CN104263443B - 一种从液化天然气中分离氮气的方法和系统 - Google Patents

一种从液化天然气中分离氮气的方法和系统 Download PDF

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CN104263443B
CN104263443B CN201410480303.8A CN201410480303A CN104263443B CN 104263443 B CN104263443 B CN 104263443B CN 201410480303 A CN201410480303 A CN 201410480303A CN 104263443 B CN104263443 B CN 104263443B
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nitrogen
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CN104263443A (zh
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张会军
王道广
王英军
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Beijing Encryo Engineering Co Ltd
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Abstract

本发明涉及一种从液化天然气中分离氮气的方法和系统,该系统包括脱氮塔、脱氮塔再沸器、闪蒸罐、冷箱、冷分离器、LNG储罐和挥发气压缩机等。该方法首先将脱酸脱水后的富氮天然气冷却至‑145~‑162℃进行节流对氮气进行一次分离,在LNG储罐气液分离后得到挥发气,挥发气经复热、压缩、冷却并在冷箱深冷后进入脱氮塔进行精馏对氮气进行二次深度分离,塔顶气进一步冷却后在闪蒸罐对氮气进行三次分离,得到的气相回收热量后即得到富氮尾气。本发明的方法通过两次闪蒸和一次精馏过程将液化天然气中的氮气脱除,使产品LNG中的氮含量降低至1%以下,并使尾气中氮含量达99.9%、甲烷含量降低至0.1%。本发明的方法脱氮效果好,能耗低,分离后的氮气可作为冷剂补充或工厂氮气使用,具有很好的环保效益和经济效益。

Description

一种从液化天然气中分离氮气的方法和系统
技术领域
本发明涉及液化天然气生产领域,特别涉及一种从液化天然气中分离氮气的方法和系统。
背景技术
天然气作为一种清洁、优质的能源,其需求量正随着我国经济的发展和环境保护要求的提高迅速扩大。由于液化天然气(LNG)在天然气存储及运输中具有的巨大优势,液化天然气正逐渐成为天然气需求的首选。
在LNG产业链中,天然气液化、运输和存储是重要的三个环节。在存储和运输过程中,LNG通常以饱和液体的形态储存在绝热罐中。当有热量通过传导或者辐射传递至储罐中时,变回导致部分液体蒸发为气体,这种气体称为挥发气。一般而言,LNG中的氮含量越高,液体越容易蒸发,挥发气的量也就越大。而且,当LNG中氮含量过高时容易发生翻滚事故,此时不同密度层的LNG在储罐内迅速上下翻滚混合,瞬间产生大量的挥发气,气化量约为平时自然蒸发量的10~50倍,导致储罐内气压迅速上升并超过设定的安全压力,使储罐出现超压现象。如果不及时通过安全阀排放,就可能造成储罐的机械损伤,带来经济上的损失及环境污染。因此在GB/T19024-2003《液化天然气的一般特性》中指出“预防此类型翻滚的最好方法是保持LNG的含氮量低于1%,并且密切监测气化速率”。
