CN1058266A - 空气分离 - Google Patents

空气分离 Download PDF

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CN1058266A
CN1058266A CN91104809A CN91104809A CN1058266A CN 1058266 A CN1058266 A CN 1058266A CN 91104809 A CN91104809 A CN 91104809A CN 91104809 A CN91104809 A CN 91104809A CN 1058266 A CN1058266 A CN 1058266A
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heat exchanger
air
nitrogen
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stream
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J·T·拉文
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Abstract

提供了一种分离空气的方法和装置。该方法包 括在主热交换器中利用热交换将压缩空气流的温度 降低到适合用精馏将其分离的温度，在双精馏柱中精 馏空气，从其低压柱排出氧和氮气流，使之以与空气 流逆流的方式通过主热交换器，至少部分氮气流在涡 轮中膨胀并以与空气流相反的方向通过主热交换器， 从而产生制冷作用并保持该膨胀的氮气与被冷却的 空气流之间的平均温差至少为10K。因此热交换器 的尺寸可比常规工厂大大减小。

Description

本发明涉及空气分离。
包括氧化步骤的现代工业和化学过程需要很大量的氧来进行该氧化步骤。利用空气分离法每天可以制出2000吨以上的氧，该方法包括将空气流压缩，由空气流中除去诸如水蒸汽和二氧化碳这类挥发性较低的组分从而将该空气流纯化，将这样纯化的空气流冷却到适合用分馏或精馏法进行分离的温度，然后进行该分离以得到所要求纯度的氧产物。最好是用吸附剂床进行该纯化，该床吸附低挥发性的组分，例如水蒸汽和二氧化碳。空气的分馏最好是在双柱分馏器内进行，它包括一个高压分馏柱和一个低压分馏柱，二者共用一个热交换器，该交换器在高压柱的顶部将氮冷凝，在低压柱的底部使富氧的液体再沸。这样形成的液体氮的一部分作为高压柱的回流使用，其余的则从高压柱中取出，低温冷却，通过一个膨胀阀进入低压柱的顶部，为该柱提供回流。将空气引入高压柱。富氧的液态空气则由高压柱的底部排出，通到低压柱，在那里通常分离成基本上纯的氧和氮产物。这些产物可以从低压柱中以气态形式排出，以与输入的空气逆流热交换的方式温热到环境温度，从而将输入的空气冷却。因为此过程在低温下操作，所以必须制冷。通常是将一部分输入空气在涡轮中膨胀，或是从高压柱中取出氮气流并使其通过膨胀式涡轮来实现制冷。
这种空气分离工厂现在很常见。几乎是普遍地，低压柱都在1.3至1.7巴、高压柱在5.5至6.5巴的范围内的压力下操作。选择这样的操作压力是因为可以使产物氮和氧气流在温热至环境温度之后处于略高于大气压的压力。
实际上，当柱体要在远离空气分离工厂的预定地点处制造时，机械工程和运输限制决定了这种空气分离工厂的规模的上限。用工厂每天制造的氧的总吨数表示，这一限制是在每天2500吨的量级。因此，所谓的由煤制油的Sasol方法需要几个空气分离工厂以满足它对氧的需求，因为它的需氧量远超过每天5000吨。
曾经提出高压柱和低压柱分别在远大于常规的5.5-6.5巴和1.3-1.7巴的压力下进行操作。采用这样高的压力的主要理由是在低压柱中实现更有效的分离。这一建议的缺点是，当生产出的氮供大于求时，就会产生如何处理所得到的高压产物氮气流的问题。曾经提议从氮气流中回收能量来解决这一问题，作法是使氮气流在涡轮中膨胀，利用这一能量产生电力输出。这一建议一般来说确实有利。但是，有些地方电力的输出是不可能的或不需要的。本发明涉及利用氮气产物的另一种方法和设备。
根据本发明，提供了一种分离空气的方法，包括利用在至少一个主热交换器中的热交换将压缩的空气流的温度降低到适合用精馏法进行分离的温度，在双精馏柱中精馏该空气，从双精馏柱的低压柱中排出氧气流和氮气流，将氧气和氮气流以与空气流逆流热交换的方式通过主热交换器，其中低压精馏柱在至少2巴的压力下操作，至少部分氮气流在涡轮中膨胀并且以与空气流逆流的方式流过主热交换器以产生制冷作用，同时维持主热交换器内膨胀的氮气流与被冷却的空气流之间的平均温差至少为10K。
