CN107001034A - 用于消除氨装置中的挥发性有机化合物和有害空气污染物的方法 - Google Patents
用于消除氨装置中的挥发性有机化合物和有害空气污染物的方法 Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 23
- 231100001244 hazardous air pollutant Toxicity 0.000 title claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 239000006227 byproduct Substances 0.000 claims abstract 2
- 239000000446 fuel Substances 0.000 claims description 15
- 238000002485 combustion reaction Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明涉及一种用于消除在氨装置的变换工段(SS)中以副产物形式形成的挥发性有机化合物(VOC)和有害空气污染物(HAP)的方法，其中来自排气管线(其被设置在变换工段和CO2去除工段的下游)的二氧化碳(CO2)流被再循环到氨装置的一段重整器(TR)。以该方法，包含在二氧化碳排放物中的含氧化合物在一段重整器燃烧器中被分解，并且VOC和HAP的总排放量将显著降低。
Description
本发明涉及一种用于消除氨装置的二氧化碳(CO2)排放物中的挥发性有机化合物(VOC)和有害空气污染物(HAP)的排放的方法。更具体地，本发明涉及合成气制备过程中VOC和HAP的消除。
在氨装置中，在变换工段特别是低温变换(LTS)工段中形成某些副产物(主要是含氧化合物，并且主要是甲醇)。这些化合物(包括甲醇)中的一些是非常易挥发的，并且它们将进入到CO2去除工段的气相中。然而，由于CO2去除工段中的液/气比非常高，因此这些含氧化合物的浓度在CO2去除溶液中将会增加，直到最终达到平衡。引入到CO2去除工段的含氧化合物主要与CO2流一起排出。该CO2或其至少一部分将被排放到大气中并成为污染物。
根据现有技术，通常通过用液体优选水洗涤CO2流来去除含氧化合物。然而，一些副产物太易挥发而不能被吸收在洗涤液中。相反，它们将被排到大气中，造成不可接受的污染。
US 2010/0310949公开了一种制备适用于生产甲醇和氨的含氢产品气体的方法，由此捕获CO2并减少其向大气中的排放。该方法基于在具有炉的重整器的管中的蒸汽/烃混合物的重整，由此形成包含H2、CO、甲烷(CH4)和蒸汽的重整产物流。该步骤之后是任选的二次重整步骤，然后是变换步骤(例如，LTS)，以形成包含CO2、CO、H2和CH4的第二工艺流。洗涤该第二工艺流以去除二氧化碳，然后所得的二氧化碳贫化流的一部分可用作重整器的炉中的燃料，以防止惰性化合物，氮气和氩气的累积。
US 2010/0310949的方法与本发明的方法无关。因此，已知的方法使用CO2贫化流作为燃料，同时预期利用CO2富集流中的CO2。目的是通过以使CO2再循环的方式从燃料气体中去除CO2来减少混入大气中的CO2。本发明是基于从CO2富集流中去除CO2并将其供应至重整器以在CO2排放到大气之前从其中去除任何VOC。该步骤是合理的，因为在任何情况下CO2都要排放到大气中。
US 2014/0186258公开了通过生物甲烷的蒸汽重整，然后通过变换步骤来制备氢气的方法。通过包括以下步骤的至少一个步骤的变压吸附(PSA)纯化经变换的合成气：纯化包含(除其它化合物)VOC的沼气的第一部分，供应所述沼气以用于生产生物甲烷，将其重整，将所得合成气变换并通过PSA纯化。来自PSA的废气用作重整炉的次要燃料，粗或部分纯化的沼气被用作炉的主要燃料。在US 2014/0186258中指出，将沼气纯化为生物甲烷的方法包括消除CO2，同时消除存在于沼气中的有害物质包括VOC。在该方法中，通过使用它作为用于重整的燃料，从燃料中消除有害的VOC。
WO 2013/049368公开了一种方法，借此将从重整的蒸汽和变换的沼气获得的干燥合成气通过PSA分离成它的各个组分以获得氢气富集流和PSA废气流。将PSA废气再循环以向蒸汽重整炉的燃烧器供应燃料。通过使用例如在调制温度(TSA)下的吸附来消除VOC使沼气预纯化。
US 2006/0260193和US 2011/0232277都描述了用于从烃类气体源生产重整产物燃料的方法和装置。将具有低浓度的烃类的气体(其容易蒸发到空气中并且可包含直链、支链、芳香族或含氧烃类)浓缩成气体或液体VOC燃料。然后，将浓缩的VOC燃料转化为氢和碳氧化物的重整产物，其更容易被诸如内燃机或燃料电池的能量转换装置(其将化学能转化为动能或电能)消耗。
本发明涉及一种用于消除在氨装置的变换工段中形成为副产物的挥发性有机化合物(VOC)和有害空气污染物(HAP)的方法，其中来自排气管线(其被设置在变换工段和CO2去除工段的下游)的二氧化碳(CO2)流被再循环到氨装置的一段重整器。
因此，本发明涉及一种用于消除氨装置中二氧化碳(CO2)排放物中的挥发性有机化合物和有害空气污染物的排放的方法。在氨装置中进行的方法包括将燃料供应到管状重整工段，使流出物从管状重整工段通过二段重整器，然后通过变换工段，并使流出物从变换工段通过CO2去除单元，在那里将CO2与合成气分离。该CO2或其至少一部分被排放到大气中。
氨装置的合成气生成部分大致由脱硫工段，例如加氢脱硫(HDS)工段(为了避免下游蒸汽重整器中的催化剂中毒是必需的)、重整工段、变换工段、二氧化碳去除单元、甲烷转化器和氨合成单元组成。重整段可例如基于在预重整器之前的管状重整器。预重整器用于诸如天然气的烃类进料的低温蒸汽重整。其提供高级烃类的完全转化和硫的去除，并且它还保护下游催化剂。
将预重整器放置在管状重整单元的上游。为了获得所需的蒸汽/碳比率，在进入预重整器之前将进料与工艺蒸汽混合。在预重整器中，所有高级烃类被转化为碳氧化物、氢气和甲烷的混合物。
在氨装置中，一氧化碳转化单元位于二段重整器的下游。
变换工段的目的是使氢输出最大化并降低合成气中的一氧化碳水平。
