CN110831892A - 生产氨合成气的方法和催化剂 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 29
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 20
- 239000006227 byproduct Substances 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 238000000629 steam reforming Methods 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- -1 zinc aluminate Chemical class 0.000 claims abstract description 5
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 4
- 239000011029 spinel Substances 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000011143 downstream manufacturing Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000009466 transformation Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001991 steam methane reforming Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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Abstract
在由含烃原料生产氨合成气的方法中，该方法包括使原料进行蒸汽重整和处理所获得的合成气，合成气的变换包括两个变换步骤，两个步骤均包括稳定的催化剂，从而避免了有害副产物的形成或使其至少减少到可接受的低水平。这两个变换步骤可以均是HTS，或者可以一个是HTS和一个是LTS，或者可以一个是HTS和一个是MTS。在HTS和LTS步骤中使用的催化剂是基于氧化锌和锌铝尖晶石，而在MTS和LTS步骤中使用的催化剂可以是基于铜的催化剂。
Description
技术领域
本发明涉及生产氨合成气的方法和用于该方法的催化剂。
背景技术
典型的制氨厂首先通过蒸汽重整将脱硫的烃气体(例如天然气(即甲烷)或LPG(液化石油气，例如丙烷和丁烷)或石脑油)转化为气态氢气。然后，将氢气与氮气混合以通过Haber-Bosch工艺来生产氨
3H2+N2→2NH3
因此，氨(NH3)的合成需要合成气(syngas)以合适摩尔比(约为3:1)包含氢气(H2)和氮气(N2)。
诸如蒸汽甲烷重整(SMR)的常规重整涉及初级重整器和次级重整器。例如EP 2065 337 A1和EP 2 886 513 A2中公开了通过SMR生产氨合成气的方法。
在本领域中众所周知，氨合成气的生产主要通过组合的重整过程进行，在该过程中，脱硫的烃与蒸汽以适当的比例混合，然后将所得混合物送入初级重整器中，其中将进料中的大多数烃通过在中等压力(通常为15至40巴)和高温(780至820℃)下暴露于合适的催化剂而蒸汽重整(转化)为CO、CO2和H2的混合物。
将离开初级重整器的气体产物送入次级重整器，该次级重整器通常在催化床和该床上覆的反应空间中包含合适的催化剂，在其中对来自初级重整器的气体产物进行处理，以提供适合于氨合成的气体组成，即氢气/氮气比接近3:1。
离开次级重整器的气体需要纯化以除去碳氧化物和残留的甲烷。根据现有技术，所述纯化包括一氧化碳的变换(CO转化为CO2)，其通常在基于铁的催化剂上在高温变换(HTS)转化器中进行；然后在低温变换(LTS)转化器中在基于铜的催化剂上进行。HTS转化器在320-500℃左右运行，而LTS转化器在190-250℃左右运行。变换后，通过除去二氧化碳和任选地通过甲烷化来处理合成气。
这些变换转化器中使用的典型催化剂是分别基于铁和铜，并且生成痕量的副产物，但是副产物的该含量足够高，这既会造成潜在的环境问题，又会导致下游CO2去除装置中溶液的降解。随着蒸汽/碳比的降低，该问题加剧。在非常低的蒸汽/碳比下，某些催化剂(例如基于铁的催化剂)往往会劣化。其他(如基于铜的)催化剂往往会在更低的蒸汽/碳比下增强。
