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CN111065872A - 从空气分离单元回收不可冷凝气体诸如氖气、氦气、氙气和氪气的系统和方法 - Google Patents

从空气分离单元回收不可冷凝气体诸如氖气、氦气、氙气和氪气的系统和方法 Download PDF

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Publication number
CN111065872A
CN111065872A CN201880055204.1A CN201880055204A CN111065872A CN 111065872 A CN111065872 A CN 111065872A CN 201880055204 A CN201880055204 A CN 201880055204A CN 111065872 A CN111065872 A CN 111065872A
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stream
column
liquid nitrogen
neon
separation unit
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CN111065872B (zh
Inventor
V·S·查克拉瓦西
脱瀚斐
M·R·谢莱特
J·R·德雷
N·J·德根斯坦
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Praxair Technology Inc
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Praxair Technology Inc
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04642Recovering noble gases from air
    • F25J3/04745Krypton and/or Xenon
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    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04006Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04048Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams
    • F25J3/0406Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams of nitrogen
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    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
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    • F25J3/04078Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
    • F25J3/0409Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of oxygen
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    • F25J3/0429Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
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    • F25J2220/02Separating impurities in general from the feed stream
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    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30Compression of the feed stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/50Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being oxygen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/52Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being oxygen enriched compared to air ("crude oxygen")
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • F25J2240/10Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid being air
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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    • F25J2245/00Processes or apparatus involving steps for recycling of process streams
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    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2250/00Details related to the use of reboiler-condensers
    • F25J2250/02Bath type boiler-condenser using thermo-siphon effect, e.g. with natural or forced circulation or pool boiling, i.e. core-in-kettle heat exchanger