本发明还提供了用于分离空气的装置，包括至少一台主热交换器，用来将压缩空气流的温度降低到适合用精馏进行分离的温度，一台双精馏柱，它有一个与贯穿上述主热交换器的空气流通道相连的空气入口，双精馏柱中低压柱有用来排出氧气流和氮气流的出口，所述出口与贯穿主热交换器的通道相连，一台膨胀式涡轮用来使至少一部分氮气流膨胀并且以与压缩空气流逆流的方式将其送回到所述主热交换器，该涡轮的安排使得氮气流与使用该装置进行冷却的空气流之间的平均温度差能保持至少10K。
最好是，采用至少部分氮气流在精馏柱和主热交换器所位于的保温室外起冷却作用。这种在保温室外进行的冷却作用可以例如是从压缩空气流中除掉压缩热、将用来在空气分离装置处进行冷却作用的水冷却、或是将在空气分离装置处产生的气体混合物中至少一种组分冷凝下来。
所述的温度差最好是至少20K。
在空气分离技术中通常设法使在其热交换器内被温热的气流与被冷却的气流之间保持小的温差。这样一种措施使能量的利用更为有效，但是需要更大的热交换器。被温热的气流和被冷却的气流之间的温差大时，主热交换器可以制作得较小。特别是当主热交换器是矩阵型时，它可以由较少的部件构成，从而减少对歧管、管道及其它辅助设备的需要。这不仅使主热交换器本身的成本降低，而且也减小了该空气分离装置中低温操作的部件位于其中的保温室（有时称作“低温箱”）的尺寸。另外，氮气流本身在离开主热交换器时的温度较低，这有利于将它用于低温箱外的冷却作用。
再者，在低压精馏柱的压力为至少2巴（最好是压力为2.5-4.5巴）下操作，由给定尺寸的双精馏柱生产氧的产率可能会更高。
使用氮气流从压缩空气流中除去压缩热有助于减少空气分离装置对冷水的需求，因此可以减小用来向空气分离装置和其它装置供应这种冷却水的冷却塔的尺寸。
氮气流也可以直接用来冷却冷却塔中的水。氮的这一用途有可能减小用来冷却水的机械制冷设备的尺寸，或完全不用它。另外，与常规的工厂比较，有可能将水冷却至更低的温度，使其成为更有效的冷却剂，从而有可能减小为将水冷却所需的装置的尺寸。水的冷却最好是以把氮气直接通入水中与之接触的方式来进行。
现在通过实施例并参照附图说明本发明的方法和设备，这些附图是一个空气分离工厂的示意图。
参照附图，画出的装置包括一个多级压缩机2，它具有压缩级4、6和8，紧随其后的分别是后冷却器10、12和14。后冷却器10和12是水冷式。空气流在压缩机2中被压缩至约11巴的压力。然后将空气通过一台纯化装置16，它能有效地从输入的空气中除掉低挥发性的杂质，主要是水蒸汽和二氧化碳。装置16使用吸附剂床从输入的空气中吸附水蒸汽和二氧化碳。这些吸附床可以相互无顺序地工作，以便当用一个或几个吸附床纯化空气时，对剩下的一个或几个吸附床进行再生，通常是用氮气流法再生。然后将纯化过的空气流分成主气流和次气流。
主气流通过主热交换器18，气流的温度在其中被降到适合于用精馏法在低温下进行空气分离的程度。
如图所示，主热交换器18是一个单件设备。但是可以用多个主热交换器彼此串联或并联，或是串联与并联排列相结合。主空气流在主热交换器18中通常被冷却到它在支配压力下的饱和温度，并且以此温度离开热交换器18的冷端。然后经由入口20将主空气流引入构成双精馏柱22一部分的高压精馏柱24中。这里所用的术语“双精馏柱”是指一种包含两个精馏柱和一个冷凝-再沸器的装置，两个精馏柱中的一个在比另一个更高的压力下操作，冷凝-再沸器将来自高压精馏柱的氮蒸汽冷凝，将低压柱的富氧液体馏分再沸。因此，在附图中的柱24之上还画出了低压精馏柱26。精馏柱24和26都包含着液体-蒸汽接触塔板和相连的泄液管（或其它装置，未画出），藉此使下降的液相与上升的蒸汽相紧密接触，使得在此两相之间发生质量传递。在每个柱中，下降的液相逐渐地富集氧，而上升的蒸汽相则逐渐地富集氮。高压柱24在压力略低于输入空气被压缩的压力下操作。柱24的操作条件最好是使其顶部产生基本上纯的氮馏分，但其底部的氧馏分中仍含有相当比例的氮。
柱24和26通过冷凝-再沸器28连在一起。冷凝-再沸器从高压柱24的顶部接收氮蒸汽，通过与柱26中的沸腾液态氧进行热交换而冷凝。所得到的冷凝物送回到高压柱24。一部分冷凝物为柱24提供回流，其余的则收集在一起，经由出口40排出其液流，在热交换器42中低温冷却，经过膨胀阀44通入低压柱26的顶部，从而为低压柱26提供回流。
低压精馏柱26在大约3.3巴的压力下操作，由两个来源接收氧-氮混合物用于分离。第一个来源是由离开纯化装置16的空气流分出的次空气流。该次空气流在增压压缩机34中被压缩（通常压缩至20巴左右），然后与主空气流并流地通过主热交换器18，由主热交换器18的温热端到它的某个中间位置，由其该中间位置在200K左右的温度下排出，然后在膨胀式涡轮36中膨胀到低压精馏柱26的操作压力。经过入口38将膨胀的次空气流引入柱26中。膨胀式涡轮36可以与增压压缩机34结合以驱动压缩机34，从而不必为此再提供外部动力。但是，另一种作法是两台机器可以彼此独立。这种独立的安排常常更好，因为这样可以使每种机械的出口压力彼此独立地设定。