鉴于此,含氮气的天然气(特别是高含氮天然气)生产LNG一直是天然气液化技术的难点,通常采用汽提的方式对LNG进行脱氮处理从而有效地避免LNG储罐翻滚事故的发生。比如,在专利《一种液化天然气联产液氮的装置及方法》(公开号:CN 102994184 B)中,公开了一种两塔深冷精馏分离甲烷和氮气生产LNG并联产液氮的装置和方法,首先将天然气冷却至-120~-100℃减压节流送入脱氮塔,脱氮塔底液相再次深冷后送入LNG闪蒸罐,脱氮塔顶气相再次深冷后进入氮-甲烷分馏塔,氮-甲烷分馏塔底液相经深冷后进入LNG闪蒸罐,氮-甲烷分馏塔顶气相经深冷后得到的液氮送入液氮储罐。
在专利《从液化天然气中两段去除氮》(公开号:CN 101163934 B)中,公开了一种从LNG中两段去除氮的方法及装置,LNG首先被部分冷凝后进入分馏塔完成第一次分馏,以提供第一富氮蒸汽流好含氮底部液体流,随后底部液体经过换热、减压后返回至设置在分馏塔顶部回流冷却器完成第二次分馏,回流冷却器底部的液体物流送回至分馏塔顶部作为回流液,而回流冷却器顶部的气体为第二富氮蒸汽流。不同浓度的两个含氮蒸汽流的供应允许控制在天然气液化装置中使用的燃料气体的含氮浓度范围内。
在专利《从液化天然气中除去氮气的方法》(公开号:CN 1098447 C)中,公开了使用散热片式回流热交换器从液化天然气(LNG)中去除氮的方法。一个温度较高LNG流在热交换器中被预冷后减压闪蒸,产生低压LNG流回到热交换器中为温度较高的LNG预冷提供冷量,低压LNG流在立式的热交换器换热通道中同时发生了传质和传热,产生的蒸汽回到闪蒸罐中与高压LNG闪蒸气混合即为高含氮气体流,而从热交换器换热通道的底部得到贫含氮的产品液化天然气。
在专利《含氮甲烷气脱氮至天然气/液化天然气的方法》(公开号:CN 102021056B)中公开了一种甲烷和氮气的深冷双塔精馏工艺,其目的是针对煤层气和合成氨驰放气中的氮气和甲烷分离,得到的产品氮气纯度可以到95%以上,作为合成工段的原料气,也可作为工程氮气用。
在专利《在液化天然气的生产中用氮气汽提从天然气气流中分离氮气的方法》(公开号:CN 102220176 A)公开的方法中,原料天然气经过预冷后进入汽提塔中脱除氮气,汽提塔的底部得到LNG产品,汽提塔顶部得到高含氮气体流,该流体在理想情况下依然含有摩尔分数为5%的甲烷。
在以上专利中,采用了不同方法脱除LNG产品中的氮气,确保了LNG产品质量,避免了LNG储罐发生翻滚事故。但是,由于LNG脱除氮的过程中所有物料须先经过脱氮汽提塔,导致脱氮能耗极高;并且,脱氮过程中产生的脱氮尾气纯度不高,再利用较为困难,放空时无法避免甲烷气的损失,加之甲烷的温室效应问题,脱氮尾气的放空从经济和环境保护上均不利。
发明内容
为了克服现有技术的上述缺点,本发明提供了一种从液化天然气中分离氮气的方法和系统,能从富含氮的天然气中生产液化天然气,拓展了LNG原料来源,同时,脱氮尾气中的氮含量可达99.9%,纯度高,放空基本无甲烷损失,也可直接用于工厂氮气或者冷剂补充氮气,提高了天然气液化装置的经济效益和环保效益。
本发明首先提供了一种从液化天然气中分离氮气的方法,该方法包括以下步骤:
1)将富氮天然气通入冷箱1的第一流道A1冷却至-40~-75℃后通入冷分离罐2进行气液分离,得到气相的天然气I和液相重烃;
2)将天然气I经第二阀门V2通入脱氮塔再沸器11的管程作为再沸器热源,之后经第三阀门V3进入冷箱1的第二流道A2继续深冷至-145~-162℃得到天然气II;
3)将天然气II经第五阀门V5减压节流得到的天然气III通入LNG储罐3进行气液分离,得到挥发气I和LNG;
4)将挥发气I通入挥发气加热器4加热至-20~20℃后通入挥发气压缩机5的进行逐级压缩,挥发气压缩机出口气体的压力为1300~2800kPa,经四级冷却器冷却后通入挥发气加热器与挥发气I换热得到挥发气II;