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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Abstract

本发明提供了一种用于在空气分离单元中回收稀有气体诸如氖气、氦气、氙气和氪气的系统和方法。所述稀有气体回收系统包括不可冷凝物汽提塔,所述不可冷凝物汽提塔经由辅助冷凝器‑再沸器与氙气‑氪气塔以热传递关系相连。所述不可冷凝物汽提塔产生的稀有气体包含塔顶馏出物,所述塔顶馏出物被引导至所述辅助冷凝器‑再沸器,其中大部分所述氖气被捕集在不可冷凝排放流中,所述不可冷凝排放流还被处理以产生粗氖蒸气流,所述粗氖蒸气流含有大于约50%摩尔份数的氖气,所述总氖气回收率超过95%。所述氙气‑氪气塔还从所述低压塔接收两股液氧流,并且从所述不可冷凝物汽提塔接收含所述稀有气体的塔顶馏出物,并且产生粗氙气和氪气液流和富氧塔顶馏出物。

Description

从空气分离单元回收不可冷凝气体诸如氖气、氦气、氙气和氪 气的系统和方法
技术领域
本发明涉及用于从空气分离设备回收稀有气体诸如氖气、氦气、氙气和氪气的系统和方法,并且更具体地讲,涉及用于回收氖气和其它不可冷凝气体的系统和方法,包括热连接的不可冷凝汽提塔和按与辅助冷凝器-再沸器和第二回流冷凝器可操作地关联来布置的氙气-氪气塔,所有这些都完全集成在空气分离单元内。回收的粗氖蒸气流包含大于约50%摩尔份数的氖气,整体氖气回收率大于约95%。另外,在氙气-氪气塔中产生粗氙气和氪气液流。
背景技术
低温空气分离单元(ASU)通常被设计、构造和操作为满足一个或多个最终用户客户的基本负荷产品构成需求/要求,并且任选地满足本地或商家的液体产品市场需求。产品构成要求通常包括目标量的高压气态氧以及其它初级联产品,诸如气态氮、液氧、液氮和/或液氩。通常部分地基于所选择的设计条件来设计和操作空气分离单元,这些设计条件包括典型的日间环境条件以及可用的公用设施/供电成本和条件。
尽管诸如氖气、氙气、氪气和氦气之类的稀有气体在空气中存在的量非常小,但能够借助于产生包含目标稀有气体的粗物流的稀有气体回收系统将这些稀有气体从低温空气分离单元中提取出来。因为空气中稀有气体的浓度低,所以通常并未将对这些稀有气体联产品的回收设计在空气分离单元的产品构成要求中,并且因此稀有气体回收系统常常并未完全集成到空气分离单元中。
例如,通过使来自低温空气分离单元的含氖流通过独立的氖气净化机组,可在空气的低温蒸馏过程中回收氖气,该独立的氖气净化机组可包括产生粗氖产物的不可冷凝物汽提塔和非低温变压吸附系统(参见例如美国专利No.5,100,446)。然后将粗氖产物传递到氖气精炼厂,在那里通过除去氦气和氢气来处理粗氖气流以产生精制的氖气产品。例如,美国专利No.5,100,446中所公开的氖气回收系统仅具有约80%的中等氖气回收率,因为进料至下游氖气汽提塔的含氖流来自于主冷凝器-再沸器的不可冷凝排放流。
此外,在稀有气体回收系统如美国专利No.5,167,125和No.7,299,656中所示联接或部分地集成到空气分离单元中时;稀有气体回收系统常常对空气分离单元涉及对空气的其它组分的生产的设计和操作产生不利影响,因为必须从空气分离单元中取出相对大流量的氮气才能产生粗氖蒸气流。例如,美国专利No.7,299,656中所公开的低压(即,约20psia)氖气回收系统的粗氖蒸气流中的氖气浓度非常低,仅为约1300ppm,因此从空气分离单元取出的粗氖产物高达进料至低压塔的液氮回流的近4%。原本将用作低压塔中的液体回流的液体流的如此显著的缺失对其它产品构成物的分离和回收产生了不利影响。此外,如此低氖气浓度(即,1333ppm)粗产物将在压缩功率和液氮使用方面导致以更高的相关操作成本来产生最终的精制氖气产品。还可参见美国专利申请公开NO.2010/0221168,其公开了一种氖气回收系统。粗氖蒸气流中的氖气浓度在约5.8%时也相对较低,并且回收系统仅适用于具有污浊盘架液体抽出的空气分离单元,其中进料至低压塔的液体回流从高压塔的中间位置取出。
需要的是一种稀有气体或不可冷凝气体回收系统,这种系统可产生包含大于约50%摩尔份数的氖气的粗氖蒸气流,并且展示大于约95%的总体氖气回收率,与此同时消耗最少的液氮并且对空气分离单元中氩气的回收的影响最小。另外,由于上述现有技术中的氖气回收系统均没有能力轻松、高效地共同产生氙气和氪气,进一步的需求包括稀有气体回收系统,该系统的总氖气回收率大于约95%,并且可以共同产生粗氖蒸气流,其中含有大于约50%摩尔份数的氖气和大于约50%摩尔份数的氦气,并且可以产生商业量的氙气和氪气。
发明内容
本发明可被表征为用于双塔或三塔空气分离单元的稀有气体回收系统,该系统包括:(i)不可冷凝物汽提塔,该不可冷凝物汽提塔被构造成接收来自主冷凝器-再沸器的液氮冷凝物流的一部分以及来自高压塔的富氮盘架蒸气流,该不可冷凝物汽提塔被构造成产生液氮塔底馏出物和含稀有气体的塔顶馏出物;(ii)氙气-氪气塔,该氙气-氪气塔经由辅助冷凝器-再沸器与不可冷凝物汽提塔以热传递关系相连,该氙气-氪气塔被构造成接收从空气分离单元的低压塔泵送的第一液氧流和来自辅助冷凝器-再沸器的富氧蒸气的第一汽化流,该氙气-氪气塔被构造成产生含氙气和氪气的塔底馏出物和富氧塔顶馏出物;(iii)辅助冷凝器-再沸器,该辅助冷凝器-再沸器被构造成从不可冷凝物汽提塔接收含稀有气体的塔顶馏出物,并且从空气分离单元的低压塔接收第二液氧流作为制冷源,该辅助冷凝器-再沸器还被构造成产生冷凝物回流流和富氧蒸气的第一汽化流,冷凝物回流流被释放到或引导至不可冷凝物汽提塔,富氧蒸气的第一汽化流被释放到氙气-氪气塔和含不可冷凝物排放流中;(iv)回流冷凝器,该回流冷凝器被构造成接收来自辅助冷凝器-再沸器和冷凝介质的含不可冷凝物排放流,该回流冷凝器还被构造成产生被引导至不可冷凝物汽提塔的冷凝物、以及包含大于约50%摩尔份数的氖气的粗氖蒸气流。含氙气和氪气的一部分的塔底馏出物被看作粗氙气和氪气液流。另外,将液氮塔底馏出物的全部或一部分过冷以产生经过冷液氮流,并且用于回流冷凝器的冷凝介质是经过冷液氮流的一部分。
