CN1125962C - 生产高纯氩的低温杂化方法和设备 - Google Patents

生产高纯氩的低温杂化方法和设备 Download PDF

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CN1125962C
CN1125962C CN98105855A CN98105855A CN1125962C CN 1125962 C CN1125962 C CN 1125962C CN 98105855 A CN98105855 A CN 98105855A CN 98105855 A CN98105855 A CN 98105855A CN 1125962 C CN1125962 C CN 1125962C
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argon
oxygen
fluid
tower
air
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CN1199851A (zh
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T·C·古吟
M·S·A·巴克思
J·A·维贝尔
D·P·波纳奎斯特
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Praxair Technology Inc
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Praxair Technology Inc
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Abstract

用于生产高纯氩的系统，其中在低温精馏设备中制得的粗氩在变压吸附单元中得到处理。来自变压吸附单元的残留气体被循环至低温精馏设备，高纯氩在回收之前迎着含氧的流体被冷却，随后被送入低温精馏设备中。

Description

生产高纯氩的低温杂化方法和设备
本发明总的涉及从进料空气的分离中氩的生产，更具体地涉及高纯氩的生产。
目前通过加工由与低温精馏设备连在一起的氩气塔所制得的粗氩来生产高纯氩。通过使用将氢气与粗氩混合然后流过一种催化剂的催化脱氧合作用来净化粗氩。粗氩内的氧与氢气反应生成水，然后在干燥步骤中将水去除。此后该氩经过一氮去除步骤(一般通过低温分离)得到产品高纯氩。虽然该系统是有效的，但却昂贵且复杂，而且如果不能连续提供氢气，该系统是不可行的。
我们知道通过使用具有大量平衡段(一般不少于150个平衡段)的氩气塔可生产基本不含氧气的氩。然而这种超级氩气塔同时具有高的建造费及高的维修费。此外，由于空气各种组分的相对挥发度的原因，在该超级氩气塔的操作时氮气将与氩气在一起，因此为了生产高纯氩还需要一个单独的除氮步骤。
因此，本发明的一个目的是提供可以生产高纯氩而无需粗氩流的催化脱氧合作用以及无需使用一超级氩气塔的系统。
本领域技术人员在阅读本公开后将显而易见的上述目的及其它目的由本发明来实现，本发明的一个方面是：
用于生产高纯氩的低温杂化方法，它包括：
(A)将进料空气送入同时也包含低压塔和氩气塔的低温精馏设备的高压塔中，在高压塔内通过低温精馏分离进料空气以制得富氧流体，并将富氧流体送入低压塔中；
(B)将包含氧和氩作为氩气塔进料的流体从低压塔送入氩气塔中，并在氩气塔内通过低温精馏分离氩气塔进料以制得最多含有10％(摩尔)氧的粗氩流体；
(C)将粗氩流体从氩气塔送到含有氧选择性吸附剂的变压吸附单元中，并将氧从粗氩流体吸附到氧选择性的附剂上以制得高纯氩流体和含氧的残留气体；
(D)将含氧的残留气体从变压吸附单元再循环至低温精馏设备；