用于在低压精馏柱26中进行分离的氧-氮混合物的第二个来源是取自高压柱24底部的富氧馏分液流。将该液流在热交换器30中低温冷却，然后通过一个焦耳-汤姆逊阀32流入柱26中。
经过出口46从低压柱26中排出产物氧气流，将其以与输入空气流逆流的方式通过主热交换器18，温热到近于环境温度。此外，经过出口50从低压精馏柱26的顶部排出产物氮气流，先以与在热交换器42中低温冷却的液氮流成逆流的方向通过该热交换器42然后流过热交换器30，其方向与在其中冷却的富氧液体成逆流热交换关系。该氮气由于通过热交换器30而被进一步温热。然后流入主热交换器的冷端，流过该热交换器的一部分通路。随后将该氮气流分成两份。它的一部分由主热交换器排出（例如在大约130K的温度下），在膨胀式涡轮52中膨胀到压力略高于大气压。该氮气流在离开膨胀式涡轮52时的温度通常比主空气流离开热交换器18时的温度低10K左右。在热交换器18温热端方向上的温差最好大些，使得在温热端处的温差为20K左右，而两个液流在热交换器长度上的平均温差大于10K。然后使如此膨胀的氮气流返回热交换器，由其冷端流到其温热端，从而能保持它与被温热的主空气流之间的相当大的平均温差。一旦离开主热交换器18的温热端，膨胀的氮气流就可以用于在纯化装置16中的再生处理。
没有从主热交换器18中取出并在涡轮52中膨胀的那部分氮气流继续与主空气流以逆流的方式流过热交换器18。它离开主热交换器18的温热端的温度通常比环境温度低大约10-20K。这部分氮特别适合在工厂中那些在低温下操作的部分的外面起冷却或制冷作用。例如，如附图所示，该气流可用来为后冷却器10、12和14中的一个提供冷却。如图所示，后冷却器14是用氮冷却的。然后将生成的温热的氮在例如膨胀式涡轮54中减压，从而使其温度再次降至低于环境温度，并且通入到冷却塔56中，该塔用来向空气分离工厂所处地区的其它部位的机械提供冷却作用。因此，来自涡轮54的膨胀的氮气可以直接引入冷却塔56的水中。进一步骤造成了水的蒸发冷却，结果水温可以降低大约5℃。由于利用氮气来冷却压缩机2，对冷却水的需求减少了，从而有可能减小冷却塔56的尺寸。另外，由于使用氮来冷却水，有可能进一步减小对使用氟利昂或其它制冷剂的辅助制冷设备的需求及其大小。在一个实施例中，在涡轮54中的膨胀可以用来将氮的温度从约350K降至约285K。
利用膨胀式涡轮52来维持主热交换器中被冷却的气流与被温热的气热之间较大的温差，对于以指定产率生产氧的工厂而言，热交换器的尺寸可以比常规的小。另外，通过在3巴左右的压力下操作低压柱，有可能在工厂中每天生产3000吨以上的氧，而该工厂的柱体尺寸仍能使它们能在异地制造。如果对氧的需求量特别大，例如每天10000吨左右，则可以用三个工厂而不是四个工厂满足这一需要。考虑到在制造热交换器方面可能另外节省的开支，成本可以大大降低。再者，由于主热交换器可以制作得较小，工厂中在低温下操作的部分位于其中的低温箱或保温室的尺寸也因此减小，这就可以进一步节省资金（保温室在图中用虚线示出）。由于在主热交换器18中被冷却的气流与被温热的气流之间维持较大的温差，工厂的功率消耗会增加，但是对于有丰富的天然能源但是离主要工业中心很远的地点，能量的输出变得不经济，上述因素也就变得不重要。这类地点的实例是边远地区的天然气田。
对于示于附图的工厂可以作许多改动和变化。使用膨胀的氮气流对冷却塔和压缩机2的一台后冷却器提供冷却作用仅仅是作为实例，说明在环境温度左右而不是在低温下能利用的氮的冷却能力。
另外，最好是利用一小股离开热交换器18温热端的氮气辅助气流（未画出）从纯化装置16的吸附剂床中除去热作为再生处理的一部分。然后可以将这股辅助气流与主氮气流在热交换器14和涡轮54的中间部位或涡轮54和冷却塔56的中间部分重新汇合。
如果需要的话，可以省去压缩机34和涡轮36，则所有的空气均通入柱24中。那么对于空气分离过程的制冷需求可由氮涡轮52满足。另一种更理想的作法是，将两个氮涡轮彼此并联使用。其中之一的出口温度可以在例如90-100K的范围，另一个的出口温度可以为例如140-150K。利用这样的安排，有可能在从热交换器18的冷端到从具有较高出口温度的涡轮引入氮气的位置处，被冷却的空气流和氮气流之间采用被温热的、较小的温差（例如5至10K的范围），而在从该位置到热交换器18的温热端采用较大的温差（例如至少20K）。
某些氮也可以用来在低于环境温度下起制冷作用。例如，参照附图，取自热交换器18用于在涡轮52中膨胀的一部分氮气流可以用来对热交换器（未画出）和其它装置（未画出）提供冷却，在这些装置中将气体混合物的至少一种组分冷凝。这种氮气流最好是取自涡轮52的上游，但是也可以取自其下游。
还可以这样改动图1中所示的装置：在氮气进入冷却塔56之前用一个阀或几个阀而不用膨胀式涡轮降低氮气的压力。

