CN1121174A - 带液态空气汽提操作的低温空气分离系统 - Google Patents

带液态空气汽提操作的低温空气分离系统 Download PDF

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CN1121174A
CN1121174A CN95108925.0A CN95108925A CN1121174A CN 1121174 A CN1121174 A CN 1121174A CN 95108925 A CN95108925 A CN 95108925A CN 1121174 A CN1121174 A CN 1121174A
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stripper
tower
liquid
sent
argon
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D·P·邦纳奎斯特
M·J·洛凯特
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Praxair Technology Inc
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Abstract

有利地分离原料空气的低温精馏系统，其中利用双塔主装置上游的汽提塔来减小氩塔顶部冷凝器和低压塔的热力学不可逆性。

Description

带液态空气汽提操作 的低温空气分离系统
本发明总的来说涉及原料空气的低温精馏，更具体地说，涉及采用具有相连的氩侧塔的双塔系统进行的原料空气的低温精馏。
生产氧、氮和/或氩的空气低温精馏是一种成熟的工业方法。原料空气通常在双塔系统中被分离成氮和氧，其中高压塔的富氮(nitrogen-rich)顶部蒸汽用于再沸低压塔的富氧釜底液。来自低压塔的流体送至氩侧塔中生产氩。
在低压塔中连有生产氩的测塔的双塔低温空气分离系统中，存在明显的热力学不可逆性，即氩塔顶部冷凝器中沸腾的釜液和冷凝氩之间存在大的温差。该温差可高于5℃，而连接高压塔和低压塔的主冷凝器中通常的温差小于1.5℃。由氩冷凝器的不可逆性而损耗的功的量值与现代空气分离系统中通过其它改进而获得的效益而言是很大的。为此，其中不可逆程度降低改进的低温空气分离系统是有意义的。
因此，本发明的目的是提供改进的低温精馏系统，其中降低了氩顶部冷凝器和低压塔之间的热力学不可逆性。
通过本发明能达到上述目的和其它目的，这对于阅读了本说明书的本专业人员来说是显而易见的。本发明的一个方面是：
采用包括高压塔和低压塔的双塔主装置和具有顶部冷凝器的氩塔进行的原料空气低温精馏方法，包括：
(A)冷凝一部分原料空气产生液态原料空气；
(B)将液态原料空气和气态原料空气送入汽提塔，并使液态原料空气与气态原料空气在汽提塔中逆向流动产生氮浓度比空气高的汽提塔产品气体和氧浓度高于25摩尔％的汽提塔产品液体；
(C)将汽提塔产品气体送入高压塔通过低温精馏进行分离；
(D)通过在氩塔顶部冷凝器中与含氩流体进行间接热交换至少部分汽化汽提塔产品液体产生含氧气体；和
(E)将含氧气体送入低压塔通过低温精馏进行分离。
本发明的另一方面是：
低温精馏设备，包括：
(A)包括第一塔和第二塔的双塔主装置和具有顶部冷凝器的氩塔；
(B)汽提塔，将液体送入汽提塔上部的装置和将气体送入汽提塔下部的装置；
(C)将流体自汽提塔上部送入第一塔的装置：
(D)将流体自汽提塔下部送入顶部冷凝器的装置；和
(E)将流体自顶部冷凝器送入第二塔的装置。
本说明书所用“原料空气”指主要包括氮、氧和氩的混合物，如空气。
本说明书所用“涡轮膨胀”和“涡轮膨胀机”分别指使高压气流通过涡轮机以减小气体的压力和温度从而产生致冷作用的方法和设备。
