CN111854324A - 一种从天然气中提取氦气的系统及其方法 - Google Patents

一种从天然气中提取氦气的系统及其方法 Download PDF

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CN111854324A
CN111854324A CN202010819902.3A CN202010819902A CN111854324A CN 111854324 A CN111854324 A CN 111854324A CN 202010819902 A CN202010819902 A CN 202010819902A CN 111854324 A CN111854324 A CN 111854324A
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helium
heat exchanger
air
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main heat
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张正雄
郝文炳
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Shanghai Yingfei Energy Technology Co ltd
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Abstract

本发明公开了一种从天然气中提取氦气的系统，包括空气膨胀机、冷却器、冷箱、氦气纯化系统；所述冷箱包括E1主换热器、C1精馏塔、设置于所述C1精馏塔底部的K1空气再沸器和K2 LNG再沸器、E2过冷器、K3冷凝蒸发器；所述氦气纯化系统包括加氧除氢反应炉、冷却器、氦气纯化器、压缩机和杜瓦瓶，所述杜瓦瓶内设置有换热器、气液分离器和吸附器。本发明还公开了采用本发明的系统从天然气中提取氦气的方法，其流程设计合理，操作简单，氦气的提取率高，解决了含氢气原料的浓缩问题，使用低温吸附制取纯氦气，提高了产品的经济价值。

Description

一种从天然气中提取氦气的系统及其方法
技术领域
本发明涉及氦气提取技术领域，尤其涉及一种从天然气中提取氦气的系统及其方法。
背景技术
氦气是一种战略性物质，在航天、国防、医疗和检漏等领域具有非常重要的作用。氦气是惰性气体，其在空气中的含量仅为5.24×10-6。氦气在空分设备精馏塔内为不凝气，而以气态聚集在主冷凝器顶部和氮回流液中，不易被分离。氦气主要存在于天然气中，从天然气中提取氦气是氦气生产的主要方法。但中国天然气中的氦含量极少，而液化天然气的闪蒸气(BOG)或其它以天然气为原料的化工尾气中富含氦，从中提取的经济价值更高。但部分BOG气体中会含有少量氢气，使用深冷法分离氦气与氢气的能耗较高，会使氦气的经济价值下降。
因此，本领域的技术人员致力于开发一种从天然气BOG气体中，浓缩并提纯氦气的方法。
发明内容
本发明为解决现有氦气提取技术中的问题，提供一种从天然气中提取氦气的系统及其方法。
为实现上述目的，本发明采用以下技术方案：
本发明第一方面是提供一种从天然气中提取氦气的系统，包括空气膨胀机、冷却器、冷箱、氦气纯化系统；所述冷箱包括E1主换热器、C1精馏塔、设置于所述C1精馏塔底部的K1空气再沸器和K2 LNG再沸器、E2过冷器、K3冷凝蒸发器；所述氦气纯化系统包括加氧除氢反应炉、冷却器、氦气纯化器、压缩机和杜瓦瓶，所述杜瓦瓶内设置有换热器、气液分离器和吸附器。
