CN110958988A - 用于改善氨合成气装置的效率的方法 - Google Patents
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 37
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 58
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 238000011144 upstream manufacturing Methods 0.000 claims 1
- 238000000629 steam reforming Methods 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000002407 reforming Methods 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
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Abstract
本发明涉及通过设置使用来自水电解的氧气并结合次级蒸汽重整以生产氨合成气来改善现有氨合成气装置或新型氨合成气装置的效率的方法。
Description
本申请涉及氨合成气的制备。更具体地，本发明是通过将水的电解与烃原料的常规初级和次级蒸汽重整相结合以制备含氢和氮的氨合成气来改善常规氨合成气装置的效率的方法。
氨合成气通常通过使烃进料(通常为天然气和/或高级烃)在燃烧的(fired)管式初级蒸汽重整器中通过与蒸汽重整催化剂接触而进行吸热蒸汽重整反应来制备。然后将经初级重整的气体进料到次级绝热重整器中，其中来自初级蒸汽重整的气体中的在初级蒸汽重整中形成的一部分氢和残留量的烃被空气和蒸汽部分氧化，并且随后在次级重整催化剂的存在下被重整。从次级重整器中取出粗合成气，其含有在原料的上述蒸汽重整反应的反应过程中形成的氢气、一氧化碳和二氧化碳，以及在次级重整步骤中通过添加空气而被引入的氮气。
初级和次级重整过程的缺点是，用于在燃烧的初级蒸汽重整器中加热吸热的初级蒸汽重整的烃原料和燃料的消耗较高，因此来自用于加热重整器的燃烧器的烟道气中的CO2排放较大。可以从该过程中捕获二氧化碳产品，并将其用于下游过程，例如尿素生产或提高石油采收率。
但是，工业中仍经常采用初级和次级蒸汽重整，特别是在现有的用于生产氨合成气的重整装置中。
次级蒸汽重整包括使用含氧气氛将经初级重整的进料气体部分氧化为CO、CO2、H2、H2O和剩余的烃，然后将烃进行蒸汽重整以形成粗合成气。
近来，至少在专利文献中，已经设想了将用于生产氢气的电解水与用于生产氮气的空气分离相结合，来制备氨合成气。如此产生的氢气和氮气以化学计量比结合以形成用于氨生产的合成气。然而，电解和空气分离相结合的缺点在于，氧气在电解和空气分离中均作为副产物产生，其在氨合成中没有用途，并且可被认为是能量损失。
通常，如上所述，现有的工业氨合成气装置(即所谓的氨装置的前端)包括燃烧的初级蒸汽重整器、在气体入口侧带有燃烧器且在气体出口侧带有蒸汽重整催化剂床的次级蒸汽重整器。燃烧器通常使用空气操作。
从次级蒸汽重整器中取出的粗氨合成气随后在水煤气变换单元中进行处理，以通过已知的水煤气变换反应进一步生产氢气并将一氧化碳转化为二氧化碳。
然后，在二氧化碳去除过程中，去除变换后的氨合成气中包含的二氧化碳。
在将一氧化碳和/或二氧化碳转化为甲烷的化学反应中，通过甲烷化作用去除来自二氧化碳去除过程的氨合成气中剩余的二氧化碳和/或一氧化碳。
将如此制备的氨合成气引入到氨补充气体压缩机中，并送入氨生产单元中。
本发明是基于设置燃烧的初级蒸汽重整过程和次级重整过程以及新的电解水的执行步骤的组合来生产氨合成气，其在次级重整燃烧器的操作中使用空气或富氧空气。
因此，本发明提供了改善氨合成气装置的效率的方法，该氨合成气装置包括燃烧的初级蒸汽重整器和用含氧气氛运行的次级蒸汽重整器、水煤气变换单元、二氧化碳去除单元、甲烷化步骤和氨合成气压缩机，所述方法包括以下步骤：
(a)设置电解单元，并通过电解水制备单独的含氢气流和单独的含氧气流；
(b)设置用于将单独的含氢气流从电解单元输送到合成气压缩机和/或甲烷化步骤的气体管道；和
(c)设置用于将至少一部分单独的氧气流从电解单元输送到次级重整器中的燃烧器的气体管道。
本发明的方法可用于改善通过初级和次级重整操作的现有氨合成气装置或具有初级和次级重整的新装置的效率。通过本发明的方法对现有的或新的氨合成气装置进行的改善旨在增加装置的产能和/或以固定的容量节省燃烧的初级蒸汽重整器中的燃料，因为来自水电解的氧气提供了用于次级重整器中的重整反应的热量。因此，当次级重整器中含氧气氛中的氧含量随着在水电解中制备的氧气而增加时，初级重整器的负荷降低。结果是，来自初级重整器的气体中的烃逸出(slip)增加，且气体出口温度降低，这又导致用于燃烧初级重整器的燃料消耗降低。由于较低的燃料消耗，降低了重整器管壁的温度，从而显著延长了管的使用寿命。
另一个优点是，离开次级重整装置的总烃逸出可以与不带电解的常规装置相同，或者可以减少以获得改善的合成气组成，这是因为减少了惰性气体含量，导致来自氨回路的吹扫减少，因此更有效地利用了原料。
