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CN1934225B - 天然气转化为长链烃类的工艺 - Google Patents

天然气转化为长链烃类的工艺 Download PDF

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CN1934225B
CN1934225B CN2005800084576A CN200580008457A CN1934225B CN 1934225 B CN1934225 B CN 1934225B CN 2005800084576 A CN2005800084576 A CN 2005800084576A CN 200580008457 A CN200580008457 A CN 200580008457A CN 1934225 B CN1934225 B CN 1934225B
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M·J·鲍
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Abstract

一种将天然气转化为长链烃类的工艺，该工艺包括天然气与蒸汽进行重整反应从而产生了一氧化碳和氢气的混合物，接着将该混合物进行费-托合成反应。重整反应(20)的操作压力为0.4-0.6MPa，费-托合成反应(50)的操作压力为1.8-2.1MPa，并且用两个压缩机(36、44)来升高压力，进入和流出第一压缩机(36)的气体混合物被冷却(26、32、40)。这样既降低了操作成本又降低了设备成本。

Description

天然气转化为长链烃类的工艺
技术领域
本发明涉及一种将天然气转化为长链烃类的化学工艺，和一种适用于进行该工艺的装置，其包括催化反应器。
背景技术
WO01/51194和WO03/048034(Accentus plc)公开了一种工艺，其中，甲烷与蒸汽在第一反应器中反应，产生了一氧化碳和氢气；接着将产物气体混合物在第二反应器中进行费-托(Fischer-Tropsch)合成反应。总的结果是将甲烷转化为较高分子量的烃类，该烃类在通常条件下是液体。在该工艺两步反应中，即蒸汽/甲烷重整和费-托合成两步反应中需要不同的催化剂；并且也公开了每个步骤中所用的催化反应器。随着反应的吸热和放热，催化反应器将热量转移给反应气体或从反应气体中吸收热量；可以通过燃烧为蒸汽/甲烷重整反应提供所需的热量。在不同的压力下进行两步反应效率最高，但是升高两步反应间的压力会使得成本昂贵并且也很消耗能源。
发明内容
本发明提供了一种处理天然气以生成长链烃类的工艺，该工艺包括天然气与蒸汽在0.4-0.6MPa的压力(4-6个大气压)下进行重整反应从而产生了一氧化碳和氢气的混合物，冷却该混合物，用两步连续压缩步骤对该混合物进行压缩使其压力达到1.8-2.2MPa(18-22个大气压)，在两个压缩步骤之间设有冷却，接着该混合物进行费-托合成反应生成长链烃类。
在重整前的天然气与蒸汽混合之前，通常需要将天然气的压力调整至适宜的压力(例如0.4-0.6MPa)。优选费-托合成反应的操作压力为19-21个大气压。(各种情况下的压力值为绝对压力值。)
该工艺也产生了含有氢气和部分气化烃类的尾气。优选至少将一部分尾气用于发电，例如用作驱动发电机的叶轮机的燃料。这样不仅可以为本工艺的运行提供电能，例如压缩机的运行提供电能，也可以将剩余的电能用作其他用途。
也可以通过进行费-托合成上游的逆向水煤气转换反应，用尾气将天然气中的二氧化碳转化为一氧化碳。