管路连接顺序为：
所述空气膨胀机增压端、冷却器、E1主换热器顶部的空气进口端依次连接，所述E1主换热器中部的空气出口端通过所述K1空气再沸器后与E1主换热器中部的空气进口端连接，所述E1主换热器的中下部一路通过所述空气膨胀机膨胀端后与所述E1主换热器的冷端连接，另一路通过所述E1主换热器的冷端后与所述E2过冷器连接，所述E2过冷器的液空出口端分别连接所述K3冷凝蒸发器和杜瓦瓶；
液化天然气BOG管线通过所述E1主换热器后与所述K2 LNG再沸器连接，所述K2LNG再沸器的LNG液体出口通过节流阀V2与所述C1精馏塔中部连接，所述C1精馏塔的塔顶与所述K3冷凝蒸发器连接，所述K3冷凝蒸发器顶部的不凝气出口端通过所述E1主换热器出冷箱后与所述加氧除氢反应炉连接；
所述加氧除氢反应炉依次连接所述冷却器、氦气纯化器、压缩机、所述杜瓦瓶内的换热器粗氦气进口和气液分离器，所述气液分离器的底部设有液体排出口，所述气液分离器上部的氦气出口依次连接所述吸附器、所述换热器后出所述杜瓦瓶与纯氦气管线连接。
进一步地，所述K3冷凝蒸发器的蒸发侧通过所述E1主换热器后与冷箱外部连通，放空或循环。
进一步地，所述C1精馏塔塔底部的重组分气体出口通过所述E1主换热器与所述冷箱外部的天然气用户管线连接。
进一步地，所述杜瓦瓶还连通有液体排出管线，所述液体排出管线上设有真空泵。
进一步地，所述纯氦气管线连接用户或充瓶压缩机。
进一步地，所述气液分离器、吸附器、所述换热器与气液分离器之间连接的管线、所述换热器与吸附器之间连接的管线均浸泡在液态空气中。
本发明的第二方面是提供采用上述系统的从天然气中提取氦气的方法，包括如下步骤：
S1：将除水和二氧化碳后的干燥空气送入所述空气膨胀机增压端的进口，经增压、冷却后送入所述冷箱，所述干燥空气经过所述E1主换热器降温后，由所述E1主换热器中部抽出进入所述K1空气再沸器，对所述K1空气再沸器中的LNG液体加热，同时进一步降温的所述干燥空气被送回所述E1主换热器后分两流流出，一流从所述E1主换热器中下部抽出后进入所述空气膨胀机膨胀端增压后送回所述E1主换热器作为冷源，另一流被所述E1主换热器的冷端液化后送入所述E2过冷器；出所述冷器E2的液态空气分为两流，一流经过节流阀V1调节压力后送入所述K3冷凝蒸发器，另一流抽出冷箱作为冷源送入所述杜瓦瓶中；
S2：带压力的液化天然气BOG原料由管线送入所述冷箱，由所述E1主换热器降温至部分带液状态后送入所述C1精馏塔底部的K2 LNG再沸器，对所述K2 LNG再沸器另一侧的LNG液体加热，其本身被进一步液化后抽出、经过所述节流阀V2调节压力至比所述C1精馏塔塔压略高后进入所述C1精馏塔中部参与精馏；设置于所述C1精馏塔塔底的所述K1空气再沸器和K2 LNG再沸器对塔底液体加热，CH4为主的重组分以气体形式从所述C1精馏塔的塔底抽出；所述C1精馏塔塔顶的主要含有氮气、氦气、氢气的轻组分送入所述K3冷凝蒸发器中液化，被液化的液体流回所述C1精馏塔内，部分不凝气则从所述K3冷凝蒸发器的顶部抽出，经所述E2过冷器冷却、所述E1主换热器回收冷量后，常温出所述冷箱；
S3：S2中出所述冷箱的常温不凝气进入所述氦气纯化系统，首先由所述氧除氢反应炉中反应除去氢气，由所述冷却器降温至10～40℃后，采用氦气纯化器除去水，得粗氦气，经所述压缩机加压后送入所述杜瓦瓶；所述杜瓦瓶内设置的换热器将所述粗氦气降温后，再经过浸泡在液态空气中的管线冷却，大部分组分已经被液化后进入所述气液分离器，其中的液体部分由所述气液分离器底部排出进入所述杜瓦瓶，然后被真空泵抽出，其中主要为氦气的气体部分排出所述气液分离器后，通过所述氦气吸附器将少量的氧气、氮气、氩气吸附掉，得到的纯氦气经过所述换热器回收冷量后送出所述杜瓦瓶。
