CN102564060B - 从天然气分离出氮和氢的方法 - Google Patents

从天然气分离出氮和氢的方法 Download PDF

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CN102564060B
CN102564060B CN201110294067.7A CN201110294067A CN102564060B CN 102564060 B CN102564060 B CN 102564060B CN 201110294067 A CN201110294067 A CN 201110294067A CN 102564060 B CN102564060 B CN 102564060B
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H·施密特
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Abstract

本发明描述了从至少含有甲烷、氮和氢的待液化的原料馏分中分离出氮和较轻成分尤其是氢、一氧化碳、氖和氩的方法，其中原料馏分与至少一个制冷回路的制冷剂或制冷剂混合物相对地进行冷却和液化。根据本发明，a)部分冷凝(E1)原料馏分(1)，b)在至少一个精馏塔(T)中分离成富含甲烷的馏分(6)和含有氮和较轻成分的馏分(4)，及c)使富含甲烷的馏分(6)过冷，d)其中通过一个或至少一个制冷回路(20-24)的制冷剂或制冷剂混合物或制冷剂的支流或制冷剂混合物的支流而冷却精馏塔(T)的塔顶冷凝器(E2)。

Description

从天然气分离出氮和氢的方法
技术领域
本发明涉及从至少含有甲烷、氮和氢的、待液化的原料馏分中分离出氮和较轻成分尤其是氢、一氧化碳、氖和氩的方法，其中原料馏分与至少一个制冷回路的制冷剂或制冷剂混合物相对地进行冷却和液化。
背景技术
不久以前利用新的“天然气源”以获取液化甲烷(LNG)。新的天然气源例如是煤炭气化或甲烷化。从这些过程排出的气体混合物除了具有主要成分甲烷之外，还具有含量高至超过20体积％的氢以及含量大于10体积％的氮。除此之外，该气体混合物可以含有痕量的一氧化碳、二氧化碳、氖和氩。从待液化的甲烷除了必须分离出氮之外，还必须分离出氢，从而可以遵守所要求的LNG产品的技术规范。问题在于，虽然氢的沸点比较低，但是非常容易溶解在液化的甲烷中。
若如同通常的情况临时储存LNG产品，则氮含量不允许超过1体积％的数值，因为否则会在LNG储存容器中出现非期望的“翻滚效应”。
发明内容
本发明的目的在于，阐述从至少含有甲烷、氮和氢的、待液化的原料馏分中分离出氮和较轻成分的方法，其一方面能够充分分离出氮，另一方面优选在比较高的压力下同时分离出氢。
为了实现该目的，推荐从至少含有甲烷、氮和氢的、待液化的原料馏分中分离出氮和较轻成分的方法，其特征在于，
a)部分冷凝原料馏分，
b)在至少一个精馏塔中分离成富含甲烷的馏分和含有氮和较轻成分的馏分，及
c)使富含甲烷的馏分过冷，
d)其中通过一个或至少一个制冷回路的制冷剂或制冷剂混合物或制冷剂的支流或制冷剂混合物的支流而冷却精馏塔的塔顶冷凝器。
根据本发明，现在在精馏塔中从原料馏分中一同分离出在原料馏分中所含的氮以及同样所含的较轻成分。因为通常将原料馏分在其液化之前压缩到40至90巴的压力，并在将其送入精馏塔中之前降低到20至40巴的压力，所以可以在比较高的压力下获得分离的成分。尤其是在比较有价值的成分氢的情况下，期望在高压下获得，因为氢通常送至其他用途。根据本发明的方法的优点此外是，通过将较轻成分的分离步骤整合在氮分离过程中，从而可以节约投资成本，否则就需要单独分离较轻成分。
根据本发明的从至少含有甲烷、氮和氢的原料馏分中分离出氮和较轻成分的方法的其他有利的实施方案的特征在于，
-原料馏分的甲烷含量为50至90体积％，氮含量为1至30体积％，氢含量为1至30体积％，
-将含有氮和较轻成分的馏分与待冷却的原料馏分相对地进行加热，其中在任选干燥原料馏分之前和/或之后进行冷却，
-可以改变精馏塔的塔顶冷凝器的冷凝器温度，
-若临时储存富含甲烷的液化的馏分，则将在临时储存过程中产生的储罐回气(Tankrückgas)进行压缩，并送至待液化的原料馏分，
-将冷却精馏塔的待液化的原料馏分的支流作为精馏塔塔底和/或精馏塔煮沸器中的汽提气流进行冷却，并作为另一原料流送至精馏塔，及
-若原料馏分与至少两个制冷回路的制冷剂和/或制冷剂混合物相对地进行冷却和液化，则利用分离的制冷回路或者通过最轻制冷回路的制冷剂或制冷剂混合物的至少一股支流对精馏塔的塔顶冷凝器进行冷却，其中根据本发明的方法的该有利的实施方案尤其适合于具有更大产能的LNG设备。
以下将根据附图所示的实施例，详细解释根据本发明的从至少含有甲烷、氮和轻的待液化原料馏分中分离出氮和较轻成分的方法及其其他的有利的实施方案。
附图说明
图1所示为根据本发明的实施方案。
具体实施方式
经过管路1将至少含有甲烷、氮和氢的原料馏分送至任选设置的预净化单元R。其包括在原料馏分的低压下压缩到40至90巴的压力，以及通常去除二氧化碳和汞，以及干燥。随后将如此预处理的原料馏分经过管路2送至热交换器E1，并在其中进行冷却和部分冷凝。热交换器E1通常设计成片式热交换器或螺旋管热交换器。在相应地大产能的情况下，任选设置多个相互平行和/或前后依次排列的热交换器。
原料馏分与至少一个任意形式的制冷回路相对地进行冷却和液化，该制冷回路在附图中仅由管路区段20-24图示出，下面更详细地加以描述。优选将该制冷回路设计成膨胀回路或混合回路。
将部分冷凝的原料馏分经过其中可以设置减压阀a的管路3送至精馏塔T，及在该精馏塔中分离成为液态馏分和气态馏分。在精馏塔T的塔顶经过管路4排出氮以及较轻的成分，尤其是含有氢的馏分。将其在热交换器E1中与待冷却的原料馏分相对地进行加热，随后经过设备边缘处的管路5排出。作为替代性的或补充的方案，经过管路4排出的馏分还可在其于R中干燥之前用于预冷却原料馏分1，从而在R中干燥之前降低原料馏分1的水含量。
若待液化的原料馏分1含有重的烃类，则优选在精馏塔T上游分离出该重的烃类。可以在SKW-分离塔、脱乙烷塔、脱丙烷塔等中进行分离。
从精馏塔T的塔底经过管路6排出氮含量典型地小于3体积％的富含甲烷的液态馏分，并在热交换器E1中与制冷回路的制冷剂或制冷剂混合物23相对地进行过冷。经过管路7将如此获得的LNG产品在阀门b中减压后送至储存容器S。
将在储存容器S中产生的储罐回气经过管路8从储存容器S排出，条件是需要在压缩机V中进行单级或多级压缩，并优选在其冷却之前送至原料馏分1。替代性地，还可将储罐回气送至燃气系统，或者在设备边缘处排出。
根据本发明通过制冷剂或制冷剂混合物或制冷剂的支流或制冷剂混合物的支流对精馏塔T的塔顶冷凝器E2进行冷却。在附图中所示的实施方案中，将一部分制冷剂(混合物)流经过管路22送至塔顶冷凝器E2，并在通过塔顶冷凝器之后经过管路23使其通过热交换器E1。随后将在其中与待冷却的原料馏分相对地加热的制冷剂(混合物)经过管路24从热交换器E1排出。将制冷剂或制冷剂混合物的未被送至塔顶冷凝器E2的支流引导经过其中设置有调节阀d的管路21。
可以将该塔顶冷凝器E2设计成片式交换器、螺旋管热交换器或TEMA-交换器，并且设置在精馏塔T之中或上方，其中在精馏塔T上方的设置可以省略掉再循环泵。通过改变塔高度和冷凝器温度，几乎可以任意地，即在约10ppm至几个体积百分比之间调节在经过管路4排出的馏分中的甲烷含量。
优选经过管路9使待液化的原料馏分的支流通过精馏塔T的煮沸器E3，通过该煮沸器可以保持储存在储存容器S中的LNG产品的氮含量低于1体积％，随后在阀门c中进行减压，并经过管路9′送至精馏塔T作为附加的原料流。替代性地，还可以将待液化的原料馏分的支流在热交换器E1中进行冷却之前或之后用作精馏塔T的塔底中的汽提气流，或者使用制冷剂(混合物)的支流作为煮沸器E3的热源。
在氮含量和氢含量均高至30体积％的情况下，优选使用根据本发明的从至少含有甲烷、氮和氢的待液化的原料馏分中分离出氮和较轻成分的方法。在此，在待液化的原料馏分中比较高的氢含量对于本发明方法的总能耗仅有无关紧要的影响，这是因为通过加热从精馏塔T的塔顶排出的、含有氮以及较轻成分尤其是氢的馏分而回收一部分冷量。