(E)通过与含氧的冷却流体进行间接热交换而冷却高纯氩流体，并将所得的含氧冷却流体送入低温精馏设备中；和
(F)将高纯氩流体作为产品高纯氩回收。
本发明的另一方面是：
用于生产高纯氩的设备，它包括：
(A)包含第一塔、第二塔和氩气塔的低温精馏设备，将进料空气送入第一塔的装置，以及将来自第一塔下部的流体送入第二塔的装置；
(B)将来自第二塔的流体送入氩气塔的装置；
(C)含有氧选择性吸附剂的变压吸附单元，以及将来自氩气塔上部的流体送入变压吸附单元的装置；
(D)将来自变压吸附单元的流体送入低温精馏设备的装置；
(E)一换热器以及将含氧冷却流体送至换热器和从换热器送入低温精馏设备的装置；和
(F)将来自变压吸附单元的高纯氩送至换热器的装置以及将来自换热器的产品高纯氩回收的装置。
此处所用的术语“进料空气”指主要包含氧气、氧气和氩气的混合物如环境空气。
此处所用的术语“塔”指蒸馏塔或分馏塔或区，即接触塔或区，其中液相和气相逆流接触以完成流体混合物的分离，如通过气相和液相在一系列安置于塔内的垂直放置的塔盘或塔板和/或在如结构填料或无规填料的填料单元上接触。对蒸馏塔的进一步讨论，参见《化学工程师手册》，第五版，R.H.Perry和C.H.Chilton编，Mc Graw-Hill Book Company出版，纽约，第13章，“连续蒸馏法”。术语“双塔”用来指一高压塔的上部与一低压塔的下部处于热交换关系。双塔的进一步讨论见于Ruheman的《气体的分离》，牛津大学出版社出版，1949，第VII章，“工业气体分离”。
气液接触分离法取决于各组分蒸气压的不同。高蒸气压(或易挥发或低沸点)组分将易于浓缩在气相而低蒸气压(或难挥发或高沸点)组分将易于浓缩在液相中。部分冷凝是一种藉气体混合物的冷却以将易挥发组分浓缩于气相中而难挥发组分浓缩于液相中的分离方法。精馏或连续蒸馏是一种结合由气液相的逆流处理获得的连续部分蒸发和冷凝的分离方法。气液相的逆流接触通常是绝热的，并可包括各相之间的积分(阶段)或微分(连续)接触。利用精馏的原理以分离混合物的分离法设备常可互换地称为精馏塔、蒸饱塔或分馏塔。低温精馏是一种至少部分在温度不大于150度开尔文(K)下进行的精馏法。
此处所用的术语“间接热交换”指流体之间在没有任何物理接触或混合的情况下将两种流体导入热交换关系。
此处所用的术语“顶部冷凝器”指从塔蒸汽中产生塔下流液体的热交换设备。
此处所用的术语“汽轮膨胀”和“汽轮骤冷器”分别指高压气流通过汽轮机以降低气体的压力和温度藉以产生制冷作用的方法和设备。
此处所用的术语“上部”和“下部”指分别位于塔的中点以上和以下的塔的那些部分。
此处所用的术语“平衡段”指气-液接触段，在其中离开该段的蒸汽和液体达到传质平衡，如具有100％效率的塔盘或一填料单元高度相当于一理论塔板(HETP)。
此处所用的术语“氩气塔”指处理包含氩气的进料并生产产品的氩气浓度超过进料的氩气浓度的塔。一个氩气塔一般包含一个顶部冷凝器。
此处所用的术语“变压吸附单元”指进行包含主要吸附步骤的分离过程的系统，在吸附期间混合物中的各成分被优先吸附到吸附剂上，并进行再生或解吸，其中通过减压将各种优先吸附的成分从吸附剂中除去。
此处所用的术语“氧选择性吸附剂”指从包含氧和其它组分的混合物中优先吸附氧的物质。
此处所用的术语“氮选择吸附剂”指从包含氮和其它组分的混合物中优先吸附氮的物质。
图1是本发明一特别优选实施方案的图解说明，其中除了高纯氩产品外，还制造了氧和/或氮产品。
图2是可用于实施本发明的两个变压吸附单元的床的图解说明。
图3是示意变压吸附单元操作的图解说明。
对于各普通单元各图中的数字是一样的。