5)将挥发气II通入冷箱1的第三流道D1冷却至-135~-160℃通入脱氮塔10精馏,脱氮塔再沸器11的温度为-100~-130℃,塔顶操作压力为1200~2700kPa,精馏后从脱氮塔再沸器11得到天然气IV,塔顶得到挥发气III;
6)将天然气IV经第九阀门减压节流后与天然气III汇合,将挥发气III送入冷箱1的第四流道D2冷却至-138~-162℃进入闪蒸罐12进行气液分离得到液相的天然气V和挥发气IV;
7)将天然气V作为回流送入脱氮塔1的塔顶,将挥发气IV送入冷箱1的第五流道D3复热至10~35℃得到甲烷含量不大于1%的尾气。
上述的技术方案中,步骤1)中所述的富氮天然气为脱除酸性气、水和汞后的净化天然气,其中的氮含量为1%~15%。
上述的技术方案中,步骤3)中所述的天然气III的压力为常压至450kPa。其中,常压是指大气压。
上述的技术方案中,步骤5)天然气IV中氮气的含量不大于3%,挥发气III中甲烷的含量不大于2%。
本发明还提供了一种从液化天然气中分离氮气的系统,包括:脱氮塔10、脱氮塔再沸器11、闪蒸罐12、冷箱1、冷分离罐2、LNG储罐3、挥发气加热器4、挥发气压缩机5、一级冷却器6、二级冷却器7、三级冷却器8、四级冷却器9、第一阀门V1至第十阀门V10、以及连接管道,其中,冷箱1的第一流道A1入口与富氮天然气管道连接、出口与冷分离罐2的入口连接,冷分离罐2的底部出口与重烃管线连接、顶部出口经第二阀门V2与脱氮塔再沸器11的管程入口连接,冷箱1第二流道A2的入口经第三阀门V3与脱氮塔再沸器11的管程出口连接、出口经第五阀门V5与LNG储罐3的入口连接,LNG储罐3的气相出口与挥发气加热器4的壳侧入口连接,挥发气加热器4的壳侧出口依次连接挥发气压缩机5的一级、一级冷却器6、挥发气压缩机5的二级、二级冷却器7、挥发气压缩机5的三级、三级冷却器8、挥发气压缩机5的四级、四级冷却器9、以及挥发气加热器4的管程入口,冷箱1的第三流道D1的入口与挥发气加热器4的管程出口连接、出口经第六阀门与脱氮塔10的进料口连接,脱氮塔再沸器11的壳侧液相出口经第九阀门V9与LNG储罐入口管道连接,脱氮塔10顶部的气相出口与冷箱1的第四流道入口连接,闪蒸罐12的入口经第七阀门V7与冷箱1的第四流道出口连接、底部液相出口经第八阀门V8与脱氮塔10的回流口连接、顶部气相出口与冷箱1的第五流道入口连接,冷箱1的第五流道出口与尾气管线连接。
上述的从液化天然气中分离氮气的系统中,脱氮塔为板式塔或填料塔,理论板数为8~16块,进料口位于第3块板至第8块板,回流口位于第1块板。
上述的从液化天然气中分离氮气的系统中,挥发气压缩机5为往复机,共3级或4级,级间设置冷却器。
上述的从液化天然气中分离氮气的系统中,冷分离罐2的顶部气相出口经第一阀门V1与冷箱1的第二流道A2入口连接。
上述的从液化天然气中分离氮气的系统中,闪蒸罐12的底部液相出口经第十一阀门V11与LNG储罐的入口管线连接。
本发明的方法通过先闪蒸再精馏的方式将氮气从LNG分离出来,不仅确保了LNG产品质量,避免了LNG储罐发生翻滚事故,拓展了液化天然气原料来源,而且产生的脱氮尾气纯度高,便于利用,也可以直接放空,避免了因脱氮而产生的甲烷损失,具有较好的经济效益和环保效益。
本发明的优势和积极效果具体在于:
1)良好的经济效益:本发明闪蒸罐顶部得到的脱氮尾气氮含量可达99.9%,甲烷损失小,原料天然气转化率高,产品收率高,而且高纯度的含氮尾气可以用作冷剂补充或工厂氮气。因而原料天然气得以完全利用,提高了装置的经济效益。
2)良好的环保效益:现有技术脱除天然气中氮的过程中多采用两塔精馏流程,待处理的天然气全部经过一级脱氮塔,物流温度叠加造成脱氮能耗高。本专利中采用闪蒸-脱氮的方式可将脱氮能耗由现有技术的70kWh/吨LNG降低至25kWh/吨LNG,能耗大大降低,环保效益较高。而且本专利脱氮尾气纯度高,基本上避免了甲烷损失,避免了温室气体排放。
