CN111156787B - 氢液化与气体处理单元的一体化 - Google Patents

氢液化与气体处理单元的一体化 Download PDF

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CN111156787B
CN111156787B CN201911074536.7A CN201911074536A CN111156787B CN 111156787 B CN111156787 B CN 111156787B CN 201911074536 A CN201911074536 A CN 201911074536A CN 111156787 B CN111156787 B CN 111156787B
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hydrogen
stream
compressor
compressed
liquefaction
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CN111156787A (zh
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迈克·特尼
阿兰·吉亚尔
亚历山大·勒施
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/0062—Light or noble gases, mixtures thereof
    • F25J1/0067—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
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Abstract

披露了一种将氢液化的方法，该方法包括将氢流分成至少第一部分和第二部分，将该第一部分引入氢液化单元的制冷循环中，从而液化产物氢流，从该氢液化单元抽取一股或多股暖的氢流，以及使该一股或多股暖的氢流返回到该氢流中，其中该第二部分与高压氮流组合以形成氨合成气流。

Description

氢液化与气体处理单元的一体化
背景技术
氢液化单元以及氨生产单元的资本和运营支出的主要部分来自压缩设备。这典型地为氢压缩但也包括氮压缩。
对于氨生产单元，此压缩设备包括典型地从20-30绝对巴(例如来自PSA的出口)至>90绝对巴的氢压缩用于在氨生产反应器中与氮进行处理。氮气可以来自空气分离单元(ASU)或管道。
对于氢液化器单元，氢压缩典型地用于提供进料气体压缩以及制冷能量。这典型地呈小的低压水平压缩(典型地从1.1绝对巴入口至5-10绝对巴出口)以及大的高压水平压缩(典型地从5-10绝对巴至50-70绝对巴)的形式。通过制冷热传递的过程循环优化来选择中间压力水平(例如典型地5-10巴)作为流速与压力比之间的折衷，以得到最佳的高压压缩机和涡轮机设计。需要许多压缩和膨胀阶段，因为氢由于其非常低的分子量而难以压缩和膨胀。
已知工业场所通常具有可供使用的协同效应，使其成为多个过程单元的希望位置。这些协同效应典型地为电力、冷却水、仪表空气、允许甚至共享氢源的可用性。然而，进一步详述的过程协同效应由于对一个或两个过程的一体化限制而通常是不被预见或不可行的。
本发明的目的是减少工业氢液化和氨生产场所的资本和运营成本。
发明内容
本发明可通过以下已编号的句子进一步部分地定义：句1，一种将氢液化的方法，该方法包括：将氢流105分成至少第一部分303和第二部分304，将该第一部分303引入氢液化单元201的制冷循环中，从而液化产物氢流208，从该氢液化单元201抽取一股或多股暖的氢流212、215，以及使该一股或多股暖的氢流212、215返回到该氢流105中，其中该第二部分304与高压氮流110组合以形成氨合成气流111。
句2，如句1所述的方法，其中，该一股或多股暖的氢流212、215和该氢流105在同一压缩机408中被压缩。
句3，如句2所述的方法，其中，该第一部分303在该压缩机408下游被移除。