本发明还可被表征为用于从双塔或三塔空气分离单元回收稀有气体的方法,该方法包括以下步骤:(a)将来自主冷凝器-再沸器的液氮流和来自高压塔的富氮盘架蒸气流引导至不可冷凝物汽提塔,该不可冷凝物汽提塔被构造成产生液氮塔底馏出物和含稀有气体的塔顶馏出物;(b)将该液氮塔底馏出物过冷以产生经过冷液氮流;(c)在辅助冷凝器-再沸器中,将来自含稀有气体的塔顶馏出物的氮气与来自空气分离单元的低压塔的第一液氧流冷凝,以产生冷凝物和含不可冷凝物排放流,同时蒸发或部分蒸发液氧,以产生由液氧的蒸发或部分蒸发形成的第一汽化流;(d)经由辅助冷凝器-再沸器,从空气分离单元的低压塔将第二液氧流泵送至与不可冷凝物汽提塔以热传递关系相连的氙气-氪气塔;(e)将来自辅助冷凝器-再沸器的第一汽化流释放到氙气-氪气塔中;(f)将含不可冷凝物排放流和经过冷液氮流的第一部分引导至回流冷凝器,该回流冷凝器被构造成产生被引导至不可冷凝物汽提塔的冷凝物流、由经过冷液氮流的蒸气或部分蒸气形成的第二汽化流、以及含有大于约50%摩尔份数的氖气的粗氖蒸气流;以及(g)将含氙气和氪气的一部分的塔底馏出物看作粗氙气和氪气液流。该粗氖蒸气流也可包含大于约10%摩尔份数的氦气。
在利用氙气-氪气塔的实施方案中,富氧塔顶馏出物的全部或一部分可被引导回空气分离单元的低压塔或空气分离单元的主换热系统,其中可以对其进行处理并且将其看作气态氧产物。另外,在所公开的实施方案的一些或全部中的经过冷液氮回流流可以经由与空气分离单元的低压塔的氮气塔顶馏出物的间接换热而过冷。除了将经过冷液氮回流流的一部分引导至回流冷凝器或氖气质量改善装置之外,还可将经过冷液氮回流流的其他部分作为回流流引导至低压塔并且/或者将其看作液氮产物流。
附图说明
虽然本发明的结论是申请人视为他们的发明内容且清楚地指出发明主题的权利要求,但相信本发明在结合附图考虑时将得到更好的理解,其中:
图1是具有本发明的不可冷凝气体回收系统的实施方案的低温空气分离单元的局部示意图;
图2是图1的不可冷凝气体回收系统的更详细示意图;
图3是具有不可冷凝气体回收系统的另选实施方案的低温空气分离单元的局部示意图;
图4是图3的不可冷凝气体回收系统的一个实施方案的更详细示意图;
图5是图3的不可冷凝气体回收系统的另一实施方案的更详细示意图;
图6是具有本发明的不可冷凝气体回收系统的又一实施方案的低温空气分离单元的局部示意图;
图7是图6的不可冷凝气体回收系统的更详细示意图;
图8是图6的不可冷凝气体回收系统的更详细示意图;
图9是具有适用于回收稀有气体的不可冷凝气体回收系统的实施方案的低温空气分离单元的局部示意图;
图10是图9的不可冷凝气体回收系统的更详细示意图;
图11是具有适用于回收氖气、氦气、氙气和氪气的不可冷凝气体回收系统的另一个实施方方案的低温空气分离单元的局部示意图;并且
图12是图11的不可冷凝气体回收系统的更详细示意图。
具体实施方式
现在转到图1、图3、图6、图9和图11,示出了通常也称为空气分离单元10的低温空气分离设备的简化例示。从广义上讲,所描绘的空气分离单元包括主进料空气压缩机组20、涡轮空气回路30、增压器回路40、主或初级换热器系统50、基于涡轮的致冷回路60以及蒸馏塔系统70。如本文所用,主进料空气压缩机组、任选的涡轮空气回路和增压器空气回路共同包括“热端”空气压缩回路。类似地,主换热器或初级换热器、基于涡轮的致冷回路的部分和蒸馏塔系统的部分被称为通常容纳在一个或多个绝缘冷箱中的“冷端”系统/设备。
热端空气压缩回路
在图1、图3、图6、图9和图11所示的主进料压缩机组中,进入的进料空气22通常被抽吸穿过吸气过滤器外壳(ASFH)并且在多级中间冷却的主空气压缩机布置24中被压缩至可介于约5巴(a)至约15巴(a)之间的压力。该主空气压缩机布置24可包括串联或并联布置的整体齿轮式压缩机级或直接驱动压缩机级。离开主空气压缩机布置24的经压缩空气26被进料至具有一体式除雾器的后冷却器或(未示出),以移除进入的进料空气流中的游离水分。通过用冷却塔水冷却经压缩进料空气,在后冷却器中将来自主空气压缩机布置24的最后压缩级的压缩的压缩热移除。来自该后冷却器以及主空气压缩布置24中的一些中间冷却器的冷凝物优选地输送到冷凝物罐,并且用于向空气分离设备的其他部分供应水。
然后将冷却且干燥的经压缩空气进料26在预纯化单元28中纯化以从该冷却的干的经压缩空气进料中移除高沸点污染物。如本领域所熟知,预纯化单元28通常包含根据变温和/或变压吸附循环操作的氧化铝和/或分子筛的两个床,在该吸附循环中水分及其他杂质(诸如二氧化碳、水蒸气和烃类)被吸附。这些床中的一个床用于预纯化该冷却且干燥的经压缩空气进料,而另一个床是优选地利用来自空气分离单元的废氮的一部分再生的。这两个床定期交换功用。在设置在预纯化单元28下游的粉尘过滤器中,从经压缩且预纯化的进料空气中移除颗粒以产生经压缩且纯化的进料空气流29。
该经压缩且纯化的进料空气流29在包括高压塔72、低压塔74和任选的氩塔76的多个蒸馏塔中被分离为富氧馏分、富氮馏分和富氩馏分(或氩产物流170)。然而,在这种蒸馏之前,通常将经压缩且预纯化的进料空气流29分成多个进料空气流42、44和32,该多个进料空气流可包括锅炉空气流42和涡轮空气流32。锅炉空气流42和涡轮空气流32可在压缩机41、34和36中进一步压缩,并且随后在后冷却器43、39和37中冷却以形成经压缩物流49和33,这些经压缩物流然后被进一步冷却至主换热器52中的精馏所要求的温度。优选地通过与包括氧气流190的加热流和来自蒸馏塔系统70的氮气流193、195的间接换热来在主换热器52中完成对空气流44、45和35的冷却,以产生经冷却的进料空气流47、46和38。
如下文更详细的说明,将经冷却的进料空气流38在基于涡轮的致冷回路60中膨胀,以产生被引导至高压塔72的进料空气流64。随后将液体空气流46分成液体空气流46A、46B,然后这些液体空气流在膨胀阀48、49中部分膨胀以被引入到高压塔72和低压塔74中,而经冷却的进料空气流47被引导至高压塔72。空气分离单元10的致冷也通常由涡轮空气流回路30和其他相关的冷的和/或热的涡轮布置生成,该涡轮布置诸如设置在基于涡轮的致冷回路60内的涡轮62或任何任选的闭环加热致冷回路,如本领域中所公知的。
冷端系统/设备
主或初级换热器52优选地是钎焊铝制板翅式换热器。此类换热器是有利的,因为它们具有紧凑设计、高传热速率,而且它们能够处理多个流。它们被制造为完全钎焊和焊接的压力容器。对于小型空气分离单元而言,具有单个芯的换热器可能已足够。对于处理较高流量的较大空气分离单元而言,换热器可由必须并联或串联连接的若干芯构造而成。
基于涡轮的致冷回路通常被称为下塔涡轮(LCT)布置或上塔涡轮(UCT)布置,这些布置用于向双塔或三塔低温空气蒸馏塔系统提供致冷。在图1所示的LCT布置中,经压缩且经冷却的涡轮空气流35优选地在约20巴(a)至约60巴(a)之间的压力下。将经压缩且经冷却的涡轮空气流35引导至或引入主或初级换热器52中,在其中将该经压缩且经冷却的涡轮空气流部分冷却至约160开尔文至约220开尔文之间的范围内的温度以形成经部分冷却且经压缩的涡轮空气流38,该经部分冷却且经压缩的涡轮空气流随后被引入涡轮膨胀机62中以产生被引入到蒸馏塔系统70的高压塔72中的冷排气流64。由该经部分冷却且经压缩的涡轮空气流的膨胀而产生的补充致冷由此被直接施加到高压塔72,从而减轻了主换热器52的一些冷却负荷。在一些实施方案中,涡轮膨胀机62可与用于直接或通过适当的齿轮装置进一步压缩涡轮空气流32的增压压缩机36联接。
