CN1232165A - 制备氧的有效方法 - Google Patents
制备氧的有效方法 Download PDFInfo
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- CN1232165A CN1232165A CN99101340A CN99101340A CN1232165A CN 1232165 A CN1232165 A CN 1232165A CN 99101340 A CN99101340 A CN 99101340A CN 99101340 A CN99101340 A CN 99101340A CN 1232165 A CN1232165 A CN 1232165A
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- fluid
- process fluid
- pressure column
- steam
- oxygen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes 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
- F25J3/04—Processes 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
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04048—Providing 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
- F25J3/04066—Providing 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 oxygen
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- F25J2250/42—One fluid being nitrogen
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Abstract
本发明涉及空气在蒸馏塔***中低温蒸馏的方法,其中在氧制品生产蒸馏塔底部的沸腾是通过冷凝氮浓度等于或大于给料空气流体氮浓度的一种流体提供的。包括;(a)蒸馏塔***全部冷冻需求至少10%的作功能量,是由(1)作功膨胀氮含量等于或大于给料空气氮含量的第一工艺流体,然后冷凝至少部分膨胀流体产生,和/或(2)冷凝氮含量等于或大于给料空气氮含量的至少第二工艺流体产生;(b)作功膨胀第三工艺流体,产生额外作功能量;和(c)利用超过蒸馏塔***冷冻需要所产生的功,冷压缩温度低于室温工艺流体。
Description
本发明涉及用低温空气分离法有效制备氧的几种方法。特别是,本发明涉及低温空气分离工艺,其中具有吸引力的是制备至少一部分全氧,其纯度低于99.5%,且优选低于97%。
有几篇美国专利,教导有效制备纯度低于99.5%氧。两个例子是美国专利4,704,148和4,936,099。
美国专利No.2,753,698公开了一种用于分馏空气的方法,其中要分离的总空气在复式分馏器的高压塔中预分馏,以制备粗(不纯)液态氧(粗LOX)塔底液和气态氮塔顶馏出物。如此制备的粗液态氧膨胀至中等压力,并靠氮冷凝热交换而完全蒸发。蒸发的粗氧然后稍微温热,对生产动力负载膨胀,并在复式分馏器的低压塔中用高压塔内冷凝的氮洗涤,然后进入低压塔的顶部。低压塔的底部用来自高压塔的氮再沸腾。提供冷冻作用的这种方法,以后就称作CGOX膨胀法。该专利不使用其它冷冻源。因此用于低压塔的常规空气膨胀法要用所提出的CGOX膨胀法代替。实际上,该专利引用了因额外空气送入高压塔达到的改进效果(如对低压塔没有气态空气要膨胀),而这导致高压塔顶部产生的额外氮回流。这说明额外氮回流量等于送入高压塔空气外加氮量。为克服低压塔底部蒸出物不足,主张改进低压塔上部用液体氮洗涤的效率。
美国专利No.4,410,343,公开了一种采用低压和中压塔制备低纯度氧的方法,其中低压塔的塔底液靠冷凝空气再沸腾,而获得的空气送入中压和低压塔两者。
美国专利No.4,704,148公开了一种方法,利用高压和低压蒸馏塔分离空气,制备低纯度氧和废氮流体。主热交换器冷端的给料空气,用于再沸腾低压蒸馏塔,并蒸发低纯度氧制品。用于塔再沸腾和氧制品蒸发的热功,靠冷凝空气馏分提供。该专利中,空气给料分成三路子流体。一路子流体全部冷凝,并用于为低压和高压蒸馏塔两者提供回流。第二路子流体部分冷凝,该部分冷凝子流体的气体部分送入高压蒸馏塔底部,而液体部分为低压蒸馏塔提供回流。第三路子流体膨胀以回收冷冻作用,然后作为塔给料送入低压蒸馏塔。此外,高压塔冷凝器在低压塔中用作中间再沸腾器。