句4，如句2所述的方法，其中，在压缩机408与冷却器409之间抽取该第二部分304。
句5，如句2所述的方法，其中，在该压缩机408的压缩阶段之间抽取该第一部分303。
句6，如句2所述的方法，其中，该产物氢流208在该压缩机408上游被移除。
句7，如句2所述的方法，其中，在该压缩机408的压缩阶段之间抽取该产物氢流208。
句8，如句2所述的方法，其中，产物氢流208在该压缩机408下游被移除。
句9，如句1所述的方法，其中，该氢流105来源于在氢发生器中产生的合成气流。
句10，如句1所述的方法，其中，该氢流105来源于甲烷裂化器。
句11，如句9所述的方法，其中，该氢发生器包括部分氧化反应器或自热重整器。
句12，如句9所述的方法，其中，该氢流105通过变压吸附单元从该合成气流分离。
附图说明
为了进一步理解本发明的本质和目的，应结合附图来参考以下详细说明，在附图中相似元件给予相同或类似的参考号，并且其中：
图1是如本领域已知的典型的氨合成过程循环的示意图。
图2是如本领域已知的典型的氢液化过程循环的示意图。
图3是本发明的一个实施例的示意图。
图4是根据本发明的一个实施例的组合的氢液化单元和氨反应器的示意图，其中用于氢液化的制冷通过高压氮流的膨胀而产生。
图5是根据本发明的一个实施例的与图4中的***相容的气体分离单元的示意图。
图6是根据本发明的一个实施例的组合的氢液化单元和氨反应器的示意图，其中用于氢液化的制冷通过中压氮流的压缩以及随后的膨胀而产生。
图7是根据本发明的一个实施例的与图6中的***相容的气体分离单元的示意图。
图8是根据本发明的一个实施例的组合的氢液化单元和氨反应器的示意图，其中用于氢液化的制冷通过液氮流产生。
图9是根据本发明的一个实施例的与图8中的***相容的气体分离单元的示意图。
图10是根据本发明的一个实施例的以上***的细节的示意图。
图11是根据本发明的一个实施例的氢液化单元的细节的示意图。
图12是根据本发明的一个实施例的以上***的细节的示意图。
具体实施方式
元件编号101＝制氢单元
102＝合成气流
103＝氧流
104＝氢分离装置
105＝氢入口流
106＝空气分离单元(ASU)
107＝气态氮流
108＝氮压缩机
109＝氮冷却器
110＝高压气态氮流
111＝共混的反应物气流
112＝氨合成气压缩机
114＝氨合成气流
115＝氨反应器
116＝产物氨流
201＝氢液化冷箱
201a＝第一冷却区(在氢液化冷箱中)
201b＝第二冷却区(在氢液化冷箱中)
201c＝第三冷却区(在氢液化冷箱中)
202＝氮制冷循环
203＝第二制冷循环
204＝焦耳-汤姆逊(Joule-Thompson)膨胀机
205＝膨胀涡轮机
206＝闪蒸气体压缩机
207＝氢再循环压缩机
208＝产物液化的氢流
208a＝气态氢流(在氢液化冷箱内)
208b＝冷气态氢流(在氢液化冷箱内)
208c＝液化的氢流(在氢液化冷箱内)
209＝压缩的氢再循环流
210＝(压缩的氢再循环流的)第一部分
211＝冷的膨胀的第一部分
212＝暖的氢再循环气流
213＝(压缩的氢再循环流)的第二部分
214＝冷的膨胀的第二部分(闪蒸气流)
215＝暖的闪蒸气流
216＝闪蒸气体冷却器
217＝压缩和冷却的闪蒸气流
218＝氢再循环冷却器
301＝(氢入口流的)第一部分
302＝(氢入口流的)第二部分
303＝(压缩的氢再循环的)第一部分
304＝(压缩的氢再循环的)第二部分
401＝(氢入口流的)第一部分
402＝液氮流(至第二制冷循环)
403＝汽化的氮流(至第二制冷循环)
404＝压缩的氮流(至第二制冷循环)
405＝氮膨胀机(用于第二制冷循环)
406＝膨胀的氮流(至第二制冷循环)
407＝组合的氢气流
408＝氢气压缩机
409＝氢气冷却器
410＝冷却的压缩的氢气流
501＝进料空气流(至空气分离单元)
502＝主空气压缩机
503＝增压器/膨胀机
504＝主热交换器
505＝到HP柱的冷却的进料空气
506＝HP柱
507＝到LP柱的冷却/膨胀的空气
508＝LP柱
509＝液氧流
510＝液氧流泵