进一步地，所述作为冷源的空气复热至0～17℃出所述冷箱放空或循环利用。
进一步地，经所述氦气纯化器脱水后，不凝气中生成的水被脱除至1～3ppm。
进一步地，所述C1精馏塔塔底的压力为0.4～0.56MPaA、温度为-130～-135.6℃，并且与所述K1空气再沸器和K2 LNG再沸器的温差为0.5～2℃；所述C1精馏塔塔顶的压力为0.45～0.55MpaA，温度为-175～-181.6℃。
本发明采用上述技术方案，与现有技术相比，具有如下技术效果：
本发明流程设计合理，操作简单，氦气的提取率高，解决了含氢气原料的浓缩问题，使用低温吸附制取纯氦气，提高了产品的经济价值。
附图说明
图1为本发明从天然气中提取氦气系统的示意图；
附图标记为：
1-空气膨胀机；2-冷却器；3-冷箱；4-E1主换热器；5-K1空气再沸器；6-K2 LNG再沸器；7-C1精馏塔；8-E2过冷器；9-K3冷凝蒸发器；10-加氧除氢反应炉；11-冷却器；12-氦气纯化器；13-压缩机；14-杜瓦瓶；15-换热器；16-气液分离器；17-吸附器；18-真空泵。
具体实施方式
下面通过具体实施例对本发明进行详细和具体的介绍，以使更好的理解本发明，但是下述实施例并不限制本发明范围。
实施例1
如图1所示，本实施例提供一种从天然气中提取氦气的系统，包括空气膨胀机1、冷却器2、冷箱3、氦气纯化系统；冷箱3包括E1主换热器4、C1精馏塔7、设置于C1精馏塔7底部的K1空气再沸器5和K2 LNG再沸器6、E2过冷器8、K3冷凝蒸发器9；上述氦气纯化系统包括加氧除氢反应炉10、冷却器11、氦气纯化器12、压缩机13和杜瓦瓶14，杜瓦瓶14内设置有换热器15、气液分离器16和吸附器17。
管路连接顺序为：
空气膨胀机1增压端、冷却器2、E1主换热器4顶部的空气进口端依次连接，E1主换热器4中部的空气出口端通过K1空气再沸器5后与E1主换热器4中部的空气进口端连接，E1主换热器4的中下部一路通过空气膨胀机1膨胀端后与E1主换热器4的冷端连接，另一路通过E1主换热器4的冷端后与E2过冷器8连接，E2过冷器8的液空出口端分别连接K3冷凝蒸发器9和杜瓦瓶14；
液化天然气BOG管线通过E1主换热器4后与K2 LNG再沸器6连接，K2 LNG再沸器6的LNG液体出口通过节流阀V2与C1精馏塔7中部连接，C1精馏塔7的塔顶与K3冷凝蒸发器9连接，K3冷凝蒸发器9顶部的不凝气出口端通过E1主换热器4出冷箱3后与加氧除氢反应炉10连接；
加氧除氢反应炉19依次连接冷却器11、氦气纯化器12、压缩机13、杜瓦瓶14内的换热器15粗氦气进口和气液分离器16，气液分离器16的底部设有液体排出口，气液分离器16上部的氦气出口依次连接吸附器17、换热器15后出杜瓦瓶14与纯氦气管线连接，上述纯氦气管线连接用户或充瓶压缩机。
在本实施例中，K3冷凝蒸发器9的蒸发侧通过E1主换热器4后与冷箱3外部连通，放空或循环。
在本实施例中，C1精馏塔7塔底部的重组分气体出口通过E1主换热器4与冷箱3外部的天然气用户管线连接。
在本实施例中，杜瓦瓶14还连通有液体排出管线，液体排出管线上设有真空泵18。
在本实施例中，气液分离器16、吸附器17、换热器15与气液分离器16之间连接的管线、换热器15与吸附器17之间连接的管线均浸泡在液态空气中。
实施例2
采用实施例1提供的系统，本实施例提供了一种从天然气中提取氦气的方法：