优选，蒸汽/甲烷重整反应和费-托合成反应均在紧凑催化反应器中进行。此类催化反应器，优选含有多个金属板的叠层，其形状和设置确定了第一和第二流体流动通道。叠层中通道的交替设置从而确保了其间的流体具有良好的热接触。根据所要求的反应来提供所必需的适宜催化剂。为了确保所需的良好热接触，蒸汽/甲烷重整反应器中的第一和第二物流通道的深度为2-10mm，优选垂直于金属板方向上的深度小于6mm，更优选为5mm-3mm深；在费-托反应器中，反应通道优选深度小于10mm。波纹状或凹状金属箔片、金属筛网、或波纹状或褶皱状金属毡状片材可以用作流体通道中催化剂结构的基底以提高热传递和催化剂表面积。优选，可以将催化剂结构从叠层的凹槽中移出，这样当催化剂成为废催化剂时，其就可以被替换了。
此类反应器提供了较短的扩散通道，因此热传递和质量传递的速度可以比较高，从而化学反应速度可以较高。因此该反应器提供了高的能量密度。
通过列举实施例并参考附图来进一步并更为详细的介绍本发明，其中：
图1是本发明化学工艺的流程图。
本发明涉及一种将天然气(主要是甲烷)转化为长链烃类的化学工艺。第一步骤涉及蒸汽重整，即天然气与蒸汽混合并进行下列反应
H2O+CH4→CO+3H2
该反应是吸热反应，并在第一气体物流通道中被铑或铂/铑催化剂催化。该反应所需的热量可以通过可燃气体(如甲烷或氢气)的燃烧反应来提供，该燃烧反应是放热反应并也可以被邻近第二气体物流通道的钯催化剂催化。上述情况中的催化剂优选均在定形铝载体上，该载体通常在金属基底上形成100μm厚的覆盖层。可以在常压下进行该燃烧反应，但是重整反应应该在4-5个大气压下进行。燃烧产生的热量可以通过分隔相邻通道的金属板进行传递。
接着将蒸汽/甲烷重整反应所产生的气体混合物进行费-托合成反应以产生长链烃类，即
n CO+2n H2→(CH2)n+nH2O
该反应是放热反应，其在升高的温度、升高的压力并在催化剂存在的条件下进行，通常升高的温度为190-280℃，例如210℃，升高的压力通常为1.8-2.1MPa(绝对压力)，例如2.0MPa，催化剂可以是例如铁、钴或熔融的磁铁并且使用钾作助催化剂。优选用于费-托合成反应的催化剂包含具有比表面积140-230m2/g的γ-氧化铝覆盖层、其上约有10-40％的钴(相对于铝的重量)、以及低于10％钴重量的助催化剂，如钌、铂或钆。一般金属箔层表面上的承载钴的γ-氧化铝层厚度为120-180μm。
参考图1，该图为总化学工艺流程图，其中显示了该流程装置的各元件。天然气原料5主要包括甲烷和，在这个实施例中，一定比例的C2-C11的高碳烃类。通常根据天然气来源的不同，这些高碳烃类可以为10％v/v。例如气体原料5的压力可以为1.0MPa(10个大气压)。
通过阀门8将气体压力调整为0.6MPa，接着利用来自催化燃烧中的热废气在热交换器10中将气体5预热至约400℃，接着进入固定床脱硫系统12将气体中的硫含量降低至0.1ppm或更低。脱硫后的天然气5接着与蒸汽混合，例如在流体涡流混合器14中混合。利用来自催化燃烧中的热废气在热交换器16中将气体/蒸汽混合物加热至500℃。混合物进入到绝热固定床预重整器18中，在此混合物与镍或铂/铑基甲烷化催化剂接触。高碳烃类与蒸汽反应形成了甲烷和CO。
气体混合物，包括主要是甲烷和蒸汽以及一小部分的一氧化碳，以较低温度通常为450℃从预重整器18中流出。接着，再进入重整反应器20前通过阀门19将压力降低至0.45MPa(绝对压力值)。重整器20是上述的板叠层紧凑催化反应器，该板叠层形成了用于吸热和放热反应的流体通道，该反应器具有良好的热接触性能，并且含有，例如在波纹状金属箔片基底上的适宜催化剂。重整器20的重整通道上含有铂/铑催化剂，并且蒸汽和甲烷反应生成了一氧化碳和氢气。反应器的温度从进口处的450℃升高至出口处的800-850℃。进入混合物14中的蒸汽和气体流速要使得进入重整器20中的蒸汽∶碳的摩尔比为1.2-1.6，优选为1.3-1.5。考虑到气体5中的高碳烃类的含量，因此预重整器18进口处的蒸汽与碳的比例要高于上述比例。
重整反应器20中的吸热反应所需的热量由短链烃类和氢气的混合物进行催化燃烧来提供，该混合物为费-托合成的尾气22；该尾气22与来自空气压缩器24的空气流进行混合。在重整反应器20内的邻近物流通道中的钯/铂催化剂上进行燃烧反应。燃烧气体通道至少和重整气体通道接近平行。催化剂包括γ-氧化铝载体，其上覆有钯/铂混合物3∶1，该催化剂在很宽的温度范围内都很有效。沿着反应器20提供各步骤中的可燃气体混合物以确保在燃烧通道的长度方向上发生燃烧反应。