在本发明的方法中，小于2.6的蒸汽/碳比具有几个优点。例如，通常降低蒸汽/碳比会导致通过重整段以及下游冷却和合成气制备段的质量流量(进料+蒸汽)减少。
但是，低于2.6的蒸汽/碳比也可能会有差异。因此，众所周知，在不形成副产物的情况下不能进行变换反应，其中甲醇以及在某种程度上的甲酸甲酯和高级醇是主要的副产物。在已知技术的氨方法中，当在除去CO2步骤之前从合成气中冷凝出水时，这些副产物将被部分冷凝。未被冷凝的甲醇部分将与CO2一起在CO2吸收器中被吸收，最终进入CO2产品中。CO2产品中的典型甲醇含量为500-1000ppm。因此，进入已知工艺的CO2去除步骤的副产物(包括甲醇)会污染CO2产品，如果要在下游工艺单元中使用CO2或将CO2释放到大气中，则会产生问题，因为副产品算作VOC。已知技术的另一个问题是甲酸甲酯对于在各种CO2去除步骤中使用的CO2吸收液中的重要组分有害，导致容量较小和更换成本较高。
US 8.404.156 B2公开了一种在高温变换反应器中，通过在包含Zn和Al的氧化物以及一种或多种助催化剂的催化剂上转化CO和蒸汽而使合成气富集氢气的方法。在此方法中，合成气通过第一(HTS)转化器中进行反应CO+H2O->CO2+H2(水煤气变换反应)，然后通过第二(LTS)转化器(两个转化器均包含合适的催化剂)，从而被进一步转化。
WO 2010/037598 A1涉及一种生产氨合成气的方法，其中仅使用一个包含基于铜的催化剂的(中温变换(MTS))转化器，并且随后通过物理吸收从合成气中除去CO2。
在WO 2012/004032 A1中，描述了用于生产氨合成气的类似方法，其中使次级重整器中产生的合成气在Cu-Zn催化剂的存在下，在200-350℃的温度下进行MTS，在蒸汽/碳比低于2的情况下进行一次重整
WO 2016/124886 A1、GB 2536996 A和WO 20167132092 A1均描述了从含烃原料生产氨合成气的方法，该方法包括原料的蒸汽重整，然后处理所获得的合成气。用于该方法的催化剂可以是例如用于HTS的氧化锌/氧化铝催化剂以及用于LTS和MTS的包含铜、氧化锌和氧化铝的催化剂。
在WO 2014/180763 A1中描述了用于生产氨合成气的另一种方法。该方法包括以下步骤：对进料进行蒸汽重整，以获得包含H2、CO和CO2的合成气，通过CO变换和随后除去CO2来处理合成气，其中合成气的变换包括具有基于铁的催化剂和温度高于300℃的HTS，并且前端的总蒸汽/碳比降至2.6。
现已证明，通过用基于锌和铝的催化剂代替HTS和LTS转化器催化剂，可以克服上述环境问题和溶液的降解。
通过使用这样的催化剂，尽管仍然可能存在痕量甲醇，但实际上将消除副产物的形成。但是，这些痕量物很容易去除。考虑到催化剂也是稳定的，使用这种催化剂选择蒸汽/碳比实际上不受工艺要求的任何限制。
发明内容
在本发明的方法中，氨厂中的初级重整器和次级重整器都可以是自热重整器(ATR)，其是耐火衬里的压力容器。当氨方法基于ATR时，可以使用低或非常低的蒸汽/碳比。因此，当使用基于铁和铜的典型HTS和LTS催化剂时，副产物的形成以及还有催化剂的稳定性都成为问题。
即使将基于锌和铝的催化剂作为HTS催化剂与基于铜的催化剂作为LTS催化剂一起使用也不足以解决该问题，因为在低温变换期间会形成副产物。消除低温变换可能是一种选择，但这通常是没有意义的，例如由于一氧化碳的不良转化。
因此，解决方案是使用催化剂，其是：
-稳定的，并且
-不催化有害副产物的形成，或至少
-将产生的副产物量减少到较低水平。
最关键的副产品是：
甲醇，其含量至少应降至2000ppm以下，
乙酸，其含量至少应降至1000ppm的水平，以及
甲酸甲酯，其含量至少应降至50ppm以下。
更具体地，本发明涉及一种由含烃原料生产氨合成气的方法，其包括以下步骤：
-使原料进行蒸汽重整，从而获得包含氢气(H2)、一氧化碳(CO)和二氧化碳(CO2)的合成气，和
-处理所获得的合成气，包括CO的变换和随后CO2的去除，
其中
合成气的变换包括两个变换步骤，并且
在两个变换步骤中均使用基于氧化锌和锌铝尖晶石的稳定催化剂，
从而避免了有害副产物的形成或使其至少减少到可接受的低水平。
在本发明的方法中，可以在下游方法中优选通过使用水洗来除去任何有害的副产物，其中根据需要，水为环境温度或冷冻的。
这两个变换步骤都可以是高温变换(HTS)步骤。另一可能性是高温变换(HTS)步骤和低温变换(LTS)步骤。此外，可以是高温变换(HTS)步骤和中温变换(MTS)步骤。
