CN106029570A - 制造用于尿素合成的氨气和co2的方法 - Google Patents

制造用于尿素合成的氨气和co2的方法 Download PDF

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CN106029570A
CN106029570A CN201480067678.XA CN201480067678A CN106029570A CN 106029570 A CN106029570 A CN 106029570A CN 201480067678 A CN201480067678 A CN 201480067678A CN 106029570 A CN106029570 A CN 106029570A
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ammonia
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克里斯托夫·迈斯纳
丹尼斯·克罗托夫
奥拉夫·冯·莫施泰因
马蒂亚斯·帕特里克·克吕格尔
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Abstract

本发明涉及一种制造用于尿素合成的氨气和CO2的方法。在按照本发明的方法中，由冶金气(1)产生工艺气(2)，该冶金气含有至少作为混合组分的高炉煤气或者由高炉煤气组成，而该工艺气含有作为主要成分的氮气、氢气和二氧化碳。工艺气(2)分成含有CO2部分的废气(6)和基本上由N2和H2组成的混合气(5)。由该混合气(5)通过氨合成(7)形成适于尿素合成(9)的氨气(8)。从含有CO2的废气(6)中分出适于尿素合成(9)的纯度和量的CO2。

Description

制造用于尿素合成的氨气和CO2的方法
技术领域
本发明涉及一种制造用于尿素合成的氨气和CO2的方法。
背景技术
从技术上而言，尿素是由NH3和CO2经过中间阶段氨基甲酸铵而获得。当通过足够高的反应压力避免了分解时，可以快速且完全地形成氨基甲酸铵。放热形成的氨基甲酸铵在接下来的分解阶段在低压下吸热地转化成尿素，其中多余气体可以再次回到反应器中。形成氨基甲酸铵的反应通过NH3过量而实施，其中，在实际中通常选择NH3/CO2的摩尔比为大约4。
用于尿素合成的原料为NH3和CO2。由于在氨合成中二氧化碳作为副成分产生，因此尿素设备通常连接氨气设备而运行。使用这样的设备，其通过氢气制造、氨气制造、尿素合成这些过程步骤而由天然气、空气和水最终制成尿素。
发明内容
在该背景下，本发明的目的在于，说明一种高效的、产生用于尿素合成的气态反应物的方法。为了实施该方法应使用在工业过程中作为副产物的原料气。在此应这样选择原料气和方法步骤，以便于原料气的气体组分尽可能完全地并且以对于尿素合成而言所必需的比重转换成为氨气和CO2。
本发明的主题和该目的的解决方案为根据权利要求1所述的方法。按照本发明的方法的有利设计在权利要求2至9中描述。
按照本发明，为了制造用于尿素合成的气态反应物而使用冶金气，该冶金气含有至少作为混合成分的高炉煤气或者由高炉煤气组成。高炉煤气是在生铁制造过程中在高炉中产生。在高炉中，由铁矿、添加剂以及焦煤和其他还原剂(比如煤、油或者气)获得生铁。不可避免的CO2、氢气和水蒸气作为还原反应的产物而产生。从高炉过程中抽出的高炉煤气除了以上组成成分之外还具有高含量的氮气。高炉煤气的组成成分通常取决于原料、操作方式并且受到波动。但是高炉煤气通常含有：35至60体积％N2、20至30体积％CO、20至30体积％CO2和2至15体积％H2。
另外还将一种由混合气组成的冶金气用于按照本发明的方法，该混合气由高炉煤气和转炉煤气组成或者由高炉煤气、转炉煤气以及焦炉煤气组成。在转炉炼钢厂中将生铁转换成为原钢的过程中所产生的转炉煤气具有高含量的CO并且另外还含有氮气、氢气和CO2。典型的转炉煤气组成具有：50至70体积％CO、10至20体积％N2、约15体积％CO2和约2体积％H2。焦炉煤气在煤的焦化过程中产生并且具有高的氢气含量以及显著的CH4含量。通常，焦炉煤气具有：55至70体积％H2、20至30体积％CH4、5至10体积％N2和5至10体积％CO。焦炉煤气还额外地具有CO2、NH3和H2S的部分。