511＝第一液氮流
512＝第一液氮流泵
513＝第二液氮流
514＝第二液氮流泵
如本文使用的，术语“氢气压缩机”被定义为用于使氮纯度大于99％的气流增压的装置。此氢气压缩机可以是单个压缩机或多个串联或并联的压缩机。此氢气压缩机可以是往复式的。此氢气压缩机可以是离心式的。氢气压缩机可以被配置为允许一次或多次级间注射或抽取。
在本发明中，氨(NH3)生产单元和氢液化单元的氢和氮压缩要求是一体化的以降低设备成本并提高整体***效率。
在一个实施例中，将进料气体至氨单元的氢压缩与氢液化单元的氢再循环制冷压缩相组合。氢液化器的一个或多个制冷膨胀涡轮机的出口压力处于或接近来源氢的压力(约20-25绝对巴)。此氢液化器的一个或多个制冷膨胀涡轮机的出口压力也可以类似于氢液化压力或者液化压力可以类似于氢制冷压缩机的出口压力。类似地，液化器制冷剂回路的高压侧压力处于或接近氮混合的压力。此压力可以通过钎焊铝热交换器技术、低温氢膨胀机技术、来自空气分离单元(ASU)或压缩机的氮源压力、以及氨单元的要求的限制来优化。
这使得氢到氨单元的压缩服务能够与氢制冷再循环组合，这具有降低设备成本并提高效率的优点。例如，这可能是由于使用单个大压缩机，而不是两个较小的压缩机。
与典型的氢液化单元相比，结果是膨胀涡轮机出口与高压再循环压缩机入口之间的流的操作压力(从典型的5-10绝对巴至约20-25绝对巴)增加。这降低了氢压缩机和一个或多个膨胀机之间的膨胀比，导致较少的阶段和进一步的成本降低。降低的膨胀机压力比意味着对于产生相似量的制冷，流速必须增加。然而，由于现在压缩机与氨设备的氢压缩组合，因此净流速影响小。虽然，设想氢压缩机可以是往复式的，但也可以使用其他技术，如离心式的，其最近正在被开发用于接近这些压力的氢压缩。本领域技术人员将理解降低离心式氢压缩机的压力比的重要性，在该氢压缩机中每阶段低分子量产生低压力比，从而减少压缩和膨胀阶段的数量。
在另一个实施例中，使用单个ASU提供用于氨单元的气态氮以及用于向氢液化器制冷的N2(液体或高压气体)。任选地，同一个ASU可用于为部分氧化反应器(POX)或自热重整器(ATR)提供氧以产生氢。
LH2/NH3生产比率的优化
ASU将空气(其通常含有78％氮、21％氧和1％氩)分离成其组分元素。典型地，ASU的尺寸为基于一种组分(氮或氧)的需求，而另一种组分过量并且可能因此排放到大气中。例如，对于典型的氨设施，制氢单元的氧需求决定了ASU的分离能力，而氨反应器使用ASU的一些(但不是全部)可用N2。来自ASU的过量N2通常被排放到大气中。因此，对于根据其他过程如制氢单元、氨生产和氢液化的需求来优化从ASU中产生的可用的氧和氮的利用率存在需要。
因此，本领域技术人员将认识到出于将待液化的氢预冷却的制冷目的，所需的N2量与液氢生产流速成正比例。
还认识到氨反应器所需的高压气态N2的量与氨生产的量成比例。类似地，制氢单元(POX或ATR)所需的氧量与氨单元(除了氢液化器)所需的氢量成比例。
因此ASU所需的总N2是氨加上所产生的液氢的组合的函数[例如总ASU N2需求＝f(NH3产物流，LH2产物流)，场所设备]，同时ASU所需的氧是离开氨单元和液化单元的总氢的函数。[即来自ASU的氧需求＝f(NH3产物流，LH2产物流)]。结果，LH2/NH3产物的最佳比率可以基于以下确定：充分利用ASU中分离的可用的氧分子和氮分子，优选地不排放(或至少最小化排放)经分离的组分之一。
当液N2用作氢液化器的预冷却制冷剂时，然后可以使用以上三个函数1)氧需求、2)N2需求、和3)ASU性能来确定最佳的LH2/NH3生产比率是在0.12-0.15的范围内。类似地，当使用高压气态N2而不是液N2作为预冷却制冷剂时，取决于N2压力，最佳的LH2/NH3生产比率是在0.03-0.1的范围内。
现转向图1，展示了如现有技术中理解的氨合成过程循环的一个非限制性实例。根本地，氨合成需要氢入口流105和高压气态氮(N2)流110。典型地，这些反应物气流以基本上化学计量比共混。共混的反应物气流111然后被常规压缩112。压缩的共混的反应物气体、或氨合成气114然后被引入包含在氨反应器115内的一个或多个催化剂床(未示出)中，由此产生产物氨流116。