本说明书所用“塔”指蒸馏塔或精馏塔或蒸馏区或精馏区，即这样一种接触塔或接触区，液相和汽相在其中逆向接触以实现流体混合物的分离，例如通过在塔内安装的一系列竖向间隔的塔盘或塔板上和/或在结构填料、无规填料等填料上使气相和液相接触。关于蒸馏塔可进一步参见the Chemical Engineer′s Handbook fifth edition，由R.H.Perry和C.H.Chilton编辑，McGraw-Hill Book Compang，New York出版，Section 13，The Continuous Distillation Process。“双塔”优选意味着高压塔的顶端与低压塔的底部具有热交换关系。关于双塔可进一步参见Ruheman“The Separation of Gases”，Oxford University Press，1949，Chapter VII，Commercial AirSeparation。利用高压塔和低压塔结合的其他双塔装置也可用于本发明的实际操作。
蒸汽和液体的接触分离过程取决于各组分的蒸汽压差。高蒸汽压(易挥发或低沸点)组分将倾向于在汽相浓缩，而低蒸汽压(难挥发或高沸点)组分将倾向于在液相浓缩。部分冷凝是这样一种分离过程，借助于这种分离过程蒸汽混合物的冷却可用于在汽相中浓缩易挥发组分，而在液相中浓缩难挥发组分。精馏或连续蒸馏是这样一种分离过程，它结合了由汽相和液相逆流处理而获得的连续部分汽化和冷凝过程。汽相和液相的逆流接触是绝热的，并且包括各相间的积分或微分接触。利用精馏原理分离混合物的分离过程装置常称为精馏塔、蒸馏塔或分馏塔，这些名称可换用。低温精馏是至少部分地在温度等于或低于150K的温度下进行的精馏过程。
本说明书所用“间接热交换”指使两股流体物流处于热交换关系而不直接接触或相互混合的过程。
本说明书所用“氩塔”指处理包含氩的进料并产出氩浓度高于进料的产品的塔。
本说明书所用“顶部冷凝器”指由塔顶蒸汽产生塔内降流液体的热交换装置。
本说明书所用“上部”和“下部”分别指高于或低于塔中间点的区域。
本说明书所用“结构填料”指各单个填料相互之间以及相对于塔轴都具有特定取向的填料。结构填料的实例可参见USP4,186,159-Huber，USP4,299,050-Meier，USP4,929,399-Lockett等和USP5,132,056-Lockett等。
本说明书所用的“液氮”指氮浓度至少为78摩尔％的液体。
本说明书所用的“液氧”指氧浓度至少为20摩尔％的液体。
本说明书所用的“平衡级”指离开的汽体和液体物流处于平衡的汽液接触过程。
本说明书所用的“过冷却”指将液体冷却到低于所在压力下液体的饱和温度。
本说明书所用的“汽提塔”指这样一个塔，其中液体引入到该塔的上部，通过上升蒸汽从下行液体中脱除或汽提易挥发的组分。
图1—4是本发明低温精馏系统优选实施方案的各示意流程图。
图5是本发明另一实施方案某些方面的横剖面简图，其中汽提塔置入装有高压塔的壳体。
本发明是一个低温空气分离系统，其中，液体在氩塔的顶部冷凝器中沸腾，它含有的氧摩尔分数通常比来自常规系统的高压塔槽中的液体高。本发明利用较矮的汽提塔以提高进入高压塔底的蒸汽含氮量，并提供用于氩塔顶部冷凝器的氧摩尔分数高的液体。来自高压塔槽的流体，即釜液，在氩塔顶部冷凝器中不汽化或部分汽化，而是被过冷却并在比常规方法中釜液和汽化釜液通常进入塔的位置高的位置进入低压塔。这种液体用作中间回流物流(intermediate reflux stream)，通过松开通常位于釜液和汽化的釜液通常进入常规方法的低压塔的位置的上边一点的夹子(pinch)，提高低压塔的分离程度。分离程度的提高表现为用给定高度的塔以给定的纯度回收更多的进料空气中更大部分的进入氩，或在固定的回收率和固定的塔高条件下提高了氩的纯度，或在固定的回收率和固定的纯度条件下减小了所需的塔高。这样就至少部分降低了前述氩塔顶部冷凝器的热力学不可逆性，提高了氩的回收率，或提高了氩的纯度，或降低了塔的高度。
