、氮气、未转化的甲烷和其它原料烃、未转化的一氧化碳、二氧化碳、氢气和水。
在步骤(f)中，再循环物流供给步骤(a)和/或(b)。再循环物流优选供给步骤(a)的燃烧器，或者直接供给部分氧化反应器的内部。
任选地，再循环物流供给步骤(a)之前，将再循环物流中存在的部分或全部二氧化碳从再循环物流中分离。部分二氧化碳适于供给步骤(a)。
步骤(e)和(f)可以用公知的费-托工艺如Sasol工艺和ShellMiddle Distillate工艺实施。合适的催化剂的例子基于铁和钴。一般的反应器结构包括浆液反应器和管式反应器。这些工艺和其它工艺例如详细描述在EP-A-776959、EP-A-668342、US-A-4943672、US-A-5059299、WO-A-9934917和WO-A-9920720中。
图3示出图2的结构与费-托合成工艺单元(64)及其下游加氢转化单元(66)(即步骤(g))的组合。除图2外，图3还示出合成气(63)如何供给费-托合成工艺单元(64)。在单元(64)中，气态再循环物流(54)从烃产品(65)中分离后再循环到部分氧化反应器(51)。图3还示出H2/CO摩尔比较高的蒸汽重整产品(55)的一部分(60)如何供给氢气回收单元(61)，以得到适用于加氢处理单元(66)的氢气(62)。在所述单元中，(65)中存在的烃产品一般包括较大比例的沸点高于370℃的化合物，用公知的加氢裂解和加氢异构化方法将这种烃产品转化为中间馏分(67)。任何剩余的残渣都可以通过催化脱蜡工艺(图中未示出)进一步转化为基础油，这些工艺也需要氢气。这些下游加氢处理单元的例子描述在如WO-A-0107538、WO-02070631、WO-02070629和WO-02070627以及这些公开专利所引用的文献中。
下面的实施例示出本发明的反应器如何用于制备一氧化碳和氢气的混合物的方法。所给出的计算值接近实际值，这是因为使用的是气化和蒸汽重整领域的普通技术人员公知的热动力学关系式。
对比例1
向图3所示的蒸汽重整反应器中加入天然气和蒸汽，其中蒸汽与碳的比是0.75。另外，部分氧化反应器的热流出物通过27供给所述反应器。质量流量、温度和得到的产品物流示于表1。
对比例2
重复实施例1，不同之处是在图3中的CSR反应器原料中蒸汽与碳的比是1。
实施例3
在该实施例中，反应器管的流出物首先如图2所示供给部分氧化反应器(管线55)。反应器51中没有催化剂床53。
Figure C20048001008100111
Figure C20048001008100121
Figure C20048001008100131
Figure C20048001008100141

Claims (3)

1.一种由碳质原料制备含氢气与一氧化碳的气体的方法，该方法进行下述步骤：
(a)在上端包括燃烧器的垂直取向管式部分氧化反应器中在没有催化剂的情况下部分氧化碳质原料，从而得到氢气和一氧化碳的第一气态混合物，
(b)在包括配有装有重整催化剂的一个或多个管的管式反应器的对流蒸汽重整装置中催化蒸汽重整碳质原料，作为单独的产品得到蒸汽重整产品，其中步骤(b)的原料中蒸汽与碳的摩尔比小于1，
(c)将蒸汽重整产品供给部分氧化反应器的上端，得到步骤(a)的流出物和蒸汽重整产品的混合物，和
(d)通过在步骤(c)中得到的混合物与蒸汽重整反应器管之间对流换热为步骤(b)中的蒸汽重整反应提供所需的热量，从而得到温度下降的含氢气和一氧化碳的气体。
2.权利要求1的方法，其中步骤(b)原料中蒸汽与碳的摩尔比是0.5-0.9。
3.权利要求1-2任一项的方法，其中步骤(c)中得到的混合物的温度是800-1050℃。
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