虽然图1所示的基于涡轮的致冷回路被示出为下塔涡轮(LCT)回路,在该回路中经膨胀排气流被进料至蒸馏塔系统70的高压塔72,但可设想到基于涡轮的致冷回路另选地可以是上塔涡轮(UCT)回路,在该回路中涡轮排气流被引导至低压塔。此外,基于涡轮的致冷电路可以是LCT回路和UCT回路的组合。
类似地,在采用UCT布置(未示出)的另选实施方案中,纯化的且经压缩的进料空气的一部分可在初级换热器中部分冷却,然后该经部分冷却的物流的全部或一部分被转移到热涡轮膨胀机中。然后将来自热涡轮膨胀机的经膨胀气流或排气流引导至双塔或多塔低温空气蒸馏塔系统中的低压塔。因此直接向低压塔赋予由该排气流的膨胀所形成的冷却或补充制冷,从而减轻主换热器的一些冷却负荷。
在包括高压塔72和低压塔74的蒸馏塔系统70内分离进料空气流的上述组分(即,氧气、氮气和氩气)。应当理解,如果氩气是来自空气分离单元10的必要产物,则氩塔76和氩冷凝器78可结合到蒸馏塔系统70中。高压塔72通常在约20巴(a)至约60巴(a)之间的范围内操作,而低压塔74在约1.1巴(a)至约1.5巴(a)之间的压力下操作。高压塔72和低压塔74优选地以热传递关系相连,使得从接近高压塔的顶部提取为物流73的富氮蒸气塔顶馏出物在位于低压塔74的基部的冷凝器-再沸器75中因富氧液体塔底馏出物77沸腾而冷凝。富氧液体塔底馏出物77的沸腾引发低压塔内上升汽相的形成。该冷凝产生含液氮流81,该含液氮流被分成回流流83和液氮源流80,该回流流回流低压塔以引发低压塔内下降液相的形成,该液氮源流被进料至氖气回收系统100。
来自涡轮空气致冷回路60的排气流64与物流46和47一起被引入到高压塔72中,用于通过在多个传质接触元件(示出为塔盘71)内使此类混合物的上升汽相与由回流流83引发的下降液相接触来进行精馏。这产生了粗液氧塔底馏出物86(也称为釜液体)和富氮塔顶馏出物87。
低压塔74还设置有多个传质接触元件,这些接触元件可以是塔盘或规整填料或散堆填料或低温空气分离领域中的其他已知元件。低压塔74中的这些接触元件被示出为规整填料79。如前所述,在低压塔74内发生的分离产生被提取为富氧液体流90的富氧液体塔底馏出物77和被提取为氮产物流95的富氮蒸气塔顶馏出物91。如附图所示,富氧液体流90可经由泵180泵送并被看作被泵送的液氧产物185,或被引导至主换热器52,在该主换热器中将该富氧液体流加热以产生气态氧产物流190。另外,还从低压塔74提取了废物流93以控制氮产物流95的纯度。氮产物流95和废物流93两者均穿过被设计为使釜流88和/或回流流过冷的一个或多个过冷单元99。经过冷回流流260的一部分可任选地被看作液体产物流98,并且其余部分可在穿过膨胀阀96之后被引入到低压塔74中。在穿过过冷单元99之后,氮产物流95和废物流93在主或初级换热器52内被完全加热,以产生经加热氮产物流195和经加热废物流193。尽管未示出,但是经加热废物流193可用于再生预纯化单元28内的吸附剂。
用于回收氖气和氦气的系统/设备
图2、图4、图5、图7和图8示意性地描绘了不可冷凝气体回收系统,该系统被构造成用于增强对粗不可冷凝气体流(诸如含粗氖蒸气流)的回收。
如图2所示,不可冷凝气体回收系统100的实施方案包括不可冷凝物汽提塔(NSC)210;汽提塔冷凝器220、制冷压缩机230和氖气质量改善装置240。不可冷凝物汽提塔210被构造成接收来自高压塔72的氮气盘架蒸气215的一部分以及来自汽提塔冷凝器220的汽化氮蒸气225的经再循环部分。将这两个物流215、225结合,然后在氮气制冷压缩机230中进一步压缩。该经进一步压缩的氮气流235作为上升蒸气流被引入到接近不可冷凝物汽提塔210底部,而不可冷凝物汽提塔210的下降液体回流包括:(i)离开主冷凝器-再沸器80的液氮流;(ii)离开汽提塔冷凝器227的液氮冷凝物流;和(iii)离开氖气质量改善装置240(即,回流冷凝器242)的液氮冷凝物流245。不可冷凝物汽提塔210产生液氮塔底馏出物212和包含更高浓度的氖气的塔顶馏出气体214,该塔顶馏出气体被进料至汽提塔冷凝器220中。
在例示实施方案中,不可冷凝物汽提塔210在比空气分离单元10的高压塔72的压力更高的压力下操作,以便为汽提塔冷凝器220提供热传递温差。因为不可冷凝物汽提塔210在比高压塔72的压力更高的压力下操作,所以不可冷凝物汽提塔210优选地设置在比离开主冷凝器-再沸器80的液氮流(即,来自高压塔的盘架液体脱离物)更低的高度,使得通过获得重力压差来将下降液体回流进料至不可冷凝物汽提塔210。随着上升蒸气(即,汽提蒸气)沿不可冷凝物汽提塔210上升,在不可冷凝物汽提塔210中发生的传质将使较重的组分如氧气、氩气、氮气集中在下降液相中,而上升汽相富含轻组分如氖气、氢气和氦气。如上所指出,上升蒸气被引入或进料至汽提塔冷凝器220。
汽提塔冷凝器220优选地是优选与不可冷凝物汽提塔210集成的回流式或非回流式钎焊铝制换热器。来自不可冷凝物汽提塔210的富氮液体塔底馏出物212的小物流或部分为汽提塔冷凝器220提供第一冷凝介质216,而富氮液体塔底馏出物212的剩余部分是液氮回流流218,该液氮回流流因来自空气分离单元10的废氮流93而在过冷器单元99中过冷。经过冷液氮回流流218的部分可任选地被看作液氮产物217,转移到氖气质量改善装置240中或在阀219中膨胀,并且作为回流流260返回到空气分离单元10的低压塔74中。例示的过冷器单元99可以是空气分离单元10中现有的过冷器,或者可以是形成不可冷凝气体回收系统100的一部分的独立的过冷器单元。
来自汽提塔冷凝器220的汽化氮气蒸气225经由氮气制冷压缩机230再循环回到不可冷凝物汽提塔210。在汽提塔冷凝器220的冷凝侧,将不可冷凝物诸如氢气、氦气、氖气作为含不可冷凝物排放流229从不可冷凝物排放口中抽出,该排放流被引导或进料至氖气质量改善装置240。氖气质量改善装置240优选地包括液氮回流冷凝器242、相分离器244和氮气流量控制阀246。液氮回流冷凝器242优选地是回流式钎焊铝制换热器,该换热器用第二冷凝介质248将含不可冷凝物排放流229冷凝,该第二冷凝介质优选地是经过冷液氮回流流的一部分。将汽化流249从氖气回收系统100中移除并进料至废物流93中。在液氮回流冷凝器242内不冷凝的残余蒸气被作为包含大于约50%摩尔份数的氖气的粗氖蒸气流250从液氮回流冷凝器242的顶部抽出。该粗氖蒸气流优选地还包含大于约10%摩尔份数的氦气。