本发明将参照各附图做详尽描述。现参照图1，已去除高沸点杂质如二氧化碳、水蒸汽和碳氢化合物并通过进料空气压缩机(图中未示出)被压缩成绝对压力一般在70-500磅/平方英寸(绝对压)(psia)范围内的进料空气1通过与主换热器32中的回流进行间接热交换而得到冷却。所得冷却的进料空气流2被分成第一部分3和第二部分4。包含20-55％进料空气1的第二部分4可进一步分成流6和流8。包含0-10％进料空气1的流8通过与换热器33中的回流进行间接热交换而得到液化，来自换热器33的所得流9被送入高压塔37中。包含20-45％进料空气1的流6被送往产品锅炉36，在其中通过与来自液体泵51的沸腾的高压液氧进行间接热交换而得到冷凝。所得液体进料空气7被送入高压塔中。在示于图1的实施方案中，流7与流9汇合形成流10然后送入塔37。进料空气流3被分成主流20和次流5。流20在汽轮骤冷器35中被汽轮膨胀以产生制冷作用，所得流120被送入塔37。包含大约1％进料空气1的次流5最后也被送入塔37，这将在下面详述。
塔37是包含塔37和第二或低压塔38的双塔的第一或高压塔。双塔和氩气塔53组成本发明的低温精馏设备。塔37在压力一般在70-150psia的范围内操作。在塔37内，通过低温精馏进料空气被分离成富氮蒸汽和富氧液体。富氮蒸汽在管线39中被送入主冷凝器43，在其中通过与塔38的底部液体进行间接热交换而得到冷凝。所得富氮液体以流44被送出主冷凝器43。富氮液体的一部分45作为回流被送回高压塔37中而富氮液体的另一部分21在换热器33中被低温冷却并流经阀46作为回流送入低压塔38中。若需要，如流25所示的富氮液体的一部分可作为产品液氮回收。
富氧液体含有大部分的氧以及被送入塔37的进料空气中的氩。富氧液体以流11从高压塔37的下部导出，迎着回流在过冷器或换热器33中低温冷却，然后经阀49送入氩气塔顶部冷凝器48的沸腾侧。氩气浓度至少为90％(摩尔)的粗氩蒸汽被送入顶部冷凝器48的冷凝侧。在顶部冷凝器48内，富氧液体通过与粗氩流体进行间接热交换而至少部分得到蒸发。所得富氧气体以流12从顶部冷凝器48被送入低压塔38中。残留的富氧液体可以流13从顶部冷凝器48送入低压塔38中。
低压塔或第二塔38在小于高压塔或第一塔37的压力下(一般在15-25psia的范围内)操作。在塔38内进入该塔的各种进料通过低温精馏被分离成富氮蒸汽和富氧液体。富氮蒸汽以流29从塔38的上部导出，通过流经换热器33和32而得到加热并以流31从系统中导出，它可作为氮气浓度不少于99％(摩尔)的氮气产品来回收。为了控制产品纯度的目的，废气流40可在流29被导出的位置下从塔38中导出，通过流经换热器33和32而得到加热，并以流42从系统中导出。
蒸发塔38底部的富氧液体以为塔38提供迎着冷凝的富氮蒸汽的蒸汽上流。所得的富氧气体的一部分可直接从塔38中回收。在示于图1的优选实施方案中，富氧液体的一部分以流89从塔38中导出然后送入产品锅炉36中。若需要，通过流经液体泵51或通过由于换热器43和36之间的高度差所造成的液体压头可增加富氧液体的压力。同时若需要，如流88所示的富氧液体的一部分可作为产品液氧来回收。进入产品锅炉36的富氧液体通过在产品锅炉36内迎着上述冷凝的进料空气进行间接换交换而得到蒸发。所得富氧气体以流90从产品锅炉36中导出，通过流经主换热器32而得到加热，并作为流91从系统中除去，它可作为氧气浓度一般在99-99.9％(摩尔)的氧气产品来回收。
在本发明的实施中顶部冷凝器48是氩气塔53的一部分。氩气塔53也包含具有大约40至65个平衡段的塔区，并制得氩气浓度在90-99％(摩尔)范围内的粗氩流体。含有大约8-25％(摩尔)的氩和余下大部分为氧的流体以流115作为氩气塔进料从低压塔38送入氩气塔53中。优选低压塔38根据Bianchi等人在美国专利第5133790号(通过引用并入本文)中所述并权利要求的实施来操作，使得氩气塔进料流115具有很低的氮气浓度(一般不超过5ppm，优选不超过1ppm)。在氩气塔53内，氩气塔进料115通过低温精馏被分成富氧液体和粗氩蒸汽。富氧液体以流116从氩气塔53被送回进低压塔38中。最多含有大约10％(摩尔)氧气的粗氩蒸汽在管线56中被送入顶部冷凝器48的冷凝侧，在其中迎着上述来自塔37的富氧液体11粗氩蒸汽至少部分被冷凝。所得粗氩流体在管线57中被送往用于回流的氩气塔区。粗氩流体的一部分以气态或液态的形式作为粗氩流体被送往变压吸附(PSA)单元52以做进一步的精炼。