在国际专利申请#PCT/US87/01665(美国专利No.4,796,431)中,Erickson提出一种从高压塔引出氮流体的方法,部分膨胀这种氮至中等压力,然后将其冷凝的方法是,对高压塔底部粗LOX或对低压塔中间高度液体进行热交换。这种冷冻方法如今就称为后跟冷凝氮膨胀(NEC)。通常,NEC提供冷箱的全部冷冻需要。Erickson指出只有单独NEC不能提供冷冻作用的那些应用,才需要通过膨胀某些空气来提供补充的冷冻作用。然而,没有指出采用这种补充冷冻作用来降低能量消耗。这种补充冷冻作用是针对一种流程提出的,其中对流程作了其它改进以降低空气供给压。这降低了氮对膨胀器的压力,并因此降低了从NEC可获得的冷冻量。该专利中,Erickson也提出采用两次NEC。高压塔的氮分成两路流体,每一路流体部分膨胀到不同压力,且靠不同的液体冷凝。例如,一路膨胀氮流体靠粗LOX冷凝,而另一路靠低压塔中间高度液体冷凝。Erickson主张,采用第二次NEC增加可用于启动冷压缩机的冷冻输出,以便进一步提高氧传输压。
在美国专利No.4,936,099中,Woodward等人采用与低纯度氧制备有关的CGOX膨胀。这种情况,气态氧制品制备方法是,对部分给料空气进行热交换,蒸发低压塔底部的液态氧。
某些空气分离厂,过量的冷冻作用可自然获得。这通常是因为两个原因之一,(1)操作设备的强制力导致过量流体通过膨胀器,(2)蒸馏***产品回收率低,且在提高压力条件下产生随后要膨胀的过量废物。这种情况下,某些专利建议,将过量冷冻作用在低温温度下用于压缩适当的工艺流体。低温温度下这种压缩方法以后称为冷压缩。
由于第一种原因产生过量冷冻作用并采用冷压缩的一个实例,可以在美国专利No.4,072,023中找到。该专利,将可逆热交换剂用于从给料空气除去水和二氧化碳。这样一种可逆热交换剂的成功操作要求采用平衡流体。平衡流体通常由蒸馏塔***引出,在主热交换器的冷却部件中,同进来给料空气间接热交换而部分温热,然后在膨胀器中膨胀以提供所需要的冷冻作用。不幸,平衡流体的流速不能低于某部分给料空气流速。对于每单位产品流量冷冻需求不是那么大的工厂,使平衡流体流量大于某部分给料空气流量的强制力,就能产生过量冷冻作用。美国专利No.4,072,023提出将这种过量冷冻用于冷压缩工艺流体。
由于第二种原因产生过量冷冻作用并采用冷压缩的一些实例,可以在美国专利No.4,966,002和No.5,385,024中找到。这两个专利,空气给到单一蒸馏塔底部附近以制备高压氮。因为单一蒸馏塔在底部不采用再沸腾器,氮的回收率低。在提高压力下,这产生大量富氧废流体。一部分这种富氧废流体部分温热并膨胀,以提供所需的冷冻作用,而过量冷冻作用用于冷压缩该废流体的另一部分。冷压缩的废流体返回蒸馏塔。
在美国专利No.5,475,980中,冷压缩用于改善热交换器的冷却效果,以蒸发压力大于约15bar的泵送液态氧。为此,从热交换器中间位置取出中等温度辅助流体。然后,将该辅助流体冷压缩,并再引入热交换器进一步冷却。至少一部分进一步冷却流体在膨胀器中膨胀。当要冷压缩辅助流体的压力比高压塔压力高得多时,其中仅仅一部分在冷压缩和部分冷却后膨胀到高压塔。这种情况,在工厂温热端提供额外能量,以满足冷冻和冷压缩的需要。然而,当辅助流体是从高压塔引出时,在其冷压缩和冷却后全部膨胀。这保证大部分冷压缩所需能量由膨胀器回收,且用于冷压缩。结果,为产生作功能量而流过膨胀器的额外蒸气需要量减少,且如早先引用的美国专利No.4,072,023;4,966,002和5,385,024,不需要过量冷冻作用。
在丹麦专利2854508中,一部分处在高压塔压力下空气给料,利用对冷箱提供冷冻作用的膨胀器作功能量,在温热水平上再压缩。这种再压缩空气流体然后部分冷却,并在同一驱动压缩机的膨胀器中膨胀。在这种设计中,要再压缩然后膨胀用于冷冻的部分给料空气流体是相同的。结果,已知部分给料空气在冷箱中产生更多冷冻作用。该专利提出两种方法来利用这种过量冷冻作用:(ⅰ)从冷箱制备更多的液态产品;(ⅱ)降低通过压缩机和膨胀器的流量,并因此增加到高压塔的流量。据认为,增加到高压塔的流量会使冷箱产品产率更高。
本发明涉及空气在蒸馏塔***中低温蒸馏的方法,该***包括至少一个蒸馏塔,其中在生产氧制品蒸馏塔底部的沸腾(boil-up)是通过冷凝氮浓度等于或大于给料空气流氮浓度的一种流体提供的。本发明方法包括以下步骤:(a)蒸馏塔***全部冷冻需求至少百分之十(10%)的作功能量,是由以下两个方法中至少一个产生:(1)作功膨胀氮含量等于或大于给料空气氮含量的第一种工艺流体,然后冷却至少部分膨胀流体,其方法包括对下述两种液体中至少一种进行潜热交换:(ⅰ)生产氧制品蒸馏塔的中间高度的一种液体;(ⅱ)该蒸馏塔液体给料之一,其氧浓度等于或优选大于给料空气氧浓度;和(2)冷凝氮含量等于或大于给料空气氮含量的至少一个第二种工艺流体,方法是对至少部分富氧液态流体进行潜热交换,富氧液态流体其氧浓度等于或优选大于给料空气氧浓度,且其压力也大于生产氧制品蒸馏塔压力,在至少部分富氧液体因潜热交换蒸发成蒸气馏分后,作功膨胀至少部分获得的蒸气流体;(b)作功膨胀第三种工艺流体,产生额外作功能量,使与步骤(a)一起产生的总功超过低温厂总的冷冻需要,且如果第三个工艺***与步骤(a)(1)中第一个工艺***相同,则至少部分第三种工艺流体在作功膨胀后,没有被步骤(a)(1)所述两种液态流体任何一种所冷凝;和(c)利用超过蒸馏塔***冷冻需要所产生的功,冷压缩温度低于室温的工艺流体。
图1-9描绘本发明不同实施方案的示意图。在图1-9中,相同的流体采用同一流体代号。
图10(a)-10(c)描绘本发明为采用多级低压蒸馏塔而设计的实施方案示意图。