例示的不可冷凝气体回收系统100的总体氖气回收率高于95%。所描绘的不可冷凝气体回收系统100的附加有益效果是液氮消耗最低,并且由于大量液氮被进料至空气分离单元10的低压塔74,因此对空气分离单元10的其它产品构成物的分离和回收的影响最小。这是因为使用有效的制冷压缩系统将汽化氮气再循环至不可冷凝物汽提塔以及使用富氮塔底馏出物来为汽提塔冷凝器220提供致冷负荷。
在许多方面,图4和图5的实施方案与图2所示的实施方案相当相似,对应的元件和物流具有对应的附图标号,但在图4中以300序列标号,在图5中以400系列标号。图2与图4和图5的实施方案之间的主要差异在于:汽提塔冷凝器320、420和冷凝介质322、422的布置;氮气制冷压缩机230的消除;以及汽提塔冷凝器320、420与空气分离单元10的蒸馏塔系统70的集成。
在图4所示的实施方案中,汽提塔冷凝器320是热虹吸式冷凝器,该冷凝器可以是将含不可冷凝物排放流329释放到氖气质量改善装置340的回流冷凝器342中的管壳式冷凝器或钎焊铝制换热器。在图5所示的实施方案中,汽提塔冷凝器420是直流沸腾式冷凝器,该冷凝器可以是将含不可冷凝物排放流429释放到氖气质量改善装置440的回流冷凝器442中的回流式或非回流式冷凝钎焊铝制换热器。
在这两个实施方案中,汽提塔冷凝器320、420的冷凝介质是从空气分离单元10的低压塔72中取出的液氧流322、422,并且沸腾的氧气324、424返回到空气分离单元10的低压塔72中。更具体地讲,液氧优选地从空气分离单元10的低压塔74的贮槽中抽出并通过重力进料至汽提塔冷凝器320、420的沸腾侧。液氧在汽提塔冷凝器320、420中沸腾以为蒸气部分冷凝提供致冷。因为汽提塔冷凝器320、420在比空气分离单元10的低压塔74的压力更高的压力下操作,所以汽化氧气蒸气324、424被返回至接近低压塔74的底部的位置。优选地,汽提塔冷凝器320、420被定位在低压塔贮槽的下方以允许氧气流在图4和图5所示的实施方案中由重力驱动。有利的是,与图2所示的实施方案相比,使用液氧来提供用于汽提塔冷凝器320、420的致冷负荷消除了对氮气制冷压缩机的使用。
与图2的实施方案一样,来自高压塔72顶部的盘架蒸气315、415作为上升蒸气被进料至不可冷凝物汽提塔320的底部,而不可冷凝物汽提塔的下降液体回流包括:(i)离开主冷凝器-再沸器80的液氮流;(ii)离开汽提塔冷凝器327、427的液氮冷凝物流;和(iii)离开氖气质量改善装置340、440(即,回流冷凝器342、442)的液氮冷凝物流345、445。在不可冷凝物汽提塔320、420内,较重的组分如氧气、氩气、氮气集中在下降液相中,而上升汽相富含轻组分如氖气、氢气和氦气。
在图4和图5的实施方案中,来自不可冷凝物汽提塔310、410的所有液氮塔底馏出物312、412提供液氮回流流318、418,该液氮回流流因来自空气分离单元10的废氮流93而在过冷器单元99中过冷。如上所述,经过冷液氮回流流的部分可任选地被看作液氮产物317、417,作为物流348、448转移到液氮回流冷凝器342、442或在阀319、419中膨胀,并且作为回流流360、460返回到空气分离单元10的低压塔74中。
类似于图2的氖气质量改善装置,图4和图5的氖气质量改善装置340、440优选地包括液氮回流冷凝器342、442;相分离器344、444;以及氮气流量控制阀346、446。液氮回流冷凝器342、442用第二冷凝介质348、448将含不可冷凝物排放流329、429冷凝,该第二冷凝介质优选地是经过冷液氮回流流的一部分。将汽化流349、449从氖气回收系统100中移除并进料至废物流93中。在液氮回流冷凝器342、442内不冷凝的残余蒸气被作为粗氖蒸气流350、450从液氮回流冷凝器342、442的顶部抽出。
现在转到图7和图8,示出了不可冷凝气体回收系统100的附加实施方案,该系统包括不可冷凝物汽提塔(NSC)510、610和冷凝器-再沸器520、620。图7和图8所示的不可冷凝物汽提塔510、610被构造成接收来自高压塔72的氮气盘架蒸气515、615的一部分,该氮气盘架蒸气的一部分作为上升蒸气流被引入到接近不可冷凝物汽提塔510、610底部。不可冷凝物汽提塔510、610的下降液体回流包括:(i)离开主冷凝器-再沸器75的液氮流80;和(ii)离开冷凝器-再沸器520、620的液氮冷凝物流545、645。随着上升蒸气(即,汽提蒸气)在不可冷凝物汽提塔510、610内上升,在不可冷凝物汽提塔510、610中发生的传质将使较重的组分如氧气、氩气、氮气集中在下降液相中,而上升汽相富含轻组分如氖气、氢气和氦气。由于该传质,不可冷凝物汽提塔510、610产生液氮塔底馏出物512、612和包含更高浓度的不可冷凝物的塔顶馏出气体529、629,该塔顶馏出气体被进料至冷凝器-再沸器520、620中。
来自不可冷凝物汽提塔510、610的液氮塔底馏出物512、612形成液氮回流流518、618,并且该液氮回流流优选地在过冷器单元99中因来自空气分离单元10的废氮流93而过冷。经过冷液氮回流流的部分可任选地被看作液氮产物517、617;转移到冷凝器-再沸器520、620;或在阀519、619中膨胀,并且作为回流流560、660返回到空气分离单元10的低压塔74中。类似于先前所述的实施方案,例示的过冷器单元99可以是空气分离单元10中现有的过冷器,或者可以是形成不可冷凝气体回收系统100的一部分的独立单元。
在图7和图8的实施方案中,冷凝器-再沸器520、620优选地是双级冷凝器-再沸器,该双级冷凝器-再沸器提供双级别致冷以将来自不可冷凝物汽提塔510、610的大部分塔顶馏出蒸气529、629部分冷凝。图7所示的回流冷凝器-再沸器520被构造成接收来自不可冷凝物汽提塔510的包含氖气和其他不可冷凝物的塔顶馏出气体529、包括从空气分离单元10的氮气过冷器转移来的釜沸腾流的第一冷凝介质522、以及包括经由经过冷液氮回流流的阀546的节流部分的第二冷凝介质548。该双级回流冷凝器-再沸器520被构造成产生作为回流返回到不可冷凝物汽提塔510的液氮冷凝物流545、被引导至空气分离单元10的氩冷凝器78的双相汽化流525、以及被从冷凝器-再沸器520的顶部抽出并且包含大于约50%摩尔份数的氖气的粗氖蒸气流550。该粗氖蒸气流还可包含大于约10%摩尔份数的氦气。将汽化流549从相分离器544中移除并进料至废物流93中。与其他上述实施方案一样,例示的不可冷凝气体回收系统的总体氖气回收率高于95%。所描绘的不可冷凝气体回收系统的附加有益效果是液氮消耗最低,并且由于大量液氮被再循环回到低压塔,因此对空气分离单元10中其它产品构成物的分离和回收的影响最小。