氢入口流105可以由任何来源如反应出口气体(未示出)提供，或有目的地在氢发生器101中产生。此种制氢***101可包括例如蒸汽甲烷重整器、甲烷裂化器、自热重整器(ATR)、或部分氧化重整器(POX)、或其组合。制氢***101产生合成气102，其含有氢和一氧化碳，通常连同一些二氧化碳和残余烃。氢分离装置104然后用于由此合成气流产生氢入口流105。此种氢分离装置104可以是变压吸附单元、和/或膜分离单元、或本领域已知的其他***。
高压气态N2流110可以由任何来源如反应出口气体(未示出)提供，或有目的地在空气分离单元(ASU)106中产生。通常通过使用ASU 106与需要氧流103的制氢***101(如POX或ATR)组合来实现协同效应。一种这样的协同效应将是当ASU 106中同时共同产生的气态N2流107被压缩108、被冷却109、并且然后与通过制氢***101产生的氢105共混、并且然后用于生产氨116。
在热力学上，氢入口流105和高压气态氮流110反应成氨流116需要该反应在升高的温度和压力下进行。这些条件通常为超过100绝对巴以及在约600℃的温度下。制氢***101如POX典型地在显著较低的压力(通常约30绝对巴)下操作。同样，虽然存在产生高压N2流的ASU 106设计，但典型地气态N2 107在大约40绝对巴的压力下产生。因此，单独地或作为组合流，此反应物流将需要在进入氨反应器115之前进行压缩112。
转向图2，展示了如现有技术中理解的典型的氢液化循环的一个非限制性实例。在典型的氢液化设施中，氢入口流105被送至氢液化冷箱201，在该冷箱中该氢入口流被首先冷却至大约-190℃。通常氢入口流105处于中等压力，典型地在20-30绝对巴。氢入口流105可以由以下来源如以上讨论的蒸汽甲烷重整器(SMR)、POX、ATR、变压吸附器(PSA)以及其他来源如需要附加压缩的氯碱单元的副产物、反应出口气体、或管道中的一种或多种提供。
制氢单元101之后通常是氢分离装置104如PSA、干燥器等。然而，这些暖的纯化单元在其将可能在氢液化温度(约-252℃)之前冻结的所有污染物去除的能力方面是受限的。氢PSA的典型出口可以排放具有在50至100ppm之间的N2以及ppm水平的Ar、CO和CH4的氢。这些污染物将冻结、堵塞、或损坏冷端氢液化设备。因此，工业内常见的是使用在大约-190℃温度下操作的冷吸附过程来将这些杂质去除至ppb水平。此冷吸附可以是分子筛类型吸附剂，随着温度变化再生。
在此种***中，通过在低温下通过含有活性炭(尽管具有安全问题)、硅胶、或分子筛的吸附床来进一步纯化经纯化的氢(典型地具有在1.0％与0.1％之间的杂质)。
在H2制冷剂循环中使用冷吸附器也是本领域已知的。需要从被液化的H2以及H2制冷剂循环二者中去除任何杂质(N2、Ar等)。理论上，对于完全封闭的H2制冷剂循环，仅可以在进入循环之前去除杂质。然而，实际上，由于密封损失所需的补充流，封闭的氢回路上存在吸附器，并且进入的任何小的杂质将随时间积累。
所需的制冷的至少一部分典型地由N2制冷202提供。N2制冷202除了利用氨、丙烷、或其他制冷剂的机械制冷单元之外，还可包括单个涡轮机、多个涡轮机、和/或具有增压器的涡轮机，汽化和加热液N2(未示出)。N2或其他制冷剂(未示出)可以从外部供应或由附近ASU供应。另外，N2制冷202可采用多级N2再循环压缩机来完成闭合回路(未示出)。
然后将由氮制冷循环冷却的气态氢典型地由第二制冷循环203在大约-252℃的氢液化冷箱201内进一步冷却并液化。用于此冷却水平的制冷可以由以下提供：开式氢制冷循环、或具有焦耳-汤姆逊膨胀机的封闭式氢制冷循环、或稠密流体机械涡轮机204、单个或多个涡轮机205、闪蒸气体压缩机206、以及氢再循环压缩机207。产物液化的氢流208离开氢液化冷箱201。
