CN1145003C - 生产燃料及高纯甲烷的深冷精馏系统 - Google Patents

生产燃料及高纯甲烷的深冷精馏系统 Download PDF

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CN1145003C
CN1145003C CNB001199528A CN00119952A CN1145003C CN 1145003 C CN1145003 C CN 1145003C CN B001199528 A CNB001199528 A CN B001199528A CN 00119952 A CN00119952 A CN 00119952A CN 1145003 C CN1145003 C CN 1145003C
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carbon dioxide
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cryogenic rectification
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CN1292486A (zh
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M・M・沙
M·M·沙
马洛尼
J·J·马洛尼
德尔尼维奇
R·F·德尔尼维奇
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Praxair Technology Inc
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Abstract

一种能够生产燃料及如高纯甲烷或高纯天然气的高纯烃产品二者的天然气纯化系统，其中高温二氧化碳去除之后再进行深冷精馏，以生产燃料及高纯烃产品。

Description

生产燃料及高纯甲烷的深冷精馏系统
本发明一般涉及深冷精馏，更具体地说，涉及提纯天然气的深冷精馏。
在天然气的生产中，有时必须对粗天然气流进行提纯处理，以生产含足量可燃成分的天然气，从而可使其在天然气分配网如管线系统内得以有效利用。已知有一些这样的天然气提纯系统，并获得工业应用。
甲烷，天然气的主要成分，广泛用于化学合成的原料。为此，甲烷必须是高纯的，以保证下游有效的合成。最希望生产高纯甲烷，将它与天然气提纯过程结合一起，以适用于后续的化学合成反应。
因此，本发明目的在于提供一种能处理粗天然气进料物流并生产燃料及高纯度甲烷的系统。
处理含氮粗天然气流的传统天然气提纯系统，一般生产管道品级的天然气，其含氮量很高，达5％(摩尔)甚至更多。尽管对于大多数的天然气应用场合，这都是可接受的，但在某些场合，这样的氮含量也是不能容许，如某些冶金过程，其中氮有损于金属。因此，本发明的另一目的在于，提供一种能处理粗天然气进料并生产燃料及高纯天然气的系统。
以上和其它目的，对于本领域技术人员在阅读本发明之后会是明显的，是可通过本发明达到的，其一方面为：
一种生产燃料及高纯度烃产品的方法包括：
(A)、提供一种包括氮、甲烷及二氧化碳进料，其中进料包含1-40％(体积)的二氧化碳；
(B)、去除进料中的二氧化碳，产生一种贫二氧化碳的进料；
(C)、冷却该贫二氧化碳的进料，并将冷却后的贫二氧化碳进料送入深冷蒸馏塔；
(D)、通过在深冷蒸馏塔内的深冷精馏，将贫二氧化碳进料分离为燃料及高纯烃产品；以及
(E)、从深冷精馏塔的上部回收燃料，并从深冷精馏塔的下部回收高纯烃产品。
本发明的另一方面是：
生产燃料及高纯烃产品的装置包括：
(A)、去除二氧化碳的系统及对该系统提供包含氮、甲烷及二氧化碳的进料的设备；
(B)、热交换器及用于将来自二氧化碳去除系统的贫二氧化碳进料输送至热交换器设备；
(C)、深冷精馏塔及用于将来自热交换器的贫二氧化碳进料输送至深冷精馏塔设备；
(D)、从该深冷精馏塔上部回收燃料的设备；
(E)、从深冷精馏塔下部回收高纯烃产品的设备。