在氨装置中，变换工段通常由高温变换(HTS)反应器，随后是低温变换(LTS)反应器组成。变换工段可任选地由中等温度变换(MTS)反应器，随后是低温变换(LTS)反应器组成。为了确保进料到氨合成回路中的氨装置中的合成气不含碳氧化物，使其通过甲烷转化器，这将使来自变换工段的任何痕量的二氧化碳和未转化的一氧化碳转化为甲烷。
由于未转化的一氧化碳将消耗氢气并在甲烷转化器中形成甲烷(CH4)，从而减少进料并增加合成回路中的惰性气体水平，因此变换单元的性能强烈影响氨装置的整体能量效率。
在下文中，将参照附图详细说明本发明，附图示出了与本发明有关的氨装置的部件。来自预重整器的进料流f被引导通过管状重整器TR，燃料和任选的燃烧空气CA也被供应到管状重整器TR。将来自管状重整器的烟气通过废热回收工段(WHS)送至烟囱。
来自管状重整器的流出物被送入二段重整器SR和变换工段SS以冷却和分离。然后，将二氧化碳从流中分离，然后该流由待送入甲烷转化器(未示出)的合成气组成。在排出一些分离的CO2之后，剩余部分被送入例如尿素生产。
根据图1所示的现有技术，通过在洗涤系统WS中使用液体优选水将通常包含约300ppm的甲醇、5ppm的二甲醚、50ppm的甲酸甲酯和15ppm的乙醛的CO2排放物洗涤。然而，如已经提及的，CO2排放物中的污染化合物通常太易挥发而不能被充分吸收在洗涤液中。更具体地，在洗涤过程之后排放到大气中的气体仍包含约15ppm的甲醇、5ppm的二甲醚、40ppm的甲酸甲酯和15ppm的乙醛。
与之相比，在根据本发明的用于消除氨装置中二氧化碳(CO2)排放物中的挥发性有机化合物(VOC))的排放的方法中，CO2排放气体被送入管状(一段)重整器(图2)，特别是一段重整器的燃烧室。优选地，CO2排放物被送入一段重整器的燃料系统(图3)，且最优选地送入燃烧空气系统(图4)。
通过将来自排放管线的二氧化碳流再循环到氨装置的一段重整器，二氧化碳排放物中所含的含氧化合物在一段重整器燃烧器中被分解，并且与现有技术的洗涤器溶液相比，VOC和HAP的总排放量显著降低。此外，消除了对于洗涤器溶液和废液流的处理而言所必需的昂贵设备的需要。
Claims (4)
1.一种用于消除在氨装置的变换工段中以副产物形式形成的挥发性有机化合物(VOC)和有害空气污染物(HAP)的方法，其中来自排气管线的二氧化碳(CO2)流被再循环到所述氨装置的一段重整器，所述排气管线被设置在变换工段和CO2去除工段的下游。
2.如权利要求1所述的方法，其中所述CO2流被再循环到所述一段重整器的燃料系统。
3.如权利要求1或2所述的方法，其中所述CO2流被再循环到所述一段重整器的燃烧空气系统。
4.如权利要求1或2所述的方法，其中所述CO2流被再循环到所述一段重整器的燃烧室。
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| IN3495/DEL/2014 | 2014-12-01 | ||
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| DKPA201500076 | 2015-02-11 | ||
| PCT/EP2015/077598 WO2016087275A1 (en) | 2014-12-01 | 2015-11-25 | A process for the elimination of volatile organic compounds and hazardous air pollutants in ammonia plants |
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| EP (1) | EP3227229A1 (zh) |
| KR (1) | KR20170088888A (zh) |
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| EA201990087A1 (ru) * | 2016-06-21 | 2019-06-28 | Хальдор Топсёэ А/С | Способ снижения выбросов метанола из установки по производству аммиака |
| KR20190065890A (ko) | 2017-12-04 | 2019-06-12 | 동아대학교 산학협력단 | 독립 제어 공조 시스템을 이용한 공장 내부 오염 관리를 위한 장치 및 방법 |
| DE102018210910A1 (de) | 2018-07-03 | 2020-01-09 | Thyssenkrupp Ag | Verfahren zur Vermeidung von VOC und HAP Emissionen aus Synthesegas verarbeitenden Anlagen |
| DE102018210921A1 (de) | 2018-07-03 | 2019-08-14 | Thyssenkrupp Ag | Vermeidung von VOC und HAP Emissionen aus dem Entgaser von Synthesegas verarbeitenden Anlagen |
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| CA2968730A1 (en) | 2016-06-09 |
| EA201791176A1 (ru) | 2017-12-29 |
| WO2016087275A1 (en) | 2016-06-09 |
| EP3227229A1 (en) | 2017-10-11 |
| KR20170088888A (ko) | 2017-08-02 |
| MX2017006980A (es) | 2017-08-14 |
| US20170320728A1 (en) | 2017-11-09 |
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