图11-12描绘两个先有技术工艺示意图。
本发明提供一种用于制备低纯度氧的更有效低温工艺。低纯度氧定义为氧浓度低于99.5%且优选低于97%的一种产品流体。该方法中,给料空气用包括至少一个蒸馏塔的蒸馏***进行蒸馏。在生产氧制品蒸馏塔底部的沸腾是通过冷凝氮浓度等于或大于给料空气流体氮浓度的一种流体提供的。本发明包括以下步骤:
(a)蒸馏塔***全部冷冻需求至少百分之十(10%)的作功能量,是由以下两个方法中至少一个产生:
(1)作功膨胀氮含量等于或大于给料空气氮含量的第一种工艺流体,然后冷却至少部分膨胀流体,其方法是对下述两种液体中至少一种进行潜热交换:(ⅰ)生产氧制品蒸馏塔的中间高度的一种液体;(ⅱ)该蒸馏塔液体给料之一,其氧浓度等于或优选大于给料空气氧浓度;
(2)冷凝氮含量等于或大于给料空气的至少第二种工艺流体,其方法是对至少部分富氧液态体流进行潜热交换,富氧液态体流其氧浓度等于或优选大于给料空气氧浓度,且其压力也大于氧制品生产蒸馏塔压力,在至少部分富氧液体因潜热交换蒸发成蒸气馏分后,作功膨胀至少部分获得的蒸气流体;
(b)作功膨胀第三种工艺流体,产生额外作功能量,使与步骤(a)一起产生的总功超过低温厂总的冷冻需要,且如果第三个工艺***与步骤(a)(1)中第一个工艺***相同,则至少部分第三种工艺流体在作功膨胀后,没有被步骤(a)(1)所述两种液态流体任何一个所冷凝;和
(c)利用超过蒸馏塔***冷冻需要所产生的功,冷压缩温度低于室温的工艺流体。
在优选模式中,只使用步骤(a)(1)和(a)(2)作功膨胀方法中的一个;步骤(a)(2)中第二种工艺流体,往往也与步骤(a)(1)中第一种工艺流体相同。
在大部分优选模式中,蒸馏***包括由高压(HP)塔和低压(LP)塔组成的复式塔***。至少部分给料空气送入HP塔。氧制品由塔底部产生。步骤(a)(1)中第一种工艺流体或步骤(a)(2)中第二种工艺流体,通常是从HP塔引出的高压富氮蒸气流体。若采用步骤(a)(1)作功膨胀法,则高压富氮蒸气流体膨胀,且随后冷凝,其方法是对LP塔中间高度液态流体,或对HP塔底部产生的粗液态氧(粗LOX)流体进行潜热交换,并构成LP塔的给料。该方法中,粗LOX流体压力降到LP塔压力附近。高压富氮流体膨胀之前可以部分温热。若采用步骤(a)(2)的作功膨胀法,则高压富氮流体冷凝,其方法是对压力高于LP塔压力的至少部分粗LOX流体进行潜热交换;而至少部分蒸发粗LOX获得的蒸气作功膨胀到LP塔。作功膨胀之前,至少部分蒸发粗LOX获得的蒸气可以部分温热。作为蒸发粗LOX的一种替代方法,氧浓度大于空气的富氧液体可以从LP塔引出,并用泵打到大于LP塔压力的所需压力,然后至少部分蒸发。
当采用复式塔***最优选模式时,则步骤(b)中第三种工艺流体可以是任何适合的工艺流体。某些实例包括:作功膨胀到HP塔和/或LP塔的部分给料空气;作功膨胀HP塔引出的富氮产品流体;和作功膨胀LP塔引出的流体。
作功膨胀,它意味着当工艺流体在膨胀器内膨胀时,产生功。这种功可以在油制动器中分散,或用于发电,或用于直接压缩另一种工艺流体。
其它制品也可以同低纯度氧一起生产。这包括高纯度氧(纯度等于或大于99.5%)、氮、氩、氪和氙。如需要,也可副产某些液态制品,如液态氮、液态氧和液态氩。
现在参照图1对本发明进行详细说明。不合较重组分如水和二氧化碳的压缩给料空气流体,表示为流体100。该压缩空气流体的压力,通常大于3.5bar绝对压力而小于24bar绝对压力。优选压力范围是5bar绝对压力-约10bar绝对压力。较高给料空气压力,有助于减小用于除去水和二氧化碳的分子筛床尺寸。给料空气流体分成两路流体102和110。主要部分流体102在主热交换器190中冷却,然后作为流体106送入较高压力(HP)塔196的底部。高压塔给料蒸馏成顶部的高压氮蒸气流体150,和底部的粗液态氧(粗LOX)流体130。粗LOX流体最终送入较低压力(LP)塔198,在那蒸馏产生顶部的较低压力氮蒸气流体160,和底部的液态氧制品流体170。另外,氧制品也可以作为蒸气从LP塔底部引出。液态氧制品流体170用泵171打到所需压力,然后对适当加压工艺流体进行热交换而蒸发,以提供气态氧制品流体172。图1中,适当加压工艺流体是管线118部分给料空气。在LP塔底部的沸腾是通过冷凝从管线150到管线152的第一部分高压氮流体提供的,从而提供第一路高压液态氮流体153。
根据本发明步骤(a)(2),其氧浓度大于给料空气氧浓度的至少部分粗LOX通过阀门135后,压力降低到HP塔和LP搭压力的中间压力。图1中,降压之前,粗LOX在再冷却器192中再冷却,其方法是对从LP塔返回的气态氮流体进行热交换。这种再冷却是任选的。降低压力的粗LOX流体136送到再沸腾器/冷凝器194,在那它至少部分沸腾,其方法是对管线150到管线154第二部分高压氮流体(本发明(a)(2)的第二路工艺流体)进行潜热交换,以提供第二路高压液态氮流体156。第一和第二路高压液态氮流体为HP塔和LP塔提供了所需的回流。管线137中蒸发了的部分降压粗LOX流体(以后称为粗GOX流体),在主热交换器190中部分温热,然后在膨胀器139中作功膨胀到LP塔,作为附加给料。粗GOX流体137的部分温热是任选的,且类似地,作功膨胀后流体140在其给入LP塔之前可以再冷却。