一氧化碳和氢气的混合物以高于800℃的温度从重整器20中流出，并且通过将其流经蒸汽发生热交换器26而急冷至低于400℃。用泵28将水泵入进到该热交换器26中，因而将用于重整工艺的蒸汽通过控制阀门30输送到混合器14中。用冷却水将气体混合物在热交换器32中进一步冷却至约60℃，因此过量的水得到了冷凝并通过流经旋流器33和分离容器34而得到分离。接着用压缩机36将气体混合物压缩至约压力的2.5倍，在流经第二旋流器41和分离容器42之前，用热交换器40对该气体混合物进行再次冷却以除去冷凝水。被分离的水再次循环回到蒸汽发生回路中。接着用第二压缩机44将气体压缩至20个大气压。
高压一氧化碳和氢气流入到催化费-托反应器50中，该反应器为上述的板叠层紧凑催化反应器；反应物流在一套通道中流动，而冷却剂在另一套通道中流动。
费-托合成的反应产物主要是水和烃类，例如石蜡。该反应产物流经热交换器54和旋流分离器56被冷却凝结为液体接着在分离室58中被分离为水、烃类和尾气三相，并且烃类产物在常压下保持稳定。收集并分离气相中的烃类和多余的氢气(费-托尾气22)。一部分流经降压阀60为重整反应器20中的催化燃烧工艺提供燃料(如下所述)。剩余尾气62进入气体涡流机63来驱动发电机64。
气体涡流机64产生了装置所需的全部能量，并且还有剩余能量可以输出。主要需要电力的装置是压缩机36和44，以及泵24和28；电能也可以用于操作真空蒸馏单元以提供用于产生蒸汽的工艺用水和提供饮用水。
从上述讨论的方程式中可以看出蒸汽重整反应所形成的氢气要多于费-托合成所需要的氢气。因此尾气22中含有大量的氢气以及少量的链烷烃(C1-C5)。然而，尾气22中同样也含有大量的一氧化碳。因此可以通过将其流经第二该类反应器(未显示)来进行第二费-托合成反应，从而一氧化碳的总转化量有所增加，并且在某种程度上还能获得更多所需的产品。
压缩机36和44的实际压缩比为约2.5∶1。在较高的压力比下操作压缩机会将气体的温度提升得很高从而所需的轴动力也会变得相当大。如果在约2.0MPa下进行费-托合成，只要，两个压缩机36和44就足以使得重整器20的压力超过约0.4MPa了。在该升高的压力下操作蒸汽/甲烷重整反应器20的缺点在于，甲烷转化率通常会降低约5-10％，但是这也超过了资本和操作成本降低所能做出的补偿。作为对比，若只用一台压缩机，则有必要在约0.8MPa的压力下进行重整反应，这样甲烷转化率会降低15％。并且在另一方面，如果重整反应在0.1MPa(1个大气压)下进行，则有必要进行4个连续压缩步骤，这就需要接近两倍的能量。
在此升高的压力下进行重整反应的进一步优点在于所需的管道尺寸。气体流速通常不大于18ms-1，这样对于特定的质量流速来说，随着气体压力和密度的减少，所需管径会有显著增加。例如，对于产量为1000桶/日的装置来说，压力为0.5MPa下的氢气/一氧化碳混合物(合成气)的体积流速约为48000m3h-1，其需要的管径为约1.0m。作为对比，如果在常压下操作，则气体体积会增加5倍，并且管径必须为2.2m。
在一些情况下天然气中也含有二氧化碳。在上述工艺的一个改进方式中，一部分尾气22(富氢气体)回流到混合器14的天然气/蒸汽混合物中，因此其可以流经预重整器18。尾气22中含有短链烃类，但是可以通过预重整器18转化为甲烷。因此进入重整器20的气体混合物含有甲烷、蒸汽、氢气和二氧化碳。氢气可以和二氧化碳进行逆向水煤气转换反应：
CO2+H2→CO+H2O
将在重整器20中发生该反应，这样在重整器20的压力和温度条件下，二氧化碳的浓度会降低为平衡浓度。(即使天然气5不含有二氧化碳，且蒸汽/甲烷比例为1.5，也会在重整器20中产生少量的约5％的二氧化碳)。只要存在足够的自由氢气，则原料气体中任何额外的二氧化碳都会被转化为一氧化碳。对混合器14中蒸汽/甲烷的初始比例进行选择时，必须要考虑尾气22中的水蒸气以及逆向水煤气转换反应所产生的水。