Claims (11)

1、一种分离空气的方法，包括在至少一个主热交换器中利用热交换将压缩空气流的温度降低到适合用精馏将其分离的温度，在双精馏柱中精馏该空气，从双精馏柱的低压柱中排出氧气流和氮气流，使该氧和氮气流以与空气流成逆流热交换关系的方向通过主热交换器，其中低压精馏柱在至少2巴的压力下操作，至少部分氮气流在一台涡轮中膨胀并且以与空气流相反的方向通过主热交换器，从而产生制冷作用并保持主热交换器中膨胀的氮气与被冷却的空气流之间的平均温差至少为10K。
2、根据权利要求1所述的方法，其中平均温差至少为20K。
3、根据权利要求1或2所述的方法，其中至少部分氮气流被用来在精馏柱和主热交换器位于其中的保温室的外面起冷却作用。
4、根据权利要求3所述的方法，其中在保温室外的冷却作用是从压缩空气流中除去压缩热。
5、根据权利要求3或4所述的方法，其中在保温室外的冷却作用是将水冷却。
6、根据权利要求5所述的方法，其中水是保存在冷却塔中的。
7、根据权利要求5所述的方法，其中氮与水直接接触，从而产生蒸发冷却作用。
8、根据权利要求3所述的方法，其中冷却作用是气体混合物中至少一种组分冷凝。
9、根据上述权利要求中任何一项所述的方法，其中低压精馏柱在2.5至4.5巴的压力范围内操作。
10、分离空气的装置，包括至少一个主热交换器，用来将压缩空气流的温度降至适合用精馏将其分离的温度，一个双精馏柱，它有空气入口与贯穿所述主加热器的空气流通道相连，双精馏柱的低压柱有氧气流和氮气流出口，该出口与贯穿主热交换器的通道相连，一台膨胀式涡轮用来将至少一部分氮气流膨胀并且以与压缩空气流成逆流的方式将该氮气流返送到所述主热交换器中，涡轮的安排使得在使用该装置时膨胀的氮气流和被冷却的空气流之间的平均温差能维持为至少10K。
11、根据权利要求10所述的装置，它另外还包括用至少部分氮气流在主热交换器和双精馏柱所位于的保温室外起冷却作用的装置。
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US5146756A (en) 1992-09-15
ZA915030B (en) 1992-09-30
GB9015377D0 (en) 1990-08-29
KR100192874B1 (ko) 1999-06-15
KR920002208A (ko) 1992-02-28
GB2245961A (en) 1992-01-15
GB9113618D0 (en) 1991-08-14
GB2245961B (en) 1994-09-28

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