根据本发明步骤(b),部分冷却空气流体的一部分作为流体104(第三路工艺流体),从主热交换器引出并在膨胀器103中作功膨胀,然后送到LP塔。两个膨胀器103和139产生比工厂冷冻平衡所需更多的功。在低温空气分离厂,图1所示的所有热交换器、蒸馏塔和有关阀门、管线以及其它设备,都包围在一个称作冷箱的绝缘箱内。既然,此箱内部处于低温状态,就存在周围对冷箱的热渗漏。离开冷箱的产品流体(如流体164和172),也处于比给料空气流体温度低的状态。由于产品离开冷箱,导致热焓损失。为了使工厂运转,需要从冷箱提取出等量的能来平衡这两种损失。通常,这种能量是以作功能量方式提取。本发明中,两个膨胀器103和139的输出功,超过为保持冷箱冷冻平衡所必须提取的功。这种潜在产生的额外功,则用于冷压缩冷箱内工艺流体。这样,额外功不离开冷箱,且冷冻平衡得以维持。
图1中,为了蒸发来自泵171的泵打液态氧,给料空气流体100的一部分,即流体110在一个任选增压器113中再增压,并靠冷水(图中未标出)冷却,然后在主热交换器190中部分冷却。这种部分冷却的空气流体114然后由冷压缩机115冷压缩。冷压缩机的输入能量是膨胀器103和139产生的额外作功能量(即冷冻不需要的能量)。然后,冷压缩过的流体116再送回主热交换器,其冷却方法是对泵打液态氧流体进行热交换。一部分冷却的液态空气流体118送入HP塔,而另一部分(流体122),在再冷却器192内再冷却一些之后送入LP塔。
几种已知的改进可以应用到图1的流程实例中。例如,HP塔所有粗LOX流体130可以全送到LP塔,而一点也不送到再沸腾器/冷凝器194。代替这种作法,从LP塔中间高度引出液体,用泵将其增压至HP塔和LP塔之间压力,并送到再沸腾器/冷凝器194。在再沸腾器/冷凝器194内其余的处理,类似于早先解释过的134流体。在另一个改进中,再沸腾器/冷凝器193和194分别冷凝的两路高压氮流体152和154,可以不从HP塔的同一点产生。各自可以从HP塔不同高度获得,并在其再沸腾器(193和194)内冷凝后,各自送到蒸馏***适当位置。例如,流体154可以从高压塔顶部下面位置引出,在再沸腾器/冷凝器194内冷凝后,一部分可以返回到HP塔中间位置,而另一部分送到LP塔。
图2表示工艺流体按照步骤(a)(1)作功膨胀的另一种实施方案。这里,再冷却的粗LOX流体134,通过阀门135后使其压力降低到非常接近LP塔的压力,然后送入再沸腾器/冷凝器194。管线154内第二部分高压氮流体(如今是步骤(a)(1)第一路工艺流体),在主热交换器内部分温热(任选),然后在膨胀器139内作功膨胀,以提供较低压力氮流体240。该流体240在再沸腾器/冷凝器194内经潜热交换而冷凝,提供流体242,再冷却一些后送入LP塔。来自再沸腾器/冷凝器194的蒸发流体137和液态流体142送入LP塔适当位置。若需要,管线242内一部分冷凝氮流体可以用泵打到HP塔。两路氮流体,一路在再沸腾器/冷凝器193内冷凝,和另一路在再沸腾器/冷凝器194内冷凝,再次可以从HP塔不同高度引出,并因此具有不同的组分。
图2根据步骤(a)(1)采用作功膨胀的另一种变化,如图3所示,在这种设计中,去掉了再沸腾器/冷凝器194,HP塔底部所有粗LOX流体不做任何蒸发送到LP塔。代替再沸腾器/冷凝器194,是在LP塔中间高度采用中间再沸腾器394。如今,来自膨胀器139的作功膨胀氮流体240,在再沸腾器/冷凝器394中冷凝,其方法是对LP塔中间高度液体进行潜热交换。冷凝的氮流体342以类似图2的方式进行处理。图3的其它操作特点也与图2相同。
可以对图1-3所提发明作出几种变化。其中某些变化现在要作为另外的实例进行讨论。
由两个膨胀器提取的额外作功能量,可以用于冷压缩任何适宜的工艺流体。虽然图1-3表明,冷压缩的部分给料空气流体,靠泵打LOX流体冷凝,但直接冷压缩气态氧流体是可能的。这种气态氧流可以直接从LP塔底部引出,或由泵171泵打的LOX已经靠适当工艺流体蒸发后获得。也可以冷压缩富氮流体。这种用于冷压缩的富氮蒸气流体,可以取自如LP塔或HP塔那样的任何来源。图4表示这种富氮蒸气流体由HP塔引出的一种变化。除了泵171泵打液态氧的蒸发方法,不靠冷压缩过的空气流体而靠冷压缩过的HP塔氮流体进行潜热交换外,图4所有特点与图1相同。虽然用于冷压缩的富氮流体可以从HP塔任何适当位置引出,但图4表明它作为流体480从HP塔顶部引出。该流体480在主热交换器内部分温热(任选),在484内冷压缩,靠蒸发来自泵171液态氧进行潜热交换而冷凝。然后,该冷凝流体487送到蒸馏塔***。若需要,图4中富氮流体480,可以首先在主热交换器内温热到温度接近室温,并用辅助压缩机增压,然后在主热交换器内部分冷却并送到冷压缩机484。冷压缩富氮流体,然后靠来自泵171的至少部分液态氧将其冷凝的优点是,它为蒸馏塔***提供更多的氮回流,并且这改善了氮制品的回收率和纯度。例如,尽管图4没表示出来,人们可以从图4副产比相应图1压力更高的氮制品。