3)提高了装置的原料适应性:由于LNG含氮量过高易导致LNG储罐翻滚引发安全事故,因而含氮气的天然气(特别是高含氮天然气)生产LNG一直是天然气液化技术的难点。采用本发明通过闪蒸和精馏两步分离处理可以将LNG中的含氮量控制在1%以下,有效地避免LNG储罐安全事故的发生,从而克服了现有技术的局限性拓展了LNG原料来源,提高了LNG液化装置的原料适应性。
附图说明
图1为本发明的工艺流程示意图。
1.冷箱
2.冷分离罐
3.LNG储罐
4.挥发气加热器
5.挥发气压缩机
6.一级冷却器
7.二级冷却器
8.三级冷却器
9.四级冷却器
10.脱氮塔
11.脱氮塔再沸器
12.闪蒸罐
V1~V11.第一阀门至第十一阀门
具体实施方式
以下结合实施例和附图对本发明做详细地说明
实施例1
本实施例的具体工艺流程请参见图1。
一种从液化天然气中分离氮气的系统,包括:脱氮塔10、脱氮塔再沸器11、闪蒸罐12、冷箱1、冷分离罐2、LNG储罐3、挥发气加热器4、挥发气压缩机5、一级冷却器6、二级冷却器7、三级冷却器8、四级冷却器9、第一阀门V1至第十阀门V10、以及连接管道等,其中:
冷箱1的第一流道A1入口与富氮天然气管道连接、出口与冷分离罐2的入口连接,冷分离罐2的底部出口与重烃管线连接、顶部出口经第二阀门V2与脱氮塔再沸器11的管程入口连接,冷箱1第二流道A2的入口经第三阀门V3与脱氮塔再沸器11的管程出口连接、出口经第五阀门V5与LNG储罐3的入口连接,LNG储罐3的气相出口与挥发气加热器4的壳侧入口连接。
挥发气加热器4的壳侧出口依次连接挥发气压缩机5的一级、一级冷却器6、挥发气压缩机5的二级、二级冷却器7、挥发气压缩机5的三级、三级冷却器8、挥发气压缩机5的四级、四级冷却器9、以及挥发气加热器4的管程入口,冷箱1的第三流道D1的入口与挥发气加热器4的管程出口连接、出口经第六阀门与脱氮塔10的进料口连接。
脱氮塔再沸器11的壳侧液相出口经第九阀门V9与LNG储罐入口管道连接,脱氮塔10顶部的气相出口与冷箱1的第四流道入口连接,闪蒸罐12的入口经第七阀门V7与冷箱1的第四流道出口连接、底部液相出口经第八阀门V8与脱氮塔10的回流口连接、顶部气相出口与冷箱1的第五流道入口连接,冷箱1的第五流道出口与尾气管线连接。
脱氮塔为填料塔,理论板数为10块,进料口位于第5块板,回流口位于第1块板,挥发气压缩机5为往复机,共4级,级间设置冷却器。
将脱除酸性气、水和汞后含氮量为3%的富氮天然气通入冷箱1的第一流道A1,冷却至-60℃后通入冷分离罐2进行气液分离,得到气相的天然气I和液相重烃。将天然气I经第二阀门V2通入脱氮塔再沸器11的管程作为再沸器热源,之后经第三阀门V3进入冷箱1的第二流道A2继续深冷至-161℃得到天然气II。将天然气II经第五阀门V5减压节流至常压得到的天然气III通入LNG储罐3进行气液分离,得到挥发气I和LNG。
将挥发气I通入挥发气加热器4加热至-10℃后通入挥发气压缩机5的进行逐级压缩,挥发气压缩机出口气体的压力为2050kPa,经四级冷却器冷却后通入挥发气加热器与挥发气I换热得到挥发气II。将挥发气II通入冷箱1的第三流道D1冷却至-153℃通入脱氮塔10精馏,脱氮塔再沸器11的温度为-110℃,塔顶操作压力为2000kPa,精馏后从脱氮塔再沸器11得到氮气含量为2%的天然气IV,塔顶得到甲烷含量为1.7%的挥发气III。
将天然气IV经第九阀门减压节流后与天然气III汇合,将挥发气III送入冷箱1的第四流道D2冷却至-159℃进入闪蒸罐12进行气液分离得到液相的天然气V和挥发气IV。将天然气V作为回流送入脱氮塔1的塔顶,将挥发气IV送入冷箱1的第五流道D3复热至25℃得到氮含量为99.35%、甲烷含量为0.65%的尾气。
