CN102171135B - 生产氨合成气的方法 - Google Patents

生产氨合成气的方法 Download PDF

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CN102171135B
CN102171135B CN200980139250.0A CN200980139250A CN102171135B CN 102171135 B CN102171135 B CN 102171135B CN 200980139250 A CN200980139250 A CN 200980139250A CN 102171135 B CN102171135 B CN 102171135B
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埃马诺·菲利皮
马科·巴达诺
杰弗里·弗雷德里克·斯金纳
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Abstract

一种生产氨合成气的方法，其中天然气原料(10)于至少35巴压力下在一段蒸汽转化炉(12)和二段转化炉(14)中转化；二段转化炉输出的产物合成气(16)被冷却并进行催化中温变换，将CO转变为CO2和H2；在所述中温变换的下游，通过物理吸收将所述CO2从所述合成气中去除。

Description

生产氨合成气的方法
发明领域
本发明涉及烃的转化，以制备生产氨所需的合成气体(合成气)。
现有技术
制备氨需要含氢(H2)和氮(N2)的合适比例为3∶1的合成气。
本领域技术人员熟知，通过对烃(HC)原料进行转化生产所述合成气。所述HC原料通常为氢和碳的原料来源，例如甲烷、天然气、石脑油(naphtha)、GPL(液化石油气)或炼厂气及其混合物。通常，该原料为天然气或甲烷。
在一种众所周知的方法中，将脱硫的烃以合适的比例与蒸汽混合，所得混合物被允许进入一段转化炉，其中，所述混合物在适当压力范围15-35巴、高温范围780-820℃下通过合适的催化剂上方，使进料中大多数烃被蒸汽转化(转变)为一氧化碳、二氧化碳和氢的混合物。
所述转化为吸热反应，所述催化剂装在众多催化管中，所述催化管由燃料气体与空气燃烧提供的反应热量进行外部加热。所述催化管外部的压力通常接近大气压。
由一段转化炉出来的产物气供给二段转化炉，通常所述二段转化炉内的催化床中含有合适的催化剂且催化床上方有反应空间，所述二段转化炉还接收一股控制流量的空气以供给下游氨合成所需的氮。
氧气在所述催化床上方的空间与来自一段转化炉的产物气中的易燃组分反应，所得的组合产物气以升高的温度进入催化床。
在向下通过所述催化剂期间，剩余的甲烷与蒸汽恒温反应，导致二段转化炉产物气出口的典型温度约1000℃、超过99％的烃进料被转变为碳的氧化物和氢。
由二段转化炉排出的转化气接着由一系列的下游设备常规处理，以去除碳的氧化物并得到适于氨合成的气体组合物(即H2/N2摩尔比接近3∶1)。这些设备包括至少：
-“高温”CO变换炉和其后的“低温”变换炉，其中，大多数转化气中的一氧化碳(CO)与未反应的蒸汽一起被催化转变为二氧化碳和额外量的氢；
-CO2洗涤塔，在该洗涤塔中通过用合适的溶剂如胺或碳酸钾的水溶液洗涤所述气体而去除所述二氧化碳，从而得到包括摩尔比约3∶1的氢和氮以及微量的甲烷、碳的氧化物和氩的气流；
-甲烷化反应器，其中剩余的碳的氧化物被催化转变为甲烷，从而避免含氧化合物造成下游的氨合成催化剂中毒。
接着，在典型地为15-25巴的低压下得到氨合成气，并将其压缩以达到氨合成回路的压力，通常该压力的范围为80-300巴，典型地为约150巴。
由于需要较大的压缩区，输出合成气的低压是该方法的缺陷。同样，由于这种相对低的压力，其它设备如管道工程管也要较大的，因而更加昂贵。另一个缺陷为一段转化炉中的水碳比(SC比)必须维持在高于某个下限，通常为约2.7。这是因为在低SC比下，常规“高温”CO变换炉的催化剂会因费托合成(Fischer-Tropsch synthesis)而产生过度还原和不良副产物。然而，高SC比意味着以更大的流速通过一段转化炉，因而在给定产率下，一段转化炉就会更大和更昂贵，或相反，产率的增加受到转化炉大小的限制。
还有一个缺陷为，将CO转变为CO2和不断去除CO2通常是花费昂贵的工艺步骤。尤其是，前述去除CO2的化学工艺是基于与胺或碳酸钾反应，需要大量的热量，因而成为保持高SC比的另一个理由。低SC比的气流无法提供化学去除CO2所需的热量。
发明概述
本发明要解决的问题是克服上述缺陷。
该问题由一种以含烃为原料生产氨合成气的方法解决，该方法包括如下步骤：在一段转化炉中对含烃原料进行蒸汽转化，得到部分转化(partial reformed)气蒸汽，再在二段转化炉中对所述部分转化气蒸汽进行二段转化，在有过量空气的情况下运行，其特征在于：
-所述一段转化和二段转化于至少35巴压力下运行；
-冷却二段转化输出的合成气被并进行催化中温变换，将CO转变为CO2和H2；和
-在所述中温变换的下游，通过物理吸收将CO2从所述合成气中去除。
根据一个优选的实施方案，所述中温变换在等温条件下实施，优选为220-320℃范围的基本恒定的温度下。在一个更优选的实施方案中，所述中温变换于所述220-320℃范围以基本恒定的温度在铜基催化剂上实施。