应当强调,冷压缩的目的不限于升高氧压力。它可以用于冷压缩本发明步骤(c)中任何适合的工艺流体。例如,图4中或部分或全部冷压缩氮流体486在主热交换器内可以不靠再冷却而冷凝,但可以再温热以提供加压氮制品流体。另一个实例如图5所示。该实例与图3实例之间的差别在于,HP塔196顶部所有高压氮流体都从管线554引出。该流体在主热交换器内(流体556)部分温热,并分成两路流体538和551。流体538要以处理图3流体238类似方式再处理,同时流体551根据本发明步骤(c)进行冷压缩。冷压缩流体552不靠来自泵171的泵打液态氧冷凝,而靠LP塔底部再沸腾器/冷凝器593内液体进行潜热交换而冷凝。这在LP塔底部提供所需沸腾。管线542和553内冷凝的液态氮流体作为回流送到HP塔和LP塔。若一部分较低压力液态氮流体542要送到HP塔,则泵543就是有帮助的。另一个变化,用于冷压缩的高压氮流体551,可以从流体554立即引出。类似地,管线552内冷压缩氮流体可以部分地冷却,其方法是对任何适合的工艺流体进行热交换,然后在再沸腾器/冷凝器593内冷凝。这些实例清楚说明,本发明可以用于冷压缩任何适合的工艺流体。此外,538和551不必具有相同组分,即各自可以从HP塔不同位置引出。
图1-5中,使LP塔部分给料空气膨胀,以满足本发明步骤(b)的需要。正如早先所述,可以膨胀任何适合的工艺流体来满足本发明该步骤的需要。某些实例包括:作功膨胀去HP塔的空气,和作功膨胀来自LP塔或HP塔的流体。图6表示HP塔富氮流体作功膨胀的一个实例。除了去掉流体104和105的管线之外,图6与图1类似。代之,一部分高压氮蒸气从HP塔顶部经管线604引出。根据本发明步骤(b),该流体如今是第三路工艺流体。流体604高压氮在主热交换器内部分温热,然后在膨胀器603内作功膨胀。作功膨胀后的流体605在主热交换器内温热,经管线606提供较低压力氮流体。氮流体606压力可以等于或大于流体164中氮压力。
图1-6的实例说明,本发明的步骤(a),(b),(c)中所有第一或第二工艺流体、第三工艺流体和冷压缩流体都不由同一工艺流体产生。这些流体至少两个具有不同组成。虽然如今可以容易地做出不同工艺流体的这种设计,但图7表示的一个实例是,本发明所有三个步骤所有流体,都是从HP塔顶部引出。HP塔顶部一部分高压氮是经管线754引出。该流体然后分成两路流体704和780,且两者在主热交换器内温热到其各自适合的温度。流体780部分温热后,再分成两路流体738和782。流体738提供本发明步骤(a)(1)的第一种工艺流体,并按与图3流体238类似的方式处理。流体704提供本发明步骤(b)的第三种工艺流体,并按与图6流体604类似的方式处理。流体782提供本发明步骤(c)用于冷压缩所需的工艺流体,并按与图4流体482类似的方式处理。注意,图7中来自膨胀器703的作功膨胀氮流体705,不是按本发明步骤(a)(1)提出的方式,靠进出LP塔的任何富氧液体而冷凝。
迄今,所有实例流程显示出至少两个再沸腾器/冷凝器。然而,应该强调,本发明并不排除在LP塔采用比图1-7所示更多的附加再沸腾器/冷凝器。若需要,可以在LP塔底部区段采用更多的再沸腾器/冷凝器,以便在该区段产生更多的蒸气。任何适合的工艺流体都可以在这些附加的再沸腾器/冷凝器中或部分或全部冷凝。例如图8表示的一个实例,是将图5的工艺修改成在LP塔内包含另一个再沸腾器/冷凝器。虽然再沸腾器/冷凝器893和894类似于再沸腾器/冷凝器593和597,但再沸腾器/冷凝器895是附加的再沸腾器/冷凝器。如今部分温热高压氮流体856(类似于流体556)分成三路流体。管线857的附加流体在附加再沸腾器/冷凝器895中靠LP塔液态流体冷凝,并作为回流送到高压塔。流体838和851的进一步处理与图5中流体538和551相同。图8也正是一个在LP塔采用多个再沸腾器/冷凝器的实例。采用本发明从已知技术很容易引出许多这种实例。例如,人们可以考虑在底部再沸腾器/冷凝器893内,部分或全部冷凝部分给料空气的可能性。也可以考虑从HP塔中间高度引出的蒸气流体在位于LP塔的再沸腾器/冷凝器中冷凝的可能性。这种情况下,当部分冷凝含有大量氧的或者空气流体或者HP塔引出的流体时,则未冷凝的蒸气部分就可以提供步骤(a)(1)的第一种工艺流体,或步骤(a)(2)的第二种工艺流体。
本发明按步骤(a)(1)指出方法提取功的那些工艺设计中,作功膨胀后所有第一种工艺流体,可以不靠如步骤(a)(1)指出的潜热交换法冷凝。部分这种流体可以作为产品流体回收,或用于工艺设计的其它目的。例如图2-3、5、7-8所示工艺设计中,高压塔的至少部分高压氮流体,是根据本发明步骤(a)(1)在膨胀器139中作功膨胀。离开膨胀器139的部分流体可以在主热交换器中再温热,并作为中等压力氮制品从任何一个这些工艺流程中回收。
当一部分给料空气作功膨胀时,可以利用从冷箱提取的作功能量将给料空气在接近室温条件下预压缩,然后将其送往主热交换器。例如,除了流体901是从管线102的部分给料空气引出外,图9显示图1工艺设计。该引出流体在压缩机993内增压,然后,用冷水冷却(图中未标出)并在主热交换器内再冷却,以提供流体904。该流体904以处理图1流体104类似方式进一步处理。为驱动压缩机993所需的作功能量来自冷箱中膨胀器。图9表明,压缩机993只由膨胀器103驱动。采用这种***的优点是,它可能从膨胀器提取更多的过量功,并因此可获取更多的作功能量用于冷压缩。管线901部分给料空气流体增压的一个替代方法是,可以首先在冷箱中温热要作功膨胀的其它工艺流体,在压缩机如993中增加它们的压力,在适当的热交换器中部分冷却它们,然后将它们送到适当的膨胀器。