现在参考图对本发明进行更详细说明。图1说明本发明的一个特别优选实施方案。现参见图1，压力通常为70—500psia(磅/平方英寸，绝对压力)的原料空气1在主热交换器32中与返回物流间接换热而冷却。产生的冷却原料空气物流2可分为主要部分3和次要部分8。包括进入系统的原料空气总量的0～10％的次要部分8在热交换器33中与返回物流间接换热而被液化，而热交换器33产生的物流9送入汽提塔34，这将在后面做更详细的描述。主要部分3在涡轮膨胀机35中进行涡轮膨胀产生致冷作用，同时产生的物流4被分为次要部分6和主要部分5。
包括系统中所用的全部原料空气(即送入双塔主设备的全部原料空气)的约20％至45％的物流6送入产品蒸发器36，在此与沸腾的液氧进行间接热交换而被冷凝。产出的液态原料空气7送入汽提塔34的上部。在图1所示的优选实施方案中，物流7与物流9结合形成物流10，然后送入汽提塔34的上部。气态原料空气物流5送入汽提塔34的下部。
汽提塔34是一个较小的塔，一般有大约1至10个平衡级，典型的是具有约5个平衡级。在汽提塔34中，液态原料空气向下流动，与向上流动的气态原料空气逆向流动。在该过程中，氮从向下流动的液体中汽提出来进入向上流动的气体中，结果生成氮浓度超过空气的汽提塔产品气体和氧含量超过空气的汽提塔产品液体。通常，汽提塔产品气体的氮浓度在79～90摩尔％范围内，优选高于85摩尔％。汽提塔产品液体的氧浓度至少为25摩尔％，通常在33～45摩尔％范围，优选高于40摩尔％。而在常规的系统中，从高压塔送到氩塔顶部冷凝器的釜液的氧浓度一般仅约为33摩尔％。
汽提塔产品气体随物流15从汽提塔34的上部送入塔37，塔37是包括塔37和第二塔即低压塔38的双塔主设备的第一塔即高压塔37。塔37通常在压力为70～150psia的范围内操作。在塔37内通过低温精馏将汽提塔产品气体分离成为氮增浓(nitrogen-enriched)蒸汽和氧增浓液体。氮增浓蒸汽经管线39进入主冷凝器43，在其中与塔38塔底液通过间接热交换被冷凝。生成的氮增浓液体随物流44流出主冷凝器43。一部分氮增浓液体45作为回流返回高压塔37，氮增浓液体的另一部分21在热交换器33中被过冷却并且通过阀门46作为回流进入低压塔38。如果需要，例如由物流25表示的一部分氮增浓液体可作为产品液氮回收。
氧浓度通常在22～32摩尔％的氧增浓液以物流20形式从塔37下部引出。氧增浓液体的氧浓度一般小于常规双塔系统的高压塔釜液的氧浓度。物流20中的氧增浓液体在热交换器33中过冷却，然后通过阀门47在低于氧增浓液体物流21进入塔38的位置处进入低压塔38。
汽提塔产品液体以物流11形式从汽提塔34的下部引出，在过冷却器即热交换器33中与返回物流逆流流动而过冷却，并送入顶部冷凝器48的沸腾侧。氩浓度至少为90摩尔％的含氩蒸汽送入顶部冷凝器48的冷凝侧，这在后边将作详细说明。在顶部冷凝器48内，汽提塔产品液体通过与顶部冷凝器48内的含氩流体间接热交换而至少部分汽化。生成的含氧气体随物流12从顶部冷凝器48通过阀门49在低于高压塔釜液随物流20进入塔38的位置处进入低压塔38。剩余的含氧液体可随物流13从顶部冷凝器48通过阀门50进入低压塔38。
低压塔即第二塔38在低于高压塔即第一塔37的操作压力下操作，并通常为15～25psia。在塔38中，进入该塔的各种进料通过低温精馏分离成为富氮蒸汽和富氧液体。富氮蒸汽随物流29从塔38的上部引出，流经热交换器33和32而被暖热，并随物物流31从系统中引出，它可作为氮浓度等于或高于99摩尔％的氮气产品回收。为控制产品纯度，废料物流40可在低于物流29引出的位置处从塔38中引出，流经热交换器33和32而被暖热，并随物流42从系统中引出。