根据按照本发明的方法，由冶金气产生工艺气，该工艺气含有作为主要成分的氮气、氢气和二氧化碳并随后分成含有CO2部分的气流和基本上由N2和H2组成的混合气。由混合气通过氨合成形成适于尿素合成的氨气。从含有CO2的气流中分出适于尿素合成的纯度和量的CO2。冶金气的预处理和上述分离步骤可以相互协调，从而可以以对于尿素合成而言所必要的比重来形成氨气和CO2而且可以将冶金气几乎完全地用于制造尿素合成所需的气态的反应物。
冶金气在用于产生工艺气之前预先有针对性地进行气体净化。该气体净化用于分离干扰成分，特别是焦油、硫和硫化物、芳香族的碳氢化合物(BTX)和高沸点的碳氢化合物。
冶金气的CO部分可以通过水煤气反应而转换成CO2和H2，其中，产生了含有作为主要成分的氮气、氢气和二氧化碳的工艺气。
该工艺气随后优选通过变压吸附(PSA)分成基本上由N2和H2组成的混合气和含有CO2部分的废气(也称为PSA废气)。现有技术中已知的变压吸附(PSA-pressure swing adsorption)的使用是指氢气的获取和净化。在按照本发明的方法的范围内，变压吸附与设置在前的气体预处理相结合这样实施，以使得调整到所期望的N2和H2的浓度比。因此，按照本发明的方法的一个方面将气体预处理(特别是水煤气反应)与变压吸附结合，从而由含有至少作为混合组分的高炉煤气或者由高炉煤气组成的冶金气产生适合于氨合成的合成气。另外可以通过变压吸附除去对于氨合成不利的副成分，比如氩气、甲烷或一氧化碳或者减少它们的含量。
在变压吸附过程中产生了富含能量的废气(PSA废气)，其含有工艺气的CO2部分和可能的CO剩余部分。从PSA废气中可以得到用于尿素合成的CO2。根据按照本发明的方法的一个优选实施，从变压吸附的废气(PSA废气)中分离出CO2，并随后分离成含有高浓度二氧化碳的用于尿素合成的气体和具有较低CO2浓度的剩余气体。
本发明的主题还在于用于制造尿素的方法，其中，在氨过量的条件下由氨气和CO2产生氨基甲酸铵，氨基甲酸铵分解成水和尿素。按照本发明，对于尿素的合成所必需的氨气以及对于尿素的合成同样必需的CO2由冶金气产生，该冶金气含有至少作为混合组分的高炉煤气或者由高炉煤气组成。对于按照本发明的方法重要的是，用于尿素合成的气态的反应物完全由冶金气获得。用于尿素合成的气态的反应物可以按照上述方法而获得。
附图说明
随后借助仅示出了一个实施例的附图说明本发明。唯一的附图以极简的方块图的形式示意性示出了制造用于尿素合成的气态反应物的方法。
具体实施方式
通过在附图中示出的方法由冶金气1产生工艺气2，该冶金气含有至少作为混合成分的高炉煤气并且在该实施例中由高炉煤气组成，工艺气含有作为主要成分的氮气(N2),氢气(H2)以及二氧化碳(CO2)。
高炉煤气1例如具有典型的组分：50体积％N2、24体积％CO2、21体积％CO和大约4体积％H2。在气体净化3(其中，分离出了干扰成分，比如焦油、硫和硫化物、芳香族的碳氢化合物(BTX)和高沸点的碳氢化合物)之后，由高炉煤气组成的冶金气1借助气体处理4转变为工艺气2，该工艺气主要由N2、H2和CO2组成。气体处理4特别是包括CO转换，其中冶金气1的CO部分通过水煤气变换(Wasser-Gas-Shift-Reaktion)反应：
CO+H2O→CO2+H2
转换为CO2和H2。在转换之后或水煤气变换反应之后，工艺气具有组分：约37体积％CO2、21体积％H2和42体积％N2。
工艺气2通过变压吸附(PSA)16分成基本上由N2和H2组成的混合气5和含有CO2部分的废气6。由含有N2和H2的混合气通过氨合成7形成适于合成尿素的氨气8。在氨合成7中，氢气和氮气的混合气例如在150到200bar之间的压力下以及350至550℃的反应温度下与氧化铁混合催化剂发生反应。
从变压吸附的废气6中得到用于尿素合成9的CO2。通过在附图中示出的过程示意图，在第一个分离步骤10中CO2部分11从变压吸附的废气6中分离。随后在第二个分离步骤12中进行含有高浓度二氧化碳的气体13与具有较低CO2浓度的剩余气体14的分离。气体13特别是对于尿素合成所必需的纯度的二氧化碳。
CO2和NH3以对于尿素合成9必需的量输入到尿素设备。在尿素设备中在氨过量的条件下产生氨基甲酸铵，氨基甲酸铵在接下来的分解阶段在低压下转换为尿素5。
借助附图说明的方法也可以通过由高炉煤气和转炉煤气组成的混合气或者通过由高炉煤气、转炉煤气以及焦炉煤气组成的混合气作为冶金气1而实施。