Claims (6)

1.从至少含有甲烷、氮和氢的待液化的原料馏分中分离出氮、氢、一氧化碳、氖和氩的方法，其中原料馏分(1)的甲烷含量为50至90体积％，氮含量为1至30体积％，氢含量为1至30体积％，原料馏分与至少一个制冷回路的制冷剂或制冷剂混合物相对地进行冷却和液化，其特征在于，
a)部分冷凝(E1)原料馏分(1)，
b)在至少一个精馏塔(T)中分离成富含甲烷的馏分(6)和含有氮和氢的馏分(4)，及
c)使富含甲烷的馏分(6)过冷，
d)其中通过一个或至少一个制冷回路(20-24)的制冷剂或制冷剂混合物或制冷剂的支流或制冷剂混合物的支流而冷却精馏塔(T)的塔顶冷凝器(E2)。
2.根据权利要求1的方法，其特征在于，将含有氮和氢的馏分(4)与待冷却的原料馏分(1，2)相对地进行加热，其中在任选干燥(R)原料馏分(1)之前和/或之后冷却原料馏分(1)。
3.根据权利要求1或2的方法，其特征在于，改变精馏塔(T)的塔顶冷凝器(E2)的冷凝器温度。
4.根据权利要求1或2的方法，其中临时储存富含甲烷的液化的馏分，其特征在于，将在临时储存(S)期间产生的储罐回气(8)进行压缩，并送至待液化的原料馏分(1)。
5.根据权利要求1或2的方法，其特征在于，将精馏塔(T)的待液化的原料馏分(1)的支流作为精馏塔(T)的塔底和/或精馏塔(T)的煮沸器(E3)中的汽提气流进行冷却，并作为另一原料流送至精馏塔(T)。
6.根据权利要求1或2的方法，其中将原料馏分与至少两个制冷回路的制冷剂和/或制冷剂混合物相对地进行冷却和液化，其特征在于，利用分离的制冷回路或者通过最轻制冷回路的制冷剂或制冷剂混合物的至少一股支流对精馏塔(T)的塔顶冷凝器(E2)进行冷却。
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