实施例2
本实施例的具体工艺流程请参见图1。
如图所示一种从液化天然气中分离氮气的系统,其中:脱氮塔为板式塔,理论板数为8块,进料口位于第3块板,回流口位于第1块板,挥发气压缩机5为往复机,共4级,级间设置冷却器。
将脱除酸性气、水和汞后含氮量为1%的富氮天然气通入冷箱1的第一流道A1,冷却至-40℃后通入冷分离罐2进行气液分离,得到气相的天然气I和液相重烃。将天然气I经第二阀门V2通入脱氮塔再沸器11的管程作为再沸器热源,之后经第三阀门V3进入冷箱1的第二流道A2继续深冷至-145℃得到天然气II。将天然气II经第五阀门V5减压节流至450kPa得到的天然气III通入LNG储罐3进行气液分离,得到挥发气I和LNG。
将挥发气I通入挥发气加热器4加热至-20℃后通入挥发气压缩机5的进行逐级压缩,挥发气压缩机出口气体的压力为2800kPa,经四级冷却器冷却后通入挥发气加热器与挥发气I换热得到挥发气II。将挥发气II通入冷箱1的第三流道D1冷却至-135℃通入脱氮塔10精馏,脱氮塔再沸器11的温度为-100℃,塔顶操作压力为2700kPa,精馏后从脱氮塔再沸器11得到氮气含量为1.5%的天然气IV,塔顶得到甲烷含量为1%的挥发气III。
将天然气IV经第九阀门减压节流后与天然气III汇合,将挥发气III送入冷箱1的第四流道D2冷却至-138℃进入闪蒸罐12进行气液分离得到液相的天然气V和挥发气IV。将天然气V作为回流送入脱氮塔1的塔顶,将挥发气IV送入冷箱1的第五流道D3复热至35℃得到氮含量为99.9%、甲烷含量为0.1%的尾气。
实施例3
本实施例的具体工艺流程请参见图1。
脱氮塔为填料塔,理论板数为16块,进料口位于第8块板,回流口位于第1块板,挥发气压缩机5为往复机,共3级,级间设置冷却器。
将脱除酸性气、水和汞后含氮量为15%的富氮天然气通入冷箱1的第一流道A1,冷却至-75℃后通入冷分离罐2进行气液分离,得到气相的天然气I和液相重烃。将天然气I经第二阀门V2通入脱氮塔再沸器11的管程作为再沸器热源,之后经第三阀门V3进入冷箱1的第二流道A2继续深冷至-162℃得到天然气II。将天然气II经第五阀门V5减压节流至常压得到的天然气III通入LNG储罐3进行气液分离,得到挥发气I和LNG。
将挥发气I通入挥发气加热器4加热至20℃后通入挥发气压缩机5的进行逐级压缩,挥发气压缩机出口气体的压力为1300kPa,经四级冷却器冷却后通入挥发气加热器与挥发气I换热得到挥发气II。将挥发气II通入冷箱1的第三流道D1冷却至-160℃通入脱氮塔10精馏,脱氮塔再沸器11的温度为-130℃,塔顶操作压力为1200kPa,精馏后从脱氮塔再沸器11得到氮气含量为2.5%的天然气IV,塔顶得到甲烷含量为0.5%的挥发气III。
将天然气IV经第九阀门减压节流后与天然气III汇合,将挥发气III送入冷箱1的第四流道D2冷却至-162℃进入闪蒸罐12进行气液分离得到液相的天然气V和挥发气IV。将天然气V作为回流送入脱氮塔1的塔顶,将挥发气IV送入冷箱1的第五流道D3复热至10℃得到氮含量为99.8%、甲烷含量为0.2%的尾气。

Claims (7)

1.一种从液化天然气中分离氮气的方法,其特征在于,该方法包括以下步骤:
1)将富氮天然气通入冷箱(1)的第一流道(A1)冷却至-40~-75℃后通入冷分离罐(2)进行气液分离,得到气相的天然气I和液相重烃;
2)将天然气I经第二阀门(V2)通入脱氮塔再沸器(11)的管程作为再沸器热源,之后经第三阀门(V3)进入冷箱(1)的第二流道(A2)继续深冷至-145~-162℃得到天然气II:
3)将天然气II经第五阀门(V5)减压节流得到的天然气III通入LNG储罐(3)进行气液分离,得到挥发气I和LNG;