空气经过压缩、预冷纯化(空气的压缩、预冷纯化为现在空分中常规技术，本发明中不再叙述)，去除水和二氧化碳后，得到压力为0～0.7MPaA(绝压，下同)、流量为4800Nm3/h，温度为10～20℃的干燥空气。上述干燥空气经由管路GA-101进入空气膨胀机1增压端的进口，被增压至0.9～1MPaA后，进入冷却器2冷却降温至40℃，经管路GA-103送入冷箱3。进入冷箱3的空气首先进入E1主换热器4降温至-107～-109℃，从E1主换热器4中部抽出后送入K1空气再沸器5，利用空气的热量为K1空气再沸器5中的LNG液体加热，空气进一步被降温至-133～-135℃后，返回E1主换热器4的中。
上述返回E1主换热器4的空气分两流流出，一流从E1主换热器4中下部抽出，抽出流量为0～4100Nm3/h、空气温度为-140℃～-145℃，送入空气膨胀机1膨胀端膨胀至压力0.13MPaA，空气本身温度降低至-189℃，被送回E1主换热器4冷端，作为冷源，复热至0～17℃出冷箱3放空或循环利用；另一流，其流量为0～700Nm3/h的空气，在E1主换热器4冷端被液化后，由管路LA-106进入E2过冷器8，进一步过冷降温至-173～-178℃，上述过冷降温至-173～-178℃的液态空气分为两流，一流(0～640Nm3/h，折算0℃，1ata下的气态)在管路LA-107经过节流阀V1调节压力至0.2～0.3MpaA后，由管路LA-107送入K3冷凝蒸发器9，吸收热量被蒸发汽化为空气后，汽化后的空气由管路GA-108进入E2过冷器8回收冷量，再送入E1主换热器4复热出冷箱3，通过管路GA-109放空或循环使用；另一流(0～50Nm3/h，折算0℃，1ata下的气态)液态空气抽出冷箱3，作为冷源送到杜瓦瓶10中，为氦气的低温吸附提供低温环境。
带压力的天然气BOG(组分：He：1.7％，H2:0.26％，N2:10.3％，余量CH4)进入冷箱3，流量为2500Nm3/h，压力为1.2MPa。上述进入冷箱3的天然气BOG首先进入E1主换热器4被降温至-122～-124℃，部分带液后，由管路GNG-301抽出送入C1精馏塔7底部的K2 LNG再沸器6中对另一侧的LNG液体加热，本身被进一步液化后由管路LNG-302出K2 LNG再沸器6，温度降至-134～-135℃，由节流阀V2调节压力至比C1精馏塔7的塔压略高0.6MpaA后送入C1精馏塔7中部参与精馏。在C1精馏塔7内，有多块塔板或者填料，以供各组分在上面精馏，重组分(主要为CH4)在塔底积聚，塔底甲烷浓度可达>97％)。设置于塔底的K1空气再沸器5和K2 LNG再沸器6加热塔底液体，重组分以气体形式从塔底部通过管路GNG-303抽出，压力为0.56MpaA，经过E1主换热器4复热回收冷量后，送出3冷箱，送给用户。
本实施例中C1精馏塔7底部压力为0.56MPaA，塔底温度为-135.6℃，与两个再沸器保持温差；塔顶压力为0.55MpaA，塔顶温度为0～-181.6℃。
轻组分(主要为氮气、氦气、氢气)在C1精馏塔7顶部聚集，由管路GN-404送入K3冷凝蒸发器9中液化，被液化的液体流回C1精馏塔7内，为精馏提供液体；部分不凝气(其组分为：He:51.5％；H2:7.6％；N2:40.8％)从K3冷凝蒸发器9顶部抽出，流量为218Nm3/h，上述不凝气由管路GHe-401送入E2过冷器8后，再送入E1主换热器4回收冷量，被复热为常温后送出冷箱3，此时，天然气BOG原料中的氦气大部分(>95％)都在不凝气中。
出冷箱3的常温不凝气进入氦气纯化系统，首先根据含氢量加入微过量的氧气，控制氧气过量在0.5％，在加氧除氢炉6中，上述不凝气中的氢气与加入的氧气反应生成水，并放出热量使管路GHe-404中的不凝气温度升至0～590℃，然后经冷却器7降温至20～40℃(如使用冷冻水，则可降至10℃，更有利于氦气纯化器8对水的吸附)，经过过氦气纯化器8后，生成的水被脱除至1～3ppm。此时不凝气的压力为0.5MPa，经压缩机13加压至4MPa，送入杜瓦瓶14。