在许多方面,图8的实施方案与图7所示的实施方案相当相似,对应的元件和物流具有对应的附图标号,但在图8中以600序列标号,在图7中以500系列标号。例如,图7中由附图标号522、525、544、545、546、548、549和550指定的项目分别与图8中由附图标记号622、625、644、645、646、648、649和650指定的项目相同或相似。图7的实施方案与图8的实施方案之间的主要差异在于来自空气分离单元的氮气过冷器的釜沸腾流被来自空气分离单元10的氩冷凝器78的釜沸腾流622替代。此外,由双级回流冷凝器-再沸器620产生的沸腾流625被引导至相分离器670,所得蒸气流671和液体流672被返回到空气分离单元10的低压塔74的中间位置。
用于回收氙气和氪气的系统/设备
图10和图12示意性地描绘了不可冷凝气体回收系统,该系统被构造成用于增强对粗氖蒸气流和粗氙气和氪液流的回收。如图10所示,不可冷凝气体回收系统100的实施方案包括不可冷凝物汽提塔710;氙气-氪气塔770;设置在氙气-氪气塔770中的冷凝器-再沸器720,以及氖气质量改善装置740。
不可冷凝物汽提塔710被构造成从高压塔72接收氮气盘架蒸气715的一部分并且作为上升蒸气流被引入到接近不可冷凝物汽提塔710底部,而不可冷凝物汽提塔710的下降液体回流包括:(i)离开主冷凝器-再沸器80的液氮流;(ii)离开冷凝器-再沸器720的液氮冷凝物流727;和(iii)离开氖气质量改善装置740(即,回流冷凝器742)的液氮冷凝物流745。将来自设置在氙气-氪气塔770中的冷凝器-再沸器720的冷凝物727用作不可冷凝物汽提塔710回流的一部分,将不可冷凝物汽提塔710与氙气-氪气塔770热连接。
随着上升蒸气(即,汽提蒸气)沿不可冷凝物汽提塔710上升,在不可冷凝物汽提塔710中发生的传质将使较重的组分如氮气集中在下降液相中,而上升汽相富含轻组分如氖气、氢气和氦气。如上所指出,上升蒸气被引入或进料至冷凝器-再沸器720。不可冷凝物汽提塔710产生液氮塔底馏出物712和含有较高浓度稀有气体的塔顶馏出气体714,该塔顶馏出气体被进料至氙气-氪气塔770的冷凝器-再沸器720中。
从不可冷凝物汽提塔710中提取富氮液体塔底馏出物712作为液氮回流流718。液氮回流流718在过冷器单元99中与来自空气分离单元10的废氮流93过冷。经过冷液氮回流流218的部分可任选地被看作液氮产物717,转移到氖气质量改善装置740中或在阀719中膨胀,并且作为回流流760返回到空气分离单元10的低压塔74中。与前述实施方案一样,过冷器单元99可以是空气分离单元10中现有的过冷器,或者可以是形成不可冷凝气体回收系统100的一部分的独立的过冷器单元。
氙气-氪气塔770从空气分离单元的低压塔74接收液氧流。具体地讲,从低压塔74的贮槽中抽出液氧流90,经由泵180将其泵送,并且将所得的泵送液氧流775进料至氙气-氪气塔770上的两个位置。初级液氧进料靠近氙气-氪气塔770的顶部,用作氙气-氪气塔770的回流。次级液氧进料在邻近塔贮槽的中间或下部在氙气-氪气塔770中释放,用于污染物控制,同时保持氙气和氪气的回收。
氙气-氪气塔770的贮槽中的液体由冷凝器-再沸器720再沸腾,以对抗来自不可冷凝物汽提塔710的冷凝塔顶馏出蒸气。汽化氧气蒸气通过氙气-氪气塔770上升,从而富集氧气和氩气,而液体则集中在重组分中诸如氪气和氙气中。从氙气-氪气塔770贮槽中抽出富含氪气/氙气的液氧,作为另一种粗氙气和氪气液体产物780。
冷凝器-再沸器720是直流沸腾式冷凝器,该直流沸腾式冷凝器可以是回流式或非回流式冷凝式钎焊铝制换热器或热虹吸式冷凝器,该热虹吸式冷凝器可以是管壳式冷凝器或钎焊铝制换热器。在冷凝器-再沸器720的冷凝侧,将不可冷凝物诸如氢气、氦气、氖气作为含不可冷凝物排放流729从不可冷凝物排放口中抽出,该排放流被引导或进料至氖气质量改善装置740。
与前述实施方案一样,氖气质量改善装置740优选地包括液氮回流冷凝器742、相分离器744和氮气流量控制阀746。液氮回流冷凝器742优选地用第二冷凝介质748将含不可冷凝物排放流729冷凝,该第二冷凝介质优选地是经过冷液氮回流流的一部分。来自液氮回流冷凝器742的汽化流749被相分离,并且蒸气被从稀有气体回收系统100中移除并且被进料至废气流93中。在液氮回流冷凝器742内不冷凝的残余蒸气被作为包含大于约50%摩尔份数的氖气的粗氖蒸气流750从液氮回流冷凝器742的顶部抽出。该粗氖蒸气流优选地还包含大于约10%摩尔份数的氦气。
在许多方面,图12的实施方案与图10所示的实施方案相当相似,对应的元件和物流具有对应的附图标号,但在图10中以700系列标号,在图12中以800系列标号。图10的实施方案与图12的实施方案之间的主要区别是从空气分离单元10产生氧气产物。在图10中,液氧流90从低压塔74抽出并且在LOX泵180中加压。将泵送的液氧分成两个或更多个流,这些两个或更多个流包括:将被引入到氙气-氪气塔770中的液氧流775;液氧产物流185;和/或在主或初级换热器52中蒸发以产生加压气态氧产物的氧气产物流186。来自氙气-氪气塔770的富氧塔顶馏出物785返回到低压塔74。相反,在图12中,液氧流90从低压塔74抽出并且在LOX泵180中加压。泵送的液氧875被引导至不可冷凝气体回收系统100,而来自氙气-氪气塔870的富氧塔顶馏出物885作为物流890被引导至主或初级换热器52,其中,该换热器可以被汽化以产生气态氧产物。
另一个不同之处在于,在图10中,没有从低压塔74到氙气-氪气塔770抽取气态氧,而在图12中,从低压塔74中抽出气态氧流91并且引导至氙气-氪气塔770。
类似于图10的氖气质量改善装置740,图12的氖气质量改善装置840优选地包括液氮回流冷凝器842;相分离器844;以及氮气流量控制阀846。液氮回流冷凝器842用第二冷凝介质848将含不可冷凝物排放流829冷凝,该第二冷凝介质优选地是经过冷液氮回流流的一部分。将汽化流849从稀有气体回收系统100中移除并进料至废物流93中。在液氮回流冷凝器842内不冷凝的残余蒸气被作为粗氖蒸气流850从液氮回流冷凝器842的顶部抽出。
例示的不可冷凝气体回收系统100的总体氖气回收率高于95%。所描绘的不可冷凝气体回收系统100的附加有益效果是,因为冷凝器-再沸器720、820将不可冷凝物汽提塔710、810和氙气-氪气塔770,870(即,冷凝器-再沸器720、820的冷凝侧上的富含氖气的不可冷凝气体以及沸腾侧上的富含氪气/氙气的液体)两者热相连接,因此该布置具有共同产生稀有气体的能力。并且,由于稀有气体回收系统中使用的大部分氮气返回到空气分离单元10的蒸馏塔系统中,因此对通过空气分离单元10分离和回收其他产物构成物的影响最小。