压缩的氢再循环流209进入氢液化冷箱201。压缩的氢再循环流209的第一部分210离开氢液化冷箱201并且在一个或多个膨胀涡轮机205中膨胀。冷的膨胀的第一部分氢流211然后再进入氢液化冷箱201并且与高纯度氢流105和压缩的氢再循环流209间接交换热。当加热的氢再循环气流212离开氢液化冷箱201时，其与压缩和冷却的闪蒸气体217(下方)组合，在氢再循环压缩机207中被压缩，被冷却218并作为压缩的氢再循环流209返回到氢液化冷箱201。
压缩的氢再循环流209的第二部分213继续通过氢液化冷箱201，离开之后经过焦耳-汤姆逊膨胀机或机械涡轮机204，因此产生冷的膨胀的第二部分氢流214。冷的膨胀的第二部分氢流、或闪蒸流214然后被再引入氢液化冷箱201中以与高纯度氢流105间接交换热。当加热的闪蒸气流215离开氢液化冷箱201时，然后将其在闪蒸气体压缩机206中压缩，冷却216，并与膨胀和加热的氢流212组合。此第二制冷循环典型地具有约60绝对巴的高侧压。
转向图3，展示了本发明的一个实施例。制氢***101和分离装置104可以提供氢入口流105，然而氢入口流可以由其他可用的来源如反应出口气体(未示出)提供。此种制氢***101可包括例如蒸汽甲烷重整器、甲烷裂化器、ATR、或POX、或其组合。制氢***101产生合成气102，其含有氢和一氧化碳，通常连同一些二氧化碳和残余烃。氢分离装置104然后用于由此合成气流产生氢入口流105。此种氢分离装置104可以是变压吸附单元、膜分离单元、或本领域已知的其他***。
氢入口流105的第一部分301被送至氢液化冷箱201，在该冷箱中该第一部分被首先冷却至大约-190℃。通常氢入口流105处于中等压力，典型地在20-30绝对巴。氢入口流105的第二部分302被送至与压缩和冷却的闪蒸气流217和加热的氢再循环气流212(二者均在以下讨论)共混。
所需制冷的至少一部分由N2制冷202提供。N2制冷202除了利用氨、丙烷、或其他制冷剂的机械制冷单元之外，还可包括单个涡轮机、多个涡轮机、和/或具有增压器的涡轮机，汽化和加热液N2(未示出)。N2从外部或由附近ASU、或其他制冷剂(未示出)供应。另外，N2制冷202可采用多级N2再循环压缩机来完成闭合回路(未示出)。
然后将冷却的气态氢由第二制冷循环203在大约-252℃的氢液化冷箱201内进一步冷却并液化。用于此冷却水平的制冷可以由以下提供：具有焦耳-汤姆逊膨胀机的氢制冷循环、或稠密流体机械涡轮机204、单个或多个涡轮机205、闪蒸气体压缩机206、以及氢再循环压缩机408。产物液化的氢流208离开氢液化冷箱201。
压缩的氢再循环流209的第一部分303(以下讨论的)进入氢液化冷箱201。第一部分303可以在氢气冷却器409(如图4、6和8中所示)之前抽取，或者可以在氢气冷却器409(如图12中所示)之前抽取。压缩的氢再循环流209的第二部分304离开液化***并且可以被送至氨反应器115。压缩的氢再循环流303的第一部分210离开氢液化冷箱201并且在一个或多个膨胀涡轮机205中膨胀。冷的膨胀的第一部分氢流211然后再进入氢液化冷箱201并且与高纯度氢流301和303间接交换热。当加热的氢再循环气流212离开氢液化冷箱201时，其与压缩和冷却的闪蒸气体217(下方)以及氢入口流105的第二部分302组合。然后将此组合流在氢再循环压缩机408中压缩并冷却409，从而产生压缩的氢再循环流209。
压缩的氢再循环流303的第二部分213继续通过氢液化冷箱201，离开之后经过焦耳-汤姆逊膨胀机或机械稠密流体涡轮机204，因此产生冷的膨胀的第二部分氢流214。冷的膨胀的第二部分氢流、或闪蒸气流214然后被再引入氢液化冷箱201中以与高纯度氢流105间接交换热。当加热的闪蒸气流215离开氢液化冷箱201时，然后将其在闪蒸气体压缩机206中压缩，冷却216，从而产生压缩和冷却的闪蒸气流217。此第二制冷循环典型地具有约60绝对巴的高侧压。
转向图4至11，展示了本发明的附加实施例。制氢***101可以提供氢入口流105，然而氢入口流可以由其他可用的来源如反应出口气体(未示出)提供。此种制氢***101可包括例如蒸汽甲烷重整器、甲烷裂化器、ATR、或POX、或其组合。制氢***101产生合成气102，其含有氢和一氧化碳，通常连同一些二氧化碳和残余烃。氢分离装置104然后用于由此合成气流产生氢入口流105。此种氢分离装置104可以是变压吸附单元、膜分离单元、或本领域已知的其他***。