杜瓦瓶14内设置换热器11，用来将粗氦气降温至-170℃，经过浸泡在液空中的管道GHe-408冷却后，不凝气温度降至-200℃，其中的大部分组分已经液化，然后进入浸泡在液空中的气液分离器16，大部分被液化的氮、氧、氩在气液分离器16中以液体形式从底部排出，进入杜瓦瓶14后被真空泵18抽出杜瓦瓶14。主要为氦气的气体由管路GHe-409排出气液分离器16，通过氦气吸附器17，将粗氦气中的氧气、氮气、氩气吸附掉，纯氦气经过换热器回15收冷量，由氦气管线送出杜瓦瓶10，可直接供给用户或者压缩机充瓶。
本实施例中，冷箱3输送的液态空气经管路LA-131进入杜瓦瓶14，与气液分离器16底部排出的液体混合，在常压下，液态空气的温度在-196℃(纯氮)至-184℃(纯氧)之间，为了保证气液分离器16的高效，使用真空泵18对杜瓦瓶14进行抽真空，杜瓦瓶14的压力为绝压17kPa，此时的液态空气的沸点约-205℃。
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。

Claims (10)

1.一种从天然气中提取氦气的系统，其特征在于，包括空气膨胀机、冷却器、冷箱、氦气纯化系统；所述冷箱包括E1主换热器、C1精馏塔、设置于所述C1精馏塔底部的K1空气再沸器和K2 LNG再沸器、E2过冷器、K3冷凝蒸发器；所述氦气纯化系统包括加氧除氢反应炉、冷却器、氦气纯化器、压缩机和杜瓦瓶，所述杜瓦瓶内设置有换热器、气液分离器和吸附器。
管路连接顺序为：
所述空气膨胀机增压端、冷却器、E1主换热器顶部的空气进口端依次连接，所述E1主换热器中部的空气出口端通过所述K1空气再沸器后与E1主换热器中部的空气进口端连接，所述E1主换热器的中下部一路通过所述空气膨胀机膨胀端后与所述E1主换热器的冷端连接，另一路通过所述E1主换热器的冷端后与所述E2过冷器连接，所述E2过冷器的液空出口端分别连接所述K3冷凝蒸发器和杜瓦瓶；
液化天然气BOG管线通过所述E1主换热器后与所述K2 LNG再沸器连接，所述K2 LNG再沸器的LNG液体出口通过节流阀V2与所述C1精馏塔中部连接，所述C1精馏塔的塔顶与所述K3冷凝蒸发器连接，所述K3冷凝蒸发器顶部的不凝气出口端通过所述E1主换热器出冷箱后与所述加氧除氢反应炉连接；
所述加氧除氢反应炉依次连接所述冷却器、氦气纯化器、压缩机、所述杜瓦瓶内的换热器粗氦气进口和气液分离器，所述气液分离器的底部设有液体排出口，所述气液分离器上部的氦气出口依次连接所述吸附器、所述换热器后出所述杜瓦瓶与纯氦气管线连接。
2.根据权利要求1所述的从天然气中提取氦气的系统，其特征在于，所述K3冷凝蒸发器的蒸发侧通过所述E1主换热器后与冷箱外部连通，放空或循环。
3.根据权利要求1所述的从天然气中提取氦气的系统，其特征在于，所述C1精馏塔塔底部的重组分气体出口通过所述E1主换热器与所述冷箱外部的天然气用户管线连接。
4.根据权利要求1所述的从天然气中提取氦气的系统，其特征在于，所述杜瓦瓶还连通有液体排出管线，所述液体排出管线上设有真空泵。
5.根据权利要求1所述的从天然气中提取氦气的系统，其特征在于，所述纯氦气管线连接用户或充瓶压缩机。
6.根据权利要求1所述的从天然气中提取氦气的系统，其特征在于，所述气液分离器、吸附器、所述换热器与气液分离器之间连接的管线、所述换热器与吸附器之间连接的管线均浸泡在液态空气中。
7.一种采用如权利要求1～6任一项所述系统的从天然气中提取氦气的方法，其特征在于，包括如下步骤：