Claims (8)

1.一种处理天然气以生成长链烃类的工艺，该工艺包括天然气与蒸汽进行重整反应从而产生了一氧化碳和氢气的混合物，冷却该混合物，用一系列连续压缩步骤对该混合物进行压缩，在这些连续压缩步骤之间设有冷却，接着该被压缩的混合物进行费-托合成反应生成长链烃类，其中费-托合成反应的产物被冷凝分离为液相和尾气，其特征在于
-在0.4-0.6MPa的压力下进行蒸汽重整反应；
-用于压缩所述混合物的连续压缩步骤的数目为2；
-所述两个连续压缩步骤使压力达到1.8-2.2MPa，从而使每个压缩步骤的压缩比为约2.5∶1；和
-使用至少一部分的所述尾气发电，产生的电能为所述两个压缩步骤提供了能量。
2.一种如权利要求1所述的工艺，其中费-托合成反应的操作压力为1.9-2.1MPa。
3.一种如权利要求1或2所述的工艺，其中用于蒸汽重整反应的水至少一部分来自真空蒸馏单元。
4.一种如权利要求3所述的工艺，其中尾气所产生的电能为该真空蒸馏单元提供了能量。
5.一种如权利要求1或2所述的工艺，其中蒸汽/甲烷重整反应和费-托合成反应分别在紧凑催化反应器中进行，这些催化反应器各自包含多个金属板，形成叠层，并确定了第一和第二流体物流通道，叠层中的通道交替设置从而确保具有良好的热接触。
6.一种如权利要求1或2所述的工艺，其中天然气含有甲烷和二氧化碳，并且该工艺还包括使用至少部分来自费-托合成的尾气来进行费-托合成上游的逆向水煤气转换反应。
7.一种装置，该装置适用于进行如上述任意一项权利要求所述的工艺，该装置包括进行蒸汽/甲烷重整的第一反应器和用于费-托合成的第二反应器，在第一和第二反应器中设有两个连续压缩器，每个压缩器提供了约2.5∶1的压缩比，以及在两个压缩器之间设置了用于冷却压缩气体的装置，并且其中上述的每个反应器中含有多个金属板的叠层，其确定了第一和第二流动通道，通道交替设置从而确保其间的流体具有良好的热接触，通过冷凝为液相和尾气而将费-托合成反应的产物分离的装置，以及被供应了至少一部分所述尾气以产生电能从而为所述压缩提供能量的发电机。
8.一种如权利要求7所述的装置，其中每个反应发生的流动通道均含有位于金属基底上的催化剂结构，该催化剂结构是可移出的。
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