这里所用术语“塔”指的是一种蒸馏或分馏塔或蒸馏或分馏区，即接触塔或接触区，其中为实现流体混合物的分离，液相及汽相按逆流方式接触，例如可通过装在塔内一系列垂直间隔的塔盘或塔板及/或诸如结构式或无规则的填料单元来进行汽、液相间的接触。对蒸馏塔进一步的讨论，可参考R.H.佩里及C.H.希尔顿合编的“化学工程师手册”，第五版，第13节“连续蒸馏方法”(迈克格偌-席尔图书公司(McGraw-Hill Book Company)，纽约)。汽液接触的分离过程取决于组分间的蒸汽压差。高蒸汽压(或高挥发性或低沸点)的组分倾向于在汽相中浓缩，而低蒸汽压(或低挥发性或高沸点)的组分倾向于在液相中浓缩。部分冷凝是一种利用对蒸汽混合物进行冷却，使汽相中高挥发性组分浓缩及液相中低挥发性组分浓缩的分离的方法。精馏，或连续蒸馏是一种将连续部分汽化及冷凝组合一起，尤如汽液相间逆流处理所达到那样的分离方法。汽、液相间的逆流接触是绝热的，可包括积分或微分的相间接触。利用精馏原理分离混合物的分离装置通常可互通称为精馏塔、蒸馏塔、或分馏塔。深冷精馏是一种在至少部分温度处于或低于150°K(绝对)下进行的精馏方法。
这里所用术语“间接热交换”指的是，两流体在无任何实体接触或彼此互不混合的情况下进行的热交换关系。
这里所用术语“上部”及“下部”分别指在蒸馏塔中点之上或之下的塔段。
这里所用术语“燃料”指含有15-40％(体积)甲烷的流体。
这里所用术语“高纯甲烷”指含至少99％(体积)的甲烷、0.5％(摩尔)以下的氮及0.5％(摩尔)以下的重质烃的流体。
这里所用术语“高纯天然气”指基本由烃，如甲烷及重质烃组成的流体，并且含有不超过200ppm的氮，优选不超过50ppm的氮。
这里所用术语“高纯烃产品”指的是高纯甲烷或高纯天然气。
这里所用术语“塔顶冷凝器”指的是通过塔内蒸汽产生塔内下流液体的热交换装置。
这里所用术语“塔底再沸器”指的是通过塔内液体产生塔内上流蒸汽的热交换装置。
图1为本发明一个优选实施方案的流程示意图，其中二氧化碳去除系统为化学吸收系统，尤其适于二氧化碳浓度较高的进料，并生产高纯度甲烷和燃料。
图2为本发明另一优选实施方案的流程示意图，其中二氧化碳去除系统为膜分离系统，尤其适于二氧化碳浓度较低的进料，并生产高纯度甲烷和燃料。
图3是本发明另一优选实施方案的流程示意图，其中生产高纯度天然气和燃料。
现参照附图对本发明作更详细的说明。参照图1，将压力一般在150-600磅/平方英寸绝对压力(psia)范围的进料102引至分离器204中，在此分离器内物流102中的液体以物流103去除。将包含氮、甲烷及二氧化碳的气体进料104送至二氧化碳去除系统208。一般这种进料按照干气计含2-85％(体积)的氮、15-95％(体积)的甲烷和1-40％(体积)的二氧化碳。在进料流104中可含的其它物质包括重质烃如乙烷及丙烷。
二氧化碳去除系统208是以示意形式表示的。它属于热碳酸钾系统，尤其适宜于进料104中二氧化碳浓度在3-40％(体积)范围。该热碳酸钾系统包括吸收塔，其中热碳酸钾溶液与进料接触以吸收二氧化碳。通过加热并另用部分燃料产物作为汽提气进行汽提可使吸收了二氧化碳的吸收剂再生，此后将有描述。再生后的吸收剂可再循环至吸收塔中。
从二氧化碳去除系统208中以物流108抽出贫二氧化碳进料，其二氧化碳的浓度一般为0.05-1.0％(体积)，并将其送至干燥器212，通过在吸附剂颗粒上的吸附过程，去除贫二氧化碳进料中的所有水分。将所得干燥贫二氧化碳进料110送至热交换器214，使之通过与返回物流的间接热交换被冷却。将部分流经热交换器214后的物流110的一部分112从中抽出，并送至上游塔220的塔底再沸器222，通过与塔220的塔底液的间接热交换，使之进一步冷却和部分冷凝。将所得物流114流经阀216以物流115送至塔220。物流110其余部分116完全穿过热交换器214进一步进行冷却。将所得进一步冷却的尚可部分冷凝的物流通过阀218并以物流117送至塔220。
塔220操作一般在145-595psia的压力范围。在该塔220内贫二氧化碳进料经精馏被分离为塔底液和塔顶蒸汽。塔底液内包含重质烃及二氧化碳以及一些甲烷，将其从塔220下部以物流118抽出，再经阀226以物流119与其它物流合并，以进行下述的进一步处理。顶部蒸汽从塔220上部抽出，作为贫二氧化碳进料130，再将其进一步冷却至所需深冷温度。物流130包含大部分氮及甲烷，并可含少量二氧化碳及乙烷。
将贫二氧化碳进料130送至热交换器234，通过与返回物流的间接热交换加以冷却。将部分流经热交换器234的物流130的一部分132从热交换器234抽出，送至深冷精馏塔240的塔底再沸器242中，通过与塔240的塔底液的间接热交换，进行冷却及部分冷凝。再将所得流体134经阀236以物流135送至深冷精馏塔240中。将130物流的其余部分136完全穿过热交换器234，进行进一步的冷却及部分冷凝。将所得进一步冷却后的物流经阀238以物流137送进塔240。