如前所述，富氧液体被汽化以便向塔38提供上流的蒸汽，与冷凝氮增浓液体逆向流动。一部分生成的富氧气体可直接从塔38回收。图1表明本发明的优选实施方案，其中富氧液体用于进行部分原料空气的冷凝，产生液态原料空气，送入汽提塔。在该优选实施方案中，一部分富氧液体从塔38或主冷凝器43中以物流89形式引出，然后进入产品蒸发器36。如需要，富氧液体可流经液体泵51或利用单元43和36之间的高度差所产生的液体压头来增加压力。同样，如需要，一部分富氧液体也可作为产品液氧回收，如物流88所示。进入产品蒸发器36的富氧液体在其中与前述的冷凝原料空气逆流流动而被汽化。生成的富氧气体随物流90从产品蒸发器36中引出，并流经主热交换器32而被暖热，并以物流91形式离开系统，它可作为氧浓度通常在99～99.9摩尔％范围的氧气产品回收。
本发明的实际操作中，顶部冷凝器48是氩塔顶部冷凝器，氩塔可以是粗氩塔，即具有约40～60个平衡级并产生氩浓度为90～99摩尔％的粗氩的塔。优选氩塔是精氩塔，其中使用结构填料作为塔的传质内构件，这样能够进行具有150或更多个平衡级的塔操作，并生产出氩浓度为99.999摩尔％或更高的含氩流体。当使用这样一个大的或超级的氩塔时，优选塔分为两部分，这种两部分的氩塔示于附图中。
现在再参考图1，氩塔由第一部分52和第二部分53组成。含有约8～25摩尔％的氩而其它主要成分为氧的流体随物流115从低压塔38进入氩塔第一部分52，在此通过低温精馏分成更富氧的液体和中间蒸汽。更富氧的液体随物流116从氩塔第一部分52送回到低压塔38。中间蒸汽随物流54从氩塔第一部分52送入氩塔第二部分53，在其中通过低温精馏分成为含氩蒸汽和中间液体。中间液体沿管线117从氩塔第二部分53送入氩塔第一部分52作为低温精馏的降流液体。如需要可由液体泵55将物流117的液体泵至氩塔第一部分52顶部。通常氩塔第一部分52具有40至60个平衡级，而氩塔第二部分53具有110至140个平衡级。
含氩蒸汽沿管线56从氩塔送入顶部冷凝器48的冷凝侧，在此该蒸汽与前述的蒸发汽提塔产品液体逆流流动而至少部分冷凝。在顶部冷凝器48内的含氩流体可以是粗氩，也可以是氩浓度为99.999摩尔％或更高的精氩，这取决于所用氩塔的类型。生成的冷凝的含氩流体作为回流沿管线57返回氩塔。在图1所示的实施方案中，管线57从顶部冷凝器48连至氩塔第二部分53。一部分含氩流体以气体或以液体形式沿管线125作为产品回收。
本发明能够改进运转性能，即通过在氩塔顶部冷凝器中采用具有较高氧浓度的液体作为沸腾流体，较之常规方法降低了功的输入。这样能够使得氩塔顶部冷凝器中的温度差减小。此外，由于送入高压塔的原料空气的氮摩尔分数比常规系统高，所以从高压塔送入低压塔的釜液也具有更高的氮浓度。这导致与低压塔内的液体组成的更好匹配，提高了低压塔的分离性能。这样增加了氩塔内产生的氩的回收率或纯度，或在减少功输入的情况下也有相当的回收率或纯度。例如，与具有氩侧塔和对流程具有固定净功输入的常规双塔系统比较，在所有塔的相同平衡级数目条件下，由本发明提供的附加分离作用将氩的回收率从原料空气物流中所含氩的约85％提高到约92％。对于固定的氩回收率，净功输入与常规系统比较可减少约3.5％。
图2—4说明本发明其它优选实施方案。各图中相同的部件用相同的数字表示，对这些相同的部件不再作详细描述。
参见图2，这里所描述的是这样一种实施方案，其中进入产品蒸发器36的原料空气不是来自通过涡轮膨胀机35涡轮膨胀过的原料空气。在该实施方案中，第二原料空气物流300流经主热交换器32而冷却。产生的物流301分成物流303和物流302，其中物流303在热交换器33中液化，并成为物流9，而物流302进入产品蒸发器36并成为物流7。物流303包括进入系统的原料空气总量(即物流1和300)的约0～10％，而物流302包括进入系统的原料空气总量的约20～45％。