S1：将除水和二氧化碳后的干燥空气送入所述空气膨胀机增压端的进口，经增压、冷却后送入所述冷箱，所述干燥空气经过所述E1主换热器降温后，由所述E1主换热器中部抽出进入所述K1空气再沸器，对所述K1空气再沸器中的LNG液体加热，同时进一步降温的所述干燥空气被送回所述E1主换热器后分两流流出，一流从所述E1主换热器中下部抽出后进入所述空气膨胀机膨胀端增压后送回所述E1主换热器作为冷源，另一流被所述E1主换热器的冷端液化后送入所述E2过冷器；出所述冷器E2的液态空气分为两流，一流经过节流阀V1调节压力后送入所述K3冷凝蒸发器，另一流抽出冷箱作为冷源送入所述杜瓦瓶中；
S2：带压力的液化天然气BOG原料由管线送入所述冷箱，由所述E1主换热器降温至部分带液状态后送入所述C1精馏塔底部的K2 LNG再沸器，对所述K2 LNG再沸器另一侧的LNG液体加热，其本身被进一步液化后抽出、经过所述节流阀V2调节压力至比所述C1精馏塔塔压略高后进入所述C1精馏塔中部参与精馏；设置于所述C1精馏塔塔底的所述K1空气再沸器和K2 LNG再沸器对塔底液体加热，CH4为主的重组分以气体形式从所述C1精馏塔的塔底抽出；所述C1精馏塔塔顶的主要含有氮气、氦气、氢气的轻组分送入所述K3冷凝蒸发器中液化，被液化的液体流回所述C1精馏塔内，部分不凝气则从所述K3冷凝蒸发器的顶部抽出，经所述E2过冷器冷却、所述E1主换热器回收冷量后，常温出所述冷箱；
S3：S2中出所述冷箱的常温不凝气进入所述氦气纯化系统，首先由所述氧除氢反应炉中反应除去氢气，由所述冷却器降温至10～40℃后，采用氦气纯化器除去水，得粗氦气，经所述压缩机加压后送入所述杜瓦瓶；所述杜瓦瓶内设置的换热器将所述粗氦气降温后，再经过浸泡在液态空气中的管线冷却，大部分组分已经被液化后进入所述气液分离器，其中的液体部分由所述气液分离器底部排出进入所述杜瓦瓶，然后被真空泵抽出，其中主要为氦气的气体部分排出所述气液分离器后，通过所述氦气吸附器将少量的氧气、氮气、氩气吸附掉，得到的纯氦气经过所述换热器回收冷量后送出所述杜瓦瓶。
8.根据权利要求7所述的从天然气中提取氦气的方法，其特征在于，所述作为冷源的空气复热至0～17℃出所述冷箱放空或循环利用。
9.根据权利要求7所述的从天然气中提取氦气的方法，其特征在于，经所述氦气纯化器脱水后，不凝气中生成的水被脱除至1～3ppm。
10.根据权利要求7所述的从天然气中提取氦气的方法，其特征在于，所述C1精馏塔塔底的压力为0.4～0.56MPaA、温度为-130～-135.6℃，并且与所述K1空气再沸器和K2 LNG再沸器的温差为0.5～2℃；所述C1精馏塔塔顶的压力为0.45～0.55MpaA，温度为-175～-181.6℃。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107228526A (zh) * 2017-07-03 2017-10-03 成都深冷液化设备股份有限公司 一种lng闪蒸气的提氦、脱氮和再液化装置
CN113670001A (zh) * 2021-08-18 2021-11-19 广州市粤佳气体有限公司 一种天然气bog中提取氦气低温精馏方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107228526A (zh) * 2017-07-03 2017-10-03 成都深冷液化设备股份有限公司 一种lng闪蒸气的提氦、脱氮和再液化装置
CN113670001A (zh) * 2021-08-18 2021-11-19 广州市粤佳气体有限公司 一种天然气bog中提取氦气低温精馏方法

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