在本发明的另一个方面，所述一段转化炉输出的部分转化合成气具有相对低的温度，该温度小于750℃，且优选的温度范围为650-750℃。
本发明允许在所述一段转化炉中保持显著低于现有技术的水碳比(SC)。在一个优选的实施方案中，一段转化炉中的水碳比(SC)小于2.7。
根据本发明的另一个方面，在所述中温变换(MTS)的下游进一步实施低温变换(LTS)。因此，MTS反应器输出的合成气被进一步冷却并送往LTS反应器(其本身为常规反应器)，从而最大程度地将CO转变为CO2和H2。然后，LTS反应器输出的合成气被冷却后送去进行CO2去除。
所述CO2去除优选以甲醇或有机化合物(例如，聚乙二醇的二甲醚)为溶剂实施。CO2去除按照例如已知商业名称为Rectisol，或商业名称为Selexol的方法实施。这两种方法都使用物理溶剂去除合成气流中的二氧化碳。但是，也可使用另外的等同方法。
一段转化炉通常配备有多个加热的催化管，且所述催化管中的运行压力优选为40-100巴，最优选为60-80巴。例如，根据本发明，可使用常规的内径约100mm且壁厚为10-12mm催化管，于60巴压力和750℃输出温度下运行，显示其使用寿命为100,000小时。
二段转化中的过量空气含量范围为15％-100％，优选20％-40％，超过氨合成所需含氮量的空气需要量。使用过量空气可在二段转化的催化床上方空间有效地转变一段转化炉输出气中所含的烃(尤其是甲烷)(一段转化炉压力升高和温度降低，使烃的含量增加)，以产生碳的氧化物和蒸汽，从而在升高的温度下得到产物气。
本发明还有一个目的为，提供适于按照上述方法运行的生产氨合成气的设备，所述设备包括一段转化炉、二段转化炉和至少一个接收来自二段转化炉的合成气的中温变换反应器，及位于该中温变换反应器下游且通过物理吸收运行的合适的CO2去除单元。
本发明又一个目的为，氨厂前段工艺的改造。作为实例，常规氨厂前段工艺的改造的特征在于，提供至少一个中温变换反应器和位于该中温变换反应器下游的CO2去除单元，所述CO2去除单元适于通过物理吸收运行。
本发明的优点为，该MTS反应器可在比常规高温变换反应器更低的SC比下运行，这样，铜基催化剂就不会受制于过度还原和费托合成的缺陷。低SC比意味着对于给定的合成气产物而言，一段转化炉中的流速可以更慢，因而该转化炉本身就会更小、更便宜且能耗少于现有技术。等温反应器为又一个优势，能使MTS催化床保持相对低的温度(220-320℃)可获得最大的效率。
使用物理溶剂而非化学溶剂进行CO2去除与转化炉中的高压力和低SC比可起到协同作用。事实上，所述CO2去除方法比化学法需要的热量少，因而适于低SC比，而效率与合成气中CO2的分压成比例，因而适于本发明的高压转化。
在高压下运行的另一优势为，可使用更小、更便宜的设备将最终合成气压缩到氨厂合成回路进行氨转化所需的压力。此外，该压缩过程所需的能量降低了，因为转化过程输出了高压的最终合成气。因此，根据本发明还可通过使用高压合成气实现降低氨厂的能耗。
通过以非限定性实例给出的下述实施方案的说明并结合附图，本发明的特征和优势将进一步显现。
附图说明
图1为根据本发明的氨合成厂前段工艺框图。
具体实施方式
参见图1，在预加热器26中将脱硫天然气原料10和蒸汽11的混合物预加热，然后在一段蒸汽转化炉12中反应，产生部分转化气蒸汽13，优选压力为60-80巴以及温度为约750℃。
在二段转化炉14中进一步处理所述部分转化气13，由于空气、氧气或富氧空气输入物15而在过量空气下运行。
一段转化炉12，例如，包括多个装有合适催化剂的管(未示出)，其本身为常规管且通过热交换液体在外部加热。二段转化炉14包括，例如，合适催化剂(例如，镍基催化剂)的催化床及其上方的反应空间，在此空间中通过空气流15向二段转化炉14供给氧气，从而与部分转化气13反应。
通常来自二段转化炉14的合成气流16温度约1000℃，然后于热交换器17中冷却至220-320℃(气流18)，再送往中温变换(MTS)反应器19。
MT反应器19为等温催化反应器，其包括铜基催化床和浸没于该催化床中的内部热交换器，并适于将反应温度维持在预定的范围。
可于MTS反应器19下游，可选的用低温度变换(LTS)反应器2将合成气20进一步处理，从而使得CO的转化最大化。
MTS反应器19输出的合成气或，LTS反应器21(如果提供)输出的合成气，在热交换器22中被进一步冷却，然后所述冷却的合成气流23被送往CO2去除单元24。该单元24使用物理溶剂，例如，通过已知的Rectisol法或Selexol法，或另外的等同方法去除二氧化碳。
来自所述CO2去除单元的合成气25在甲烷转化器中被进一步处理，在该甲烷转化器中剩余的碳的氧化物被催化转变为甲烷，并在一个低温区中低温去除过量的氮、甲烷和惰性气体。该低温区输出的为含有要求的摩尔比为3∶1的氢和氮的氨合成气。
应该指出，由于转化炉12的和所有的下游设备的高运行压力，可以高压提供气流25，因此，经过甲烷化作用和低温纯化作用步骤，在合成气压缩中节省了大量的能量。在一些应用中，来自该低温区的合成气可直接输送给氨合成回路。
在图1的实施例中，所有天然气原料10供给一段转化炉12；在本发明另一个实施方案中(未示出)，一部分天然气原料10供给二段转化炉14。
应当指出，图1为简化图，未示出辅助设备如阀门等......，其可根据本发明的需要而提供。当然，本领域技术人员可对本发明的方法做出许多修饰和替换性改变，所有这些改变都包括在本发明所附权利要求书的保护范围之内。