有几种方法将额外作功能量传递给冷压缩机。下面举例列出一些变换方法:
·本发明步骤(a)和(b)两个膨胀器提取的全部功,可以用于冷箱之外,而本发明步骤(c)的冷压缩机可以由电动机驱动。为此,或一个或两个膨胀器可以是发电机,负载用以发电,或者是用温热压缩机负载用以压缩室温或高于室温的工艺流体。
·从一个膨胀器提取的全部功可以在冷箱之外回收,从第二个膨胀器提取的全部功则可以用于冷压缩。这种情况,第二个膨胀器可以通过一个共同的轴与冷压缩机直接连结,以便将膨胀流体的功直接传递给冷压缩流体。例如图1,膨胀器139可以直接与冷压缩机115连结,于是冷压缩机115只由膨胀器139驱动。这种情况,从膨胀器103提取的功提供冷箱的全部冷冻作用。若适合的膨胀器是103,而不是膨胀器139,可以直接与冷压缩机115连结,那么膨胀器139就将提供工厂所需的冷冻作用。
·可以将两个膨胀器与冷压缩机直接连结。这种情况,两个膨胀器会给出冷压缩所需的至少一部分功。而且,至少一个膨胀器要在冷箱之外负载,以提供冷箱所需的冷冻作用。
·冷压缩机与一个膨胀器直接连结,并用尽从该膨胀器提取的全部功。第二个膨胀器在冷箱之外负载,以便从该膨胀器提取的全部功在冷箱外面消耗掉。现在考虑,从第二膨胀器提取的功超过冷箱冷冻需求的情况。这种情况,从第二膨胀器提取的过量功,可以经电动机帮助传递给冷压缩机。
应当看到,对于实施该技术的那些实例,包含多个再沸腾器的单个蒸馏塔,可以分解成各有一个再沸腾器的多个塔。将一个多再沸腾器塔分解成多段的理由,通常是节省投资费用。如何利用多段低压塔完成本发明的一个实例如图10所示。图10(a)是图3所示工艺的简化表示,为清楚起见,省略了几处工艺管线和单元操作。图10(a)表示的低压塔,包含中间再沸腾器上部的三个蒸馏区,和下部的一个蒸馏区。图10(b)中,中间再沸腾器下部蒸馏区和底部再沸腾器,已再装成一个分立塔。由于高差必须添加一台输送泵。图10(b)所示设计的优点是,设备的高度较低了。图10(c)中,上部包括再沸腾器的一段已再装成一个分立塔。图10(c)所示设计使设备高度最低。对大的蒸馏塔,降低设备高度是有利的,且得到节省的费用往往抵销与添加输送泵有关的投资款。
最后,当除了氧浓度低于99.5%低纯度氧之外,还存在副产品时,可以采用本发明指出的方法。例如,高纯度氧(氧含量99.5%或更高),可以从该蒸馏***副产。完成这个任务的一个方法是,从LP塔在其底部上方位置引出低纯度氧,而从LP塔底部引出高纯度氧。若高纯度氧流体以液态形式引出,则可以用泵再增压,然后靠对适当工艺流体热交换而蒸发。类似地,在提高压力下可以副产高纯度氮制品流体。完成该任务的一个方法就是,从一个适当的再沸腾器/冷凝器取一部分冷凝液态氮流体,并用泵将其打到所要求的压力,然后靠对适当工艺流体热交换使其蒸发。
本发明的价值在于它使能量消耗大大较低。将其与下列某些已知先有技术工艺进行比较,这一点就会得到证明。
·第一个先有技术工艺如图11所示。这是一个常规复式塔工艺,带有一个对LP塔的空气膨胀器。空气膨胀器的作功能量作为电能回收。去掉冷压缩机115、膨胀器139和再沸腾器/冷凝器394及其有关管线,图11的工艺可以容易地从图3工艺导出。
·第二个先有技术工艺是根据Erickson的PST/US87/011665(美国对等专利4,796,431)导出。为此,从图2工艺去掉冷压缩机115。也去掉空气膨胀器103。因此,只留下一个膨胀器139提供工厂所需全部冷冻作用。根据Erickson的指导,膨胀器139的排料,在再沸腾器/冷凝器194内靠降压的部分粗LOX流体136冷凝。冷凝的氮流体242作为回流送到LP塔,而再沸腾器/冷凝器194的沸腾侧流体137和142也送到LP塔。
·第三个先有技术工艺也是由Erickson的PST/US87/011665(美国对等专利4,796,431)导出,且如图12所示。该图中,所有冷冻作用由HP塔顶部高压氮的作功膨胀提供。因此,不采用如图2膨胀器103那样的任何空气膨胀器。然而,HP塔高压氮流体1254分成两路流体1238和1255,且每一路按照图2和3各自所述方法作功膨胀。于是,流体1238作功膨胀并进行如图2流体238的类似处理,而流体1255作功膨胀并进行如图3流体238的类似处理。从两个膨胀器提取的过量功,以图2和3所示方式用在冷压缩机115中。
·除了冷压缩机115之外,保留图1所有东西,由图1导出用于比较的第四个工艺。由此,膨胀器139和103两者产生的功用于发电。在冷箱内不做任何流体的冷压缩。
对在200磅/平方英寸绝对压力条件下生产95%氧制品作出了计算。所有流程,主给料空气压缩机最后一级的排料压力为约5.3bar绝对压力。LP塔顶部压力为约1.25bar绝对压力。计算了净动力消耗,方法是计算主给料空气压缩机、增压器空气压缩机113为蒸发泵打液态氧消耗的动力,和任何膨胀器产生电力所供献的动力。几个流程图的相对动力消耗列表如下:
情况 | 流程图 | 相对动力 |
1 | 第一先有技术工艺(图11) | 1.0 |
2 | 第二先有技术工艺 | 1.013 |
3 | 第三先有技术工艺(图12) | 1.001 |
4 | 第四先有技术工艺(图1无冷压缩) | 0.986 |