Claims (9)

1.一种制造用于尿素合成的氨气和CO2的方法，其中，由冶金气(1)产生工艺气(2)，所述冶金气含有至少作为混合组分的高炉煤气或者由高炉煤气组成，而所述工艺气含有作为主要成分的氮气、氢气和二氧化碳，其中，所述工艺气(2)分成含有CO2部分的废气(6)和基本上由N2和H2组成的混合气(5)，其中，由所述混合气(5)通过氨合成(7)形成适于尿素合成(9)的氨气(8)，而且其中，从含有CO2的所述废气(6)中分出适于所述尿素合成(9)的纯度和量的CO2。
2.根据权利要求1所述的方法，其特征在于，所述冶金气(1)由混合气组成，所述混合气由高炉煤气和转炉煤气组成或者由高炉煤气、转炉煤气以及焦炉煤气组成。
3.根据权利要求1或2所述的方法，其特征在于，所述冶金气(1)在其用于产生工艺气之前进行净化。
4.根据权利要求1至3中任意一项所述的方法，其特征在于，所述冶金气(1)的CO部分通过水煤气反应(4)而转换成CO2和H2。
5.根据权利要求1至4中任意一项所述的方法，其特征在于，所述工艺气(2)通过变压吸附(16)分成基本上由N2和H2组成的混合气(5)和含有CO2部分的所述变压吸附的废气(6)。
6.根据权利要求4或5所述的方法，其特征在于，所述变压吸附(16)这样实施，以使得所述工艺气(2)含有适于所述氨合成(7)的浓度比的N2和H2。
7.根据权利要求5或6所述的方法，其特征在于，从所述变压吸附(16)的所述废气(6)中得到用于所述尿素合成(9)的CO2。
8.根据权利要求7所述的方法，其特征在于，从所述变压吸附的所述废气(6)中分离出CO2部分(11)，并随后分离成含有高浓度二氧化碳的、用于尿素合成(9)的气体(13)和具有较低CO2浓度的剩余气体(14)。
9.一种用于制造尿素的方法，其中，在氨过量的条件下由氨气和CO2产生氨基甲酸铵，所述氨基甲酸铵在接下来的分解阶段在低压下转变为尿素，其特征在于，对于尿素的合成所必需的氨气以及对于尿素的合成同样必需的CO2由冶金气产生，所述冶金气含有至少作为混合组分的高炉煤气或者由高炉煤气组成。
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