气态N2流110可以由任何来源如反应出口气体(未示出)提供，或有目的地在ASU106中产生。通常通过使用ASU 106与需要氧流103的制氢***101(如POX或ATR)组合来实现协同效应。一种这样的协同效应将是当液N2被泵送并在ASU 106中被汽化，从而形成高压气态氢流110(在没有气态压缩机的情况下)，随后将其与通过制氢***101产生的氢105共混，并且然后用于生产氨116。
组合的氢气流407的第一部分401被送至氢液化冷箱201，在该冷箱中该第一部分被首先冷却至大约-190℃。所需制冷的至少一部分由N2制冷剂提供。氢流401可处于中等压力，典型地在20-30绝对巴。第一部分401可以在氢气压缩机408之前(401a或401b)或之后(401d)从氢入口流105移除。第一部分401可以从氢气压缩机408抽取(401c)。组合的氢气流407的第二部分302与压缩和冷却的闪蒸气流217和加热的氢再循环气流212(二者均在以下讨论)组合，因此产生组合的氢气流407，其然后被送至氢气压缩机408。
如以下更详细讨论的并且如图4和5所示，N2制冷剂403可以是通过在ASU 106内泵送和汽化在ASU 106内产生的高压气态N2流。此高压气态N2 403流将在氢液化单元中涡轮膨胀以在氢液化器中产生冷的较低压气态氢制冷剂流。
如以下更详细讨论的并且如图6和7所示，N2制冷剂403还可以是在ASU 106内产生的中压气态N2流。此中压气态N2 403流将被压缩108并冷却109，因此产生压缩的氮流404，然后可将其在氢液化单元中涡轮膨胀405以在氢液化器中产生冷的较低压气态氢制冷剂流406。
如以下更详细讨论的并且如图8和9所示，N2制冷剂402还可以是来自ASU 106的液N2，使得液N2在氢液化单元中通过热交换汽化和加热。
由于这些协同效应，在没有气态N2压缩机的情况下，通过利用ASU106的产生液N2或高压气态N2制冷剂流的能力将N2制冷提供至氢液化单元。类似地，在没有气态N2压缩机的情况下，通过在ASU中泵送和汽化将高压气态N2流提供至氨生产单元。
以下描述的附加细节可以在图11中找到。图11是氢液化冷箱201的示意图。区域201a是第一冷却区的符号表示，该第一冷却区通过与氮制冷剂的热交换占主导地位。在通过此第一冷却区后，氢流208a为冷的气态氢流208b，其将通常保持完全处于气相。区域201b是第二冷却区的符号表示，该第二冷却区通过与离开膨胀涡轮机205的冷的膨胀的氢第一部分的热交换占主导地位。在通过此第二冷却区后，氢流208b可以是部分液化或冷却的超临界流体，但通常将不是完全液化的。区域201c是第三冷却区的符号表示，该第三冷却区通过与离开焦耳-汤姆逊阀或稠密流体涡轮机204的冷的膨胀的闪蒸气流213的热交换占主导地位。在通过此第三冷却区后，氢流208c将是至少主要液化的并且作为产物液化的氢流208离开。
被液化的氢流208a、208b、208c典型地超过其13绝对巴的超临界压力。因此，流208a、208b和208c不以液态或气态而是以超临界状态存在。当储罐压力降至低于13绝对巴时，超临界流体208转变成液体。
加压的氢再循环流303的第一部分210离开氢液化冷箱201并且在膨胀涡轮机205中膨胀。第一冷却的膨胀的氢流211然后再进入氢液化冷箱201并且与氢流208间接交换热。
如图10所示，在一个实施例中，当加热的氢再循环气流212离开氢液化冷箱201时，可将其与压缩和冷却的闪蒸气体217(下方)以及第二部分105组合。然后将此组合流407在氢压缩机408中压缩并冷却409，从而产生压缩的氢流410。在另一个实施例中，当加热的氢再循环气流212离开氢液化冷箱201时，流212的至少一部分212a可以在中间位置被直接引入氢压缩机408并冷却409。
同样如图10所示，在一个实施例中，当压缩和冷却的闪蒸气流217离开氢液化冷箱201时，可将其与暖的氢再循环气流212以及第二部分302组合。然后将此组合流407在氢压缩机408中压缩并冷却409，从而产生压缩的氢流410。