5 | 本发明,图1 | 0.946 |
6 | 本发明,图2 | 0.957 |
这些计算清楚表明,本发明工艺比情况1-3所采用的任何先有技术工艺都优越得多。当比较情况4和5时,由于冷压缩作用而得到的巨大好处变得明显。这是因为这两种情况之间,除了情况4没采用冷压缩而情况5采用冷压缩之外,其流程所有特点都一样。图2为根据本发明的另一种流程,特别与情况3(图12)的先有技术工艺比较时表现出明显的改进。如今,本发明的优越性能十分清楚了。
尽管本文参照某些特殊实施方案进行描述,但并不意味着本发明限于已做出的详细说明。更确切地说,详细说明可做出的各种改进都在本权利要求书的等同范围之内,且没有离开本发明的思想。
Claims (44)
1.一种空气在蒸馏塔***内低温蒸馏的方法,蒸馏塔***包括至少一个蒸馏塔,其中在生产氧制品蒸馏塔底部的沸腾是通过冷凝氮浓度等于或大于给料空气流体氮浓度的一种流体提供的,其改进之处包括步骤:
(a)蒸馏塔***全部冷冻需求至少10%的作功能量,是由以下两个方法中至少一个产生:
(1)作功膨胀氮含量等于或大于给料空气的第一种工艺流体,然后冷凝至少部分膨胀流体,方法是对下述两种液体中至少一种进行潜热交换:(ⅰ)生产氧制品蒸馏塔中间高度的一种液体;(ⅱ)该蒸馏塔给料液体之一,其氧浓度等于或优选大于给料空气氧浓度;和
(2)冷凝氮含量等于或大于给料空气氮含量的至少第二种工艺流体,方法是对至少一部分富氧液态流体进行潜热交换,富氧液态流体其氧浓度等于或优选大于给料空气氧浓度,且其压力也大于生产氧制品蒸馏塔压力,在至少一部分富氧液体因潜热交换蒸发成蒸气馏分后,作功膨胀至少一部分获得的蒸气流体;
(b)作功膨胀第三种工艺流体,产生额外作功能量,使与步骤(a)一起产生的总功超过低温厂总的冷冻需求,且如果第三个工艺***与步骤(a)(1)中第一个工艺***相同,则至少部分第三种工艺流体在作功膨胀后,没有被步骤(a)(1)所述两种液态流体任何一种所冷凝;和
(c)利用超过蒸馏塔***冷冻需要所产生的功,冷压缩温度低于室温的工艺流体。
2.根据权利要求1的方法,其中采用至少一个包括较高压力塔和较低压力塔的复式塔***。
3.根据权利要求2的方法,其中步骤(a)(1)中第一种工艺流体是从较高压力塔引出的蒸气流体。
4.根据权利要求2的方法,其中步骤(a)(1)中第一种工艺流体是,部分给料空气。
5.根据权利要求2的方法,其中步骤(a)(1)中第一种工艺流体是,从至少部分给料空气部分冷凝获得的蒸气。
6.根据权利要求2的方法,其中冷凝第一种工艺流体的方法是,至少部分蒸发来自较低压力塔中间位置的液体。
7.根据权利要求2的方法,其中冷凝第一种工艺流体的方法是,至少部分蒸发从较高压力塔引出的至少部分富氧液体。
8.根据权利要求2的方法,其中冷凝第一种工艺流体的方法是,至少部分蒸发,由至少部分给料空气至少部分冷凝获得的至少部分富氧液体。
9.根据权利要求2的方法,其中至少部分第一种工艺流体冷凝后用泵送到较高压力塔。
10.根据权利要求2的方法,其中至少部分第一种工艺流体用泵送入热交换器并蒸发给出产品。
11.根据权利要求2的方法,其中全部第一种工艺流体冷凝后作为给料送入较低压力塔。
12.根据权利要求2的方法,其中步骤(a)(2)第二种工艺流体是,从较高压力塔引出的蒸气。
13.根据权利要求2的方法,其中步骤(a)(2)第二种工艺流体是,压力低于较高压力塔的部分给料空气。
14.根据权利要求2的方法,其中步骤(a)(2)第二种工艺流体是,由至少部分给料空气部分冷凝获得的蒸气,且该蒸气压力低于较高压力塔压力。
15.根据权利要求2的方法,其中第二种工艺流体冷凝之前已急剧膨胀。
16.根据权利要求2的方法,其中冷凝第二种工艺流体的方法是,至少部分蒸发来自较低压力塔中间位置的液体,且该液体蒸发之前用泵打。
17.根据权利要求2的方法,其中冷凝第二种工艺流体的方法是,至少部分蒸发从较高压力塔引出的至少部分富氧液体。
18.根据权利要求2的方法,其中冷凝第二种工艺流体的方法是,至少部分蒸发,由至少部分给料空气至少部分冷凝获得的至少部分富氧液体。
19.根据权利要求2的方法,其中至少部分第二种工艺流体,如必要,冷凝后用泵送到较高压力塔。
20.根据权利要求2的方法,其中至少部分第二种工艺流体用泵送入热交换器并蒸发给出产品。
21.根据权利要求2的方法,其中全部第二种工艺流体冷凝后作为给料送到较低压力塔。
22.根据权利要求2的方法,其中第三种工艺流体是,部分给料空气。
23.根据权利要求2的方法,其中第三种工艺流体是,至少部分给料空气部分冷凝后留下的蒸气。
24.根据权利要求2的方法,其中第三种工艺流体最终送到或较低压力塔,或较高压力塔,或两者。
25.根据权利要求2的方法,其中第三种工艺流体是,从较高压力塔引出的蒸气。
26.根据权利要求25的方法,其中从较高压力塔引出的蒸气要温热,膨胀后由冷箱排放。
27.根据权利要求25的方法,其中从较高压力塔引出的蒸气,膨胀后作为蒸气给料最终送到较低压力塔。
28.根据权利要求2的方法,其中从较高压力塔引出的蒸气,温热到接近室温,并在冷箱外部压缩,然后在膨胀之前冷却并再引入冷箱。
29.根据权利要求2的方法,其中第三种工艺流体是,从较低压力塔引出的蒸气,且该蒸气要温热,并在膨胀之后从冷箱排放。