深冷精馏塔240操作一般在20-400psia的压力范围。在该深冷精馏塔240内将冷却后的贫二氧化碳进料进行深冷精馏，使之分离为燃料及高纯甲烷。高纯甲烷从塔240下部以液流150抽出。用泵250将物流150的一部分162还可泵至更高的压力，然后作为物流164送至热交换器234，在234中加以汽化。所得物流166经热交换器214进一步加温，并以物流168加以回收。物流150的其余部分152经阀246减压，将低压液体物流153送至塔顶冷凝器244，进行汽化，从而通过间接热交换起到对塔240提供回流液的作用。经热交换器234使所得蒸汽154加温，所得物流156经热交换器214进一步加温。将所得加温物流158通过压缩机260增压，所得增压后的物流159与物流168合并，形成物流170作为高纯甲烷产品回收。
燃料以物流140自深冷精馏塔240上部抽出。物流140的第一部分141在热交换器234中通过间接热交换进行加温，并以物流144抽出。物流140的第二部分142旁路热交换器234。将物流144及142与已经过阀226闪蒸的物流119合并，形成混合相流145，送入塔顶冷凝器224。物流145在塔顶冷凝器224经与塔220的上升蒸汽间接热交换而被加温及汽化，并产生220塔回流液体。将来自冷凝器224的所得加温燃料流146穿过热交换器214，进一步加温，再以物流178将其抽出。将燃料流178的一部分179用于再生干燥器212，再以含水蒸气及甲烷和氮的物流181排出。按虚线所示回收178物流余下部分180，或可将其送至热碳酸钾系统的汽提塔，使碳酸钾溶液进行再生，再作为含二氧化碳的燃料流182加以排出。物流181及182或180合并一起，形成产物燃料流186。
附图2说明本发明另一实施方案，尤其适用于进料中二氧化碳的浓度在1-4％(体积)范围。在图2说明的实施方案中，所用二氧化碳去除系统是一种膜分离单元。对共同部件，图2中的数字与图1中的一样，这些共同部件将不再详尽描述。
现参照图2，将进料104送至膜分离器206，206分离器包括一种其对二氧化碳的选择性超过对甲烷及氮二者的薄膜。二氧化碳及水蒸气渗透通过该薄膜，并以渗透物流107从分离器206中分出，其一般操作压力在15-25psia范围。物流107一般也含一些甲烷，因此也可将其送入燃料流186，如图2所示。将滞留的物流109作为贫二氧化碳的进料送入干燥器212，用于如前所述的进一步处理。
对于不含大量重质烃的进料，或在除燃料外还需要高纯天然气而非高纯甲烷的场合，不必采用上游精馏塔220，可在冷却步骤之后将贫二氧化碳进料直接从二氧化碳去除系统送至深冷精馏塔。
图3说明除生产燃料外还生产高纯天然气的一个实施方案。对共同部件，图3中的数字与图2中的相同，这些共同部件将不再详尽描述。现参照图3，将干燥后的贫二氧化碳进料110送至热交换器314，通过与回流的间接热交换加以冷却。将部分流经热交换器314的物流110的一部分332抽出，送至深冷精馏塔340的塔底再沸器342，通过与塔340的塔底液的间接热交换，进一步加以冷却及部分冷凝。将所得流体334经阀386以物流335送至深冷精馏塔340。将物流110其余部分336以完全穿过热交换器314，进一步加以冷却及部分冷凝。将所得进一步冷却后的物流经阀338以物流337送至塔340中。
深冷精馏塔340操作于一般20-400psia的压力范围。在深冷精馏塔340内，该冷却后的贫二氧化碳进料通过深冷精馏分离为燃料及高纯天然气，一般含有多至约95％(摩尔)的甲烷和其余基本上是有2或2以上碳原子的诸如乙烷及丙烷的烃，即重质烃。
高纯天然气从塔340的下部以液流350排出，通过阀352作为物流364再送至热交换器314，进行加热并优选汽化。所得物流368从热交换器314抽出并加以回收。以物流380从深冷精馏塔340上部排出燃料，物流380在热交换器314中经间接热交换加温，并以物流378排出。燃料流378的一部分379用于再生干燥器212，并以含水蒸汽、甲烷及氮的物流381排出。将物流378的其余部分390与物流381合并，形成物流386，直接加以回收，如图3所示。如果需要，物流107还可与物流386合并以回收。
尽管现已参照某些实施方案对本发明进行了详细描述，但本领域技术人员都会承认在本发明所述权利要求的构思及范围内还有一些其它实施方案。