在示于图1的优选实施方案中，粗氩流体以流125作为液体从氩气塔53中送出，并通过由于顶部冷凝器48和氩气锅炉15之间的高度差所造成的液体压头而得到加压，在其中粗氩液体迎着上述进料空气流5而被蒸发。这个最多可达70psia的高压排除了对粗氩压缩机的需要。所得高压的粗氩蒸汽以流126从氩气锅炉15被送往换热器34，在其中通过迎着高纯氩流体117和从PSA单元52返回的含氧残留气流54进料间接加热而被加热至PSA单元52的操作温度。然后离开换热器34的加热的粗氩蒸汽流127被进料至PSA单元52以最后除去氧。
PSA单元52含有氧选择吸附剂。可用于本发明实施的氧选择性吸附剂当中可以提及碳分子筛、斜发沸石、A型沸石以及Ramprasad等人在美国专利第5294418中所公开的各种吸附剂。
在粗氩流体也含有大量氮气的情况下，PSA单元52也可以在与氧选择吸附剂分开的层中含有氮选择吸附剂。可在用于本发明实施的氮选择吸附剂当中，可以提及A型沸石如CaA，X型沸石如LiX、NaX和CaX，以及含有选自元素周期表族I和族II的混合阳离子的A型和X型的各种沸石如LiNaX。
当粗氩流经PSA单元52时，氧从粗氩气中被吸附到氧选择吸附剂上。如果在粗氩气中存在氮气，则氮从粗氩气中被吸附到氮选择吸附剂上。结果作为流117离开PSA单元52产生了氩气浓度一般至少为99.9％(摩尔)、优选至少为99.999％(摩尔)的高纯氩流体。在解吸中，含氧的残留气体以流54从PSA单元52中导出。
含氧的残留气体从PSA单元被再循环至低温精馏设备。参照回图1，含氧的残留气体以流54从PSA单元52中导出，并在压缩机55中压缩。在冷却器92中将压缩热冷却后，所得压缩的残留气流93被送经换热器34，在其中通过与热的粗氩进行间接热交换而得到冷却。所得的残留气体94最好作为分离的附加塔进料被送入氩气塔53中以生产粗氩。若需要，如虚线94A所示，流94的一些或全部可被送入低压塔38中以在此分离。此外，流54的一些或全部可在循环至低温精馏设备前被送往进料空气压缩机。
高纯氩流体以流117从PSA单元52中导出，并通过流经换热器34与含氧的冷却流体进行间接地交换而得到冷却。然后将含氧冷却的流体送入低温精馏设备中。在示于图1的优选实施方案中，含氧的冷却流体是已流经阀110并流入换热器34的进料空气流5。然后所得的进料空气流105从换热器34被送入高压塔37中。或者含氧的冷却液体可以是取自高压塔的富氧流体，并且在流经换热器34后可被送入低压塔中。本领域技术人员也将意识到示于图1的单元15和单元34可以合并成一单一的换热器。此外，如果粗氩流体作为蒸汽从氩气塔中取出，那么可以排除对粗氩锅炉的需要。
冷却的高纯氩流体以流118从换热器34中导出并作为产品高纯氩回收。
图2和图3更详细地示意了PSA单元52的操作。图2显示了图1中所述PSA单元52的细节，而图3则显示了用于PSA方法的塔循环。参照图2和图3，PSA法完成下述单独或任何组合形式的步骤：
步骤I：进料(粗氩流体)加压(FP)。
步骤II：恒高压吸附和产品制造(AD)。
步骤III：并流减压(CD)至中等解吸压力。
步骤IV：逆流排放(BD)/抽空(EV)。
步骤V：逆流清洗(PG)。
步骤VI：轻组分(Ar)加压至中等吸附压力(PP)。
本发明的PSA单元的基本特征可通过描述两床PSA法的操作来示意。本领域技术人员将意识到也可以将超过两床的情况应用于本发明的实施。现参照图2和图3，按超过一个循环来描述PSA法的操作。