图10还展示了加压的氢再循环流303可以从冷却的压缩的氢气流410移除，或者可以直接从氢压缩机408移除。
如图3至12所示，压缩的氢再循环流209的第二部分213继续通过氢液化冷箱201，离开之后经过焦耳-汤姆逊膨胀机或机械稠密流体涡轮机204，因此产生第二冷的膨胀的氢流214。第二冷的膨胀的氢流、或闪蒸气流214然后被再引入氢液化冷箱201中以与高纯度氢流208间接交换热。当加热的闪蒸气流215离开氢液化冷箱201时，然后将其在闪蒸气体压缩机206中压缩，冷却216，从而产生压缩和冷却的闪蒸气流217。此第二制冷循环典型地具有约60绝对巴的高侧压。
在离开压缩机408和冷却器409后，冷却的压缩的氢气流410与冷却的压缩的富N2流110共混，因此形成氨合成气流111。取决于来源流的压力，氨合成气流111可以然后(任选地)被压缩112。压缩的氨合成气114然后被引入氨反应器115，因此产生产物氨流116。
如图5所示，空气分离单元106可以在泵送循环中操作。在泵送循环中，低温泵510/512/514用于使液氧509或液氮511/513加压，然后使其汽化以产生加压的气态产物流103/107/403。在此过程中，冷却和冷凝至少一股高压空气流505提供了使泵送的氧和氮产物流汽化的能量。
图7中所示的循环类似于图5中所示的循环。元件编号相同且过程相同，因此循环的细节将不再重复。不同之处在于图7，第一氮流511作为中压气体离开柱并且因此不在主热交换器中被汽化，而是过热至接近环境温度。
图9中所示的循环类似于图5中所示的循环。元件编号相同且过程相同，因此循环的细节将不再重复。不同之处在于图9，第一氮流511作为中压液体离开柱并且因此不在主热交换器中被汽化，而是完全绕过该主热交换器。氮流402作为冷的中间压力(即4巴至10绝对巴)液流离开空气分离单元106并且可以任选地被过冷。
应当理解，由本领域技术人员可在如所附权利要求中所表述的本发明的原则和范围内做出本文已经描述以解释本发明的本质的细节、材料、步骤和零件布置上的许多附加的改变。因此，本发明不旨在限于以上给出的实例中的具体实施例。

Claims (11)

1.一种将氢液化的方法，该方法包括：
·将氢入口流(105)分成至少氢入口流(105)的第一部分(301)和氢入口流(105)的第二部分(302)，
·将该氢入口流(105)的第一部分(301)引入氢液化单元(201)的制冷循环中，从而液化产物氢流(208)，
·从该氢液化单元(201)抽取一股或多股暖的氢流(212、215)，以及
·使该一股或多股暖的氢流(212、215)返回到该氢入口流(105)的第二部分(302)中，
其中该氢入口流(105)的第二部分(302)与高压氮流(110)组合以形成氨合成气流(111)，
其中，该一股或多股暖的氢流(212、215)和该氢入口流的第二部分(302)在同一压缩机(408)中被压缩。
2.如权利要求1所述的方法，其中，压缩的氢再循环的第一部分(303)在该压缩机下游被移除。
3.如权利要求1所述的方法，其中，在压缩机(408)与冷却器(409)之间抽取压缩的氢再循环的第二部分(304)。
4.如权利要求1所述的方法，其中，在该压缩机(408)的压缩阶段之间抽取该压缩的氢再循环的第一部分(303)。
5.如权利要求1所述的方法，其中，该产物氢流(208)在该压缩机(408)上游被移除。
6.如权利要求1所述的方法，其中，在该压缩机(408)的压缩阶段之间抽取该产物氢流(208)。
7.如权利要求1所述的方法，其中，产物氢流(208)在该压缩机(408)下游被移除。
8.如权利要求1所述的方法，其中，该氢入口流(105)来源于在氢发生器中产生的合成气流。
9.如权利要求1所述的方法，其中，该氢入口流(105)来源于甲烷裂化器。
10.如权利要求8所述的方法，其中，该氢发生器包括部分氧化反应器或自热重整器。
11.如权利要求8所述的方法，其中，该氢入口流通过变压吸附单元从该合成气流分离。
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