根据本发明的方法的一个实施方案是在两个变换反应器中使用申请人的新型HTS催化剂，次级反应器通常但不总是在比初级反应器更低的温度下操作。实际上，新型HTS催化剂可用于HTS步骤和LTS步骤二者。每个反应器可包含一个或多个具有或不具有床间热交换的催化剂床。两个反应器甚至可以组合成设置有合适的床间冷却的单个反应器。对于中温变换(MTS)，所使用的催化剂优选为基于铜的其中载体为氧化锌的催化剂。该催化剂的特征在于低的压降。
在另一个实施方案中，使用具有等温操作的催化剂床的反应器。在该实施方案中，可能仅需要一个床。
申请人的上述新型HTS催化剂具有在任何蒸汽/碳比下运行的独特能力，从而有可能在氨生产中获得最佳的工厂效率。所述催化剂制剂基于锌和氧化铝，更具体地基于氧化锌和锌铝尖晶石，其已知用于催化水煤气变换(WGS)反应。现在令人惊讶地证明，该HTS催化剂也可用于MTS和LTS反应器中。由于该制剂不含铁，因此可防止形成不想要的碳化铁，这些碳化铁降低常规基于铁的HTS催化剂的催化剂强度。
该HTS催化剂制剂的另一个主要优点是完全不含铬，最重要的是不含形成于所有基于铁的HTS催化剂中的有害的六价铬。这消除了对工厂人员安全以及对环境的重大风险。
Claims (9)
1.一种用于由含烃原料生产氨合成气的方法，其包括以下步骤：
-使原料进行蒸汽重整，从而获得包含氢气(H2)、一氧化碳(CO)和二氧化碳(CO2)的合成气，和
-处理所获得的合成气，包括CO的变换和随后的CO2的去除，
其中
合成气的变换包括两个变换步骤，并且
在两个变换步骤中均使用基于氧化锌和锌铝尖晶石的稳定催化剂，
从而避免了有害副产物的形成或使其至少减少到可接受的低水平。
2.根据权利要求1所述的方法，其中所述两个变换步骤均是高温变换(HTS)步骤。
3.根据权利要求1所述的方法，其中所述两个变换步骤是高温变换(HTS)步骤和低温变换(LTS)步骤。
4.根据权利要求1所述的方法，其中所述两个变换步骤是高温变换(HTS)步骤和中温变换(MTS)步骤。
5.根据权利要求3和4所述的方法，其中在中温变换(MTS)步骤和低温变换(LTS)步骤中使用的催化剂是基于铜。
6.根据权利要求5所述的方法，其中用于基于铜的催化剂的载体是氧化锌。
7.根据权利要求1或2所述的方法，其中将两个变换反应器组合为设置有合适的床间冷却的单个反应器。
8.根据权利要求1或2所述的方法，其中将两个变换反应器组合为单个等温反应器。
9.根据前述权利要求中任一项所述的方法，其中在下游过程中优选通过水洗去除任何有害的副产物，其中根据需要，水为环境温度或冷冻的。
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| PCT/EP2018/067389 WO2019011659A1 (en) | 2017-07-13 | 2018-06-28 | PROCESS AND CATALYSTS FOR THE PRODUCTION OF SYNTHETIC AMMONIA GAS |
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| Publication number | Publication date |
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| EP3652107A1 (en) | 2020-05-20 |
| CA3069493A1 (en) | 2019-01-17 |
| WO2019011659A1 (en) | 2019-01-17 |
| SA520410994B1 (ar) | 2023-02-20 |
| KR20200028905A (ko) | 2020-03-17 |
| BR112020000497A2 (pt) | 2020-07-14 |
| UA127081C2 (uk) | 2023-04-05 |
| AU2018299756A1 (en) | 2020-01-23 |
| US11286159B2 (en) | 2022-03-29 |
| CL2020000018A1 (es) | 2020-07-17 |
| AU2018299756B2 (en) | 2024-04-18 |
| KR20240005207A (ko) | 2024-01-11 |
| EA202090244A1 (ru) | 2020-04-28 |
| PE20200659A1 (es) | 2020-06-11 |
| US20200180952A1 (en) | 2020-06-11 |
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