在图3所示的实施方案中，用作汽提塔上流蒸汽的原料空气物流没有经过涡轮膨胀。在这个实施方案中，另一原料空气物流400流经主热交换器32而冷却，并且产生的物流401通过涡轮膨胀机58而被涡轮膨胀，涡轮膨胀后的物流402与汽提塔34下部的沸腾液体间接热交换被进一步冷却，然后以物流403形式送入低压塔38。在这个实施方案中，涡轮膨胀后的原料空气物流包括进入系统的全部原料空气(即物流1,300和400)的0～15％，而进入汽提塔的气态原料空气包括进入系统的全部原料空气的50％至80％。
在图4所示的实施方案中，来自高压塔37的一部分氧增浓釜液体99通过阀门59送入汽提塔34的上部。这样能够增加物流11的流速。如氩塔顶部冷凝器制冷要求高的话，这是有益的。
图5表示本发明有关部分中的其他具体实施方案，其中汽提塔被装在与高压塔即第一塔相同的一个塔壳中。这个具体方案的操作基本上与其它实施方案相同，因而不再具体描述。图5中的数字与图1中相应的数字一样表示相同的作用。
利用本发明，可在减小氩塔顶部冷凝器和低压塔的热力学不可逆性的情况下，以更高的效率进行低温空气分离。虽然参考一些优选实施方案对本发明进行了详细的表述，但本专业的普通技术人员会认识到在权利要求的精神范围内本发明还有其它的实施方案。

Claims (16)

1.采用包括高压塔和低压塔的双塔主装置和具有顶部冷凝器的氩塔进行的原料空气低温精馏方法，包括：
(A)冷凝一部分原料空气产生液态原料空气；
(B)将液态原料空气和气态原料空气送入汽提塔，并使液态原料空气与气态原料空气在汽提塔中逆向流动产生氮浓度比空气高的汽提塔产品气体和氧浓度高于25摩尔％的汽提塔产品液体；
(C)将汽提塔产品气体送入高压塔通过低温精馏进行分离；
(D)通过在氩塔顶部冷凝器中与含氩流体进行间接热交换至少部分汽化汽提塔产品液体产生含氧气体；和
(E)将含氧气体送入低压塔通过低温精馏进行分离。
2.根据权利要求1的方法，其中冷凝原料空气部分占全部所用原料空气的20％至45％。
3.根据权利要求1的方法，其中通过与取自低压塔的液氧间接热交换，冷凝所述一部分原料空气。
4.根据权利要求1的方法，其中气态原料空气在送入汽提塔之前进行涡轮膨胀。
5.根据权利要求1的方法，还包括使原料空气物流与汽提塔的液体进行间接热交换，接着将所述的原料空气物流送入低压塔。
6.根据权利要求1的方法，其中汽提塔产品液体先进行过冷却，然后与含氩流体间接热交换而至少部分汽化。
7.根据权利要求1的方法，其中汽提塔产品液体的氧浓度高于33摩尔％。
8.根据权利要求1的方法，还包括回收下列产品的至少一种：i)取自低压塔的产品氮，ii)取自低压塔的产品氧，和iii)取自氩塔顶部冷凝器的产品氩。
9.低温精馏设备，包括：
(A)包括第一塔和第二塔的双塔主装置和具有顶部冷凝器的氩塔；
(B)汽提塔，将液体送入汽提塔上部的装置和将气体送入汽提塔下部的装置；
(C)将流体自汽提塔上部送入第一塔的装置；
(D)将流体自汽提塔下部送入顶部冷凝器的装置：和
(E)将流体自顶部冷凝器送入第二塔的装置。
10.根据权利要求9的装置，还包括产品蒸发器；用于将液体自第二塔送入产品蒸发器的装置；和用于将液体自产品蒸发器送入汽提塔的装置，所述装置包括将液体送入汽提塔上部的装置。
11.根据权利要求9的装置，还包括涡轮膨胀机和将气体自涡轮膨胀机送入汽提塔的装置。
12.根据权利要求9的装置，其中用于将流体自汽提塔下部送入顶部冷凝器的装置包括过冷却器。
13.根据权利要求9的装置，其中氩塔传质内构件包括结构填料(Structured packing)。
14.根据权利要求13的装置，其中氩塔包括至少150个平均级(equilibrium stage)。
15.根据权利要求14的装置，其中氩塔分为两部分。
16.根据权利要求9的装置，其中汽提塔和第一塔装在同一塔壳内。
CN95108925.0A 1994-07-14 1995-07-13 带液态空气汽提操作的低温空气分离系统 Pending CN1121174A (zh)

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