实施例
对于本发明的回收氖气的系统和方法的各种实施方案,使用各种空气分离单元操作模型来进行多个工艺模拟以表征:(i)氖气和其他稀有气体的回收;(ii)粗氖蒸气流的组成;以及(iii)来自蒸馏塔体系的氮的净损失;当使用如上所述和附图所示的氖气或稀有气体回收系统和相关联方法操作空气分离装置时。
表1示出了针对参考图2描述的回收系统和相关联方法的基于计算机的工艺模拟的结果。如表1所示,空气分离单元在4757.56kcfh的进入进料空气流和37.86kcfh的液体空气流以大致97psia的压力进入高压塔的状态下操作。大致45.00kcfh的盘架氮气蒸气以92psia的压力从高压塔转移到回收系统,而大致2174.74kcfh的液氮以92psia的压力从蒸馏塔系统的主冷凝器-再沸器转移到回收系统。除了直接从回收系统中取出的任何液氮产物之外,该回收系统能够以至低压塔的经过冷液氮的形式将约99.31%的经转移物流返回到蒸馏塔系统(即,来自不可冷凝物汽提塔的2219.58kcfh的液体回流减去至氖气质量改善装置的15.31kcfh的经过冷液氮等于返回到低压塔的2204.27kcfh的经过冷液氮)。回收氖气和其他稀有气体包括回收约96.85%的氖气。通过将粗氖流的流量(0.16kcfh)乘以粗氖流中的氖气含量(51.89%)并将该数字(0.083024kcfh)除以主空气流(4757.56kcfh*0.00182%)和进入蒸馏塔系统的液体空气流(37.86kcfh*0.00182%)中包含的氖气,计算出氖气回收率。如表1所示,粗氖蒸气流的组成包括51.89%的氖气和15.25%的氦气。
Figure BDA0002391404320000161
Figure BDA0002391404320000162
Figure BDA0002391404320000171
表1(图2的氖气回收系统和相关联方法的工艺模拟)
表2示出了针对参考图4描述的氖气回收系统和相关联方法的基于计算机的工艺模拟的结果。如表2所示,空气分离单元在4757.56kcfh的进入进料空气流和37.86kcfh的液体空气流以大致97psia的压力进入高压塔的状态下操作。约270.00kcfh的盘架氮气蒸气以大致92psia的压力从高压塔转移到氖气回收系统,而大致1949.88kcfh的液氮以大致92psia的压力从蒸馏塔系统的主冷凝器-再沸器转移到氖气回收系统。除了直接从氖气回收系统中取出的任何液氮产物之外,氖气回收系统能够以至低压塔的经过冷液氮的形式将超过99%的经转移物流返回到蒸馏塔系统(即,来自不可冷凝物汽提塔的2219.74kcfh的液体回流减去至氖气质量改善装置的15.74kcfh的经过冷液氮等于返回到低压塔的2204.00kcfh的经过冷液氮)。回收氖气和其他稀有气体包括回收约96.44%的氖气,而粗氖蒸气流的组成包括51.89%的氖气和15.25%的氦气。
Figure BDA0002391404320000172
Figure BDA0002391404320000181
Figure BDA0002391404320000182
表2(图4的氖气回收系统和相关联方法的工艺模拟)
表3示出了针对参考图7描述的氖气回收系统和相关联方法的基于计算机的工艺模拟的结果。如表3所示,空气分离单元在4757.56kcfh的进入进料空气流和37.86kcfh的液体空气流以大致97psia的压力进入高压塔的状态下操作。约140.00kcfh的盘架氮气蒸气以大致92psia的压力从高压塔转移到氖气回收系统,而大致2079.82kcfh的液氮以大致92psia的压力从蒸馏塔系统的主冷凝器-再沸器转移到氖气回收系统。除了直接从氖气回收系统中取出的任何液氮产物之外,氖气回收系统能够以至低压塔的经过冷液氮的形式将超过99%的经转移物流返回到蒸馏塔系统(即,来自不可冷凝物汽提塔的2219.67kcfh的液体回流减去至氖气质量改善装置的15.74kcfh的经过冷液氮等于返回到低压塔的2203.93kcfh的经过冷液氮)。回收氖气和其他稀有气体包括回收超过95.16%的氖气,而粗氖蒸气流的组成包括51.74%的氖气和15.41%的氦气。
Figure BDA0002391404320000191
Figure BDA0002391404320000192
Figure BDA0002391404320000201
表3(图7的氖气回收系统和相关联方法的工艺模拟)
表4示出了针对参考图10描述的稀有气体回收系统和相关联方法的基于计算机的工艺模拟的结果。如表4所示,空气分离单元在4757.56kcfh的进入进料空气流和37.86kcfh的液体空气流以大致97psia的压力进入高压塔的状态下操作。约804.53kcfh的盘架氮气蒸气以大致92psia的压力从高压塔转移到稀有气体回收系统,而大致1415.27kcfh的液氮以大致92psia的压力从蒸馏塔系统的主冷凝器-再沸器转移到稀有气体回收系统。除了直接从稀有气体回收系统中取出的任何液氮产物之外,稀有气体回收系统能够以至低压塔的经过冷液氮的形式将超过99%的经转移物流返回到蒸馏塔系统(即,来自不可冷凝物汽提塔的2219.71kcfh的液体回流减去至氖气质量改善装置的15.74kcfh的经过冷液氮等于返回到低压塔的2203.97kcfh的经过冷液氮)。回收氖气是回收超过96.57%的氖气,而粗氖蒸气流的组成包括51.91%的氖气和15.24%的氦气。如表4中的模拟数据所示,还实现了氙气和氪气的显著回收。
Figure BDA0002391404320000202
Figure BDA0002391404320000211
表4(图10的稀有气体回收系统和相关联方法的工艺模拟)
表5示出了针对参考图12描述的稀有气体回收系统和相关联方法的基于计算机的工艺模拟的结果。如表5所示,空气分离单元在4757.56kcfh的进入进料空气流和37.86kcfh的液体空气流以大致97psia的压力进入高压塔的状态下操作。约804.53kcfh的盘架氮气蒸气以大致92psia的压力从高压塔转移到稀有气体回收系统,而大致1415.27kcfh的液氮以大致92psia的压力从蒸馏塔系统的主冷凝器-再沸器转移到稀有气体回收系统。除了直接从稀有气体回收系统中取出的任何液氮产物之外,稀有气体回收系统能够以至低压塔的经过冷液氮的形式将超过99%的经转移物流返回到蒸馏塔系统(即,来自不可冷凝物汽提塔的2219.71kcfh的液体回流减去至氖气质量改善装置的15.74kcfh的经过冷液氮等于返回到低压塔的2203.97kcfh的经过冷液氮)。回收氖气是回收超过96.57%的氖气,而粗氖蒸气流的组成包括51.91%的氖气和15.24%的氦气。如表5中的模拟数据所示,还实现了氙气和氪气的显著回收。