4)将挥发气I通入挥发气加热器(4)加热至-20~20℃后通入挥发气压缩机(5)的进行逐级压缩,挥发气压缩机出口气体的压力为1300~2800kPa,经四级冷却器冷却后通入挥发气加热器与挥发气I换热得到挥发气II;
5)将挥发气II通入冷箱(1)的第三流道(D1)冷却至-135~-160℃通入脱氮塔(10)精馏,脱氮塔再沸器(11)的温度为-100~-130℃,塔顶操作压力为1200~2700kPa,精馏后从脱氮塔再沸器(11)得到天然气IV,塔顶得到挥发气III;
6)将天然气IV经第九阀门减压节流后与天然气III汇合,将挥发气III送入冷箱(1)的第四流道(D2)冷却至-138~-162℃进入闪蒸罐(12)进行气液分离得到液相的天然气V和挥发气IV;
7)将天然气V作为回流送入脱氮塔(10)的塔顶,将挥发气IV送入冷箱(1)的第五流道(D3)复热至10~35℃得到甲烷含量不大于1%的尾气;
步骤1)中所述的富氮天然气为脱除酸性气、水和汞后的净化天然气,其中的氮含量为1%~15%;
步骤5)天然气IV中氮气的含量不大于3%,挥发气III中甲烷的含量不大于2%。
2.根据权利要求1所述的方法,其特征在于,步骤3)中所述的天然气III的压力为常压至450kPa。
3.一种实施权利要求1-2之一的方法的从液化天然气中分离氮气的系统,包括:脱氮塔(10)、脱氮塔再沸器(11)、闪蒸罐(12)、冷箱(1)、冷分离罐(2)、LNG储罐(3)、挥发气加热器(4)、挥发气压缩机(5)、一级冷却器(6)、二级冷却器(7)、三级冷却器(8)、四级冷却器(9)、第一阀门(V1)至第十阀门(V10)、以及连接管道,其中,冷箱(1)的第一流道(A1)入口与富氮天然气管道连接、出口与冷分离罐(2)的入口连接,冷分离罐(2)的底部出口与重烃管线连接、顶部出口经第二阀门(V2)与脱氮塔再沸器(11)的管程入口连接,冷箱(1)第二流道(A2)的入口经第三阀门(V3)与脱氮塔再沸器(11)的管程出口连接、出口经第五阀门(V5)与LNG储罐(3)的入口连接,LNG储罐(3)的气相出口与挥发气加热器(4)的壳侧入口连接,挥发气加热器(4)的壳侧出口依次连接挥发气压缩机(5)的一级、一级冷却器(6)、挥发气压缩机(5)的二级、二级冷却器(7)、挥发气压缩机(5)的三级、三级冷却器(8)、挥发气压缩机(5)的四级、四级冷却器(9)、以及挥发气加热器(4)的管程入口,冷箱(1)的第三流道(D1)的入口与挥发气加热器(4)的管程出口连接、出口经第六阀门与脱氮塔(10)的进料口连接,脱氮塔再沸器(11)的壳侧液相出口经第九阀门(V9)与LNG储罐入口管道连接,脱氮塔(10)顶部的气相出口与冷箱(1)的第四流道入口连接,闪蒸罐(12)的入口经第七阀门(V7)与冷箱(1)的第四流道出口连接、底部液相出口经第八阀门(V8)与脱氮塔(10)的回流口连接、顶部气相出口与冷箱(1)的第五流道入口连接,冷箱(1)的第五流道出口与尾气管线连接。
4.根据权利要求3所述的从液化天然气中分离氮气的系统,其特征在于,脱氮塔(10)为板式塔或填料塔,理论板数为8~16块,进料口位于第3块板至第8块板,回流口位于第1块板。
5.根据权利要求3所述的从液化天然气中分离氮气的系统,其特征在于,挥发气压缩机(5)为往复机,共3级或4级,级间设置冷却器。
6.根据权利要求3所述的从液化天然气中分离氮气的系统,其特征在于,冷分离罐(2)的顶部气相出口经第一阀门(V1)与冷箱(1)的第二流道(A2)入口连接。
7.根据权利要求3所述的从液化天然气中分离氮气的系统,其特征在于,闪蒸罐(12)的底部液相出口经第十一阀门(V11)与LNG储罐的入口管线连接。
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