这里所述的PSA法包含两个每个用一个或多个吸附剂层(A&B)装填的床210和212。氩气进口管214分别向进料阀门222和224以及床进口226和228提供压缩的粗氩。一对排气阀230和232将床进口226和228连接到与可选的真空泵236连接的管234上。
床210和212包括经阀242和244连接到产品管246并经控制阀248连接到产品储槽250的产品出口管238和240。管252和阀254和256使产品气体的进料可分别从储槽250到床210和212。管252提供回流所需的额外气体(清洗和产品加压)。
出口管238和240还分别经阀258和260相连，以使由并流减压步骤所获得的气体进入均衡槽262。示于图2的所有阀门都经计算机系统程序逻辑来电子化操作。在本发明的实施中，用于清洗所需的气体首先取自均衡槽262。如果需要额外的清洗气，则从产品储槽250经管252取得较高纯度的气体。
完成清洗步骤后开始进行产品的加压。用于产品加压步骤所需的气体取自产品储槽250。然而如果清洗后均衡槽262含有残留气体，那么该残留气体用于产品加压的早期阶段。一旦均衡槽262中的气体用完，那么采用来自储槽250的较高纯度的气体来完成产品的加压。
重新参照图2和图3，现描述两床PSA法以示意循环的每个步骤各阀门的开启和关闭。在本描述中，除非明确表示在某个步骤中处于开启的位置，否则假设在循环的每个步骤中所有阀门都是关闭的。
步骤I：(FP)：在床的一端导入进料(粗氩流体)。在床210的情况中，开启阀222使进料气体进入床并加压床210。在此期间开启阀232而另一床(床212)进行步骤IV(排放/抽空)。该步骤期间来自床212的流出物的部分或全部如流54所示被循环至低温精馏设备。
步骤II：(AD)：总产品制造步骤。这里阀222和242是开启的。当控制阀248将开启以使产品气体进入储槽250时控制逻辑执行支配任务。例如，如果需要恒压，那么当床210达到预定的压力水平时仅开启阀248以使产品气体进入储槽250。产品制造步骤期间，开启阀232和260以清洗床212。清洗步骤所需的气体来自均衡槽262。然而如果需要额外的气体用于清洗，那么关闭阀260而开启阀256，使较高纯度的气体从储槽250进入床212。该步骤期间来自床212的流出物的部分或全部如流54所示被循环至低温精馏设备。在本发明的优选实施中，所有清洗气均来自均衡槽。
步骤III：(CD)：半闭阀门222和242而开启阀门258使床210进行并流减压(CD)步骤。在此期间关闭阀门232而开启阀门256，使得从储槽250中获得产品气体用于床212的产品加压步骤。如果床212完成清洗步骤后均衡槽262含有残留气体，那么在开启阀门256之前在产品加压的早期阶段开启阀门260以使用来自均衡槽262中的任何残留气体。消耗完所有均衡槽262中的残留气体后关闭阀门260而开启阀门256以完成床212的产品加压步骤。
步骤IV：(BD)：关闭阀门258而开启阀门230以逆流排放/抽空床210。该步骤期间来自床210的流出物的部分或全部如流54所示被循环至低温精馏设备。在此期间，关闭阀门256而开启阀门224使启得床212在床的一端进行进料加压。
步骤V：(PG)：开启阀门258使得床210获得来自均衡槽262的气体用于清洗。如果需要额外的气体用于清洗，那么关闭阀门258而开启阀门254以使来自储槽250的较高纯度的气体进入床210。在本发明优选的实施中，所有的清洗气体均来自均衡槽262。该步骤期间来自床210的流出物的部分或全部以流54被循环至低温精馏设备。在此期间，开启阀门224和244使得产床212处于生产状态。控制逻辑操作阀门248以使来自床212的产品气体能流向产品槽250。