Claims (5)

1.一种由天然气原料(10)生产氨合成气的方法，所述方法包括如下步骤：在一段转化炉(12)中对天然气原料进行蒸汽转化，其中将全部天然气原料(10)供给所述一段转化炉(12)中，得到部分转化气蒸汽(13)，再在二段转化炉(14)中对所述部分转化气蒸汽进行二段转化，在有过量空气的条件下运行，其特征在于：
-所述一段转化和二段转化在至少35巴压力下运行；
-冷却二段转化输出的产物合成气(16)并对其进行催化中温变换，将CO转变为CO2和H2；所述中温变换在220-320℃范围以基本恒定的温度在铜基催化剂上实施；
-在所述中温变换的下游，通过物理吸收将所述CO2从所述合成气中去除；
-其中所述一段转化炉(12)中的水碳比(SC)小于2.7。
2.根据权利要求1所述的方法，其中所述一段转化炉(12)输出的所述部分转化合成气(13)的温度范围为650-750℃。
3.根据权利要求1或2所述的方法，其中在所述中温变换的下游对合成气蒸汽(20)进一步实施低温变换。
4.根据权利要求1或2所述的方法，其中使用甲醇作为溶剂或使用有机溶剂去除CO2。
5.根据权利要求3所述的方法，其中使用甲醇作为溶剂或使用有机溶剂去除CO2。
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