Figure BDA0002391404320000212
Figure BDA0002391404320000221
Figure BDA0002391404320000222
表5(图12的稀有气体回收系统和相关联方法的工艺模拟)
尽管已通过参照一个或多个优选实施方案以及相关联的方法讨论了用于从空气分离单元回收稀有且不可冷凝气体的本发明的系统,但是本领域的技术人员应当理解,在不脱离所附权利要求书描述的本发明的实质和范围的情况下,可对其进行多种改变和省略。

Claims (18)

1.一种用于空气分离单元的稀有气体回收系统,所述空气分离单元包括主空气压缩系统、预纯化系统、换热器系统和精馏塔系统,所述精馏塔系统具有经由主冷凝器-再沸器以热传递关系相连的高压塔和低压塔,所述氖气回收系统包括:
不可冷凝物汽提塔,所述不可冷凝物汽提塔被构造成接收来自所述主冷凝器-再沸器的液氮冷凝物流的一部分以及来自所述高压塔的富氮盘架蒸气流,所述不可冷凝物汽提塔被构造成产生液氮塔底馏出物和含稀有气体的塔顶馏出物;
氙气-氪气塔,所述氙气-氪气塔经由辅助冷凝器-再沸器与所述不可冷凝物汽提塔以热传递关系相连,所述氙气-氪气塔被构造成接收从所述空气分离单元的所述低压塔泵送的第一液氧流和来自所述辅助冷凝器-再沸器的富氧蒸气的第一汽化流,所述氙气-氪气塔被构造成产生含氙气和氪气的塔底馏出物和富氧塔顶馏出物;
所述辅助冷凝器-再沸器,所述辅助冷凝器-再沸器被构造成从所述不可冷凝物汽提塔接收含所述稀有气体的塔顶馏出物,并且从所述空气分离单元的所述低压塔接收第二液氧流作为所述制冷源,所述辅助冷凝器-再沸器还被构造成产生冷凝物回流流和所述富氧蒸气的第一汽化流,所述冷凝物回流流被释放到或引导至所述不可冷凝物汽提塔,所述富氧蒸气的第一汽化流被释放到所述氙气-氪气塔和含不可冷凝物排放流中;
回流冷凝器,所述回流冷凝器被构造成接收来自所述辅助冷凝器-再沸器和冷凝介质的含所述不可冷凝物排放流,所述回流冷凝器还被构造成产生被引导至所述不可冷凝物汽提塔的冷凝物、以及包含大于约50%摩尔份数的氖气的粗氖蒸气流;
其中将所述液氮塔底馏出物的全部或一部分过冷以产生经过冷液氮流,并且用于所述回流冷凝器的所述冷凝介质是所述经过冷液氮流的一部分;并且
其中含所述氙气和氪气的一部分的塔底馏出物被看作粗氙气和氪气液流。
2.根据权利要求1所述的稀有气体回收系统,其中所述粗氖蒸气流还包含大于约10%摩尔份数的氦气。
3.根据权利要求1所述的稀有气体回收系统,其中所述富氧塔顶馏出物的全部或一部分被引导回所述空气分离单元的所述低压塔。
4.根据权利要求1所述的稀有气体回收系统,其中所述富氧塔顶溜出物的全部或一部分被引导至所述空气分离单元的所述主换热系统。
5.根据权利要求1所述的稀有气体回收系统,其中所述富氧塔顶馏出物的全部或一部分被看作气态氧产物。
6.根据权利要求1所述的稀有气体回收系统,其中所述经过冷液氮流经由与所述空气分离单元的所述低压塔的氮气塔顶馏出物的间接换热而过冷。
7.根据权利要求1所述的稀有气体回收系统,其中所述经过冷液氮流的第一部分作为所述冷凝介质被引导至所述回流冷凝器,并且所述经过冷液氮流的第二部分作为回流流被引导至所述空气分离单元的所述低压塔。
8.根据权利要求1所述的稀有气体回收系统,其中所述经过冷液氮流的第一部分作为所述冷凝介质被引导至所述回流冷凝器;所述经过冷液氮流的第二部分作为回流流被引导至所述低压塔;并且第三部分被看作液氮产物流。
9.根据权利要求1所述的稀有气体回收系统,其中由所述冷凝介质的所述蒸发或部分蒸发形成的所述第二汽化流的所述蒸气部分与所述空气分离单元的废氮流结合。
10.一种在空气分离单元中回收稀有气体的方法,所述空气分离单元包括主空气压缩系统、预纯化系统、换热器系统和精馏塔系统,所述精馏塔系统具有经由主冷凝器-再沸器以热传递关系相连的高压塔和低压塔,所述方法包括以下步骤:
将来自所述主冷凝器-再沸器的液氮流以及来自所述高压塔的富氮盘架蒸气流引导至不可冷凝物汽提塔,所述不可冷凝物汽提塔被构造成产生液氮塔底馏出物和含稀有气体的塔顶馏出物;
将所述液氮塔底馏出物的全部或一部分过冷以产生经过冷液氮流;
在辅助冷凝器-再沸器中,将来自含所述稀有气体的塔顶馏出物的氮气与来自所述空气分离单元的所述低压塔的第一液氧流冷凝,以产生冷凝物和含不可冷凝物排放流,同时蒸发或部分蒸发所述液氧,以产生由所述液氧的所述蒸发或部分蒸发形成的第一汽化流;
经由所述辅助冷凝器-再沸器,从所述空气分离单元的所述低压塔将第二液氧流泵送至与所述不可冷凝物汽提塔以热传递关系相连的氙气-氪气塔;
将来自辅助冷凝器-再沸器的所述第一汽化流释放到所述氙气-氪气塔中;
将含所述不可冷凝物排放流和所述经过冷液氮流的第一部分引导至回流冷凝器,所述回流冷凝器被构造成产生被引导至所述不可冷凝物汽提塔的冷凝物流、由所述经过冷液氮流的所述部分的所述蒸气或部分蒸气形成的第二汽化流、以及含有大于约50%摩尔份数的氖气的粗氖蒸气流;并且
将含所述氙气和氪气的一部分的塔底馏出物看作粗氙气和氪气液流。
11.根据权利要求10所述的回收稀有气体的方法,其中所述粗氖蒸气流还包含大于约10%摩尔份数的氦气。
12.根据权利要求10所述的回收稀有气体的方法,还包括将所述富氧塔顶馏出物的全部或一部分引导回所述空气分离单元的所述低压塔的所述步骤。
13.根据权利要求10所述的回收稀有气体的方法,还包括将所述富氧塔顶馏出物的全部或一部分引导至所述空气分离单元的所述换热系统的所述步骤。
14.根据权利要求10所述的回收稀有气体的方法,还包括将所述富氧塔顶馏出物的全部或一部分看作气态氧产物的所述步骤。
15.根据权利要求10所述的回收稀有气体的方法,其中将所述液氮塔底馏出物的全部或一部分过冷以产生所述经过冷液氮流的所述步骤还包括经由与所述空气分离单元的所述低压塔的氮气塔顶馏出物的间接换热而将所述液氮塔底馏出物的全部或一部分过冷,以产生所述经过冷液氮流;
16.根据权利要求10所述的回收稀有气体的方法,还包括将所述经过冷液氮流的第二部分作为回流流引导至所述空气分离单元的所述低压塔的所述步骤。
17.根据权利要求16所述的回收稀有气体的方法,还包括将所述经过冷液氮流的第三部分作为液氮产物流的所述步骤。
18.根据权利要求1所述的稀有气体回收系统,其中由所述第二冷凝介质的所述蒸发或部分蒸发形成的所述第二物流的蒸气部分与所述空气分离单元的废氮流结合。
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