步骤VI：(PP)：在床210的产品加压步骤(PP)期间，关闭阀门230而开启阀门254使得从储槽250中获得产品气体用于床210的产品加压。如果在床210的清洗步骤后均衡槽262含有残留气体，那么在开启阀门254之前开启阀门258以在产品加压的早期阶段使用来自均衡槽262中任何残留的气体。消耗完所有均衡槽262中的残留气体后关闭阀门258而开启阀门254以完成床210的产品加压步骤。在此期间关闭阀门224和244而开启阀门260以将来自正在进行并流减压(CD)步骤的床212的流出物导入到均衡槽262。
虽然本发明已参照特定的优选实施方案做了详述，但本领域技术人员将意识到在权利要求的精神和范畴内还有本发明的其它实施方案。

Claims (10)

1.用于生产高纯氩的低温杂化方法，它包括：
(A)将进料空气(10，120)送入同时也包含低压塔(38)和氩气塔(53)的低温精馏设备的高压塔(37)中，在高压塔内通过低温精馏分离进料空气以制得富氧流体，并将富氧流体送入低压塔中；
(B)将包含氧和氩作为氩气塔进料的流体(115)从低压塔(38)送入氩气塔(53)中，并在氩气塔内通过低温精馏分离氩气塔进料以制得最多含有10％摩尔氧的粗氩流体；
(C)将粗氩流体(125)从氩气塔(53)送入氩气锅炉(15)，其中粗氩流体通过与含氧冷却流体(5)的间接热交换而被蒸发；
(D)将得到的粗氩蒸气(126)送到含有氧选择性吸附剂的变压吸附单元(52)中，并将氧从粗氩蒸气吸附到氧选择性的吸附剂上以制得高纯氩流体和含氧的残留气体，其中所述粗氩蒸气(126)在被送到变压吸附单元之前由于与所述高纯氩流体(117)和所述含氧的残留气体的间接热交换而被加热；
(E)将含氧的残留气体(54)从变压吸附单元再循环至低温精馏设备；
(F)通过与含氧的冷却流体(5)和所述的粗氩蒸气(126)进行间接热交换而冷却高纯氩流体(117)，并将所得的含氧冷却流体(105)送入低温精馏设备中；和
(G)将高纯氩流体(118)作为产品高纯氩回收。
2.权利要求1的方法，其中残留气体(54)被再循环至氩气塔(53)。
3.权利要求1的方法，其中残留气体(54)被再循环至低压塔(38)。
4.权利要求1的方法，其中含氧冷却流体(5)是进料空气。
5.权利要求1的方法，其中含氧冷却流体是富氧流体。
6.权利要求1的方法，其中变压吸附单元(52)还含有氮选择性吸附剂。
7.权利要求1的方法，其中粗氩流体(125)在被送入变压吸附单元(52)前先加压。
8.权利要求1的方法，其中产品氮(31)和产品氧(91)中的至少一个是从低温精馏设备中回收的。
9.用于生产高纯氩的设备，它包括：
(A)包含高压塔(37)、低压塔(38)和氩气塔(53)的低温精馏设备，将进料空气(10，120)送入高压塔的装置，以及将来自高压塔下部的富氧流体(11)送入低压塔的装置；
(B)将来自低压塔的包括氧和氩的流体(115)送入氩气塔(53)的装置；
(C)含有氧选择性吸附剂的变压吸附单元(52)，以及将来自氩气塔(53)上部的粗氩流体(125)送入变压吸附单元的装置；
(D)将来自变压吸附单元(52)的含氧的流体(54)送入低温精馏设备的装置；
(E)一换热器(34)以及将含氧冷却流体(5)送至换热器和从换热器送入低温精馏设备的装置；和
(F)将来自变压吸附单元(52)的高纯氩(118)送至换热器(34)的装置以及将来自换热器的产品高纯氩回收的装置。
10.权利要求9的设备，其中变压吸附单元还含有氮选择性吸附剂。
CN98105855A 1997-03-26 1998-03-24 生产高纯氩的低温杂化方法和设备 Expired - Fee Related CN1125962C (zh)

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