30.根据权利要求2的方法,其中第三种工艺流体是,从较低压力塔引出的蒸气,且将该蒸气温热到室温并在冷箱外部压缩,然后在膨胀之前冷却并再引入冷箱。
31.根据权利要求2的方法,其中在步骤(c)要压缩的工艺流体是,至少部分给料空气。
32.根据权利要求31的方法,其中氧制品作为液体,从较低压力塔引出且最终沸腾,而用于步骤(c)的给料空气冷压缩后,至少部分冷凝的方法是,对沸腾氧进行间接热交换。
33.根据权利要求32的方法,用于步骤(c)的给料空气,在冷却及随后的冷压缩之前,也要温热压缩。
34.根据权利要求2的方法,其中在步骤(c)要压缩的工艺流体是,从较高压力塔引出的蒸气。
35.根据权利要求34的方法,其中氧制品作为液体,从较低压力塔引出且最终沸腾,而用于步骤(c)的至少部分较高压力塔蒸气,在冷压缩后至少部分冷凝的方法是,对沸腾氧进行间接热交换。
36.根据权利要求34的方法,其中用于步骤(c)的较高压力塔蒸气,在冷压缩之后温热到室温,然后再压缩。
37.根据权利要求36的方法,其中氧制品作为液体,从较低压力塔引出且最终沸腾,而至少部分温热压缩的较高压力塔蒸气冷却后,至少部分冷凝的方法是,对沸腾氧进行间接热交换。
38.根据权利要求34的方法,其中用于步骤(c)的较高压力塔蒸气,要温热到室温然后压缩,且至少部分随后冷却然后冷压缩。
39.根据权利要求38的方法,其中氧制品作为液体,从较低压力塔引出且最终沸腾,而冷压缩的较高压力塔蒸气至少部分冷凝的方法是,对沸腾氧进行间接热交换。
40.根据权利要求34的方法,其中用于步骤(c)的至少部分压力较高塔蒸气,构成富氮制品。
41.根据权利要求34的方法,其中用于步骤(c)的压力较高塔蒸气,冷压缩之后,在位于较低压力塔内的主沸腾器一冷凝器内至少部分冷凝。
42.根据权利要求2的方法,其中在步骤(c)要压缩的工艺流体是,从较低压力塔顶部引出的蒸气,并构成富氮制品。
43.根据权利要求2的方法,其中在步骤(c)要压缩的工艺流体是,较低压力塔底部引出的蒸气,并构成氧制品。
44.根据权利要求1的方法,其中步骤(a)采用的膨胀器,与步骤(c)采用的冷压缩机直接连结。
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- 1999-01-20 ZA ZA9900402A patent/ZA99402B/xx unknown
- 1999-01-21 DE DE69925769T patent/DE69925769T2/de not_active Expired - Lifetime
- 1999-01-21 EP EP99300416A patent/EP0932000B1/en not_active Expired - Lifetime
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1784579B (zh) * | 2003-05-05 | 2010-10-06 | 乔治洛德方法研究和开发液化空气有限公司 | 通过低温空气蒸馏生产加压空气的方法和*** |
CN100443838C (zh) * | 2005-04-20 | 2008-12-17 | 苏州市兴鲁空分设备科技发展有限公司 | 一种返流膨胀空气分离的方法和装置 |
CN102016467A (zh) * | 2007-03-12 | 2011-04-13 | 乔治洛德方法研究和开发液化空气有限公司 | 用于通过低温蒸馏分离空气的方法和装置 |
CN103988036A (zh) * | 2011-11-24 | 2014-08-13 | 乔治洛德方法研究和开发液化空气有限公司 | 用于通过低温蒸馏分离空气的方法和设备 |
CN103988036B (zh) * | 2011-11-24 | 2016-02-10 | 乔治洛德方法研究和开发液化空气有限公司 | 用于通过低温蒸馏分离空气的方法和设备 |
CN113874669A (zh) * | 2019-06-04 | 2021-12-31 | 林德有限责任公司 | 用于低温分离空气的方法和设备 |
Also Published As
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US5966967A (en) | 1999-10-19 |
EP0932000A3 (en) | 1999-10-20 |
DE69925769D1 (de) | 2005-07-21 |
EP0932000B1 (en) | 2005-06-15 |
CN1119606C (zh) | 2003-08-27 |
JP3084682B2 (ja) | 2000-09-04 |
ZA99402B (en) | 2000-07-20 |
EP0932000A2 (en) | 1999-07-28 |
CA2259065A1 (en) | 1999-07-22 |
JPH11257844A (ja) | 1999-09-24 |
CA2259065C (en) | 2001-04-03 |
DE69925769T2 (de) | 2006-05-04 |
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