根据本发明的方法提供了进一步的优点，即来自初级烟道气堆的CO2排放更少。
还有一个优点在于，在二氧化碳去除单元的入口处增加了CO2分压，这通过减少所需的能量消耗而改善了二氧化碳去除效率。
与使用水电解产生氢气和通过空气分离以产生氮气的现有技术方法相比，来自水电解的氧气产物有利地用于次级重整器中的部分氧化，从而导致新装置中初级重整器的尺寸减小或现有装置的负荷减少，而现有装置是一个昂贵且能源密集的单元和过程。
本发明的又一个优点是，用于操作电解单元的能量可以是由风车、太阳能电池、水力能源或其他可再生能源产生的可再生能源。
因此，在本发明的优选实施方案中，电解单元由可再生能源提供动力。
优选地，根据工艺空气压缩机的排出压力，在升高的压力下进行水的电解，其将制备的氧气流在升高的压力下递送至次级重整器的燃烧器，并将氢气流递送至合成气压缩机和/或甲烷化步骤。
因此，在本发明的优选实施方案中，电解单元被加压。
将水电解与次级重整技术相结合以生产氨合成气的协同作用在于，可总体上节省用于重整过程的烃原料和燃料。
在下面的表1中，对于2200MTPD氨装置给出了制备氨合成气的关键数据，其用于比较常规合成气技术和结合了水电解的常规合成气技术。
Claims (5)
1.一种改善氨合成气装置的效率的方法，该氨合成气装置包括燃烧的初级蒸汽重整器和用含氧气氛运行的次级蒸汽重整器、水煤气变换单元、二氧化碳去除单元、甲烷化步骤和氨合成气压缩机，所述方法包括以下步骤：
(a)设置电解单元，并通过电解水制备单独的含氢气流和单独的含氧气流；
(b)设置用于将单独的含氢气流从电解单元输送到合成气压缩机和/或甲烷化步骤的气体管道；和
(c)设置用于将至少一部分单独的氧气流从电解单元输送到次级重整器中的燃烧器的气体管道。
2.根据权利要求1所述的方法，其中所述电解单元由可再生能源提供动力。
3.根据权利要求1或2所述的方法，其中所述含氧气氛是富含来自所述单独的氧气流的氧气的空气。
4.根据权利要求1至3中任一项所述的方法，其中所述电解单元被加压。
5.改善的氨合成气装置，其包括燃烧的初级蒸汽重整器和用含氧气氛运行的次级蒸汽重整器、水煤气变换单元、二氧化碳去除单元、甲烷化反应器和氨合成气压缩机，其中氨合成气装置还包括：电解单元，其通过水的电解提供单独的含氢气流和单独的含氧气流；用于将单独的含氢气流从电解单元输送到合成气压缩机和/或甲烷化反应器的气体管道；和用于将至少一部分单独的氧气流从电解装置输送到次级重整器的燃烧器上游或其中的气体管道。
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| PCT/EP2018/068806 WO2019020377A1 (en) | 2017-07-25 | 2018-07-11 | METHOD FOR ENHANCING THE EFFICIENCY OF AN AMMONIA SYNTHESIS GAS INSTALLATION |
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| WO2022157223A1 (en) * | 2021-01-21 | 2022-07-28 | Casale Sa | Method for preparing a synthesis gas |
| JP2024512119A (ja) * | 2021-03-30 | 2024-03-18 | カサーレ ソシエテ アノニム | グリーン水素を用いるアンモニア合成のためのプロセス |
| BE1030241B1 (de) * | 2022-02-03 | 2023-09-04 | Thyssenkrupp Ind Solutions Ag | Anlage zur Erzeugung von Ammoniak |
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| CA3069871A1 (en) | 2019-01-31 |
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| BR112020001492A2 (pt) | 2020-07-21 |
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| US20230257275A1 (en) | 2023-08-17 |
| AU2018305811A1 (en) | 2020-01-23 |
| NZ760482A (en) | 2023-10-27 |
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| PE20200687A1 (es) | 2020-06-11 |
| CL2020000152A1 (es) | 2020-07-31 |
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| WO2019020377A1 (en) | 2019-01-31 |
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