Claims (10)

1、一种生产燃料及高纯烃产品的方法包括：
(A)、提供一种包括氮、甲烷及二氧化碳的进料，其中进料包含体积为1-40％的二氧化碳；
(B)、去除进料中的二氧化碳，产生一种贫二氧化碳的进料；
(C)、冷却该贫二氧化碳的进料，并将冷却后的贫二氧化碳进料送入深冷蒸馏塔中；
(D)、通过在深冷精馏塔内的深冷精馏，将贫二氧化碳进料分离为燃料及高纯烃产品；及
(E)、从深冷精馏塔的上部回收燃料，并从深冷精馏塔的下部回收高纯烃产品。
2、按照权利要求1所述方法，其中通过将进料与热碳酸钾接触并使进料中的二氧化碳吸收至热碳酸钾中以去除进料中的二氧化碳。
3、按照权利要求1所述方法，其中采用使进料通过薄膜分离器并使进料中二氧化碳选择性地渗透穿过薄膜分离器的薄膜以去除进料中二氧化碳。
4、按照权利要求1所述方法，其中进料含一种或数种另外的具有2个或2个以上碳原子的烃物质，和其中使贫二氧化碳进料在进入深冷精馏塔之前进行精馏，以去除具有2个或2个以上碳原子的烃类。
5、按照权利要求1所述方法，其中高纯烃产品是高纯甲烷。
6、用于生产燃料及高纯烃产品的装置包括：
(A)、去除二氧化碳的系统及对该系统提供包含氮、甲烷及二氧化碳的进料的设备；
(B)、热交换器及用于将来自二氧化碳去除系统的贫二氧化碳进料输送至热交换器设备；
(C)、深冷精馏塔及用于将来自热交换器的贫二氧化碳进料输送至深冷精馏塔设备；
(D)、从深冷精馏塔上部回收燃料的设备；
(E)、从深冷精馏塔下部回收高纯烃产品的设备。
7、按照权利要求6的装置，还包括上游精馏塔，和其中用于将来自二氧化碳去除系统的贫二氧化碳进料输送至热交换器的设备包括该上游精馏塔。
8、按照权利要求6的装置，还包括干燥器，和其中用于从深冷精馏塔的上部回收燃料的设备包括输送部分燃料通过干燥器的设备。
9、按照权利要求6的装置，其中深冷精馏塔具有塔底再沸器和其中热交换器设备包括塔底再沸器。
10、按照权利要求6的装置，其中深冷精馏塔具有塔顶冷凝器，和其中从深冷精馏塔下部回收高纯烃产品的设备包括塔顶冷凝器。
CNB001199528A 1999-07-01 2000-06-30 生产燃料及高纯甲烷的深冷精馏系统 Expired - Fee Related CN1145003C (zh)

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